CN115124568A - Recovery processing method of methyl tin mercaptide white precipitate - Google Patents
Recovery processing method of methyl tin mercaptide white precipitate Download PDFInfo
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- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 title claims abstract description 60
- 239000002244 precipitate Substances 0.000 title claims abstract description 56
- 238000011084 recovery Methods 0.000 title claims abstract description 17
- 238000003672 processing method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000000126 substance Substances 0.000 claims abstract description 51
- 239000012074 organic phase Substances 0.000 claims abstract description 46
- 239000012071 phase Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 29
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 23
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005191 phase separation Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 38
- 229910052729 chemical element Inorganic materials 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 3
- JHHJZXAFNAJSCA-UHFFFAOYSA-N methyl(oxo)tin Chemical compound C[Sn]=O JHHJZXAFNAJSCA-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NJURIYSLCWOESR-UHFFFAOYSA-L SC(C(=O)[O-])S.C[Sn+2]C.SC(C(=O)[O-])S Chemical compound SC(C(=O)[O-])S.C[Sn+2]C.SC(C(=O)[O-])S NJURIYSLCWOESR-UHFFFAOYSA-L 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RZBBHEJLECUBJT-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS RZBBHEJLECUBJT-UHFFFAOYSA-N 0.000 description 1
- ORDRGXFSRBRQQG-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)C(C)S ORDRGXFSRBRQQG-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A recovery processing method of methyl tin mercaptide white precipitate comprises the steps of putting hydrochloric acid into a reaction kettle, stirring, then adding methyl tin mercaptide white precipitate to carry out acidolysis reaction, standing and phase splitting after the precipitate is completely dissolved to obtain an organic phase substance A and a water phase substance B; adding a methyl tin chloride aqueous solution and isooctyl thioglycolate into another reaction kettle, starting stirring, adding a substance A or a substance B or a mixture of the substance A and the substance B, dropwise adding ammonia water for neutralization, and taking the reaction end point when the pH value reaches 7.0-9.0; and standing for phase separation after the reaction is finished, washing an organic phase with water, performing phase separation, and finally performing reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide plastic heat stabilizer product. The method has the advantages of simple and convenient operation process, easily-controlled reaction conditions, no introduction of new chemical elements or substances, and high recovery utilization rate of tin resources up to 95.0-98.5%.
Description
Technical Field
The invention belongs to the technical field of deep processing of organic tin plastic heat stabilizers, and particularly relates to a recovery processing method of methyl tin mercaptide white precipitate.
Background
The methyl tin mercaptide is a chemical product with the best performance in the PVC plastic heat stabilizer, has the advantages of excellent initial anti-coloring property, high transparency, excellent thermal stability and the like in the plastic processing process, is widely applied to various products such as PVC extrusion, calendaring, blow molding, injection molding and the like, and is a key auxiliary agent in the PVC plastic processing process. The preparation method generally comprises the following steps: carrying out alkylation reaction on a tin metal simple substance with methyl chloride and stannic chloride under the action of a catalyst at high temperature and high pressure to generate a methyl tin chloride intermediate, and then dissolving the methyl tin chloride intermediate in water by distillation to prepare a methyl tin chloride aqueous solution; then the methyl tin chloride aqueous solution is used for reacting with isooctyl thioglycolate, alkali liquor is used for neutralization, and finally the crude product is subjected to reduced pressure distillation and filtration to remove impurities, thus obtaining the methyl tin mercaptide product. In the production and preparation process, after the crude product tank and the temporary storage tank for containing the crude product of the methyl tin are used for a long time, a large amount of white precipitates appear at the bottom, and through detection and analysis, the white precipitates mainly comprise dimethyl tin oxide and also contain a small amount of monomethyl tin oxide, tin hydroxide and other impurities. The dimethyl tin oxide and the monomethyl tin oxide can react with isooctyl thioglycolate under certain conditions to generate dimethyl tin dimercaptoacetate and isooctyl monomethylthioglycolate, and the dimethyl tin dimercaptoacetate and the isooctyl monomercaptoacetate are main components of a methyl tin mercaptide product, so that attempts are made to directly react white precipitates with the isooctyl thioglycolate for recycling, but tests show that the recycling rate of direct reaction is too low, only about 15% of tin participates in the reaction, and most of the tin exists in a solid form.
At present, no literature report about the recovery processing technology of the methyl tin mercaptide white precipitate is found at home and abroad, for methyl tin mercaptide production enterprises, the white precipitate is accumulated all year round, on one hand, a large amount of tin resources are lost, on the other hand, if the white precipitate cannot be effectively processed, great environmental protection pressure can be brought to the enterprises, and adverse effects are caused on the continuous healthy development of the enterprises.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for recovering and treating methyl tin mercaptide white precipitate, which has the advantages of simple and convenient operation process, easily-controlled reaction conditions and high recovery and utilization rate of tin resources.
The technical scheme adopted by the invention is as follows:
a method for recovering and treating methyl tin mercaptide white precipitate comprises the following steps:
(1) pretreatment: adding hydrochloric acid into a reaction kettle, starting stirring, adding a methyl tin mercaptide white precipitate to perform acidolysis reaction, wherein the mass ratio of the hydrochloric acid to the white precipitate is 1: (0.5-2.0), standing and phase splitting after the precipitated substances are completely dissolved to obtain an organic phase substance A and a water phase substance B; the substance A is a methyl tin mercaptide product mixed in an original white precipitate substance and isooctyl thioglycolate obtained by acidolysis reaction, and the substance B is a methyl tin chloride aqueous solution converted from white precipitate;
(2) and (3) recycling: and (2) adding a methyl tin chloride aqueous solution and isooctyl thioglycolate into the other reaction kettle, wherein the molar ratio of chloride ions in the methyl tin chloride aqueous solution to isooctyl thioglycolate is 1: (1.04-1.1), starting stirring, adding a substance A or a substance B or a mixture of the substance A and the substance B, slowly dropwise adding ammonia water for neutralization, and taking the reaction end point when the pH value reaches 7.0-9.0; and after the reaction is finished, standing for phase separation, washing the organic phase with water, then phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to complete recovery of white precipitate, thereby obtaining a colorless and transparent methyl tin mercaptide plastic heat stabilizer product.
In the step (2), the addition amount of the substance A or the substance B, or the total addition amount of the substance A and the substance B is 3 to 10 percent of the mass of the methyl tin chloride aqueous solution.
In the method of the present invention, the reaction equation of the pretreated acidolysis reaction is as follows:
(CH 3 ) 2 SnO+2HCl→(CH 3 ) 2 SnCl 2 +H 2 O (1)
(CH 3 Sn) 2 O 3 +6HCl→2CH 3 SnCl 3 +3H 2 O (2)
the reaction equation of the recycling process is as follows:
(CH 3 ) 2 SnCl 2 +2HSCH 2 COOC 8 H 17 →(CH 3 ) 2 Sn(SCH 2 COOC 8 H 17 ) 2 +2HCl (3)
CH 3 SnCl 3 +3HSCH 2 COOC 8 H 17 →CH 3 Sn(SCH 2 COOC 8 H 17 ) 3 +3HCl (4)
HCl+NH 3 ·H 2 O→NH 4 Cl+H 2 O (5)
the invention carries on the treatment through the two-step method, use hydrochloric acid to carry on the acidolysis to pretreat at first, turn the principal ingredients in the white precipitation into production raw materials dimethyl tin dichloride and methyl tin trichloride of methyl tin mercaptide with a small amount of methyl tin oxide; then returning the dimethyl tin dichloride, the methyl tin trichloride aqueous solution and the organic phase substance obtained by the pretreatment to the production flow of the methyl tin mercaptide to be used as reaction raw materials, and finally obtaining the methyl tin mercaptide product. The pretreatment is carried out under the conditions of normal temperature and normal pressure, operations such as temperature rise, pressure maintaining and the like are not needed, the operation process is very simple and convenient, the reaction condition is easy to control, the recovery utilization rate of tin resources is high and reaches 95.0-98.5%, the aim of recovering and reusing the white precipitate of the methyl tin mercaptide is well fulfilled, the environmental protection pressure caused by the perennial accumulation of the white precipitate in methyl tin mercaptide production enterprises can be effectively solved, and the technical blank of the domestic recovery treatment of the white precipitate of the methyl tin mercaptide is filled up.
The A substance and the B substance obtained by pretreatment are raw materials required by the preparation of the thiolmethyl tin heat stabilizer product, and can be directly utilized for subsequent production without introducing new chemical elements or substances.
Drawings
FIG. 1 is a diagram of white precipitated materials taken out of a crude methyltin mercaptide tank and a temporary storage tank;
FIG. 2 is an appearance of a white precipitate after pretreatment;
FIG. 3 is an appearance diagram of a methyl tin mercaptide product obtained by recycling and reusing white precipitates.
Detailed Description
The invention is further illustrated by the following examples in which the white precipitated tin content of the methyltin mercaptide used is 35.03%.
Example 1
The method for recovering and treating the methyl tin mercaptide white precipitate comprises the following steps:
(1) pretreatment: 300kg of hydrochloric acid with the mass concentration of 30% is put into a reaction kettle, stirring is started, then 150kg of methyl tin mercaptide white precipitate material contained in the cup shown in figure 1 is added for acidolysis reaction, and after the precipitate material is completely dissolved, the mixture is kept stand for phase splitting to obtain 30kg of organic phase A material and 420kg of water phase B material. FIG. 2 shows the organic phase A and water phase B materials which are obviously layered after the sampling and standing, the upper layer is the organic phase A material, and the lower layer is the water phase B material;
(2) and (3) recycling: 550.50kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 557.81kg of isooctyl thioglycolate are added into a reaction kettle, stirring is started, then 30kg of pretreated organic phase A substance is added, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 7.5. After the reaction is finished, standing for phase separation, taking the organic phase for water washing, then phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 758.69kg of colorless and transparent methyl tin mercaptide product shown in figure 3, wherein the tin content is 19.13%;
2097.17kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 2213.67kg of isooctyl thioglycolate are added into another reaction kettle, stirring is started, 210kg of water phase B substance is added, ammonia water is slowly dripped for neutralization, and the reaction end point is obtained when the pH value reaches 8.0. And after the reaction is finished, standing for phase separation, taking an organic phase, washing with water, performing phase separation, and finally performing reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A group of tests are further completed in parallel according to the conditions, and 5776.40kg of methyl tin mercaptide product is obtained in total in the two tests, and the tin content is 19.25 percent after uniform mixing.
The calculated recovery of tin from the white precipitate was 96.69%.
Example 2
The method for recovering and treating the methyl tin mercaptide white precipitate comprises the following steps:
(1) pretreatment: putting 200kg of hydrochloric acid with the mass concentration of 30% into a reaction kettle, starting stirring, then adding 200kg of methyl tin mercaptide white precipitate for acidolysis reaction, and after the precipitate is completely dissolved, standing and phase splitting to obtain 40kg of organic phase A substance and 360kg of water phase B substance;
(2) and (3) recycling: 880.22kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 891.93kg of isooctyl thioglycolate are added into a reaction kettle, stirring is started, then 40kg of pretreated organic phase A substance is added, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 7.0. After the reaction is finished, standing for phase splitting, washing an organic phase with water, then phase splitting, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 1205.15kg of colorless and transparent methyl tin mercaptide product with the tin content of 19.15%;
2926.55kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 3089.12kg of isooctyl thioglycolate are added into another reaction kettle, stirring is started, then 180kg of water phase B substance is added, ammonia water is slowly dripped for neutralization, and the reaction end point is obtained when the pH value reaches 9.0. And after the reaction is finished, standing for phase separation, taking an organic phase, washing with water, performing phase separation, and finally performing reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A group of tests are further completed in parallel according to the conditions, and 8057.89kg of methyl tin mercaptide product is obtained in the two tests, and the tin content is 19.23% after the two tests are uniformly mixed.
The recovery of tin from the white precipitate was calculated to be 97.77%.
Example 3
The method for recovering and treating the methyl tin mercaptide white precipitate comprises the following steps:
(1) pretreatment: adding 100kg of 30% hydrochloric acid into a reaction kettle, starting stirring, adding 150kg of methyl tin mercaptide white precipitate for acidolysis reaction, standing for phase splitting after the precipitate is completely dissolved, and obtaining 30kg of organic phase A substance and 220kg of water phase B substance;
(2) and (3) recycling: 304.38kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 308.42kg of isooctyl thioglycolate are added into a reaction kettle, stirring is started, then 30kg of pretreated organic phase A substance is added, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 7.5. After the reaction is finished, standing for phase splitting, washing an organic phase with water, then phase splitting, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 432.90kg of colorless and transparent methyl tin mercaptide product with the tin content of 19.10%;
2595.50kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 2739.68kg of isooctyl thioglycolate are added into another reaction kettle, stirring is started, then 110kg of water phase B substance is added, ammonia water is slowly dripped for neutralization, and the reaction end point is obtained when the pH value reaches 8.0. And after the reaction is finished, standing for phase separation, taking an organic phase, washing with water, performing phase separation, and finally performing reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A group of tests are carried out in parallel according to the conditions, and 7137.80kg of methyl tin mercaptide product is obtained in total in the two tests, and the tin content is 19.14 percent after uniform mixing.
The recovery of tin from the white precipitate was calculated to be 98.50%.
Example 4
The method for recovering and treating the methyl tin mercaptide white precipitate comprises the following steps:
(1) pretreatment: adding 150kg of 30% hydrochloric acid into a reaction kettle, starting stirring, adding 300kg of methyl tin mercaptide white precipitate for acidolysis reaction, standing for phase splitting after the precipitate is completely dissolved, and obtaining 60kg of organic phase A substance and 390kg of water phase B substance;
(2) and (3) recycling: 930.76kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 943.14kg of isooctyl thioglycolate are added into a reaction kettle, stirring is started, then 60kg of pretreated organic phase A substance is added, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 7.5. After the reaction is finished, standing for phase splitting, washing an organic phase with water, then phase splitting, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 1292.05kg of colorless and transparent methyl tin mercaptide product with the tin content of 19.10%;
2972.67kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 3137.80kg of isooctyl thioglycolate are added into another reaction kettle, stirring is started, 130kg of water phase B substance is added, ammonia water is slowly dripped for neutralization, and the reaction end point is obtained when the pH value reaches 7.0. And after the reaction is finished, standing for phase separation, taking an organic phase, washing with water, performing phase separation, and finally performing reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. 2 groups of tests are completed in parallel according to the conditions, and the total of 3 tests is 12275.84kg of methyl tin mercaptide product, and the tin content is 19.20 percent after uniform mixing.
The recovery of tin from the white precipitate was calculated to be 95.03%.
Example 5
The method for recovering and treating the methyl tin mercaptide white precipitate comprises the following steps:
(1) pretreatment: putting 180kg of hydrochloric acid with the concentration of 30% into a reaction kettle, starting stirring, then adding 144kg of methyl tin mercaptide white precipitate for acidolysis reaction, standing and splitting phases after the precipitate is completely dissolved to obtain 28.8kg of organic phase A substance and 295.2kg of water phase B substance;
(2) and (3) recycling: 287.44kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 291.26kg of isooctyl thioglycolate are added into a reaction kettle, stirring is started, then 28.8kg of pretreated organic phase A substance is added, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 9.0. After the reaction is finished, standing for phase splitting, washing an organic phase with water, then phase splitting, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 409.29kg of colorless and transparent methyl tin mercaptide product with the tin content of 19.08%;
2408.95kg of methyl tin chloride aqueous solution with 25.68% of tin and 16.88% of chlorine content and 2542.77kg of isooctyl thioglycolate are added into another reaction kettle, stirring is started, then 147.6kg of water phase B substance is added, ammonia water is slowly added for neutralization, and the reaction end point is obtained when the pH value reaches 7.5. And after the reaction is finished, standing for phase separation, taking an organic phase, washing with water, performing phase separation, and finally performing reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A group of tests are further completed in parallel according to the conditions, and 6626.27kg of methyl tin mercaptide product is obtained in the two tests, and the tin content is 19.15% after the two tests are uniformly mixed.
The calculated recovery of tin from the white precipitate was 97.30%.
Example 6
The method for recovering and treating the methyl tin mercaptide white precipitate comprises the following steps:
(1) pretreatment: adding 150kg of 30% hydrochloric acid into a reaction kettle, starting stirring, adding 150kg of methyl tin mercaptide white precipitate for acidolysis reaction, standing for phase splitting after the precipitate is completely dissolved, and obtaining 30kg of organic phase A substance and 270kg of water phase B substance;
(2) and (3) recycling: 2752.45kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 2886.94kg of isooctyl thioglycolate are added into a reaction kettle, stirring is started, 15kg of pretreated organic phase A substance and 135kg of pretreated water phase B substance are added, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 8.0. And after the reaction is finished, standing for phase separation, taking an organic phase, washing with water, performing phase separation, and finally performing reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A group of tests are further completed in parallel according to the conditions, 7561.53kg of methyl tin mercaptide product is obtained in the two tests, and the tin content is 19.19% after the two tests are uniformly mixed.
The recovery of tin in the white precipitate was calculated to be 98.08%.
The above embodiments are only some of the embodiments of the present invention, and do not limit the scope of the present invention. In the pretreatment step, the mass ratio of the hydrochloric acid to the methyl tin mercaptide white precipitate is 1: (0.5 to 2.0); in the recycling step, the molar ratio of chloride ions in the methyl tin chloride aqueous solution to isooctyl thioglycolate is 1: (1.04-1.1), the adding amount of the substance A or the substance B, or the total adding amount of the substance A and the substance B is 3-10% of the mass of the methyl tin chloride aqueous solution, which belong to the protection scope of the invention, and the embodiment is not exhaustive.
All percentages stated in the present invention are percentages by mass, unless otherwise stated.
Claims (2)
1. A method for recovering and treating methyl tin mercaptide white precipitate is characterized by comprising the following steps:
(1) pretreatment: adding hydrochloric acid into a reaction kettle, starting stirring, adding a methyl tin mercaptide white precipitate to perform acidolysis reaction, wherein the mass ratio of the hydrochloric acid to the white precipitate is 1: (0.5-2.0), standing and phase splitting after the precipitated substances are completely dissolved to obtain an organic phase A substance and a water phase B substance; the substance A is a methyl tin mercaptide product mixed in an original white precipitate substance and isooctyl thioglycolate obtained by acidolysis reaction, and the substance B is a methyl tin chloride aqueous solution converted from white precipitate;
(2) and (3) recycling: and (2) adding a methyl tin chloride aqueous solution and isooctyl thioglycolate into the other reaction kettle, wherein the molar ratio of chloride ions in the methyl tin chloride aqueous solution to isooctyl thioglycolate is 1: (1.04-1.1), starting stirring, adding a substance A or a substance B or a mixture of the substance A and the substance B, slowly dropwise adding ammonia water for neutralization, and taking the reaction end point when the pH value reaches 7.0-9.0; and after the reaction is finished, standing for phase separation, washing the organic phase with water, then phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to complete recovery of white precipitate, thereby obtaining a colorless and transparent methyl tin mercaptide plastic heat stabilizer product.
2. The method for recovering and treating methyl tin mercaptide white precipitate according to claim 1, wherein in the step (2), the adding amount of the substance A or the substance B, or the total adding amount of the substance A and the substance B is 3-10% of the mass of the methyl tin chloride aqueous solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210876739.3A CN115124568B (en) | 2022-07-25 | 2022-07-25 | Recovery treatment method of white precipitate of methyl tin mercaptide |
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