CN111039444A - Treatment process of aqueous solution generated in treatment process of mother liquor extract in oxidation process of terephthalic acid production device - Google Patents
Treatment process of aqueous solution generated in treatment process of mother liquor extract in oxidation process of terephthalic acid production device Download PDFInfo
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- CN111039444A CN111039444A CN201911177355.7A CN201911177355A CN111039444A CN 111039444 A CN111039444 A CN 111039444A CN 201911177355 A CN201911177355 A CN 201911177355A CN 111039444 A CN111039444 A CN 111039444A
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- 238000000034 method Methods 0.000 title claims abstract description 120
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 99
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 79
- 238000011282 treatment Methods 0.000 title claims abstract description 52
- 230000003647 oxidation Effects 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 239000012452 mother liquor Substances 0.000 title claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 408
- 239000011347 resin Substances 0.000 claims abstract description 295
- 229920005989 resin Polymers 0.000 claims abstract description 295
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 208
- 229910001868 water Inorganic materials 0.000 claims abstract description 208
- 238000001179 sorption measurement Methods 0.000 claims abstract description 186
- 150000001555 benzenes Chemical class 0.000 claims abstract description 177
- 238000001728 nano-filtration Methods 0.000 claims abstract description 154
- 150000001768 cations Chemical class 0.000 claims abstract description 99
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000001257 hydrogen Substances 0.000 claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 89
- 239000007788 liquid Substances 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims abstract description 73
- 230000008929 regeneration Effects 0.000 claims abstract description 67
- 238000011069 regeneration method Methods 0.000 claims abstract description 67
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012528 membrane Substances 0.000 claims abstract description 56
- 238000001704 evaporation Methods 0.000 claims abstract description 44
- 238000001223 reverse osmosis Methods 0.000 claims description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 78
- 239000013505 freshwater Substances 0.000 claims description 76
- 229910052742 iron Inorganic materials 0.000 claims description 69
- 239000000126 substance Substances 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 45
- 238000001914 filtration Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 40
- 239000010941 cobalt Substances 0.000 claims description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 39
- 230000008020 evaporation Effects 0.000 claims description 34
- 229910017052 cobalt Inorganic materials 0.000 claims description 33
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 26
- 238000005260 corrosion Methods 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 12
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 10
- 230000001172 regenerating effect Effects 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 8
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims 2
- 239000010865 sewage Substances 0.000 abstract description 40
- 239000007787 solid Substances 0.000 abstract description 35
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 28
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052794 bromium Inorganic materials 0.000 abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000013589 supplement Substances 0.000 abstract description 3
- -1 iron ions Chemical class 0.000 description 77
- 229910001415 sodium ion Inorganic materials 0.000 description 49
- 229910001429 cobalt ion Inorganic materials 0.000 description 46
- 229910001437 manganese ion Inorganic materials 0.000 description 46
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 40
- 238000002474 experimental method Methods 0.000 description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 22
- 239000012670 alkaline solution Substances 0.000 description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 230000009286 beneficial effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 18
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 12
- 230000002411 adverse Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000005711 Benzoic acid Substances 0.000 description 10
- 235000010233 benzoic acid Nutrition 0.000 description 10
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 229940006460 bromide ion Drugs 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000000108 ultra-filtration Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910001430 chromium ion Inorganic materials 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- MYTNTIKQVJSIER-UHFFFAOYSA-N anthracene-9,10-dione;fluoren-1-one Chemical compound C1=CC=C2C3=CC=CC(=O)C3=CC2=C1.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 MYTNTIKQVJSIER-UHFFFAOYSA-N 0.000 description 5
- 150000002391 heterocyclic compounds Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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Abstract
The invention provides a treatment process of an aqueous solution generated in the treatment process of a mother liquor extract in the oxidation process of a terephthalic acid production device, belonging to the field of water treatment. The process flow is that the water solution is absorbed by benzene series adsorption resin (a part of TA and 4-CBA are absorbed in the process), the benzene series adsorption resin is regenerated by acetic acid solution after being absorbed, the generated acetic acid regeneration liquid is subjected to acetic acid removal treatment by an acetic acid removal unit of a membrane method and/or an acetic acid removal unit of an evaporation method, the residue is added with water to separate out solid containing BA, the total amount of benzene series in the water solution entering a sewage plant is reduced, the COD load of the sewage plant is favorably reduced, and the environment is favorably protected; the benzene series adsorption resin, the nanofiltration device and the hydrogen type cation resin are combined for use, and bromide ions in the aqueous solution can be recycled, so that the amount of bromine discharged to sewage of the whole device is reduced, the required supplement amount of bromine of the terephthalic acid production device is reduced, and the operation cost is reduced.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a treatment process of an aqueous solution generated in the treatment process of a mother liquor extract in an oxidation process of a terephthalic acid production device.
Background
Terephthalic acid is an important polyester production raw material, so that the industrial application is very wide. The main process of producing terephthalic acid comprises two procedures of oxidation and refining.
The oxidation process mainly comprises the steps that p-xylene serving as a raw material reacts with oxygen in air in a reactor to generate terephthalic acid, the reaction process needs to add elements such as cobalt, manganese and bromine as catalysts, and acetic acid as a solvent. Carrying out solid-liquid separation on the product obtained after the reaction and a solution containing acetic acid, cobalt, manganese, bromine and the like, wherein the solid is crude terephthalic acid; the mother liquor of the oxidation step is a mixed solution mainly containing acetic acid, benzoic acid and acid radicals thereof, phthalic acid and acid radicals thereof, cobalt, manganese, bromine, oxidation intermediate p-carboxybenzaldehyde, metal corrosion products (such as iron and chromium ions, the metal corrosion products are mainly iron ions in concentration, the chromium ions are low in concentration compared with the iron ions), sodium ions and the like, and the mixed solution mainly contains acetic acid in concentration and also contains water in a certain proportion.
The refining process is that the product of the oxidation process is pulped by water and then enters a hydrogenation reactor, some kinds of benzene series impurities in the product of the oxidation process are subjected to hydrogenation reaction, and then the product is separated from the terephthalic acid in a solid-liquid separation mode, so that the purity of the terephthalic acid is improved, and the product is called a finished product of purified terephthalic acid.
In the prior art, a part of the mother liquor of the oxidation process is discharged (namely, the mother liquor extract of the oxidation process) and mainly contains phthalic acid and acid radicals thereof (containing ortho, meta and para positions, which are collectively referred to as phthalic acid unless otherwise specified), by-product benzoic acid and acid radicals thereof, heterocyclic compounds such as oxidation intermediate p-carboxybenzaldehyde and by-product anthraquinone fluorenone, acetic acid, sodium ions, metal corrosion products in the production process (for example, iron and chromium ions, wherein the metal corrosion products are mainly iron ions in concentration, and the chromium ions are low in concentration compared with iron ions), bromide ions, cobalt ions, manganese ions and the like.
In the existing process, one of the conventional methods for treating the mother liquor extract of the oxidation process in the factory is to pass the mother liquor extract of the oxidation process through an acetic acid removal unit (an acetic acid removal unit of a membrane method and/or an acetic acid removal unit of an evaporation method), add water to the remaining substances, make the benzene series such as the heterocyclic compounds such as phthalic acid, benzoic acid, p-carboxybenzaldehyde, anthraquinone fluorenone and the like have low solubility in water, reduce the solubility in the water adding process due to temperature reduction, crystallize and precipitate most of the benzene series such as the heterocyclic compounds such as phthalic acid, benzoic acid, p-carboxybenzaldehyde, anthraquinone fluorenone and the like, separate the solid and liquid to obtain an aqueous solution, wherein the phthalic acid and the acid radical thereof, the benzoic acid and the acid radical thereof, the p-carboxybenzaldehyde and the acid radical thereof in the aqueous solution still have certain solubility → add alkaline substances (generally, carbonate, p-carboxybenzaldehyde and the, Bicarbonate and hydroxide) → filtration → further addition of alkaline substances (carbonate, bicarbonate and hydroxide are generally used) → filtration → discharge to a sewage treatment process, wherein the alkaline substances are added for the first time to raise the pH (about 3.0-7.5) and most of metal corrosion products form solid matters to be filtered and removed (for example, iron and chromium ions, the metal corrosion products mainly contain iron ions according to the concentration, and the chromium ions are lower than the iron ions, namely, the iron ions are mainly removed in the step), and meanwhile, solid phthalic acid and benzoic acid powder leaked in the solid-liquid separation process for obtaining the aqueous solution also start to dissolve; adding alkaline substance for the second time to raise pH (pH is about 7.5-14) to form solid substance of cobalt ion and manganese ion, collecting the solid substance in the filter to recover cobalt and manganese, and periodically dissolving cobalt and manganese in the filter with hydrobromic acid and then recovering the solid substance to the oxidation reaction system (namely recovering cobalt and manganese).
In the prior art, another treatment method of the mother liquor extract of the oxidation process in the factory is that after the mother liquor of the oxidation process passes through an acetic acid removal unit (an acetic acid removal unit of a membrane method and/or an acetic acid removal unit of an evaporation method), alkaline substances (generally carbonate, bicarbonate and hydroxide) are directly added → filtration → then the alkaline substances (generally carbonate, bicarbonate and hydroxide) are added → filtration → discharge to a sewage treatment process, the alkaline substances are added for the first time to raise the pH (the pH is about 3.0-7.5), most of metal corrosion products form solid substances and are filtered and removed, and meanwhile, phthalic acid and benzoic acid powder start to dissolve; adding alkaline substances for the second time to increase the pH (about 7.5-14) to form solid matters of cobalt ions and manganese ions, collecting the solid matters in a filter to recover the cobalt and the manganese, and finally enabling the phthalic acid and the benzoic acid to enter a sewage treatment plant in the process.
Disclosure of Invention
The English symbols involved in the invention are defined as follows: TA: phthalic acid and acid radicals thereof; BA: benzoic acid and acid radicals thereof; 4-CBA: p-carboxybenzaldehyde and acid groups thereof.
The invention aims to treat the aqueous solution generated in the treatment process of the mother liquor extract of the oxidation process of a terephthalic acid production device, a part of benzene series (mainly BA) in the aqueous solution is absorbed by benzene series adsorption resin, the benzene series adsorption resin is regenerated by acetic acid, BA and 4-CBA absorbed by the benzene series adsorption resin are dissolved in the acetic acid during the acetic acid regeneration, TA powder which is generated and washed out during the regeneration process along with the insolubility of the acetic acid returns to an acetic acid removal unit, and the benzene series is added with water after the acetic acid removal to separate out solid and liquid to form solid containing BA, so that the total amount of the benzene series entering the sewage plant by the aqueous solution is finally reduced, namely the total amount of COD entering the sewage plant is reduced, the load of the sewage plant is reduced, the operation cost is reduced, and the environment is protected; the benzene series adsorption resin, the nanofiltration device and the hydrogen type cation resin are combined for use, and bromide ions in the aqueous solution can be recycled, so that the amount of bromine discharged to sewage by the whole device is reduced, namely, the bromine supplement amount of the whole terephthalic acid production device is reduced, and the enterprise operation cost is favorably reduced.
The invention aims to provide a process for mainly removing BA, sodium ions and iron ions in an aqueous solution in steps, wherein the aqueous solution mainly comprises the following components:
TA (originally the product of the oxidation process): are beneficial substances for the oxidation of terephthalic acid;
bromide ion (catalyst for oxidation step): are beneficial substances for the oxidation of terephthalic acid;
cobalt and manganese ions (catalyst in oxidation step): are beneficial substances for the oxidation of terephthalic acid;
4-CBA is a beneficial substance if it is recycled to the oxidation reaction where it can be re-oxidized to terephthalic acid;
acetic acid (originally, a solvent in the oxidation step): are beneficial substances for the oxidation of terephthalic acid;
BA is a byproduct of the oxidation reaction, and excessive BA cannot be recycled to the oxidation reaction system again, so that the BA of the oxidation mother liquor is increased to generate adverse effect;
excessive sodium ions cannot be recycled to the oxidation reaction system again, which can cause the increase of the sodium ions in the oxidation mother liquor to generate adverse effects;
the inability to recycle the excess iron ions back to the oxidation reaction system can have undesirable effects (e.g., affecting the catalyst in the hydrogenation reactor of the purification process of a terephthalic acid production plant).
The invention can treat the water solution generated after the mother liquor extract of the oxidation process of the terephthalic acid production device is treated, and one of the methods for obtaining the water solution by the mother liquor extract of the oxidation process of the terephthalic acid production device through a series of treatments can be as follows: the mother liquor extract of the oxidation process passes through an acetic acid removal unit (an acetic acid removal unit of a membrane method and/or an acetic acid removal unit of an evaporation method), then the remaining substances are added with water, the solubility of benzene series such as heterocyclic compounds such as TA, BA, 4-CBA, anthraquinone fluorenone and the like in water is low, the temperature in the water addition process is reduced, the solubility is reduced, finally most of the benzene series such as heterocyclic compounds such as TA, BA, 4-CBA, anthraquinone fluorenone and the like are crystallized and separated out, and the water solution generated by solid-liquid separation is the water solution treated by the process flow; the method for treating the mother liquor extract of the oxidation process of the terephthalic acid production device to obtain the aqueous solution can be other methods, and the method is within the protection scope of the invention as long as the method contains BA, sodium ions, iron ions or bromide ions and can be carried out in the process flow treatment of the invention.
The process flow of the invention is as follows:
the process treatment route entering the treatment of the invention is as follows: the method comprises the following steps of enabling an aqueous solution generated in the treatment process of a mother liquor extract of an oxidation process of a terephthalic acid production device to enter benzene series adsorption resin (the benzene series adsorption resin refers to resin with adsorption capacity on benzene series, and the benzene series refers to a substance containing a benzene ring structure), adsorbing the benzene series in the aqueous solution, enabling the benzene series contained in the aqueous solution entering the benzene series adsorption resin to mainly contain TA, BA, 4-CBA with relatively low concentration and the like, enabling the benzene series adsorption resin to mainly adsorb the BA and 4-CBA, enabling the adsorption of the benzene series adsorption resin on the TA to be worse and worse along with the increase of treated water quantity, enabling the aqueous solution after adsorption to be discharged from the benzene series adsorption resin, and enabling the concentration of the BA and 4-CBA in the aqueous solution to be reduced in a large gradient manner;
after benzene series adsorption resin is adsorbed, regenerating by using an acetic acid solution to recover the adsorption capacity to obtain an acetic acid regeneration liquid A, wherein the acetic acid regeneration liquid A is BA and 4-CBA adsorbed on the benzene series adsorption resin dissolved by acetic acid, and analyzing the components of the acetic acid regeneration liquid A, wherein the acetic acid regeneration liquid A obviously contains BA and 4-CBA, and meanwhile, the acetic acid regeneration liquid A also contains undissolved TA generated in the regeneration process of flushing out the resin in the regeneration process and is white powder; the acetic acid regeneration liquid A also contains cobalt, manganese, iron and other ions which are adhered to the resin with low concentration.
The benzene series adsorption resin can also be regenerated by alkaline solution (the alkaline solution is selected from sodium hydroxide solution, potassium carbonate solution, sodium bicarbonate solution, potassium bicarbonate solution or sodium carbonate solution), but the regeneration by the alkaline solution has the following defects compared with the regeneration by acetic acid:
if the regeneration liquid of the alkaline solution is directly discharged to the sewage, BA and the like absorbed by the benzene series adsorption resin enter the sewage treatment, the amount of benzene series, namely COD, entering the sewage is not reduced, the consumption of the alkaline solution is increased, and the alkaline solution entering the sewage can generate adverse effect on the sewage;
if the method of adding acid to separate out the benzene series (mainly BA) is adopted for the regeneration liquid of the alkaline solution, the back section of the regeneration liquid of the alkaline solution needs to be designed with 3 steps of filtering (cobalt and manganese with a little solid), adding acid (separating out the solid benzene series mainly containing BA) and filtering (filtering to remove the benzene series mainly containing BA), firstly adding the alkali and then adding the acid to consume acid and alkali (compared with the prior art, if the benzene series adsorption resin is regenerated by the acetic acid, the regeneration liquid of the acetic acid can directly pass through an acetic acid removing unit to recover the acetic acid, and the recovered acetic acid can directly enter an oxidation reaction system, because the oxidation reaction system needs to add the acetic acid, namely no substance is wasted); secondly, the water added with alkali and then added with acid finally enters the sewage, which can cause the ion concentration of the sewage to rise, thus being not beneficial to the operation of the sewage (in contrast, if the benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid does not enter the sewage because the acetic acid enters an acetic acid removal system to recover the acetic acid, thus the problem can not be solved); and thirdly, the later section of the alkaline solution regeneration liquid needs to be designed and filtered (cobalt and manganese with a little solid), acid is added (solid benzene series mainly containing BA is separated out), and the filtering (the benzene series mainly containing BA is removed by filtering) is carried out for 3 steps, and the length of a multi-path line of the steps is not beneficial to the actual engineering operation (compared with the prior art, if the benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid mainly contains BA, 4-CBA and a little insoluble TA, and can directly return to the acetic acid removal unit of the membrane method and/or the acetic acid removal unit of the evaporation method of the front section for treatment, no new step is added, and the actual engineering operation is facilitated).
Based on the technical scheme, preferably, the acetic acid regeneration liquid A is directly discharged; or the acetic acid regeneration liquid A is treated by an acetic acid removal unit of a membrane method and/or an acetic acid removal unit of an evaporation method, part of acetic acid is removed and recovered, and the residue after the treatment of the acetic acid removal unit is added with water to precipitate benzene series solid containing BA and the like (the acetic acid regeneration liquid A of the benzene series adsorption resin only contains substances in the original aqueous solution, so that other substances are not introduced into the whole process flow by returning to the previous acetic acid removal unit), and ions such as low-concentration cobalt, manganese, iron and the like contained in the acetic acid regeneration liquid A can return to the acetic acid removal unit again and enter the aqueous solution in the later water adding process, namely can be treated again by the process of the invention;
regenerating benzene series adsorption resin by acetic acid, washing with water, and re-adsorbing to obtain water washing solution A;
when the benzene series adsorption resin runs for many times and insoluble TA generated in the regeneration process of acetic acid is not completely flushed out to generate blockage, alkali washing can be added for one time to dissolve TA after the regeneration of the acetic acid, then the TA is washed by water to be recovered for use, and alkali washing liquid and water washing liquid are discharged.
Based on the above technical scheme, preferably, the benzene-series adsorption resin can be combined with a nanofiltration device and a hydrogen-type cationic resin, and the combination can be respectively implemented according to the following scheme I, scheme II or scheme III:
route i: the water solution enters benzene series adsorption resin to adsorb benzene series in the water solution (the main purpose is to adsorb BA, 4-CBA and part of TA is also adsorbed in a large concentration gradient), the effluent of the benzene series adsorption resin is treated by a nanofiltration device, the main purpose of the treatment by the nanofiltration device is to intercept multivalent cations such as cobalt ions, manganese ions and iron ions by a nanofiltration membrane to generate fresh water of the nanofiltration device, and the concentrated water of the nanofiltration device contains concentrated multivalent cations such as cobalt ions, manganese ions and iron ions; the fresh water of the nanofiltration device mainly contains sodium ions, bromide ions, TA and the like, and also contains low-concentration cobalt, manganese and iron ions, the fresh water of the nanofiltration device enters hydrogen type cationic resin to adsorb the sodium ions (simultaneously, the cobalt, manganese and iron ions in the fresh water are also removed) to obtain outlet water a, and the outlet water a mainly contains bromide ions, TA and the like;
route ii: the water solution is treated by a nanofiltration device before entering the benzene series adsorption resin, namely the water solution is treated by the nanofiltration device, the aim of the treatment by the nanofiltration device is to intercept multivalent cations such as cobalt ions, manganese ions and iron ions by a nanofiltration membrane to generate fresh water of the nanofiltration device, and the concentrated water of the nanofiltration device contains the concentrated multivalent cations such as cobalt ions, manganese ions and iron ions; fresh water of the nanofiltration device mainly contains sodium ions, bromide ions, TA, BA, 4-CBA and the like, and also contains low-concentration cobalt, manganese and iron ions, the fresh water of the nanofiltration device enters benzene series adsorption resin to adsorb benzene series in aqueous solution (the main purpose is to adsorb BA, 4-CBA is also adsorbed in a large concentration gradient, and a part of TA is also adsorbed), effluent water passing through the benzene series adsorption resin enters hydrogen type cation resin to adsorb sodium ions (cobalt, manganese and iron ions in the fresh water are also removed) to obtain effluent water b, and the effluent water b mainly contains bromide ions, TA and the like;
route iii: the water solution is treated by a nanofiltration device and hydrogen type cation resin before entering benzene series adsorption resin, namely the water solution is treated by the nanofiltration device, the main purpose is to intercept multivalent cations such as cobalt ions, manganese ions, iron ions and the like by a nanofiltration membrane to generate fresh water of the nanofiltration device, and concentrated water of the nanofiltration device contains the concentrated multivalent cations such as cobalt ions, manganese ions, iron ions and the like; fresh water of the nanofiltration device mainly contains sodium ions, bromide ions, TA, BA, 4-CBA and the like, and also contains low-concentration cobalt, manganese and iron ions, the fresh water of the nanofiltration device enters hydrogen type cation resin to adsorb the sodium ions (simultaneously removing the cobalt, manganese and iron ions in the fresh water), the effluent of the hydrogen type cation resin enters benzene series adsorption resin to adsorb the benzene series in the aqueous solution (the main purpose is to adsorb BA, the 4-CBA is also adsorbed in a large concentration gradient, and a part of TA is also adsorbed), and effluent c is obtained and mainly contains bromide ions, TA and the like;
the purpose of the above-mentioned benzene series adsorption resin is to remove the BA in the water solution, if it is planned that the effluent a, the effluent b or the effluent c is recycled to the oxidation reaction system after the BA is not removed, the production device of the terephthalic acid is adversely affected (the adverse effect of raising the BA of the oxidation mother liquor is caused); the nanofiltration device is used for intercepting iron ions, cobalt ions and manganese ions in an aqueous solution by using a nanofiltration membrane, and the main purpose is to reduce the content of the iron ions to a great extent in fresh water, if the recovery of effluent a, effluent b or effluent c to an oxidation reaction system is planned in the future without removing the iron ions, adverse effects can be caused on a terephthalic acid production device (for example, a catalyst of a hydrogenation reactor of the terephthalic acid production device is influenced); the purpose of using the hydrogen type cation resin is to remove sodium ions in the water solution, if the effluent a, the effluent b or the effluent c is planned to be recycled to the oxidation reaction system after the day when the sodium ions are not removed, the production device of the terephthalic acid is adversely affected (the adverse effect of causing the increase of sodium ions in the oxidation mother liquor is caused).
Based on the technical scheme, preferably, the aqueous solution is treated by a precipitation device and/or a filtration device before entering the benzene series adsorption resin; or before the aqueous solution enters the benzene series adsorption resin, the aqueous solution is cooled and treated by a precipitation device and/or a filtration device, so that the amount of the benzene series is reduced, and the adverse effect of blockage of solid benzene series powder is avoided.
Based on the technical scheme, preferably, the aqueous solution is treated by a precipitation device and/or a filtration device before entering the route I, the route II or the route III for treatment; or the aqueous solution is cooled and treated by a precipitation device and/or a filtration device before entering the route I, the route II or the route III, so that the amount of benzene series is reduced, and the adverse effect of blockage of solid benzene series powder is avoided.
Based on the technical scheme, preferably, the heat preservation device is arranged on the pipeline and the equipment after passing through the precipitation device and/or the filtering device, so that the adverse effects that the temperature is reduced in operation, the solubility of the benzene series is reduced, and the solid benzene series powder is crystallized and separated to block are avoided.
Based on the technical scheme, preferably, the effluent a of the route I, the effluent b of the route II or the effluent c of the route III can be treated as follows:
the effluent a of the route I, the effluent b of the route II or the effluent c of the route III enter an oxidation reaction system of a terephthalic acid production device;
or the effluent a of the route I, the effluent b of the route II or the effluent c of the route III are filtered and then enter an oxidation reaction system of a terephthalic acid production device;
or the effluent a of the route I, the effluent b of the route II or the effluent c of the route III firstly passes through the evaporation concentration device I in order to reduce the water content in the aqueous solution entering the oxidation reaction system of the terephthalic acid production device (the higher the water content entering the oxidation reaction system is, the higher the consumption of the oxidation reaction system is), and the concentrated solution of the evaporation concentration device I enters the oxidation reaction system of the terephthalic acid production device;
or the effluent a of the route I, the effluent b of the route II or the effluent c of the route III firstly passes through the reverse osmosis concentration device I in order to reduce the water content in the aqueous solution entering the oxidation reaction system of the terephthalic acid production device, the concentrated water of the reverse osmosis concentration device I enters the oxidation reaction system of the terephthalic acid production device, and the fresh water of the reverse osmosis concentration device I is discharged;
the oxidation reaction system entering the terephthalic acid production device refers to a feed entering an oxidation reactor or a mother liquor of the oxidation reactor, and the like, and the oxidation reaction entering any position as long as the oxidation reaction finally enters the terephthalic acid production device is included in the protection scope of the invention;
the effluent a from route I, the effluent b from route II or the effluent c from route III are all TA (originally the product of the oxidation step) and bromide ion (catalyst of the oxidation step), so that they are all useful substances for the production plant of terephthalic acid and can be recovered to the oxidation reaction system of terephthalic acid.
Based on the technical scheme, preferably, in order to reduce the treated water amount of the route I, the route II or the route III, an evaporation concentration device II or a reverse osmosis concentration device II is designed on the route; the evaporation concentration device II or the reverse osmosis concentration device II can be arranged at the following positions:
route i: at least one place in front of the benzene series adsorption resin, between the benzene series adsorption resin and the nanofiltration device, and between the fresh water of the nanofiltration device and the hydrogen type cation resin;
when the evaporation concentration device II is arranged in front of the benzene series adsorption resin, the concentrated solution of the evaporation concentration device II enters the benzene series adsorption resin; when the evaporation concentration device II is arranged between the benzene series adsorption resin and the nanofiltration device, concentrated solution of the evaporation concentration device II enters the nanofiltration device; when the evaporation concentration device II is arranged between the fresh water of the nanofiltration device and the hydrogen type cation resin, the concentrated solution of the evaporation concentration device II enters the hydrogen type cation resin; when the reverse osmosis concentration device II is arranged in front of the benzene series adsorption resin, the concentrated water of the reverse osmosis concentration device II enters the benzene series adsorption resin and the fresh water of the reverse osmosis concentration device II is discharged; when the reverse osmosis concentration device II is arranged between the benzene series adsorption resin and the nanofiltration device, the concentrated water of the reverse osmosis concentration device II enters the nanofiltration device and the fresh water of the reverse osmosis concentration device II is discharged; when the reverse osmosis concentration device II is arranged between the fresh water of the nanofiltration device and the hydrogen type cation resin, the concentrated water of the reverse osmosis concentration device II enters the hydrogen type cation resin and the fresh water of the reverse osmosis concentration device II is discharged;
route ii: at least one position between the fresh water of the nanofiltration device and the benzene series adsorption resin and between the benzene series adsorption resin and the hydrogen type cation resin is arranged in front of the nanofiltration device;
when the evaporation concentration device II is arranged in front of the nanofiltration device, the concentrated solution of the evaporation concentration device II enters the nanofiltration device; when the evaporation concentration device II is arranged between the fresh water of the nanofiltration device and the benzene series adsorption resin, the concentrated solution of the evaporation concentration device II enters the benzene series adsorption resin; when the evaporation concentration device II is arranged between the benzene series adsorption resin and the hydrogen type cation resin, the concentrated solution of the evaporation concentration device II enters the hydrogen type cation resin; when the reverse osmosis concentration device II is arranged in front of the nanofiltration device, the concentrated water of the reverse osmosis concentration device II enters the nanofiltration device and the fresh water of the reverse osmosis concentration device II is discharged; when the reverse osmosis concentration device II is arranged between the fresh water of the nanofiltration device and the benzene series adsorption resin, the concentrated water of the reverse osmosis concentration device II enters the benzene series adsorption resin and the fresh water of the reverse osmosis concentration device II is discharged; when the reverse osmosis concentration device II is arranged between the benzene series adsorption resin and the hydrogen type cation resin, the concentrated water of the reverse osmosis concentration device II enters the hydrogen type cation resin and the fresh water of the reverse osmosis concentration device II is discharged;
route iii: at least one place between the fresh water and the hydrogen type cation resin and between the hydrogen type cation resin and the benzene series adsorption resin before the nanofiltration device;
when the evaporation concentration device II is arranged in front of the nanofiltration device, the concentrated solution of the evaporation concentration device II enters the nanofiltration device; when the evaporation concentration device II is arranged between the fresh water of the nanofiltration device and the hydrogen type cation resin, the concentrated solution of the evaporation concentration device II enters the hydrogen type cation resin; when the evaporation concentration device II is arranged between the hydrogen type cation resin and the benzene series adsorption resin, the concentrated solution of the evaporation concentration device II enters the benzene series adsorption resin; when the reverse osmosis concentration device II is arranged in front of the nanofiltration device, the concentrated water of the reverse osmosis concentration device II enters the nanofiltration device and the fresh water of the reverse osmosis concentration device II is discharged; when the reverse osmosis concentration device II is arranged between the fresh water of the nanofiltration device and the hydrogen-type cation resin, the concentrated water of the reverse osmosis concentration device II enters the hydrogen-type cation resin and the fresh water of the reverse osmosis concentration device II is discharged; when the reverse osmosis concentration device II is arranged between the hydrogen type cation resin and the benzene series adsorption resin, the concentrated water of the reverse osmosis concentration device II enters the benzene series adsorption resin and the fresh water of the reverse osmosis concentration device II is discharged.
Based on the above technical solution, preferably, in the route i, the route ii or the route iii, the hydrogen cation resin is regenerated with an acid solution after adsorption to recover the adsorption capacity, and an acid regeneration solution of the hydrogen cation resin is generated; then the hydrogen type cation resin is washed by water again for reuse, and simultaneously, a water washing liquid B is generated;
the water for washing the hydrogen type cation resin by using the water is at least one of pure water, an aqueous solution which needs to enter the hydrogen type cation resin for treatment originally, fresh water of a reverse osmosis concentration device I, fresh water of a reverse osmosis concentration device II, condensed water obtained after the evaporation concentration device I is cooled and condensed water obtained after the evaporation concentration device II is cooled;
the acid of the acid solution can be selected from acetic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, etc.;
when the hydrogen type cation resin runs for many times, a small amount of TA adhered to the resin is separated out when meeting the acid solution and is not completely flushed out by the acid solution to generate blockage, the TA can be dissolved by alkaline washing once, then the TA is washed by water, regenerated by the acid solution and washed by the water for recovery, and the alkaline washing liquid and the water washing liquid are discharged.
Based on the technical scheme, preferably, the water source of the benzene series adsorption resin washed by the water is at least one of pure water, an aqueous solution which needs to enter the benzene series adsorption resin for treatment originally, fresh water of the reverse osmosis concentration device I, fresh water of the reverse osmosis concentration device II, condensed water obtained after the evaporation concentration device I is cooled, and condensed water obtained after the evaporation concentration device II is cooled.
Based on the technical scheme, preferably,
discharging the water washing liquid A;
concentrated water of the nanofiltration device is discharged;
discharging acid regeneration liquid of the hydrogen type cation resin;
discharging the water washing liquid B;
or adding alkaline substances to the water washing liquid A, the concentrated water of the nanofiltration device, and the acid regeneration liquid or the water washing liquid B of the hydrogen type cation resin for precipitation and/or filtration, removing corrosion products such as iron and the like, and then adding the alkaline substances to the liquid to recover cobalt and manganese: first adding alkaline substance to raise pH (pH about 3.0-7.5) and removing most of metal corrosion products formed as solid matter by filtration; adding alkaline substance to the liquid for the second time to raise pH (pH is about 7.5-14) to form solid substance of cobalt ion and manganese ion, collecting the solid substance in a filter to recover cobalt and manganese, and discharging effluent; dissolving the collected cobalt and manganese by hydrobromic acid and recycling the cobalt and manganese to an oxidation reaction system; the alkaline substance is selected from carbonate, bicarbonate, hydroxide, etc.;
or adding alkaline substances to the water washing liquid A, the concentrated water of the nanofiltration device, the acid regeneration liquid of the hydrogen type cation resin or the water washing liquid B for precipitation and/or filtration, removing corrosion products such as iron and the like, and then treating the liquid by using a cobalt-manganese adsorption resin to adsorb cobalt and manganese: adding alkaline substance to raise pH (pH about 3.0-7.5) and removing most of metal corrosion products formed as solid matter by filtration; then the liquid is absorbed by cobalt-manganese adsorption resin, and effluent is discharged; after cobalt and manganese are adsorbed by the cobalt-manganese adsorption resin, a hydrobromic acid solution is used for regeneration, and the hydrobromic acid regeneration solution is recycled to an oxidation reaction system; or concentrated solution obtained by evaporating and concentrating the hydrobromic acid regenerated solution or concentrated water obtained by reverse osmosis concentration is recycled to the oxidation reaction system.
Based on the technical scheme, preferably, a filtering device is arranged before water enters the nanofiltration device, the reverse osmosis concentration device I or the reverse osmosis concentration device II, and the filtering device adopts ultrafiltration; the nanofiltration device at least comprises a first-stage nanofiltration membrane; the reverse osmosis concentration device I or the reverse osmosis concentration device II at least comprises a first-stage section reverse osmosis membrane;
description of the drawings:
for nanofiltration membranes: fresh water of the primary nanofiltration membrane enters the nanofiltration membrane for treatment, and is called a secondary nanofiltration membrane; the concentrated water of the first-stage nanofiltration membrane enters a nanofiltration membrane for treatment, and is called a second-stage nanofiltration membrane; for the nanofiltration membrane, the water passing through the nanofiltration membrane is called fresh water of the nanofiltration membrane; the water which does not pass through the nanofiltration membrane is called concentrated water of the nanofiltration membrane;
for reverse osmosis membranes: fresh water of the first-stage reverse osmosis membrane enters the reverse osmosis membrane to be treated, and the reverse osmosis membrane is called a second-stage reverse osmosis membrane; the concentrated water of the first reverse osmosis membrane enters a reverse osmosis membrane for treatment, and the reverse osmosis membrane is called a second reverse osmosis membrane. For reverse osmosis membranes, the water passing through a reverse osmosis membrane is called fresh water of the reverse osmosis membrane; the water that does not pass through the reverse osmosis membrane is called concentrate water of the reverse osmosis membrane.
Based on the technical scheme, preferably, in order to ensure stable operation of the system, a plurality of buffer tanks are arranged on the process route.
The discharge of the invention is discharged from the process route of the invention after the treatment of the invention, and the protection of the invention is not affected no matter what specific treatment method (such as discharge to a sewage comprehensive treatment unit) is adopted after the discharge.
The different steps, units and the like designed by the invention have different and mutually independent purposes, and each step, unit and the like can be independently applied, can be selected and combined in different sequences according to actual requirements, and can only select and apply a part of the steps, units and the like, thereby being within the protection scope of the patent of the invention.
Advantageous effects
The method comprises the following steps of (1) adsorbing a part of benzene series (mainly BA) in an aqueous solution by using benzene series adsorption resin, regenerating the benzene series adsorption resin by using acetic acid, dissolving BA and 4-CBA adsorbed by the benzene series adsorption resin in the acetic acid during regeneration, returning TA powder which is generated in the regeneration process along with insolubilization of the acetic acid and is flushed out by the acetic acid to an acetic acid removal unit, adding the benzene series to precipitate after removing the acetic acid to form solid matter, performing solid-liquid separation to obtain solid matter containing BA, and finally reducing the total amount of the benzene series entering the sewage plant by using the aqueous solution, namely reducing the total amount of COD entering the sewage plant, thereby being beneficial to reducing the load of the sewage plant and the operation cost and being beneficial to environmental protection;
the benzene series adsorption resin, the nanofiltration device and the hydrogen type cation resin are combined for use, and bromide ions in the aqueous solution can be recycled, so that the amount of bromine discharged to sewage by the whole device is reduced, namely the required supplement amount of bromine of the whole terephthalic acid production device is reduced, and the enterprise operation cost is favorably reduced;
after the benzene series adsorption resin is adsorbed, the benzene series adsorption resin can also be regenerated by using an alkaline solution (the alkaline solution is selected from a sodium hydroxide solution, a potassium carbonate solution, a sodium bicarbonate solution, a potassium bicarbonate solution or a sodium carbonate solution), but compared with the regeneration by using the alkaline solution, the regeneration by using acetic acid has the following defects:
if the regeneration liquid of the alkaline solution is directly discharged to the sewage, BA and the like absorbed by the benzene series adsorption resin enter the sewage treatment, the total amount of benzene series, namely COD, entering the sewage is not reduced, the consumption of the alkaline solution is increased, and the alkaline solution entering the sewage can generate adverse effect on the sewage;
if the alkaline solution regeneration liquid adopts a method of precipitating benzene series (mainly BA) by adding acid, the back section of the alkaline solution regeneration liquid needs to be designed with 3 steps of filtering (cobalt and manganese with a little solid), adding acid (precipitating benzene series mainly containing BA) and filtering (removing benzene series mainly containing BA), firstly adding alkali and then adding acid to consume acid and alkali (compared with the prior art, if benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid can directly pass through an acetic acid removal unit to recover acetic acid, and the recovered acetic acid can directly enter an oxidation reaction system, because the oxidation reaction system needs to add acetic acid, namely no substance is wasted); secondly, the water added with alkali and then added with acid finally enters the sewage, which can cause the ion concentration of the sewage to rise, thus being not beneficial to the operation of the sewage (in contrast, if the benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid does not enter the sewage because the acetic acid enters an acetic acid removal system to recover the acetic acid, thus the problem can not be solved); and thirdly, the later section of the alkaline solution regeneration liquid needs to be designed and filtered (cobalt and manganese with a little solid), acid is added (benzene series substances mainly containing BA are separated out), and the filtration (benzene series substances mainly containing BA are removed) is carried out for 3 steps, and the multipath line of the steps is not beneficial to the actual engineering operation (compared with the prior art, if the benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid mainly contains BA, 4-CBA and a little insoluble TA, and can directly return to the acetic acid removal unit of the membrane method of the front section and/or the acetic acid removal unit of the evaporation method for treatment, no new step is added, and the actual engineering operation is facilitated).
Drawings
FIG. 1 is a schematic process flow diagram;
fig. 2 is a design diagram of a secondary nanofiltration device.
Detailed Description
Description of the drawings: english symbols for the samples were tested as follows:
TA: phthalic acid and acid radicals thereof; BA: benzoic acid and acid radicals thereof; 4-CBA: p-carboxybenzaldehyde and acid groups thereof.
The benzene-series adsorbent resin, the hydrogen-type cation resin and the cobalt-manganese adsorbent resin used in the present invention can be selected from the brands for producing such resins, such as Tulsion, the benzene-series adsorbent resin ADS-600, the hydrogen-type cation resin LSD-001, and the cobalt-manganese adsorbent resin LSC-500, respectively, and can selectively and mainly adsorb polyvalent cations such as cobalt and manganese from the cations.
The benzene series adsorption resin, the hydrogen type cation resin and the cobalt-manganese adsorption resin are all in the protection range of the invention no matter what brand and model is selected.
The ultrafiltration membrane, the nanofiltration membrane and the reverse osmosis membrane used in the invention can be selected from brands for producing the membrane, such as DOW, and the nanofiltration membrane in the embodiment is selected from DOW FORTILIFE XC-N series; selecting DOW FORTILIFECR100 series as the reverse osmosis membrane; the ultra-filtration membrane is an acid-resistant DOW ultra-filtration membrane, and the ultra-filtration membrane, the nano-filtration membrane and the reverse osmosis membrane are all within the protection range of the invention no matter what brand and model are selected.
In all the following examples, the units of analysis on the concentrations of the respective components in the aqueous solution were all ppm.
Example 1
Sample 1: the existing device in the sampling site is that the mother liquor extract in the oxidation process is heated to remove acetic acid, water is added to be cooled to about 95 ℃ and filtered, the temperature is cooled to about 50 ℃ again and then the filtered filtrate is filtered, the temperature is cooled to 20 ℃ again and filtered to obtain effluent, and the analysis is as follows: TA 6904 ppm; 6830 ppm of BA; 4-CBA 249 ppm; cobalt ions 1242 ppm; 588ppm of manganese ions; 1293ppm of sodium ions; 2296ppm of bromide ion; iron ion 4.98 ppm.
Experiment 1: treating the aqueous solution with benzene series adsorption resin
Sampling 200L of a sample 1 water sample, controlling the speed of treating water by the benzene series adsorption resin to be 6L/h after passing through the benzene series adsorption resin and the benzene series adsorption resin loading amount to be 6L, wherein the effluent quality of the benzene series adsorption resin is as follows (unit ppm):
after 12 hours, discharging the aqueous solution in the benzene series adsorption resin, pressing out the residual aqueous solution by using compressed air, then regenerating by using industrial acetic acid 18L, controlling the flow rate to be 6L/hour, after finishing, pressing out the acetic acid in the resin by using the compressed air by using the same method, generating about 18L of acetic acid regeneration liquid, analyzing the concentration:
then, the adsorption device is washed by 18L of pure water, the flow rate is controlled to be 9L/h, after that, the washing liquid in the resin is pressed out by the same method by using compressed air, and then the sample 1 is adsorbed by benzene series adsorption resin, the speed of treating water by the benzene series adsorption resin is controlled to be 6L/h, and the effluent quality of the benzene series adsorption resin is as follows (unit ppm):
and (4) test conclusion: the benzene series adsorption resin can adsorb TA and BA in water (the adsorption effect on BA is better than that of TA), 4-CBA is also adsorbed in the adsorption process, and cobalt ions and manganese ions are hardly adsorbed (the judgment is that only the cobalt ions and the manganese ions contained in the water remained on the resin are washed out by the acetic acid regeneration process); hardly adsorbs bromine ions; hardly adsorbs sodium ions; after the resin is adsorbed, regeneration dissociation can be carried out by using an acetic acid solution, the acetic acid regeneration solution contains BA, 4-CBA and the like adsorbed by the resin and also contains cobalt and manganese ions with relatively low concentration, the cobalt and manganese ions can be re-introduced into the aqueous solution treated by the invention after returning to an acetic acid removing system (after adding water), and white crystal powder (TA) which cannot be detected but is insoluble in acetic acid can be observed visually. The regenerated resin can be used again for adsorption.
Example 2
Experiment 1: effluent obtained in experiment 1 of example 1 after 2 passes through the benzene-based adsorbent resin for 12 hours was mixed and analyzed as follows:
| item | TA | BA | 4-CBA | Cobalt ion | Manganese ion | Sodium ion | Bromine ion | Iron ion |
| Concentration of | 4273 | 5.7 | 3.2 | 1212 | 565 | 1289 | 2288 | 4.56 |
The mixed water solution (called raw water for short) is treated by a nanofiltration device, and a 2-stage nanofiltration device is designed, namely, a water supply pump of the primary nanofiltration device is used for pumping the raw water after ultrafiltration into a circulating system of the primary nanofiltration device (the concentrated water of the primary nanofiltration device is circulated to the inlet water of the primary nanofiltration device), the primary nanofiltration device generates fresh water of the primary nanofiltration device and concentrated water of the primary nanofiltration device (discharge), the fresh water generated by the primary nanofiltration device is pumped into the circulating system of the secondary nanofiltration device by the water supply pump of the secondary nanofiltration device (the concentrated water of the secondary nanofiltration device is circulated to the inlet water of the secondary nanofiltration device), the secondary fresh water generated by the secondary nanofiltration device is final produced water, and the concentrated water generated by the secondary nanofiltration device is circulated to the circulating system of the primary nanofiltration device as.
Controlling the fresh water amount produced by the final secondary nanofiltration device to be 3 times of the concentrated water discharge amount of the primary nanofiltration device, and analyzing the fresh water of the secondary nanofiltration device as follows:
| item | TA | BA | 4-CBA | Cobalt ion | Manganese ion | Sodium ion | Bromine ion | Iron ion |
| Concentration of | 3969 | 5.1 | 2.8 | 12.5 | 6.7 | 1277 | 2279 | 0.12 |
Analyzing concentrated water of the first-stage nanofiltration device:
and (4) conclusion: cobalt ions, manganese ions and iron ions in the aqueous solution can be intercepted by the nanofiltration membrane, and the separation effect is achieved.
Experiment 2: fresh water of the secondary nanofiltration device of experiment 1 was treated with a hydrogen-type cationic resin:
the fresh water sample 80L of the secondary nanofiltration device of the sampling experiment 2 is treated by hydrogen type cationic resin, the loading of the hydrogen type cationic resin is 2L, the speed of treating water by the hydrogen type cationic resin is controlled to be 2L/h, and the effluent quality of the hydrogen type cationic resin is as follows (unit ppm):
after 12 hours, the aqueous solution in the hydrogen type cation resin was discharged and the residual aqueous solution was pressed out with compressed air, and then regenerated with 6L of 5% hydrochloric acid, the flow rate was controlled at 2L/hour, and after completion, the 5% hydrochloric acid in the resin was pressed out with compressed air in the same manner to produce about 6L of 5% hydrochloric acid regenerated solution, the analytical concentration:
| item | Cobalt ion | Manganese ion | Iron ion | Sodium ion |
| Concentration of | 53 | 22 | 0.35 | 5008 |
Then, 10L of pure water is used for washing the hydrogen type cation resin, the flow rate is controlled to be 5L/h, after that, the washing liquid in the hydrogen type cation resin is pressed out by the same method by using compressed air to measure the chloride ion of the final washing liquid to be 5.2ppm, hydrochloric acid is almost completely washed clean, the chloride ion brought into an oxidation reaction system is not much influenced obviously, then, the fresh water sample of the two-stage nanofiltration device of the experiment 1 is adsorbed by the hydrogen type cation resin, the speed of treating water by the hydrogen type cation resin is controlled to be 2L/h, and the effluent quality of the hydrogen type cation resin is as follows (unit ppm):
and (4) conclusion: BA and 4-CBA in the aqueous solution are removed in the process of the benzene series adsorption resin, and the residual TA is feasible to enter an oxidation reaction system according to the plan; the nanofiltration device intercepts cobalt ions, manganese ions and iron ions on the concentrated water side; therefore, the hydrogen type cation resin is mainly used for removing sodium ions in the fresh water of the nanofiltration device (low-concentration cobalt, manganese and iron ions remained in the fresh water of the nanofiltration device are also absorbed and removed), and the hydrogen type cation resin is proved to be capable of absorbing the sodium ions and being regenerated by acid, and the regenerated hydrogen type cation resin can be used for absorption again. That is, the aqueous solution has been removed most of BA, sodium ions and iron ions through experiments 1, 2 and 3, and the effluent can be recycled to the oxidation reaction system.
Experiment 3: the effluent of the hydrogen-type cationic resin obtained in experiment 2 was mixed and subjected to reverse osmosis:
the effluent of the hydrogen-type cation resin of experiment 2 was mixed and subjected to reverse osmosis treatment to control the reverse osmosis fresh water yield to be 3 times the concentrate water yield, and the reverse osmosis concentrate analysis results were as follows:
| item | Cobalt ion | Manganese ion | Sodium ion | Bromine ion | Iron ion |
| Concentration of | ＜0.1 | ＜0.1 | 8.3 | 8935 | ＜0.1 |
And (4) conclusion: after reverse osmosis concentration, the reverse osmosis concentrated water can finally enter an oxidation reaction system to operate: BA and 4-CBA in the initial aqueous solution are removed, iron ions are also removed, and TA entering an oxidation reaction system is a beneficial substance; finally, the operation of an oxidation reaction system is not obviously influenced due to the low content of sodium ions in the reverse osmosis concentrated water; the bromine ions entering the oxidation reaction system are beneficial substances.
Example 3
Sample 1 (i.e., sample 1 of example 1): the existing device in the sampling site is that the mother liquor extract in the oxidation process is heated to remove acetic acid, water is added to be cooled to about 95 ℃ and filtered, the temperature is cooled to about 50 ℃ again and then the filtered filtrate is filtered, the temperature is cooled to 20 ℃ again and filtered to obtain effluent, and the analysis is as follows: TA 6904 ppm; 6830 ppm of BA; 4-CBA 249 ppm; cobalt ions 1242 ppm; 588ppm of manganese ions; 1293ppm of sodium ions; 2296ppm of bromide ion; iron ion 4.98 ppm.
Experiment 1: a sample 1 (raw water for short) 500L is treated by a nanofiltration device, and a 2-stage nanofiltration device is designed, namely, a water supply pump of the primary nanofiltration device is used for pumping the raw water after ultrafiltration into a circulating system of the primary nanofiltration device (the concentrated water of the primary nanofiltration device is circulated to the inlet water of the primary nanofiltration device), the primary nanofiltration device generates fresh water of the primary nanofiltration device and concentrated water of the primary nanofiltration device (discharge), the fresh water generated by the primary nanofiltration device is pumped into a circulating system of the secondary nanofiltration device by a water supply pump of the secondary nanofiltration device (the concentrated water of the secondary nanofiltration device is circulated to the inlet water of the secondary nanofiltration device), the secondary fresh water generated by the secondary nanofiltration device is final produced water, and the concentrated water of the secondary nanofiltration device generated by the secondary nanofiltration device is circulated to the circulating system. Controlling the fresh water amount produced by the final secondary nanofiltration device to be 3 times of the concentrated water discharge amount of the primary nanofiltration device, and analyzing the fresh water of the secondary nanofiltration device as follows:
| item | TA | BA | 4-CBA | Cobalt ion | Manganese ion | Sodium ion | Bromine ion | Iron ion |
| Concentration of | 6832 | 6819 | 237 | 9.7 | 4.9 | 1286 | 2254 | 0.10 |
Analyzing concentrated water of the first-stage nanofiltration device:
| item | Cobalt ion | Manganese ion | Iron ion |
| Concentration of | 4789 | 2211 | 18.77 |
And (4) conclusion: cobalt ions, manganese ions and iron ions in the aqueous solution can be intercepted by the nanofiltration membrane, and the separation effect is achieved.
Experiment 2: fresh water of the secondary nanofiltration device in experiment 1 is passed through benzene series adsorption resin, the loading of the benzene series adsorption resin is 6L, the speed of treating water by the benzene series adsorption resin is controlled to be 6L/h, and the effluent quality of the benzene series adsorption resin is as follows (unit ppm):
after 12 hours, discharging the aqueous solution of the benzene series adsorption resin, pressing out the residual aqueous solution by using compressed air, then regenerating by using industrial acetic acid 18L, controlling the flow rate to be 6L/hour, after that, pressing out the acetic acid in the benzene series adsorption resin by using the compressed air by the same method to generate about 18L of acetic acid regeneration liquid, and analyzing the concentration:
then, the adsorption device is washed by 18L of pure water, the flow rate is controlled to be 9L/h, after that, the washing liquid in the benzene series adsorption resin is pressed out by the same method by using compressed air, and then the fresh water of the second-stage nanofiltration device of the experiment 1 is passed through the benzene series adsorption resin, the speed of treating water by the benzene series adsorption resin is controlled to be 6L/h, and the effluent quality of the benzene series adsorption resin is as follows (unit ppm):
and (4) test conclusion: the benzene series adsorption resin can adsorb TA and BA in water (the adsorption effect on BA is better than that of TA), and the adsorption process also adsorbs 4-CBA; hardly adsorbs bromine ions; hardly adsorbs sodium ions; after the adsorption of the resin, regeneration dissociation can be carried out by using an acetic acid solution, wherein the acetic acid regeneration solution contains BA, 4-CBA and the like adsorbed by the resin, and TA can not be detected but white crystal powder (TA is judged to be insoluble in acetic acid) can be observed. The regenerated resin can be used again for adsorption.
Experiment 3: effluent obtained in experiment 2 after 2 times of benzene series adsorption resin adsorption within 12 hours is mixed and analyzed as follows:
| item | TA | BA | 4-CBA | Sodium ion | Bromine ion |
| Concentration of | 3867 | 6.2 | 4.9 | 1266 | 2271 |
After the treatment of the hydrogen type cation resin, the loading of the hydrogen type cation resin is 2L, the speed of treating water by the hydrogen type cation resin is controlled to be 2L/h, and the water quality of the effluent of the hydrogen type cation resin is as follows (unit ppm):
| time of water discharge | Cobalt ion | Manganese ion | Sodium ion | Bromine ion | Iron ion |
| First stage resin yielding water in 1 hour | ＜0.1 | ＜0.1 | ＜0.1 | 2272 | ＜0.1 |
| First stage resin 4 hours of water discharge | ＜0.1 | ＜0.1 | 1.1 | 2235 | ＜0.1 |
| The first stage resin is discharged in 8 hours | ＜0.1 | ＜0.1 | 2.1 | 2299 | ＜0.1 |
| The first stage resin is discharged in 12 hours | ＜0.1 | ＜0.1 | 8.7 | 2253 | ＜0.1 |
After 12 hours, the aqueous solution in the hydrogen type cation resin was discharged and the residual aqueous solution was pressed out with compressed air, and then regenerated with 6L of 5% hydrochloric acid, the flow rate was controlled at 2L/hour, and after completion, the 5% hydrochloric acid in the resin was pressed out with compressed air in the same manner to produce about 6L of 5% hydrochloric acid regenerated solution, the analytical concentration:
| item | Cobalt ion | Manganese ion | Iron ion | Sodium ion |
| Concentration of | 32 | 19.8 | 0.41 | 4987 |
Then, 10L of pure water is used for washing the hydrogen type cation resin, the flow rate is controlled to be 5L/h, after that, the washing liquid in the hydrogen type cation resin is pressed out by the same method by compressed air to measure the chloride ion 6.7ppm of the final washing liquid, hydrochloric acid is almost completely washed clean, the chloride ion brought into an oxidation reaction system is not influenced obviously, then, the effluent mixed water sample which is absorbed by the benzene series adsorption resin for 2 times in experiment 2 within 12 hours is absorbed by the hydrogen type cation resin, the speed of treating water by the hydrogen type cation resin is controlled to be 2L/h, and the effluent quality of the hydrogen type cation resin is as follows (unit ppm):
and (4) conclusion: cobalt ions, iron ions and manganese ions are trapped on the concentrated water side by the nanofiltration device (even if the nanofiltration fresh water side has low-concentration cobalt ions, manganese ions and iron ions, the low-concentration cobalt ions, manganese ions and iron ions are also adsorbed and removed by the hydrogen type cationic resin); BA and 4-CBA in the aqueous solution are removed in the process of the benzene series adsorption resin, and the residual TA is feasible to enter an oxidation reaction system according to the plan; therefore, the hydrogen type cation resin is mainly used for removing sodium ions in the fresh water of the nanofiltration device, and the hydrogen type cation resin is proved to be capable of adsorbing the sodium ions, and the hydrogen type cation resin can be regenerated by acid, and the regenerated hydrogen type cation resin can be used for adsorption again. That is, the aqueous solution from experiments 1, 2 and 3 has most of BA, sodium ions and iron ions removed and can be recycled to the oxidation reaction system.
Experiment 4: the effluent of the hydrogen-type cationic resin obtained in experiment 3 was mixed and subjected to reverse osmosis:
the effluent of the hydrogen-type cation resin of experiment 3 was mixed and subjected to reverse osmosis treatment to control the reverse osmosis fresh water yield to be 3 times the concentrate water yield, and the reverse osmosis concentrate analysis results were as follows:
| item | Cobalt ion | Manganese ion | Sodium ion | Bromine ion | Iron ion |
| Concentration of | ＜0.1 | ＜0.1 | 7.1 | 9001 | ＜0.1 |
And (4) conclusion: after reverse osmosis concentration, concentrated water can finally enter an oxidation reaction system for operation. BA, 4-CBA and iron ions in the initial aqueous solution are removed, and TA entering an oxidation reaction system is a beneficial substance; finally, the operation of an oxidation reaction system is not obviously influenced due to the low content of sodium ions in the reverse osmosis concentrated water; the bromine ions entering the oxidation reaction system are beneficial substances.
Example 4
Experiment 1: the two-stage nanofiltration device obtained in experiment 1 of example 3 was subjected to hydrogen type cation resin treatment, wherein the loading of the hydrogen type cation resin was 10L, the water treatment speed of the hydrogen type cation resin was controlled to be 10L/h, and the effluent quality of the hydrogen type cation resin was as follows (in ppm):
after 12 hours, the aqueous solution in the hydrogen type cation resin was discharged and the residual aqueous solution was pressed out with compressed air, and then regenerated with 30L of 5% hydrochloric acid, the flow rate was controlled to 10L/hour, and after completion, the 5% hydrochloric acid in the resin was pressed out with compressed air in the same manner to produce about 30L of 5% hydrochloric acid regenerated solution, the analytical concentration:
| item | Cobalt ion | Manganese ion | Iron ion | Sodium ion |
| Concentration of | 41 | 17.1 | 0.38 | 5111 |
Then 50L of pure water is used for washing the hydrogen type cation resin, the flow rate is controlled to be 25L/h, after the washing liquid in the hydrogen type cation resin is finished, the washing liquid is pressed out by the same method by using compressed air to measure that the chloride ion of the final washing liquid is 4.8ppm, the hydrochloric acid is almost completely washed clean, the chloride ion brought into an oxidation reaction system does not generate obvious influence, the fresh water of the two-stage nanofiltration device of the experiment 1 of the embodiment 3 is adsorbed by the hydrogen type cation resin, the speed of treating the water by the hydrogen type cation resin is controlled to be 10L/h, and the effluent quality of the hydrogen type cation resin is as follows (unit ppm):
and (4) conclusion: cobalt ions, iron ions and manganese ions are trapped on the concentrated water side by the nanofiltration device; therefore, the hydrogen type cation resin is mainly used for removing sodium ions in the fresh water of the nanofiltration device (cobalt, manganese and iron ions with low concentration on the nanofiltration fresh water side are also absorbed and removed by the hydrogen type cation resin), and the hydrogen type cation resin can absorb the sodium ions, and can be regenerated by acid, and the regenerated hydrogen type cation resin can be used for absorption again.
Experiment 2: the effluent obtained in experiment 1 after 2 times of adsorption on the hydrogen-type cationic resin for 12 hours was mixed and analyzed as follows:
sampling 150L, passing through benzene series adsorption resin, the loading of the benzene series adsorption resin is 6L, controlling the speed of benzene series adsorption resin treatment water to be 6L/h, and the effluent quality of the benzene series adsorption resin is as follows (unit ppm):
after 12 hours, discharging the aqueous solution in the benzene series adsorption resin, pressing out the residual aqueous solution by using compressed air, then regenerating by using industrial acetic acid 18L, controlling the flow rate to be 6L/hour, after that, pressing out the acetic acid in the benzene series adsorption resin by using the compressed air by using the same method to generate about 18L of acetic acid regeneration liquid, and analyzing the concentration:
then, the benzene-series adsorption resin is washed by 18L of pure water, the flow rate is controlled to be 9L/h, after that, the washing liquid in the benzene-series adsorption resin is pressed out by the same method by using compressed air, and the effluent mixed sample obtained in experiment 1 after 2 times of hydrogen-type cation resin adsorption for 12 hours is adsorbed by the benzene-series adsorption resin, the speed of treating water by an adsorption device is controlled to be 6L/h, and the effluent quality of the adsorption device is as follows (unit ppm):
and (4) test conclusion: the benzene series adsorption resin can adsorb TA and BA in water (the adsorption effect on BA is better than that of TA), and the adsorption process also adsorbs 4-CBA; hardly adsorbs bromine ions; after the benzene series adsorption resin is adsorbed, regeneration dissociation can be carried out by using an acetic acid solution, the acetic acid regeneration solution contains BA, 4-CBA and the like adsorbed by the resin (the acetic acid regeneration solution contains low-concentration cobalt and manganese ions, water is added after an acetic acid removing unit, the cobalt and manganese ions can enter the aqueous solution required to be treated by the invention again), and TA can not be detected but white crystal powder (TA is judged) insoluble in acetic acid can be observed visually. The regenerated resin can be used again for adsorption. That is, the aqueous solution from experiments 1, 2 and 3 has most of BA, sodium ions and iron ions removed and can be recycled to the oxidation reaction system.
Experiment 3: the effluent of the benzene series adsorption resin obtained in experiment 2 is mixed and treated by reverse osmosis:
the effluent of the benzene series adsorption resin in experiment 2 was mixed and subjected to reverse osmosis treatment to control the reverse osmosis fresh water yield to be 3 times of the concentrate water yield, and the reverse osmosis concentrate analysis results were as follows:
| item | Cobalt ion | Manganese ion | Sodium ion | Bromine ion | Iron ion |
| Concentration of | ＜0.1 | ＜0.1 | 6.2 | 8998 | ＜0.1 |
And (4) conclusion: after reverse osmosis concentration, concentrated water can finally enter an oxidation reaction system for operation. BA, 4-CBA and iron ions in the initial aqueous solution are removed, and TA entering an oxidation reaction system is a beneficial substance; finally, the operation of an oxidation reaction system is not obviously influenced due to the low content of sodium ions in the reverse osmosis concentrated water; the bromine ions entering the oxidation reaction system are beneficial substances.
Example 5 comparison of difference between benzene-based adsorbent resin regenerated with alkaline solution and regenerated with acetic acid
Sample 1 (i.e., sample 1 of example 1): the existing device in the sampling site is that the mother liquor extract in the oxidation process is heated to remove acetic acid, water is added to be cooled to about 95 ℃ and filtered, the temperature is cooled to about 50 ℃ again and then the filtered filtrate is filtered, the temperature is cooled to 20 ℃ again and filtered to obtain effluent, and the analysis is as follows: TA 6904 ppm; 6830 ppm of BA; 4-CBA 249 ppm; cobalt ions 1242 ppm; 588ppm of manganese ions; 1293ppm of sodium ions; 2296ppm of bromide ion; iron ion 4.98 ppm.
Experiment 1: treating the aqueous solution with benzene series adsorption resin
Sampling 200L of a sample 1 water sample, controlling the speed of treating water by the benzene series adsorption resin to be 6L/h after passing through the benzene series adsorption resin and the benzene series adsorption resin loading amount to be 6L, wherein the effluent quality of the benzene series adsorption resin is as follows (unit ppm):
after 12 hours, the aqueous solution in the benzene-based adsorption resin was discharged and the residual aqueous solution was pressed out with compressed air, and then regenerated with 18L of 10% sodium hydroxide at a flow rate of 6L/hour, after which the 10% sodium hydroxide in the resin was pressed out with compressed air in the same manner to produce about 18L of 10% sodium hydroxide regenerated solution, which was observed to contain black insoluble matter in water, and the filtrate concentration was analyzed after filtration:
| analysis item | TA | BA | 4-CBA |
| Concentration of | 9206 | 26982 | 891 |
And (3) adding hydrochloric acid into the filtrate to adjust the pH to be 3.7, continuously generating a large amount of white solid in the process, and filtering again to obtain an aqueous solution and a solid.
Then, the adsorption device is washed by 54L pure water, the flow rate is controlled to be 9L/h, after that, the washing liquid in the resin is pressed out by the same method by using compressed air, and then the sample 1 is adsorbed by benzene series adsorption resin, the speed of treating water by the benzene series adsorption resin is controlled to be 6L/h, and the effluent quality of the benzene series adsorption resin is as follows (unit ppm):
and (4) test conclusion: if the benzene series adsorption resin is directly discharged to the sewage, the alkaline regeneration liquid obtained by regenerating the alkaline solution contains a large amount of TA, BA and the like with a large concentration, namely the benzene series adsorption resin is not used for adsorbing the benzene series, the benzene series enters the sewage, the amount of the benzene series entering the sewage cannot be reduced, and the amount of alkaline substances in the sewage is increased;
if the benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid can directly pass through an acetic acid removal unit to recover acetic acid, and the recovered acetic acid can directly enter an oxidation reaction system, so that the oxidation reaction system needs to add the acetic acid, which is equivalent to no material waste; meanwhile, the residual solution containing TA and BA solids is filtered and discharged into sewage, so that the ion concentration of the sewage can be increased (in contrast, if the benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid does not enter the sewage because the acetic acid regeneration liquid enters an acetic acid removal system to recover the acetic acid, so that the problem can not be solved); the process route design needs filtering (black particles), then adding acid (separating out solids containing TA, BA and the like), and then filtering (filtering out solids containing TA, BA and the like), the route is complicated (in contrast, if the benzene series adsorption resin is regenerated by acetic acid, the acetic acid regeneration liquid mainly contains BA, 4-CBA and a little insoluble TA, and can directly return to the acetic acid removal unit of the previous membrane method and/or the acetic acid removal unit of the evaporation method for treatment, no new step is added, and the process is beneficial to actual engineering operation).
The benzene series adsorption resin can adsorb TA and BA in water (the adsorption effect on BA is better than that of TA), 4-CBA is also adsorbed in the adsorption process, after the adsorption of the resin, alkaline solution can be used for regeneration and dissociation, and the regenerated resin can be used for adsorption again.
Example 6
Sample 1 (i.e., sample 1 of example 1): the existing device in the sampling site is that the mother liquor extract in the oxidation process is heated to remove acetic acid, water is added to be cooled to about 95 ℃ and filtered, the temperature is cooled to about 50 ℃ again and then the filtered filtrate is filtered, the temperature is cooled to 20 ℃ again and filtered to obtain effluent, and the analysis is as follows: TA 6904 ppm; 6830 ppm of BA; 4-CBA 249 ppm; cobalt ions 1242 ppm; 588ppm of manganese ions; 1293ppm of sodium ions; 2296ppm of bromide ion; iron ion 4.98 ppm.
Experiment 1:
sampling 1 and counting 5L of sample, adding sodium carbonate and stirring to generate a large amount of bubbles, raising the PH to 5.7, using 134.7g of sodium carbonate solid, wherein the volume is not obviously changed, and measuring TA6850ppm after filtering; BA6787 ppm; 4-CBA251 ppm; cobalt ion 1202 ppm; 542ppm of manganese ions; 13008ppm of sodium ions; bromide ion 2301 ppm; iron ion 0.21ppm, designated sample A.
The treatment of sample a was divided into 2 routes:
route 1: taking sample A and 1L
Adding sodium carbonate, raising pH to 9.5, consuming 12.1g of sodium carbonate, filtering to obtain TA6878 ppm; BA6802 ppm; 4-CBA247 ppm; cobalt ion 0.07 ppm; manganese ion 0.03 ppm; 18327ppm of sodium ions; bromide 2287 ppm; iron ion 0 ppm.
About half of the filter cake was taken and dissolved in the total with 47.5% hydrobromic acid 100 ml.
Route 2: sample A was 1L
After passing through two-stage series cobalt-manganese adsorption resin (each resin amount is 100g), the effluent flow rate below the resin column is controlled to be about 150 ml/h, the cobalt and manganese ion concentrations of the effluent are as follows, and the unit ppm is as follows:
the effluent water sample of the second-stage cobalt-manganese adsorption resin is analyzed as follows: TA6978 ppm; BA6789 ppm; 4-CBA242 ppm; 12963ppm of sodium ions; 0.15ppm of cobalt ions; manganese ion 0.09 ppm; 2282ppm of bromide ion; iron ion 0 ppm.
The first-stage cobalt-manganese adsorption resin is regenerated by using 300ml of 23.75% hydrobromic acid after removing liquid by using compressed air, and the cobalt ion content of the regenerated liquid is 3625 ppm; manganese ion 1669 ppm; sodium ion 2.87 ppm.
The conclusion of the experiment is as follows: adding sodium carbonate into the water solution, precipitating and filtering to remove iron ions, adding sodium carbonate into the water solution, precipitating and filtering cobalt ions and manganese ions, and dissolving cobalt carbonate and manganese carbonate in a filter cake obtained by secondary filtration by using hydrobromic acid to recover cobalt and manganese in the water solution; the method comprises adding sodium carbonate into the aqueous solution, precipitating, filtering to remove iron ions, adsorbing cobalt and manganese with cobalt-manganese adsorption resin, and regenerating cobalt-manganese adsorption resin with hydrobromic acid to recover cobalt and manganese (to form cobalt bromide and manganese bromide) in the aqueous solution, wherein the impurities of sodium ions in the regenerated solution are few.
Claims (11)
1. A process for treating an aqueous solution generated in the treatment process of a mother liquor extract in an oxidation process of a terephthalic acid production device is characterized in that the process route is as follows: the method comprises the following steps of (1) enabling an aqueous solution generated in the treatment process of a mother liquor extract of an oxidation process of a terephthalic acid production device to enter benzene series adsorption resin to adsorb benzene series in the aqueous solution, wherein the main purpose is to adsorb BA in the aqueous solution, TA and 4-CBA can be adsorbed in the process, and the adsorbed aqueous solution is discharged from the benzene series adsorption resin;
after benzene series adsorption resin is adsorbed, regenerating by using acetic acid solution to recover adsorption capacity to obtain acetic acid regeneration liquid A, wherein the acetic acid regeneration liquid A contains BA and 4-CBA.
2. The process according to claim 1, wherein the acetic acid regeneration liquid A is directly discharged; or the acetic acid regeneration liquid A is treated by an acetic acid removing unit of a membrane method and/or an acetic acid removing unit of an evaporation method; and after the benzene series adsorption resin is regenerated by acetic acid, the benzene series adsorption resin is washed by water and then is reused for adsorption again to obtain water washing liquid A.
3. The process of claim 1, wherein said benzene-based adsorption resin is combined with a nanofiltration device and a hydrogen-based cationic resin, according to scheme i, scheme ii or scheme iii, respectively, as follows:
route i: the water solution enters benzene series adsorption resin, effluent of the benzene series adsorption resin is treated by a nanofiltration device, and fresh water of the nanofiltration device enters hydrogen type cation resin for adsorption to obtain effluent a;
route ii: the water solution is treated by a nanofiltration device before entering the benzene series adsorption resin, namely the water solution firstly passes through the nanofiltration device, fresh water of the nanofiltration device enters the benzene series adsorption resin, and effluent water passing through the benzene series adsorption resin enters the hydrogen type cation resin for adsorption to obtain effluent water b;
route iii: the water solution is firstly treated by a nanofiltration device and hydrogen type cation resin before entering the benzene series adsorption resin, namely the water solution is firstly treated by the nanofiltration device, fresh water of the nanofiltration device enters the hydrogen type cation resin for treatment, and effluent water of the hydrogen type cation resin enters the benzene series adsorption resin to obtain effluent water c.
4. The treatment process according to claim 1 or 3, wherein the aqueous solution is treated by a precipitation device and/or a filtration device before entering the benzene series adsorption resin or entering the route I or entering the route II or entering the route III; or before the aqueous solution enters the benzene series adsorption resin or enters the route I or the route II or the route III, the aqueous solution is cooled and treated by a precipitation device and/or a filtration device.
5. The process according to claim 4, wherein a heat-insulating device is arranged on the pipeline and the equipment after the precipitation device and/or the filtering device.
6. A process according to claim 3, wherein said effluent a from line i, said effluent b from line ii or said effluent c from line iii is treated as follows:
the effluent a of the route I, the effluent b of the route II or the effluent c of the route III enter an oxidation reaction system of a terephthalic acid production device;
or the effluent a of the route I, the effluent b of the route II or the effluent c of the route III are filtered and then enter an oxidation reaction system of a terephthalic acid production device;
or the effluent a of the route I, the effluent b of the route II or the effluent c of the route III firstly pass through the evaporation concentration device I, and the concentrated solution of the evaporation concentration device I enters an oxidation reaction system of a terephthalic acid production device;
or the effluent a of the route I, the effluent b of the route II or the effluent c of the route III firstly pass through the reverse osmosis concentration device I, the concentrated water of the reverse osmosis concentration device I enters an oxidation reaction system of the terephthalic acid production device, and the fresh water of the reverse osmosis concentration device I is discharged.
7. A process according to claim 3, wherein an evaporative concentration unit ii or reverse osmosis concentration unit ii is provided in the route for reducing the amount of water treated in said route i, route ii or route iii; the evaporation concentration device II or the reverse osmosis concentration device II is arranged at the following positions:
in the route I, the evaporation concentration device II or the reverse osmosis concentration device II is arranged at least one position in front of the benzene series adsorption resin, between the benzene series adsorption resin and the nanofiltration device, and between the fresh water of the nanofiltration device and the hydrogen type cation resin;
in the route II, the evaporation concentration device II or the reverse osmosis concentration device II is arranged at least one position between the fresh water of the nanofiltration device and the benzene series adsorption resin and between the benzene series adsorption resin and the hydrogen type cation resin before the nanofiltration device;
in the route III, the evaporation concentration device II or the reverse osmosis concentration device II is arranged at least one position between the fresh water of the nanofiltration device and the hydrogen-type cation resin and between the hydrogen-type cation resin and the benzene series adsorption resin before the nanofiltration device.
8. The process of claim 3 or 7, wherein in said route I, route II or route III, said hydrogen cation resin is regenerated with an acid solution after adsorption to restore the adsorption capacity and to produce an acid regenerated solution of the hydrogen cation resin; then the hydrogen type cation resin is washed by water again for reuse, and simultaneously, a water washing liquid B is generated;
the water for washing the hydrogen type cation resin is at least one of pure water, aqueous solution entering the hydrogen type cation resin for treatment, fresh water of a reverse osmosis concentration device I, fresh water of a reverse osmosis concentration device II, condensed water obtained after the evaporation concentration device I is cooled and condensed water obtained after the evaporation concentration device II is cooled.
9. The treatment process according to claim 2, 3, 4, 5 or 7, wherein the water for washing the benzene-series adsorbent resin with water is at least one of pure water, an aqueous solution to be treated by the benzene-series adsorbent resin, fresh water in the reverse osmosis concentration device I, fresh water in the reverse osmosis concentration device II, condensed water obtained by cooling the evaporative concentration device I, and condensed water obtained by cooling the evaporative concentration device II.
10. The process according to claim 2, 3 or 8,
discharging the water washing liquid A;
concentrated water of the nanofiltration device is discharged;
discharging acid regeneration liquid of the hydrogen type cation resin;
discharging the water washing liquid B;
or the water washing liquid A, the nanofiltration device concentrated water, and the acid regeneration liquid or the water washing liquid B of the hydrogen type cation resin are added with alkaline substances for precipitation and/or filtration, iron removal and other corrosion products, and then the alkaline substances are added to recover cobalt and manganese;
or the water washing liquid A, the nanofiltration device concentrated water, and the acid regeneration liquid or the water washing liquid B of the hydrogen type cation resin are added with alkaline substances for precipitation and/or filtration, and corrosion products such as iron and the like are removed, and then cobalt and manganese are adsorbed by the cobalt-manganese adsorption resin.
11. The process according to claim 3, 6 or 7, wherein the feed water of the nanofiltration device, the reverse osmosis concentration device I or the reverse osmosis concentration device II is passed through a filtration device before being fed; the nanofiltration device at least comprises a first-stage nanofiltration membrane; the reverse osmosis concentration device I or the reverse osmosis concentration device II at least comprises a reverse osmosis membrane at one stage and a first section.
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