CN104327533A - Clean production technology of acid blue 9 dye - Google Patents
Clean production technology of acid blue 9 dye Download PDFInfo
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- CN104327533A CN104327533A CN201410447971.0A CN201410447971A CN104327533A CN 104327533 A CN104327533 A CN 104327533A CN 201410447971 A CN201410447971 A CN 201410447971A CN 104327533 A CN104327533 A CN 104327533A
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- manganese
- acid blue
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- dyestuff
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- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 239000004161 brilliant blue FCF Substances 0.000 title claims abstract description 20
- 235000012745 brilliant blue FCF Nutrition 0.000 title claims abstract description 20
- 238000005516 engineering process Methods 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000975 dye Substances 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 235000019219 chocolate Nutrition 0.000 claims description 8
- 229930013930 alkaloid Natural products 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- SHHKMWMIKILKQW-UHFFFAOYSA-N 2-formylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=O SHHKMWMIKILKQW-UHFFFAOYSA-N 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 7
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 3
- BQGRVFPPZJPWPB-UHFFFAOYSA-N 3-[(n-ethylanilino)methyl]benzenesulfonic acid Chemical compound C=1C=CC=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 BQGRVFPPZJPWPB-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- YZIFHOCUHJGEIG-UHFFFAOYSA-L [Mn](=O)(O)O.[Mn] Chemical compound [Mn](=O)(O)O.[Mn] YZIFHOCUHJGEIG-UHFFFAOYSA-L 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- -1 seed) Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JLUGKDWGQPNDGX-UHFFFAOYSA-L azanium;manganese(2+);phosphate Chemical compound [NH4+].[Mn+2].[O-]P([O-])([O-])=O JLUGKDWGQPNDGX-UHFFFAOYSA-L 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001753 sapphirine Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a clean production technology of an acid blue 9 dye. The technology mainly comprises the following steps: condensing o-benzaldehydesulfonic acid and N-ethyl-N-(3'-sulfobenzyl)aniline in an acidic medium to generate a leuco compound; oxidizing the leuco compound in a sulfuric acid medium; processing the obtained oxidation solution by liquid caustic soda or soda ash to form a manganese residue precipitate, filtering, neutralizing the obtained filtrate, concentrating, and carrying out spray drying to obtain dye raw powder; and washing the manganese residue, and oxidizing the washed manganese residue by hydrogen peroxide to generate manganese dioxide for cycle use. Compared with routine production technologiess adopting a manganese dioxide oxidation method, the clean production technology disclosed in the invention has the advantages of no exhaust gas, no waste residues and no dye wastewater through oxidizing the manganese residue in the manganese removal process for later use and through changing solid residues into valuables by developing a unique manganese dioxide recovery method.
Description
Technical field
The present invention relates to a kind of process for cleanly preparing of acid blue dye, relate to a kind of process for cleanly preparing of acid blue 9 dyestuff particularly.
Background technology
Acid blue 9 number (C.I.Acid Blue 9), this dyestuff is mainly used in the dyeing of textiles at the beginning of being born, and is mainly used in wool, polyamide fibre, the dyeing of silk and stamp, sometimes also uses as weaving mark look pigment.Afterwards because it dazzles beautiful sapphirine, excellent is water-soluble, particularly it is nontoxic, possesses the environment friendly compared favourably with natural pigment, its Application Areas that what people were deep expanded, at present the main application of this product has turned to non-textile field, as daily chemical products (liquid detergent, soap, defend that lavatory is clean, bathing beach, indoor bathroom water etc.), agrochemical product (agricultural chemicals, chemical fertilizer, seed), paper, artificial lawn, timber, leather, anodized aluminium painted, food, medicine, makeup, ink for ink-jet print etc.
this dyestuff belongs to triaryl methane class formation (sodium salt structure is shown in I formula), and corresponding chemical abstracts call number is respectively 3844-45-9, and Colour index number is: C.I.42090.
（Ⅰ）
The production technique of acid blue 9 number, from plumbous oxide oxidation style the earliest, is transitioned into the method for oxidation of dichromic, more gradually develops into manganese dioxide method.Its major cause is that first two Heavy Metal Pollution is comparatively large, and Manganse Dioxide not only oxidisability is gentleer, side reaction is few, and manganese element toxic is little, relatively little to environmental influence.But in the production process of current most of producer, main Problems existing is that the manganese slag (manganous hydroxide, manganous phosphate, ammonium phosphate manganese, manganous carbonate etc.) produced does not reclaim, and forms solid slag, causes certain environmental influence.How to address this problem, be the important topic of pendulum before numerous scientific workers.For a long time, No. 9 blue manufacturers quite a lot both at home and abroad carry out the tackling key problem of hydrogen peroxide oxidation technique always in organizational strength, but due to the fast decoupled of hydrogen peroxide and the strong defect of oxidisability, make acid blue 9 number hydrogen peroxide process rest on the laboratory study stage always.Therefore, need to provide a kind of new technical scheme to solve the problems referred to above.
Summary of the invention
For solving the problem, the invention provides a kind of process for cleanly preparing of acid blue 9 dyestuff.
The technical solution used in the present invention:
A process for cleanly preparing for acid blue 9 dyestuff, comprises the following steps:
A, N-ethyl-N-(3 '-sulfonic group benzyl) aniline and benzaldehyde-o-sulfonic acid condensation in the sour water phase medium of 102 ~ 106 DEG C generate leuco compound;
B, leuco compound, in the sulphuric acid soln medium of 20 ~ 45 DEG C, obtain oxidation solution with manganese dioxide, and oxidation pH scope is 1.5 ~ 2.5;
C, add applicable alkaloids, pH value range is 8.5 ~ 10.0, and the oxidation solution obtained to step b neutralizes, and is formed with the suspension of manganese slag precipitation;
The suspension of d, filtration step c, collects for subsequent use after filter cake washing, the reuse of filter cake washing liquid is to the oxidation of next batch, and filtrate is through neutralization, and the pH value range of neutralization is 6.0 ~ 7.0, and reconcentration, spraying dry obtain the former powder of acid blue 9 dyestuff;
The manganese slag filter cake of e, steps d gained, drops in water and forms suspension, at 30 ~ 60 DEG C, by hydrogen peroxide oxidation in tubular static mixer, obtain chocolate suspension, putting to potassium iodide starch test paper is that blueness is reaction end, centrifugal Manganse Dioxide, cyclically utilizing is to step b.
N-ethyl-the N-(3 '-sulfonic group benzyl of step a) mole ratio of aniline and benzaldehyde-o-sulfonic acid, its ratio value scope is 1.95 ~ 1.99.
The Manganse Dioxide of step b and the mole ratio of leuco compound, its ratio value scope is 1.0 ~ 1.15.
The applicable alkaloids of step c is one in sodium hydroxide, potassium hydroxide, soda ash or arbitrary combination.
Tubular static mixer described in steps d preferably adopts SX type, and material adopts Stainless steel 316 L.
The invention has the beneficial effects as follows: the advantage of the present invention compared with conventional production process is:
1. adopt hydrogen peroxide oxidation to reclaim Manganse Dioxide technology, stopped the generation (producing the waste residue that 100% intensity per ton No. 9 blue products will produce about 70 kilograms) of solid slag, thus decreased expenses of environmental protection;
2. doing oxidation reactor by introducing static mixer, significantly reducing the hydrogen peroxide consumption reclaimed in Manganse Dioxide process, thus make Manganse Dioxide recovery circulation really have vitality.Compared with traditional technology, the raw materials cost of 100% intensity per ton No. 9 blue products declines about 330 yuan.
Accompanying drawing explanation
Fig. 1 is reactive system schematic diagram of the present invention.
Embodiment
Following embodiment only for illustration of the present invention, but can not limit protection scope of the present invention.
Embodiment 1
In condensation reaction still, add water 600L, stirs lower intensification and add folding hundred benzaldehyde-o-sulfonic acid 500kg, N-ethyl-N-(3 '-sulfonic group benzyl) aniline 1300kg, add moderate amount of sulfuric acid and regulate acidity, close manhole plate, continue to be warming up to 102 ~ 106 DEG C and be incubated to terminal.After terminal arrives, put into 500L water pre-dilution;
Condensated liquid is put into the stills for air blowing having put water at the bottom of 2000L (containing front a collection of demanganize washings), add sulfuric acid and be about 160kg, opening clamp jacket water adjusts the temperature to 25-35 DEG C, add folding hundred Manganse Dioxide 225kg, control temperature is no more than 45 DEG C, pH1.5 ~ 2.5, is incubated 2 hours;
Oxidation terminal to after be cooled to 35 DEG C, slowly add soda ash and be about 380kg, control temperature is no more than 45 DEG C, regulate pH to 9.0 ~ 9.5, manganous carbonate (to be recycled) is sloughed in filtration, during filtrate proceeds to and still, add sulfuric acid and regulate pH6.0 ~ 7.0, concentrated, spraying dry obtains acid blue 9 number former powder 2288kg(intensity 284%).Omnidistance without waste gas, waste residue, discharge of wastewater.
Manganous carbonate filter cake is with a small amount of mass concentration 0.05% soda ash water washing three times, and water at the bottom of lower batch oxidation is made in washings reuse.Cleaning after manganous carbonate enter bag collect after by following process.
The recovery of Manganse Dioxide
Manganse Dioxide reclaims in still, add water 1800L, stir lower input 2400kg manganous carbonate (water ratio 37.5%), be warming up to 45 ~ 50 DEG C, evenly, unlatching bottom valve and recycle pump (flow velocity 50m3/H) circulate through static mixer (SX-37.5/150), about 2240L30% hydrogen peroxide is pumped into static mixer by unlatching hydrogen peroxide valve and high pressure constant flow pump, control to reclaim temperature 45 ~ 55 DEG C in still, feed time about 4 hours, fetch and receive chocolate suspension in still, point is that blueness is reaction end to potassium iodide starch test paper, centrifugal, obtain 2635kg chocolate Manganse Dioxide tide product (content 42.2%).Produce the nearly colourless waste water of about 4000L, COD
cr=162mg/L.
Embodiment 2
Condensation part is with example 1.
Oxidized portion is the chocolate Manganse Dioxide of the 502kg content 42.2% that obtain tide product to reclaim in example 1, and other are with example 1, final must acid blue 9 number former powder 2306kg(intensity 281%).Omnidistance without waste gas, waste residue, discharge of wastewater.
Embodiment 3
Condensation, oxidized portion are with example 2.
Oxidation terminal to after be cooled to 35 DEG C, add mass concentration 33% liquid caustic soda slowly and be about 340kg, regulate pH to 5.0 ~ 5.5, then continue to add soda ash and be about 225kg, control temperature is no more than 45 DEG C, regulates pH to 9.0 ~ 9.5.Manganous carbonate (to be recycled) is sloughed in filtration, and during filtrate proceeds to and still, add sulfuric acid and regulate pH6.0 ~ 7.0, spraying dry obtains acid blue 9 number former powder 2274kg(intensity 286%).Omnidistance without waste gas, waste residue, discharge of wastewater.
Manganous carbonate filter cake is with a small amount of mass concentration 0.05% soda ash water washing three times, and water at the bottom of lower batch oxidation is made in washings reuse.After cleaning manganous carbonate enter bag collect after by the recycling of Manganse Dioxide in example 1.
Embodiment 4
Condensation, oxidized portion are with example 2.
Oxidation terminal to after be cooled to 35 DEG C, add mass concentration 33% liquid caustic soda 860kg slowly, control temperature is no more than 45 DEG C, regulate pH to 9.0 ~ 9.5.Manganous hydroxide manganese slag (to be recycled) is sloughed in filtration, and during filtrate proceeds to and still, add sulfuric acid and regulate pH6.0 ~ 7.0, spraying dry obtains acid blue 9 number former powder 2256kg(intensity 287%).Omnidistance without waste gas, waste residue, discharge of wastewater.
Manganous hydroxide manganese slag filter cake is with a small amount of 0.05% soda ash water washing three times, and water at the bottom of lower batch oxidation is made in washings reuse.The rear manganous hydroxide manganese slag of cleaning enters bag and collects pending.
Manganse Dioxide reclaims in still, and add water 1500L, stirs lower input 2000kg manganese slag (manganous hydroxide, water ratio 40%), is warming up to 45 ~ 50 DEG C, open bottom valve and recycle pump (flow velocity 50m evenly
3/ H) circulate through static mixer (SX-37.5/150), about 2300L30% hydrogen peroxide is pumped into static mixer by unlatching hydrogen peroxide valve and high pressure constant flow pump, control to reclaim temperature 45 ~ 55 DEG C in still, feed time about 4 hours, fetch and receive chocolate suspension in still, putting to potassium iodide starch test paper is that blueness is reaction end.Centrifugal, obtain 2780kg chocolate Manganse Dioxide tide product (content 41.3%).Produce the nearly colourless waste water of about 3200L, COD
cr=155mg/L.
Embodiment 5
Condensation part is with example 1.
Oxidized portion is the chocolate Manganse Dioxide of the 513kg content 41.3% that obtain tide product to reclaim in example 4, and other are with example 1, final must acid blue 9 number former powder 2302kg(intensity 282%).Omnidistance without waste gas, waste residue, discharge of wastewater.
In above-described embodiment, add applicable alkaloids after oxidation terminates, alkaloids, except sodium hydroxide, can also be the arbitrary combination of potassium hydroxide, sodium hydroxide, soda ash.
According to above-described embodiment; technical problem to be solved by this invention reclaims manganese slag; recycle; thus really accomplished No. 9 blue supplier processes without waste water, exhaust gas emission; the enforcement of this process for cleanly preparing both protected environment; there is great social effect, turn avoid Solid state fermentation expense, have good economic implications.
In the process reclaiming Manganse Dioxide, then introduce tubular static mixer dexterously and make high efficiency reactor (Fig. 1 is shown in by reactive system schematic diagram), in Fig. 1, according to P-1, P-2, P-3, P-4, P-5 order carries out each step, and each symbol shown in figure represents: temperature regulates still E-1, still bottom valve V-1, recycle pump E-2, static mixer E-3, variable valve V-2, dioxygen water tower E-4, variable valve V-3, high pressure constant flow pump E-5.The setting of tubular static mixer solves the easy fast decoupled of hydrogen peroxide well and causes the defect of exorbitant expenditure, makes recovery process have good economy, practicality.And the cost paid is only reclaim folding hundred Manganse Dioxide per ton, about produces 3 tons of COD value and only to have an appointment the near colourless innocuous effluent of 150mg/L, do not need process can receive tube drainage.
Claims (4)
1. a process for cleanly preparing for acid blue 9 dyestuff, is characterized in that, comprises the following steps:
A, N-ethyl-N-(3 '-sulfonic group benzyl) aniline and benzaldehyde-o-sulfonic acid condensation in the sour water phase medium of 102 ~ 106 DEG C generate leuco compound;
B, leuco compound, in the sulphuric acid soln medium of 20 ~ 45 DEG C, obtain oxidation solution with manganese dioxide, and oxidation pH scope is 1.5 ~ 2.5;
C, add applicable alkaloids, pH value range is 8.5 ~ 10.0, and the oxidation solution obtained to step b neutralizes, and is formed with the suspension of manganese slag precipitation;
The suspension of d, filtration step c, collects for subsequent use after filter cake washing, the reuse of filter cake washing liquid is to the oxidation of next batch, and filtrate is through neutralization, and the pH value range of neutralization is 6.0 ~ 7.0, and reconcentration, spraying dry obtain the former powder of acid blue 9 dyestuff;
The manganese slag filter cake of e, steps d gained, drops in water and forms suspension, at 30 ~ 60 DEG C, by hydrogen peroxide oxidation in tubular static mixer, obtain chocolate suspension, putting to potassium iodide starch test paper is that blueness is reaction end, centrifugal Manganse Dioxide, cyclically utilizing is to step b.
2. the process for cleanly preparing of a kind of acid blue 9 dyestuff according to claim 1, is characterized in that: N-ethyl-the N-(3 '-sulfonic group benzyl of step a) mole ratio of aniline and benzaldehyde-o-sulfonic acid, its ratio value scope is 1.95 ~ 1.99.
3. the process for cleanly preparing of a kind of acid blue 9 dyestuff according to claim 1, it is characterized in that: the Manganse Dioxide of step b and the mole ratio of leuco compound, its ratio value scope is 1.0 ~ 1.15.
4. the process for cleanly preparing of a kind of acid blue 9 dyestuff according to claim 1, is characterized in that: the applicable alkaloids of step c is one in sodium hydroxide, potassium hydroxide, soda ash or arbitrary combination.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348846A (en) * | 2015-09-25 | 2016-02-24 | 恒升化工有限公司 | Preparation method for acid blue dye 9 with low salt content |
| CN107721887A (en) * | 2017-10-18 | 2018-02-23 | 恒升化工有限公司 | A kind of preparation method of highly acid blue dyes |
| CN111007059A (en) * | 2019-11-05 | 2020-04-14 | 北京海洋海泰科技有限公司 | Blood stain color developing agent and preparation and use methods thereof |
| CN112522515A (en) * | 2020-11-17 | 2021-03-19 | 天津三环化工有限公司 | Method for treating waste residue containing metal manganese |
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|---|---|---|---|---|
| US4566999A (en) * | 1983-03-18 | 1986-01-28 | Hoechst Aktiengesellschaft | Process for the preparation of acid dyestuffs of low electrolyte content of the triphenylmethane series |
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| CN105348846A (en) * | 2015-09-25 | 2016-02-24 | 恒升化工有限公司 | Preparation method for acid blue dye 9 with low salt content |
| CN105348846B (en) * | 2015-09-25 | 2017-07-11 | 恒升化工有限公司 | A kind of preparation method of lower salt content acid blue 9 dyestuff |
| CN107721887A (en) * | 2017-10-18 | 2018-02-23 | 恒升化工有限公司 | A kind of preparation method of highly acid blue dyes |
| CN111007059A (en) * | 2019-11-05 | 2020-04-14 | 北京海洋海泰科技有限公司 | Blood stain color developing agent and preparation and use methods thereof |
| CN112522515A (en) * | 2020-11-17 | 2021-03-19 | 天津三环化工有限公司 | Method for treating waste residue containing metal manganese |
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