CN108160055A - A kind of modified silica-gel and preparation method thereof and adsorption applications method - Google Patents
A kind of modified silica-gel and preparation method thereof and adsorption applications method Download PDFInfo
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- CN108160055A CN108160055A CN201711484976.0A CN201711484976A CN108160055A CN 108160055 A CN108160055 A CN 108160055A CN 201711484976 A CN201711484976 A CN 201711484976A CN 108160055 A CN108160055 A CN 108160055A
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- Prior art keywords
- mercaptan
- silicon substrate
- trimethoxy silicon
- gel
- modified silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 title abstract description 27
- 229960001866 silicon dioxide Drugs 0.000 claims abstract description 67
- 239000000741 silica gel Substances 0.000 claims abstract description 66
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 66
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 49
- 238000010828 elution Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims description 113
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 105
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 60
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 36
- 150000002500 ions Chemical class 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 29
- 235000019441 ethanol Nutrition 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical group 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000002443 hydroxylamines Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 52
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 30
- 239000002699 waste material Substances 0.000 abstract description 27
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 12
- 239000000499 gel Substances 0.000 abstract description 10
- 239000002440 industrial waste Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 7
- 238000010668 complexation reaction Methods 0.000 abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 15
- 239000003463 adsorbent Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000010970 precious metal Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 229910052703 rhodium Inorganic materials 0.000 description 8
- 239000010948 rhodium Substances 0.000 description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052741 iridium Inorganic materials 0.000 description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 150000003376 silicon Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- -1 nonyl Alkane Chemical class 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 2
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 2
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 2
- RKAMCQVGHFRILV-UHFFFAOYSA-N 1-chlorononane Chemical compound CCCCCCCCCCl RKAMCQVGHFRILV-UHFFFAOYSA-N 0.000 description 2
- OGSJMFCWOUHXHN-UHFFFAOYSA-N 1-iodononane Chemical compound CCCCCCCCCI OGSJMFCWOUHXHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- ACCBVLDMNMOXDN-UHFFFAOYSA-N heptane;hydrobromide Chemical compound Br.CCCCCCC ACCBVLDMNMOXDN-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical class [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical class [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention relates to a kind of modified silica-gels and preparation method thereof and adsorption applications method.The modified silica-gel is using the thiol group being bonded in above silica gel framework come complexation heavy metal ion；And elute the modified silica-gel that heavy metal ion has been complexed with the hydrochloric acid containing thiocarbamide again, to recycle heavy metal.The consumption of hydrochloric acid, so as to reduce waste during valuable heavy metal removal in industrial wastes, and reduces the discharge of waste residue, waste liquid, exhaust gas when the adsorption recovery method of the present invention can improve the rate of recovery of heavy metal ion and reduce elution.
Description
Technical field
The present invention relates to a kind of modified silica-gels and preparation method thereof and adsorption applications method.
Background technology
Noble metal is primarily referred to as gold, silver and platinum group (platinum, palladium, ruthenium, rhodium, iridium and osmium).It is expensive as scarce resource
Metal has the title of " industrial vitamin ", is widely used in the fields such as medicine, chemical industry, plating, electronics, defence and military.In these works
In the production process of industry product, inevitable that the metal residue of certain content be retained in it is in product or big
Amount is discharged into industrial wastes.On the one hand, since resource is rare, the noble metal for recycling these losses has Important Economic meaning；
On the other hand, the noble metal remained in industrial wastes can cause environmental pollution, be retained in the noble metal in drug to the mankind's
Health is unfavorable.Therefore, removing, absorption and the recovery processing of noble metal are all very in terms of economic, health and environmental protection
Important industrial link, and metal absorbent has the advantages such as efficient, stable, inexpensive, simple for process, is most promising side
Method.
The prior art generally carries out elution recycling using modified silica-gel to precious metal.Modified silica-gel refers to utilize silica gel table
Certain organic groups are bonded in Silica Surface by the hydroxyl in face and the reaction of certain active groups.Modified silica-gel utilizes silica gel bone
The supporting role of frame, the organic group being bonded in above carry out complexation heavy metal ion (including palladium, gold, platinum, yttrium, rhodium etc.)；Then
The modified silica-gel that heavy metal ion has been complexed can be eluted again with the hydrochloric acid containing thiocarbamide, to recycle heavy metal.But use existing skill
After modified silica-gel absorption noble metal in art, when heavy metal is recycled in elution, eluting agent is larger, substantially the 50 of silica gel amount
Times, while the waste residue, waste liquid, the exhaust gas that generate are more (referring to CN 104745814A).
Invention content
The present invention provides a kind of modified silica-gels and preparation method thereof and adsorption applications method, expensive in industrial wastes to reduce
Waste during weight heavy metal removal, and reduce the discharge of waste residue, waste liquid, exhaust gas.
In order to achieve the above objectives, the present invention provides following technical scheme：
According to an aspect of the present invention, a kind of modified silica-gel is provided, structural unit is as follows：
Wherein, X is halogen, and m, n are each independently selected from 0~6 integer.
According to embodiment of the present invention, the halogen is selected from chlorine, bromine or iodine.
According to embodiment of the present invention, m is selected from 0~3, n and is selected from 1~3.
Modified silica-gel provided by the invention is using the thiol group being bonded in above silica gel framework come complexation heavy metal ion；
And elute the modified silica-gel that heavy metal ion has been complexed with the hydrochloric acid containing thiocarbamide again, to recycle heavy metal, a huge sum of money can be improved
The consumption of hydrochloric acid when belonging to the rate of recovery of ion and reducing elution, during so as to reduce valuable heavy metal removal in industrial wastes
Waste, and reduce the discharge of waste residue, waste liquid, exhaust gas.
According to another aspect of the present invention, a kind of preparation method of modified silica-gel is provided, including：
The silane coupling agent of the silica gel of acidified processing, solvent, alkaline reagent, functional group containing sulfydryl and halogen is mixed
It closes, and is heated to reflux, obtain the modified silica-gel.
According to embodiment of the present invention, it is described to be heated to reflux carrying out under agitation, mixing speed for 180~
240r/min.According to embodiment of the present invention, it is heated to reflux under inert gas shielding.According to the present invention one
A embodiment, the time being heated to reflux are 20~30 hours.
According to embodiment of the present invention, the preparation method of the modified silica-gel further includes：
The modified silica-gel of generation is washed with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol successively；
It is dried under reduced pressure to obtain Solid Modified silica gel under 50~70 degrees Celsius.
According to embodiment of the present invention, the silane coupling agent of the functional group containing sulfydryl and halogen is selected from 1-
Chloro- 8- (trimethoxy silicon substrate) octane -4- mercaptan, the bromo- 8- of 1- (trimethoxy silicon substrate) octane -4- mercaptan, the iodo- 8- (front threes of 1-
Oxygroup silicon substrate) octane -4- mercaptan, the chloro- 9- of 1- (trimethoxy silicon substrate) nonane -5- mercaptan, the bromo- 9- of 1- (trimethoxy silicon substrate) nonyl
Alkane -5- mercaptan, the iodo- 9- of 1- (trimethoxy silicon substrate) nonane -5- mercaptan, the chloro- 10- of 1- (trimethoxy silicon substrate) decane -6- mercaptan,
The bromo- 10- of 1- (trimethoxy silicon substrate) decane -6- mercaptan, the iodo- 10- of 1- (trimethoxy silicon substrate) decane -6- mercaptan, the chloro- 7- of 1-
(trimethoxy silicon substrate) heptane -4- mercaptan, the bromo- 7- of 1- (trimethoxy silicon substrate) heptane -4- mercaptan, 1- iodo- 7- (trimethoxy silicon
Base) heptane -4- mercaptan, the chloro- 8- of 1- (trimethoxy silicon substrate) octane -5- mercaptan, the bromo- 8- of 1- (trimethoxy silicon substrate) octane -5-
The iodo- 8- of mercaptan, 1- (trimethoxy silicon substrate) octane -5- mercaptan, the chloro- 9- of 1- (trimethoxy silicon substrate) nonane -6- mercaptan, 1- are bromo-
9- (trimethoxy silicon substrate) nonane -6- mercaptan, the iodo- 9- of 1- (trimethoxy silicon substrate) nonane -6- mercaptan, the chloro- 6- (trimethoxies of 1-
Silicon substrate) hexane -4- mercaptan, the bromo- 6- of 1- (trimethoxy silicon substrate) hexane -4- mercaptan, the iodo- 6- of 1- (trimethoxy silicon substrate) hexane -
The chloro- 7- of 4- mercaptan, 1- (trimethoxy silicon substrate) heptane -5- mercaptan, the bromo- 7- of 1- (trimethoxy silicon substrate) heptane -5- mercaptan, 1-
Iodo- 7- (trimethoxy silicon substrate) heptane -5- mercaptan, the chloro- 8- of 1- (trimethoxy silicon substrate) octane -6- mercaptan, the bromo- 8- (front threes of 1-
Oxygroup silicon substrate) octane -6- mercaptan, the iodo- 8- of 1- (trimethoxy silicon substrate) octane -6- mercaptan, the chloro- 5- of 1- (trimethoxy silicon substrate) penta
Alkane -4- mercaptan, the bromo- 5- of 1- (trimethoxy silicon substrate) pentane -4- mercaptan, the iodo- 5- of 1- (trimethoxy silicon substrate) pentane -4- mercaptan,
The chloro- 6- of 1- (trimethoxy silicon substrate) hexane -5- mercaptan, the bromo- 6- of 1- (trimethoxy silicon substrate) hexane -5- mercaptan, the iodo- 6- (three of 1-
Methoxyl group silicon substrate) hexane -5- mercaptan, the chloro- 7- of 1- (trimethoxy silicon substrate) heptane -6- mercaptan, the bromo- 7- of 1- (trimethoxy silicon substrate)
Heptane -6- mercaptan or the iodo- 7- of 1- (trimethoxy silicon substrate) heptane -6- mercaptan.
According to embodiment of the present invention, the solvent is selected from aromatic hydrocarbon of the boiling point in 100~150 degrees centigrades
Or aliphatic hydrocarbon, such as can be the one or more in toluene, ethylo benzene, dimethylbenzene, hexamethylene and normal heptane.According to
An embodiment of the invention, the solvent are anhydrous solvent.
According to embodiment of the present invention, one kind in three fatty hydroxylamines and pyridines of the alkaline reagent or
More than one.For example, the basic solvent can be triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine etc..
According to embodiment of the present invention, the mass ratio of the silica gel and solvent is 1:2~1:4；The silica gel and
The mass ratio of the silane coupling agent of functional group containing sulfydryl and halogen is 1:1~2:1.
The mild modified silicon controllable, easy to operate, prepared of modified silica-gel preparation method reaction condition provided by the invention
Glue absorption property is stable, surface functional group content is high, has good adsorptive selectivity energy, therefore can be extensive to heavy metal ion
Removing, selective absorption, enriching and recovering for heavy metal ion in water etc..
According to another aspect of the invention, provide it is a kind of using modified silica-gel carry out it is heavy metal ion adsorbed and recycling
Method, including：
It is heavy metal ion adsorbed using modified silica-gel progress, obtain metal precipitates；
The metal precipitates are recycled in elution.
A specific embodiment according to the present invention, the method includes：
Modified silica-gel is mixed with the waste liquid containing heavy metal ion；
It is sufficiently stirred under 20~30 degrees Celsius 20~40 minutes, to be adsorbed to heavy metal ion, obtains metal and sink
Starch；
Filtering metal sediment；
The metal precipitates are recycled in elution.
According to embodiment of the present invention, elution is recycled the metal precipitates and is carried out under 40~60 degrees Celsius.
In the present invention, modified silica-gel utilizes heavy metal ion adsorbed and recycling method and is bonded in above silica gel framework
Thiol group carrys out complexation heavy metal ion, and the modified silica-gel that heavy metal ion has been complexed is eluted again with the hydrochloric acid containing thiocarbamide,
To recycle heavy metal, the consumption of hydrochloric acid when can improve the rate of recovery of heavy metal ion and reduce elution, so as to reduce industry
Waste in waste liquid during valuable heavy metal removal, and reduce the discharge of waste residue, waste liquid, exhaust gas.
Description of the drawings
Fig. 1 is the absorption principle figure of modified silica-gel that an embodiment of the present invention provides.
Specific embodiment
To reduce waste during valuable heavy metal removal in industrial wastes, and reduce the row of waste residue, waste liquid, exhaust gas
It puts, an embodiment of the present invention provides a kind of modified silica-gels and preparation method thereof and adsorption applications method.For make the purpose of the present invention,
Technical solution and advantage are clearer, and the present invention is described in further detail by the following examples.
According to an aspect of the present invention, a kind of modified silica-gel is provided, structural unit is as follows：
Wherein, X is halogen, and m, n state carbon atom number and be each independently selected from 0~6 integer.When X is selected from halogen,
Be conducive to carry out absorb-elute to metal ion.
According to embodiment of the present invention, the halogen is selected from chlorine, bromine or iodine.
According to embodiment of the present invention, m is selected from 0~3, n and is selected from 1~3.
In the present invention, silica gel is the condensate of silicic acid, and inside is with SiO4Tetrahedral geometry exist, gross formula SiO2,
But have the presence in the form of free hydroxyl of several oxygen in Silica Surface.When this kind of hydroxyl and the base of function containing sulfydryl
During the reaction of the silane coupling agent of group and halogen, three methoxyl groups on silane coupling agent can be replaced, obtain target and change
Property silica gel.In fact, ball represents the set of several silicon dioxide molecules, there are three hydroxyl, this three hydroxyls for this collective surface
Base participates in reaction, obtains structural unitThe set of several structural units is formed
Naked eyes can eye white powder -- modified silica-gel.
A huge sum of money is complexed using the thiol group (- SH) being bonded in above silica gel framework in modified silica-gel provided by the invention
Belong to ion, and the modified silica-gel that heavy metal ion has been complexed is eluted again with the hydrochloric acid containing thiocarbamide, to recycle heavy metal, Neng Gouti
The rate of recovery of high heavy metal ion and the consumption for reducing hydrochloric acid when eluting, so as to reduce valuable heavy metal ion in industrial wastes
Waste during recycling, and reduce the discharge of waste residue, waste liquid, exhaust gas.
According to another aspect of the present invention, a kind of preparation method of modified silica-gel is provided, including：
The silane coupling agent of the silica gel of acidified processing, solvent, alkaline reagent, functional group containing sulfydryl and halogen is mixed
It closes, and is heated to reflux, obtain the modified silica-gel.
The step for carrying out activity to silica gel by acidification includes：With 1:(volume ratio of concentrated nitric acid and water is 1 nitric acid
1:1) it boils three hours, cools down, be washed to neutrality, then with 1:(volume ratio of concentrated hydrochloric acid and water is 1 to 1 hydrochloric acid:1) concussion impregnates 6
Hour, it is washed to no chlorion；160 degree of dryings 12 hours cool down in drier, obtain the silica gel of the acidified processing.
According to embodiment of the present invention, it is described to be heated to reflux carrying out under agitation, mixing speed for 180~
240r/min.According to embodiment of the present invention, it is heated to reflux under inert gas shielding.According to the present invention one
A embodiment, the time being heated to reflux are 20~30 hours.
According to embodiment of the present invention, the preparation method of the modified silica-gel further includes：
The modified silica-gel of generation is washed with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol successively；
It is dried under reduced pressure to obtain Solid Modified silica gel under 50~70 degrees Celsius.
According to embodiment of the present invention, the silane coupling agent of the functional group containing sulfydryl and halogen is selected from 1-
Chloro- 8- (trimethoxy silicon substrate) octane -4- mercaptan, the bromo- 8- of 1- (trimethoxy silicon substrate) octane -4- mercaptan, the iodo- 8- (front threes of 1-
Oxygroup silicon substrate) octane -4- mercaptan, the chloro- 9- of 1- (trimethoxy silicon substrate) nonane -5- mercaptan, the bromo- 9- of 1- (trimethoxy silicon substrate) nonyl
Alkane -5- mercaptan, the iodo- 9- of 1- (trimethoxy silicon substrate) nonane -5- mercaptan, the chloro- 10- of 1- (trimethoxy silicon substrate) decane -6- mercaptan,
The bromo- 10- of 1- (trimethoxy silicon substrate) decane -6- mercaptan, the iodo- 10- of 1- (trimethoxy silicon substrate) decane -6- mercaptan, the chloro- 7- of 1-
(trimethoxy silicon substrate) heptane -4- mercaptan, the bromo- 7- of 1- (trimethoxy silicon substrate) heptane -4- mercaptan, 1- iodo- 7- (trimethoxy silicon
Base) heptane -4- mercaptan, the chloro- 8- of 1- (trimethoxy silicon substrate) octane -5- mercaptan, the bromo- 8- of 1- (trimethoxy silicon substrate) octane -5-
The iodo- 8- of mercaptan, 1- (trimethoxy silicon substrate) octane -5- mercaptan, the chloro- 9- of 1- (trimethoxy silicon substrate) nonane -6- mercaptan, 1- are bromo-
9- (trimethoxy silicon substrate) nonane -6- mercaptan, the iodo- 9- of 1- (trimethoxy silicon substrate) nonane -6- mercaptan, the chloro- 6- (trimethoxies of 1-
Silicon substrate) hexane -4- mercaptan, the bromo- 6- of 1- (trimethoxy silicon substrate) hexane -4- mercaptan, the iodo- 6- of 1- (trimethoxy silicon substrate) hexane -
The chloro- 7- of 4- mercaptan, 1- (trimethoxy silicon substrate) heptane -5- mercaptan, the bromo- 7- of 1- (trimethoxy silicon substrate) heptane -5- mercaptan, 1-
Iodo- 7- (trimethoxy silicon substrate) heptane -5- mercaptan, the chloro- 8- of 1- (trimethoxy silicon substrate) octane -6- mercaptan, the bromo- 8- (front threes of 1-
Oxygroup silicon substrate) octane -6- mercaptan, the iodo- 8- of 1- (trimethoxy silicon substrate) octane -6- mercaptan, the chloro- 5- of 1- (trimethoxy silicon substrate) penta
Alkane -4- mercaptan, the bromo- 5- of 1- (trimethoxy silicon substrate) pentane -4- mercaptan, the iodo- 5- of 1- (trimethoxy silicon substrate) pentane -4- mercaptan,
The chloro- 6- of 1- (trimethoxy silicon substrate) hexane -5- mercaptan, the bromo- 6- of 1- (trimethoxy silicon substrate) hexane -5- mercaptan, the iodo- 6- (three of 1-
Methoxyl group silicon substrate) hexane -5- mercaptan, the chloro- 7- of 1- (trimethoxy silicon substrate) heptane -6- mercaptan, the bromo- 7- of 1- (trimethoxy silicon substrate)
Heptane -6- mercaptan or the iodo- 7- of 1- (trimethoxy silicon substrate) heptane -6- mercaptan.
According to embodiment of the present invention, the solvent is selected from aromatic hydrocarbon of the boiling point in 80~150 degrees centigrades
Or aliphatic hydrocarbon, such as can be the one or more in toluene, ethylo benzene, dimethylbenzene, hexamethylene and normal heptane.According to
An embodiment of the invention, the solvent are anhydrous solvent.
According to embodiment of the present invention, one kind in three fatty hydroxylamines and pyridines of the alkaline reagent or
More than one.For example, the basic solvent can be triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine etc..
According to embodiment of the present invention, the mass ratio of the silica gel and solvent is 1:2~1:4, such as can be
1:2、1:3、1:4、1:2.5、1:3.5 it waits；The mass ratio of the silane coupling agent of the silica gel and functional group containing sulfydryl and halogen
It is 1:1~2:1, such as can be 1:1、4:3、3:2、2:1 etc..
The mild modified silicon controllable, easy to operate, prepared of modified silica-gel preparation method reaction condition provided by the invention
Glue absorption property is stable, surface functional group content is high, has good adsorptive selectivity energy, therefore can be extensive to heavy metal ion
Removing, selective absorption, enriching and recovering for heavy metal ion in water etc..
In practical manufacturing process, concrete operations can be carried out by the following method：
Prepare embodiment 1
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), toluene are added in 200L kettles
12kg, the chloro- 8- of triethylamine 200g, 1- (trimethoxy silicon substrate) octane -4- mercaptan (praise the limited public affairs of industry new chemical materials purchased from Qufu
Department) 3kg；
Start stirring, mixing speed 200r/min；Reaction 24 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 60 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.06kg。
The modified silica-gel obtained to preparing embodiment 1 carries out elemental analysis, and result is：C (5.13%), H (0.86%), S
(1.71%), Cl (1.89%).It confirms after reaction, the chloro octane of the mercapto contained is had been coupled on silica gel.And
And analyzed according to elemental constituent, the amount that can calculate the substance containing sulfydryl and chloro octane being connected on every 100g silica gel is
0.053mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 5.3mmol/g.
The modified silica-gel obtained to preparing embodiment 1 has carried out infrared test, in 700cm-1The vibration peak at place shows there is C-
The presence of Cl keys.
Prepare embodiment 2
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), hexamethylene are added in 200L kettles
12.5kg, the chloro- 9- of triethylamine 200g, 1- (trimethoxy silicon substrate) nonane -5- mercaptan (it is limited to praise industry new chemical materials purchased from Qufu
Company) 3kg；
Start stirring, mixing speed 180r/min；Reaction 20 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 55 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.07kg。
The modified silica-gel obtained to preparing embodiment 2 carries out elemental analysis, and result is：C (5.69%), H (0.95%), S
(1.69%), Cl (1.87%).It confirms after reaction, the chloro nonane of the mercapto contained is had been coupled on silica gel.And
And analyzed according to elemental constituent, the amount that can calculate the substance for being connected to the chloro nonane containing sulfydryl on every 100g silica gel is
0.053mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 5.3mmol/g.
Prepare embodiment 3
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), ethylo benzene are added in 200L kettles
11.5kg, the chloro- 10- of pyridine 200g, 1- (trimethoxy silicon substrate) decane -6- mercaptan (it is limited to praise industry new chemical materials purchased from Qufu
Company) 3kg；
Start stirring, mixing speed 240r/min；Reaction 25 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 58 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.11kg。
The modified silica-gel obtained to preparing embodiment 3 carries out elemental analysis, and result is：C (6.47%), H (1.09%), S
(1.91%), Cl (1.73%).It confirms after reaction, the chloro decane of the mercapto contained is had been coupled on silica gel.And
And analyzed according to elemental constituent, the amount that can calculate the substance for being connected to the chloro decane containing sulfydryl on every 100g silica gel is
0.0596mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 5.96mmol/
g。
Prepare embodiment 4
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), toluene are added in 200L kettles
13kg, the chloro- 8- of tripropyl amine (TPA) 200g, 1- (trimethoxy silicon substrate) octane -5- mercaptan (praise the limited public affairs of industry new chemical materials purchased from Qufu
Department) 3kg；
Start stirring, mixing speed 220r/min；Reaction 22 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 65 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.09kg。
The modified silica-gel obtained to preparing embodiment 4 carries out elemental analysis, and result is：C (5.88%), H (0.99%), S
(1.96%), Cl (2.17%).It confirms after reaction, the chloro octane of the mercapto contained is had been coupled on silica gel.And
And analyzed according to elemental constituent, the amount that can calculate the substance for being connected to the chloro octane containing sulfydryl on every 100g silica gel is
0.061mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 6.1mmol/g.
Prepare embodiment 5
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), diethylbenzene are added in 200L kettles
12kg, the iodo- 9- of tri-n-butylamine 200g, 1- (trimethoxy silicon substrate) nonane -6- mercaptan (praise the limited public affairs of industry new chemical materials purchased from Qufu
Department) 3kg；
Start stirring, mixing speed 240r/min；Reaction 30 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 70 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.03kg。
The modified silica-gel obtained to preparing embodiment 5 carries out elemental analysis, and result is：C (5.62%), H (0.95%), S
(1.69%), I (6.68%).It confirms after reaction, the iodo nonane of the mercapto contained is had been coupled on silica gel.And
It is analyzed according to elemental constituent, the amount that can calculate the substance for being connected to the iodo nonane containing sulfydryl on every 100g silica gel is
0.053mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 5.3mmol/g.
Prepare embodiment 6
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), dimethylbenzene are added in 200L kettles
12.5kg, the bromo- 7- of triethylamine 200g, 1- (trimethoxy silicon substrate) heptane -5- mercaptan (it is limited to praise industry new chemical materials purchased from Qufu
Company) 3kg；
Start stirring, mixing speed 200r/min；Reaction 28 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 67 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.09kg。
The modified silica-gel obtained to preparing embodiment 6 carries out elemental analysis, and result is：C (5.57%), H (1.00%), S
(2.13%), Br (5.30%).It confirms after reaction, the heptane bromide of the mercapto contained is had been coupled on silica gel.And
And analyzed according to elemental constituent, the amount that can calculate the substance containing sulfydryl and heptane bromide being connected on every 100g silica gel is
0.066mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 6.6mmol/g.
Prepare embodiment 7
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), normal heptane are added in 200L kettles
12kg, the bromo- 5- of pyridine 200g, 1- (trimethoxy silicon substrate) pentane -4- mercaptan (praise the limited public affairs of industry new chemical materials purchased from Qufu
Department) 3kg；
Start stirring, mixing speed 180r/min；Reaction 24 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 60 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.02kg。
The modified silica-gel obtained to preparing embodiment 7 carries out elemental analysis, and result is：C (3.94%), H (0.73%), S
(2.10%), Br (5.24%).It confirms after reaction, the bromo pentane of the mercapto contained is had been coupled on silica gel.And
And analyzed according to elemental constituent, the amount that can calculate the substance for being connected to the bromo pentane containing sulfydryl on every 100g silica gel is
0.0656mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 6.56mmol/
g。
Prepare embodiment 8
Silica gel 4.0kg (triumphant purchased from Qingdao nation, preferably 200~300 mesh silica gel powder), dimethylbenzene are added in 200L kettles
55.2kg, the chloro- 6- of tripropyl amine (TPA) 200g, 1- (trimethoxy silicon substrate) hexane -5- mercaptan (it is limited to praise industry new chemical materials purchased from Qufu
Company) 3kg；
Start stirring, mixing speed 200r/min；Reaction 24 hours are maintained the reflux for, room temperature is down to and is filtered；
It is washed successively with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol, 50 degrees Celsius are dried under reduced pressure, and obtain modified silica-gel
4.01kg。
The modified silica-gel obtained to preparing embodiment 8 carries out elemental analysis, and result is：C (5.29%), H (0.96%), S
(2.35%), Cl (2.60%).It confirms after reaction, the chloro-hexane of the mercapto contained is had been coupled on silica gel.And
And analyzed according to elemental constituent, the amount that can calculate the substance for the chloro-hexane containing sulfydryl being connected on every 100g silica gel is
0.0734mol adsorbs 1 precious metal atom/ionometer according to 1 sulfydryl, and the adsorption capacity for obtaining this silica gel is 7.34mmol/
g。
Heavy metal ion adsorbed and recycling method is carried out using modified silica-gel the present invention also provides a kind of, including：
It is heavy metal ion adsorbed using modified silica-gel progress, obtain metal precipitates；
The metal precipitates are recycled in elution.
A specific embodiment according to the present invention, the method includes：
Modified silica-gel is mixed with the waste liquid containing heavy metal ion；
It is sufficiently stirred under 20~30 degrees Celsius 20~40 minutes, to be adsorbed to heavy metal ion, obtains metal and sink
Starch；
Filtering metal sediment；
The metal precipitates are recycled in elution.
According to embodiment of the present invention, elution is recycled the metal precipitates and is carried out under 40~60 degrees Celsius.
According to embodiment of the present invention, elution recycling such as 40 degrees Celsius, 42 degrees Celsius, 44 degrees Celsius, 46 degrees Celsius, 47
Degree Celsius, 48 degrees Celsius, 50 degrees Celsius, 52 degrees Celsius, 54 degrees Celsius, 56 degrees Celsius, 58 degrees Celsius, carry out under 60 degrees Celsius.
According to embodiment of the present invention, using the hydrochloric acid containing thiocarbamide, under 40~60 degrees Celsius to the metal
Sediment carries out elution recycling.
In the present invention, modified silica-gel utilizes heavy metal ion adsorbed and recycling method and is bonded in above silica gel framework
Thiol group carrys out complexation heavy metal ion, and the modified silica-gel that heavy metal ion has been complexed is eluted again with the hydrochloric acid containing thiocarbamide,
To recycle heavy metal, the consumption of hydrochloric acid when can improve the rate of recovery of heavy metal ion and reduce elution, so as to reduce industry
Waste in waste liquid during valuable heavy metal removal, and reduce the discharge of waste residue, waste liquid, exhaust gas.
When the present invention carries out the absorption and recycling of heavy metal ion using modified silica-gel, concrete principle and operation please refer to figure
1 and the following contents：
As shown in Figure 1, modified silica-gel according to the present invention is complexed using the thiol group above silica gel framework is bonded in
Heavy metal ion (such as Pd ions shown in Fig. 1), obtains metal precipitates；The hydrochloric acid containing thiocarbamide is utilized later in fire-bar
When being eluted under part to metal precipitates, the halogen in modified silica-gel is reacted with thiol group and cyclization, while by heavy metal
Separate out.
Modified silica-gel is added in heavy metal solution, is sufficiently stirred in 20~30 degrees Celsius 20~40 minutes, filters out gold
Belong to sediment, content of beary metal in solution is measured according to sediment and determine its adsorption rate, contain then at 40~60 degrees Celsius of additions
The hydrochloric acid of thiocarbamide elutes the sediment filtered out, measures content of beary metal in eluent and determines its eluting rate.
Embodiment 1
Accurate weighing 0.5g rhodium caprylates (rhodium content 26%) are added in the volumetric flask that volume is 1L, addition methanol to scale,
The 1L methanol solutions that rhodium-containing is 130ppm are obtained, rhodium total content is 1.29mmol in the solution.Prepare the modified silicon in embodiment 1
The adsorption capacity of glue is 5.3mmol/g, it is known that the rhodium that 0.3g modified silica-gels can be completely in adsorbent solution.Using theoretical amount
Ten times or more add in adsorbent, actual interpolation amount is 4g.The modified silica-gel prepared by 4g in embodiment 1 adds in above-mentioned solution
In, be sufficiently stirred half an hour in 25 DEG C, filter, measure solution in rhodium content be 2ppm, adsorption rate 98.46%, then at 50 DEG C
It is eluted, 100 milliliters of 2N hydrochloric acid containing 5% thiocarbamide is only needed to be eluted at this time, are filtered, measure the rhodium in eluent
Content is 1246mg/L, eluting rate 98.13%.
To by eluting remaining modified silica-gel, pure water to neutrality after 60 degrees Celsius are dried under reduced pressure, carries out infrared survey
Examination, in 700cm-1The vibration peak at place disappears, and shows that the C-Cl keys in the bonded silica gel after being used herein as disappear.
Embodiment 2
Accurate weighing 0.5g palladiums (palladium content 47%) are added in the volumetric flask that volume is 1L, addition DMF to scale,
The 1LDMF solution for 235ppm containing palladium is obtained, palladium total content is 2.21mmol in the solution.Prepare the modified silicon in embodiment 2
The adsorption capacity of glue is 5.3mmol/g, it is known that the palladium that 0.5g modified silica-gels can be completely in adsorbent solution.Using theoretical amount
Ten times or more add in adsorbent, actual interpolation amount is 6 grams.The modified silica-gel prepared by 6g in embodiment 2 adds in above-mentioned solution
In, be sufficiently stirred in 23 DEG C 25 minutes, filter, measure solution in palladium content be 1ppm, adsorption rate 99.57%, then at 40 DEG C
It is eluted, 100 milliliters of 2N hydrochloric acid containing 5% thiocarbamide is only needed to be eluted at this time, are filtered, the palladium measured in eluent contains
It measures as 2330mg/l, eluting rate 99.6%.
Embodiment 3
Accurate weighing 0.5g palladium bichlorides (palladium content 60%) add in the volumetric flask that volume is 1L, add in the hydrochloric acid of 1N extremely
Scale obtains the aqueous solution for 300ppm containing palladium, and palladium total content is 3mmol in the solution.Prepare the modified silica-gel in embodiment 3
Adsorption capacity be 5.96mmol/g, it is known that the palladium that 0.5g modified silica-gels can be completely in adsorbent solution.Using theoretical amount
Ten times or more add in adsorbent, actual interpolation amount is 6 grams.The modified silica-gel prepared by 6g in embodiment 3 adds in above-mentioned solution
In, be sufficiently stirred in 20 DEG C 40 minutes, filter, measure solution in palladium content be 2ppm, adsorption rate 99.33%；Then at 45 DEG C
It is eluted, 100 milliliters of 2N hydrochloric acid containing 5% thiocarbamide is only needed to be eluted at this time, are filtered, the palladium measured in eluent contains
It measures as 2953mg/l, eluting rate 99.1%.
Embodiment 4
Accurate weighing 0.5g iridous chlorides (iridium content 58%) are added in the volumetric flask that volume is 1L, add in the hydrochloric acid of 1N
To scale, the aqueous solution for 290ppm containing iridium is obtained, iridium total content is 1.51mmol in the solution.Prepare changing in embodiment 4
Property silica gel adsorption capacity be 6.1mmol/g, it is known that the iridium that 0.25g modified silica-gels can be completely in adsorbent solution.Using reason
Adsorbent is added in by ten times or more of dosage, actual interpolation amount is 5 grams.5g is prepared to the modified silica-gel in embodiment 4 to add in
State in solution, be sufficiently stirred in 28 DEG C 22 minutes, filter, measure solution in iridium content be 2ppm, adsorption rate 99.31%；Again
It is eluted in 48 DEG C, 100 milliliters of 2N hydrochloric acid containing 5% thiocarbamide is only needed to be eluted at this time, are filtered, are measured in eluent
Iridium content for 2845mg/l, eluting rate 98.8%.
Embodiment 5
Accurate weighing 0.5g ruthenium trichlorides (platinum content 35%) are added in the volumetric flask that volume is 1L, add in the hydrochloric acid of 1N
To scale, the aqueous solution for 175ppm containing ruthenium is obtained, ruthenium total content is 1.7mmol in the solution.Prepare the modification in embodiment 5
The adsorption capacity of silica gel is 5.3mmol/g, it is known that the ruthenium that 0.33g modified silica-gels can be completely in adsorbent solution.Using theory
Ten times or more of dosage add in adsorbent, and actual interpolation amount is 5 grams.The modified silica-gel addition prepared by 5g in embodiment 5 is above-mentioned
It in solution, is sufficiently stirred 28 minutes, filters in 26 DEG C, ruthenium content is 1ppm in solution after measure absorption, and adsorption rate is
99.43%；It is eluted then at 60 DEG C, 100 milliliters of 2N hydrochloric acid containing 5% thiocarbamide is only needed to be eluted at this time, are filtered, are surveyed
Ruthenium content in eluent is determined for 1686mg/l, eluting rate 96.9%.
Embodiment 6
Accurate weighing 0.5g chloroplatinic acids (platinum content 37%) add in the volumetric flask that volume is 1L, add in the hydrochloric acid of 1N extremely
Scale obtains the aqueous solution that platiniferous is 185ppm, and platinum total content is 0.95mmol in the solution.Prepare the modification in embodiment 6
The adsorption capacity of silica gel is 6.6mmol/g, it is known that the platinum that 0.15g modified silica-gels can be completely in adsorbent solution.Using theory
Ten times or more of dosage add in adsorbent, and actual interpolation amount is 5 grams.The modified silica-gel addition prepared by 5g in embodiment 6 is above-mentioned
It in solution, is sufficiently stirred 20 minutes, filters in 30 DEG C, platinum content is 2ppm in solution after measure absorption after absorption, is adsorbed
Rate is 98.92%；It is eluted then at 55 DEG C, 100 milliliters of 2N hydrochloric acid containing 5% thiocarbamide is only needed to be eluted at this time, mistake
Filter measures the platinum content in eluent as 1810mg/l, eluting rate 98.9%.
Obviously, those skilled in the art can carry out the embodiment of the present invention various modification and variations without departing from this hair
Bright spirit and scope.In this way, if these modifications and changes of the present invention belongs to the claims in the present invention and its equivalent technologies
Within the scope of, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of modified silica-gel, which is characterized in that structural unit is as follows：
Wherein, X is halogen, and m, n are each independently selected from 0~6 integer.
2. modified silica-gel according to claim 1, which is characterized in that the halogen is selected from chlorine, bromine or iodine.
3. modified silica-gel according to claim 1, which is characterized in that m is selected from 0~3, n and is selected from 1~3.
4. according to the preparation method of claims 1 to 3 any one of them modified silica-gel, which is characterized in that including：
The silane coupling agent of the silica gel of acidified processing, solvent, alkaline reagent, functional group containing sulfydryl and halogen is mixed,
And be heated to reflux, obtain the modified silica-gel.
5. the preparation method of modified silica-gel according to claim 4, which is characterized in that further include：
The modified silica-gel of generation is washed with toluene, ethyl acetate, ethyl alcohol, water, ethyl alcohol successively；
It is dried under reduced pressure to obtain Solid Modified silica gel under 50~70 degrees Celsius.
6. the preparation method of modified silica-gel according to claim 4, which is characterized in that the functional group containing sulfydryl and halogen
Element silane coupling agent be selected from the chloro- 8- of 1- (trimethoxy silicon substrate) octane -4- mercaptan, the bromo- 8- of 1- (trimethoxy silicon substrate) octane -
The iodo- 8- of 4- mercaptan, 1- (trimethoxy silicon substrate) octane -4- mercaptan, the chloro- 9- of 1- (trimethoxy silicon substrate) nonane -5- mercaptan, 1-
Bromo- 9- (trimethoxy silicon substrate) nonane -5- mercaptan, the iodo- 9- of 1- (trimethoxy silicon substrate) nonane -5- mercaptan, the chloro- 10- (front threes of 1-
Oxygroup silicon substrate) decane -6- mercaptan, the bromo- 10- of 1- (trimethoxy silicon substrate) decane -6- mercaptan, the iodo- 10- of 1- (trimethoxy silicon substrate)
Decane -6- mercaptan, the chloro- 7- of 1- (trimethoxy silicon substrate) heptane -4- mercaptan, the bromo- 7- of 1- (trimethoxy silicon substrate) heptane -4- sulphur
The iodo- 7- of alcohol, 1- (trimethoxy silicon substrate) heptane -4- mercaptan, the chloro- 8- of 1- (trimethoxy silicon substrate) octane -5- mercaptan, the bromo- 8- of 1-
(trimethoxy silicon substrate) octane -5- mercaptan, the iodo- 8- of 1- (trimethoxy silicon substrate) octane -5- mercaptan, 1- chloro- 9- (trimethoxy silicon
Base) nonane -6- mercaptan, the bromo- 9- of 1- (trimethoxy silicon substrate) nonane -6- mercaptan, the iodo- 9- of 1- (trimethoxy silicon substrate) nonane -6-
The chloro- 6- of mercaptan, 1- (trimethoxy silicon substrate) hexane -4- mercaptan, the bromo- 6- of 1- (trimethoxy silicon substrate) hexane -4- mercaptan, 1- are iodo-
6- (trimethoxy silicon substrate) hexane -4- mercaptan, the chloro- 7- of 1- (trimethoxy silicon substrate) heptane -5- mercaptan, the bromo- 7- (trimethoxies of 1-
Silicon substrate) heptane -5- mercaptan, the iodo- 7- of 1- (trimethoxy silicon substrate) heptane -5- mercaptan, the chloro- 8- of 1- (trimethoxy silicon substrate) octane -
The bromo- 8- of 6- mercaptan, 1- (trimethoxy silicon substrate) octane -6- mercaptan, the iodo- 8- of 1- (trimethoxy silicon substrate) octane -6- mercaptan, 1-
Chloro- 5- (trimethoxy silicon substrate) pentane -4- mercaptan, the bromo- 5- of 1- (trimethoxy silicon substrate) pentane -4- mercaptan, the iodo- 5- (front threes of 1-
Oxygroup silicon substrate) pentane -4- mercaptan, the chloro- 6- of 1- (trimethoxy silicon substrate) hexane -5- mercaptan, the bromo- 6- of 1- (trimethoxy silicon substrate) oneself
Alkane -5- mercaptan, the iodo- 6- of 1- (trimethoxy silicon substrate) hexane -5- mercaptan, the chloro- 7- of 1- (trimethoxy silicon substrate) heptane -6- mercaptan,
The bromo- 7- of 1- (trimethoxy silicon substrate) heptane -6- mercaptan or the iodo- 7- of 1- (trimethoxy silicon substrate) heptane -6- mercaptan.
7. the preparation method of modified silica-gel according to claim 4, which is characterized in that the solvent is selected from toluene, ethyl
One or more in benzene, dimethylbenzene, hexamethylene and normal heptane；The alkaline reagent is selected from three fatty hydroxylamines and pyridines
In one or more.
8. the preparation method of modified silica-gel according to claim 4, which is characterized in that the mass ratio of the silica gel and solvent
It is 1:2~1:4；The mass ratio of the silane coupling agent of the silica gel and functional group containing sulfydryl and halogen is 1:1~2:1.
9. heavy metal ion adsorbed and recycling method is carried out using 3 any one of them modified silica-gel of claims 1 to 3, it is special
Sign is, including：
It is heavy metal ion adsorbed using modified silica-gel progress, obtain metal precipitates；
The metal precipitates are recycled in elution.
10. according to the method described in claim 9, it is characterized in that, the elution recycling metal precipitates are Celsius 40~60
Degree is lower to carry out.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081408A (en) * | 2018-07-20 | 2018-12-25 | 济南大学 | The recovery method of nickel ion in a kind of waste water |
| CN109621489A (en) * | 2018-12-29 | 2019-04-16 | 阜阳欣奕华材料科技有限公司 | A kind of method of liquid crystal purifying |
| CN110412159A (en) * | 2019-07-24 | 2019-11-05 | 广电计量检测(南宁)有限公司 | The method of alkyl mercury in sulfhydryl modified silica gel, preparation method and application, and detection water |
| CN111603800A (en) * | 2019-02-25 | 2020-09-01 | 贵州金之键高科技材料有限公司 | Method for selectively removing or simultaneously removing multiple ionic impurities from electronic chemicals and electronic chemical production solutions |
| CN112745367A (en) * | 2020-12-31 | 2021-05-04 | 浙江珲达生物科技有限公司 | Method for reducing content of heavy metal rhodium in ivermectin |
| CN116444688A (en) * | 2023-03-31 | 2023-07-18 | 山东省科学院生物研究所 | A method for removing laminarin heavy metals by using polymercapto silica gel |
| CN118221123A (en) * | 2022-12-21 | 2024-06-21 | 彤程化学（中国）有限公司 | Silica gel-based materials modified with bifunctional groups containing mercapto and 4-methylaminopyridine and their application in the preparation of photoresist resins |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2107725A (en) * | 1981-10-03 | 1983-05-05 | Dow Corning | Siloxane quaternary ammonium salt preparation |
| CN1948150A (en) * | 2006-10-20 | 2007-04-18 | 山东大学 | Chemical modification method of silicious material surface |
| CN101817839A (en) * | 2010-01-27 | 2010-09-01 | 北京欧凯纳斯科技有限公司 | Application of silicon gel compound in removing the heavy metal ions in fruit and vegetable juice |
| JP2011225381A (en) * | 2010-04-15 | 2011-11-10 | Furukawa Electric Co Ltd:The | Surface layer-controlled multilayer silica nanoparticles and method for producing the same |
| CN103298871A (en) * | 2010-12-30 | 2013-09-11 | 株式会社普利司通 | Rubber composition with improved bis-silane reinforcement |
| CN105749887A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Preparation method of liquid chromatographic stationary phrase and glycosyl-bonded stationary phrase |
| CN107140652A (en) * | 2017-05-27 | 2017-09-08 | 中山大学 | Azide mesoporous silica nano-particle and preparation method thereof |
-
2017
- 2017-12-29 CN CN201711484976.0A patent/CN108160055A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2107725A (en) * | 1981-10-03 | 1983-05-05 | Dow Corning | Siloxane quaternary ammonium salt preparation |
| CN1948150A (en) * | 2006-10-20 | 2007-04-18 | 山东大学 | Chemical modification method of silicious material surface |
| CN101817839A (en) * | 2010-01-27 | 2010-09-01 | 北京欧凯纳斯科技有限公司 | Application of silicon gel compound in removing the heavy metal ions in fruit and vegetable juice |
| JP2011225381A (en) * | 2010-04-15 | 2011-11-10 | Furukawa Electric Co Ltd:The | Surface layer-controlled multilayer silica nanoparticles and method for producing the same |
| CN103298871A (en) * | 2010-12-30 | 2013-09-11 | 株式会社普利司通 | Rubber composition with improved bis-silane reinforcement |
| CN105749887A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Preparation method of liquid chromatographic stationary phrase and glycosyl-bonded stationary phrase |
| CN107140652A (en) * | 2017-05-27 | 2017-09-08 | 中山大学 | Azide mesoporous silica nano-particle and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LUIZA N. H. ARAKAKI ETAL.: "New thiol adsorbent grafted on silica gel: synthesis, characterization and employment for heavy metal adsorptions", 《J. ENVIRON. MONIT.》 * |
| 屈文等: "巯基键合硅胶的制备及其对贵金属离子的吸附性能", 《贵金属》 * |
| 曲阜嘉业化工新材料有限公司: "《产品目录》", 31 December 2014 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081408A (en) * | 2018-07-20 | 2018-12-25 | 济南大学 | The recovery method of nickel ion in a kind of waste water |
| CN109621489A (en) * | 2018-12-29 | 2019-04-16 | 阜阳欣奕华材料科技有限公司 | A kind of method of liquid crystal purifying |
| CN111603800A (en) * | 2019-02-25 | 2020-09-01 | 贵州金之键高科技材料有限公司 | Method for selectively removing or simultaneously removing multiple ionic impurities from electronic chemicals and electronic chemical production solutions |
| CN110412159A (en) * | 2019-07-24 | 2019-11-05 | 广电计量检测(南宁)有限公司 | The method of alkyl mercury in sulfhydryl modified silica gel, preparation method and application, and detection water |
| CN112745367A (en) * | 2020-12-31 | 2021-05-04 | 浙江珲达生物科技有限公司 | Method for reducing content of heavy metal rhodium in ivermectin |
| CN118221123A (en) * | 2022-12-21 | 2024-06-21 | 彤程化学（中国）有限公司 | Silica gel-based materials modified with bifunctional groups containing mercapto and 4-methylaminopyridine and their application in the preparation of photoresist resins |
| CN116444688A (en) * | 2023-03-31 | 2023-07-18 | 山东省科学院生物研究所 | A method for removing laminarin heavy metals by using polymercapto silica gel |
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