CN115124568B - Recovery treatment method of white precipitate of methyl tin mercaptide - Google Patents
Recovery treatment method of white precipitate of methyl tin mercaptide Download PDFInfo
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- CN115124568B CN115124568B CN202210876739.3A CN202210876739A CN115124568B CN 115124568 B CN115124568 B CN 115124568B CN 202210876739 A CN202210876739 A CN 202210876739A CN 115124568 B CN115124568 B CN 115124568B
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- 239000002244 precipitate Substances 0.000 title claims abstract description 57
- 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 50
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000011084 recovery Methods 0.000 title claims description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000000126 substance Substances 0.000 claims abstract description 64
- 239000012074 organic phase Substances 0.000 claims abstract description 46
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005191 phase separation Methods 0.000 claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 30
- 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
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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
- 238000004064 recycling Methods 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 238000001914 filtration 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
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 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 12
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 9
- 238000003672 processing method Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- ZUOAYNYBICLREW-UHFFFAOYSA-N chloromethane;tin Chemical compound [Sn].ClC ZUOAYNYBICLREW-UHFFFAOYSA-N 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- 229910052729 chemical element Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- -1 methyl stannic chloride Chemical compound 0.000 description 9
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- JHHJZXAFNAJSCA-UHFFFAOYSA-N methyl(oxo)tin Chemical compound C[Sn]=O JHHJZXAFNAJSCA-UHFFFAOYSA-N 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction 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
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 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
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for reclaiming white precipitate of methyl tin mercaptide includes such steps as stirring hydrochloric acid in reactor, adding the tin oxide-color precipitate of methyl mercaptide for acidolysis reaction, dissolving the precipitate completely, standing for phase separation to obtain organic phase A and aqueous phase B; adding aqueous solution of methyl tin chloride and isooctyl thioglycolate into another reaction kettle, starting stirring, adding substance A or substance B or a mixture of the two substances, and then dropwise adding ammonia water for neutralization, wherein the reaction end point is 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, carrying out phase separation, and finally carrying out 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 simple operation process and easily controlled reaction conditions, does not introduce new chemical elements or substances, and has the recycling rate of tin resources as high as 95.0-98.5%.
Description
Technical Field
The invention belongs to the technical field of deep processing of organotin plastic heat stabilizer, and particularly relates to a recovery processing method of methyl tin mercaptide white precipitate.
Background
Methyl tin mercaptide is a chemical product with the best performance in PVC plastic heat stabilizer, has the advantages of excellent initial coloring resistance, high transparency, excellent heat 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 is generally as follows: under the action of high temperature, high pressure and a catalyst, the tin metal simple substance reacts with methyl chloride and stannic chloride in an alkylation way to generate a methyl stannic chloride intermediate, and then the methyl stannic chloride intermediate is distilled and dissolved in water to prepare a methyl stannic chloride aqueous solution; and then reacting with isooctyl thioglycolate by using methyl tin chloride aqueous solution, neutralizing by using alkali liquor, and finally carrying out reduced pressure distillation and filtration on the crude product to remove impurities, thus obtaining the methyl tin mercaptide product. In the production and preparation process, after a crude product tank and a temporary storage tank for containing the crude methyl tin product are used for a long time, a large amount of white precipitate substances appear at the bottom, and the white precipitate substances are detected and analyzed, wherein the main component of the white precipitate substances is dimethyl tin oxide, and meanwhile, the white precipitate substances also contain a small amount of methyl tin oxide, tin hydroxide and other impurities. Because dimethyl tin oxide and methyl tin oxide can react with isooctyl thioglycolate under certain conditions to generate dimethyl dithioglycolate tin and methyl triglycidyl acetate tin, and the dimethyl dithioglycolate tin and the methyl triglycidyl acetate tin are the main components of the methyl tin mercaptide product, an attempt is made to directly react and recycle white precipitate and isooctyl thioglycolate, but experiments show that the direct reaction recycling rate is too low, and only about 15% of tin participates in the reaction, and most of tin still exists in a solid form.
At present, no literature report on a thiol methyl tin oxide color precipitation recovery treatment technology is found at home and abroad, and for a thiol methyl tin production enterprise, white precipitates are accumulated for a year, so that on one hand, a great amount of tin resources are lost, and on the other hand, if the white precipitates cannot be effectively treated, a great environmental protection pressure is brought to the enterprise, and the sustainable healthy development of the enterprise is adversely affected.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a recovery processing method of thiol methyl tin oxide color sediment, which has the advantages of simple operation process, easy control of reaction conditions and high tin resource recovery utilization rate.
The technical scheme adopted by the invention is as follows:
A recovery processing method of white precipitate of methyl tin mercaptide comprises the following steps:
(1) Pretreatment: adding hydrochloric acid into a reaction kettle, starting stirring, and then adding a thiolmethyl tin oxide-color precipitate for acidolysis reaction, wherein the mass ratio of the hydrochloric acid to the white precipitate is 1: (0.5-2.0), standing for phase separation after the precipitated substances are completely dissolved, and obtaining an organic phase A substance and a water phase B substance; the substance A is methyl tin mercaptide product mixed in the original white precipitate substance, and isooctyl thioglycolate obtained by acidolysis reaction, and the substance B is methyl tin chloride aqueous solution converted by white precipitate;
(2) Recycling: adding aqueous solution of methyl tin chloride and isooctyl thioglycolate into another reaction kettle, wherein the molar ratio of chloride ions of the aqueous solution of methyl tin chloride to isooctyl thioglycolate is 1: (1.04-1.1), starting stirring, then adding the substance A or the substance B or the mixture of the substance A and the substance B, slowly dripping ammonia water for neutralization, and obtaining a reaction end point when the pH value reaches 7.0-9.0; after the reaction is finished, standing for phase separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to finish recovery of white precipitate substances, thereby obtaining a colorless and transparent methyl tin mercaptide plastic heat stabilizer product.
Further, 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 aqueous solution of the methyl tin chloride.
In the method of the invention, the reaction equation of the pretreated acidolysis reaction is as follows:
(CH3)2SnO+2HCl→(CH3)2SnCl2+H2O (1)
(CH3Sn)2O3+6HCl→2CH3SnCl3+3H2O (2)
The reaction equation for the recycling process is as follows:
(CH3)2SnCl2+2HSCH2COOC8H17→(CH3)2Sn(SCH2COOC8H17)2+2HCl (3)
CH3SnCl3+3HSCH2COOC8H17→CH3Sn(SCH2COOC8H17)3+3HCl (4)
HCl+NH3·H2O→NH4Cl+H2O (5)
The invention is treated by a two-step method, hydrochloric acid is adopted for acidolysis pretreatment, and the main components of dimethyl tin oxide and a small amount of monomethyl tin oxide in white precipitate are converted into the production raw materials of dimethyl tin dichloride and monomethyl tin trichloride of methyl tin mercaptide; and then returning the dimethyl tin dichloride, the monomethyl tin trichloride aqueous solution and the organic phase substances obtained by pretreatment to a production flow of methyl tin mercaptide as reaction raw materials to finally prepare the methyl tin mercaptide product. The pretreatment is carried out under normal temperature and normal pressure without heating, pressure maintaining and other operations, the operation process is very simple and convenient, the reaction condition is easy to control, the recycling rate of tin resources is higher and reaches 95.0-98.5%, the purpose of recycling white precipitate of methyl tin mercaptide is better realized, the environmental protection pressure caused by year-round accumulation of white precipitate of methyl tin mercaptide production enterprises can be effectively solved, and the technical blank of national methyl tin oxide color precipitate recycling treatment is made up.
The A substance and the B substance obtained by pretreatment are raw materials required by the preparation of the methyl tin mercaptide heat stabilizer product, and new chemical elements or substances are not introduced, so that the A substance and the B substance can be directly utilized for subsequent production.
Drawings
FIG. 1 is a diagram of white precipitate taken from a crude methyl tin mercaptide tank and a temporary storage tank;
FIG. 2 is an external view of a white precipitate after pretreatment;
FIG. 3 is an external view of methyl tin mercaptide product obtained by recycling white precipitate.
Detailed Description
The invention is further illustrated by the following examples, in which the methyl tin oxide color precipitate tin content of thiol is 35.03%.
Example 1
The recovery treatment method of the white precipitate of methyl tin mercaptide 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, 150kg of thiol methyl tin oxide color sediment substance which is contained in a cup as shown in figure 1 is put into the reaction kettle for acidolysis reaction, and after the sediment substance is completely dissolved, the reaction kettle is kept stand for phase separation, thus obtaining 30kg of organic phase A substance and 420kg of aqueous phase B substance. FIG. 2 shows the organic phase A and the aqueous phase B which are obviously layered after sampling and standing, wherein the upper layer is the organic phase A and the lower layer is the aqueous phase B;
(2) 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 put into a reaction kettle, stirring is started, then 30kg of organic phase A substance obtained by pretreatment is put into the reaction kettle, 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 an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 758.69kg of colorless 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 put into another reaction kettle, stirring is started, then 210kg of water phase B substance is put into the reaction kettle, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 8.0. After the reaction is finished, standing for phase separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A series of tests were completed again in parallel under this condition, and the total of two tests gave 5776.40kg of methyl tin mercaptide product, which after mixing was uniform had a tin content of 19.25%.
The recovery of tin in the white precipitate was calculated to be 96.69%.
Example 2
The recovery treatment method of the white precipitate of methyl tin mercaptide comprises the following steps:
(1) Pretreatment: 200kg of hydrochloric acid with the mass concentration of 30% is put into a reaction kettle, stirring is started, then 200kg of methyl tin mercaptide white precipitate is put into the reaction kettle for acidolysis reaction, after the precipitate is completely dissolved, standing and phase separation are carried out, and 40kg of organic phase A substance and 360kg of aqueous phase B substance are obtained;
(2) 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 put into a reaction kettle, stirring is started, 40kg of organic phase A substance obtained by pretreatment is then put into the reaction kettle, 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 separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 1205.15kg of colorless transparent methyl tin mercaptide product, wherein the tin content is 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 put into another reaction kettle, stirring is started, then 180kg of aqueous phase B substance is put into the reaction kettle, 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 separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A series of tests are completed in parallel according to the condition, 8057.89kg of methyl tin mercaptide products are obtained in total by two tests, and the tin content is 19.23% after uniform mixing.
The recovery of tin in the white precipitate was calculated to be 97.77%.
Example 3
The recovery treatment method of the white precipitate of methyl tin mercaptide comprises the following steps:
(1) Pretreatment: 100kg of hydrochloric acid with the concentration of 30% is put into a reaction kettle, stirring is started, then 150kg of methyl tin mercaptide white precipitate is put into the reaction kettle for acidolysis reaction, after the precipitate is completely dissolved, standing and phase separation are carried out, and 30kg of organic phase A substance and 220kg of water phase B substance are obtained;
(2) 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 put into a reaction kettle, stirring is started, then 30kg of organic phase A substance obtained by pretreatment is put into the reaction kettle, 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 an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 432.90kg of colorless transparent methyl tin mercaptide product, wherein the tin content is 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 put into another reaction kettle, stirring is started, then 110kg of water phase B substance is put into the reaction kettle, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 8.0. After the reaction is finished, standing for phase separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A series of tests were completed again in parallel under this condition, and the total of two tests gave 7137.80kg of methyl tin mercaptide product, which after mixing was uniform had a tin content of 19.14%.
The recovery of tin in the white precipitate was calculated to be 98.50%.
Example 4
The recovery treatment method of the white precipitate of methyl tin mercaptide comprises the following steps:
(1) Pretreatment: 150kg of hydrochloric acid with the concentration of 30% is put into a reaction kettle, stirring is started, then 300kg of methyl tin mercaptide white precipitate is put into the reaction kettle for acidolysis reaction, after the precipitate is completely dissolved, standing and phase separation are carried out, and 60kg of organic phase A substance and 390kg of water phase B substance are obtained;
(2) 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 put into a reaction kettle, stirring is started, 60kg of pretreated organic phase A substance is then put into the reaction kettle, 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 an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 1292.05kg of colorless transparent methyl tin mercaptide product, wherein the tin content is 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 put into another reaction kettle, stirring is started, 130kg of water phase B substance is then put into the reaction kettle, 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 separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. According to the conditions, 2 groups of tests are completed in parallel, 12275.84kg of methyl tin mercaptide products are obtained in total through 3 times of tests, and after uniform mixing, the tin content is 19.20%.
The recovery of tin in the white precipitate was calculated to be 95.03%.
Example 5
The recovery treatment method of the white precipitate of methyl tin mercaptide comprises the following steps:
(1) Pretreatment: 180kg of hydrochloric acid with the concentration of 30% is put into a reaction kettle, stirring is started, then 144kg of methyl tin mercaptide white precipitate is put into the reaction kettle for acidolysis reaction, after the precipitate is completely dissolved, standing and phase separation are carried out, and 28.8kg of organic phase A substance and 295.2kg of water phase B substance are obtained;
(2) 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 put into a reaction kettle, stirring is started, then 28.8kg of pretreated organic phase A substance is put into the reaction kettle, 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 separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain 409.29kg of colorless transparent methyl tin mercaptide product, wherein the tin content is 19.08%;
2408.95kg of methyl tin chloride aqueous solution with tin content of 25.68% and chlorine content of 16.88% and 2542.77kg of isooctyl thioglycolate are put into another reaction kettle, stirring is started, 147.6kg of water phase B substance is then put into the reaction kettle, 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 an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A series of tests are completed in parallel according to the condition, 6626.27kg of methyl tin mercaptide products are obtained in total by two tests, and the tin content is 19.15% after uniform mixing.
The recovery of tin in the white precipitate was calculated to be 97.30%.
Example 6
The recovery treatment method of the white precipitate of methyl tin mercaptide comprises the following steps:
(1) Pretreatment: 150kg of hydrochloric acid with the concentration of 30% is put into a reaction kettle, stirring is started, then 150kg of methyl tin mercaptide white precipitate is put into the reaction kettle for acidolysis reaction, after the precipitate is completely dissolved, standing and phase separation are carried out, and 30kg of organic phase A substance and 270kg of aqueous phase B substance are obtained;
(2) 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 put into a reaction kettle, stirring is started, then 15kg of organic phase A substance and 135kg of aqueous phase B substance obtained by pretreatment are put into the reaction kettle, ammonia water is slowly added dropwise for neutralization, and the reaction end point is obtained when the pH value reaches 8.0. After the reaction is finished, standing for phase separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to obtain a colorless and transparent methyl tin mercaptide product. A series of tests are completed in parallel under the condition, 7561.53kg of methyl tin mercaptide products are obtained in total by two tests, and after uniform mixing, the tin content is 19.19%.
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 are not intended to limit the scope of the present invention. In the method, in the pretreatment step, the mass ratio of hydrochloric acid to thiol methyl tin oxide color precipitate substances is 1: (0.5-2.0); in the recycling step, the molar ratio of chloride ions of the aqueous solution of methyl tin chloride to isooctyl thioglycolate is 1: (1.04-1.1), 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 3-10% of the mass of the aqueous solution of the methyl tin chloride, which belong to the protection scope of the invention, and the examples are not exhaustive.
The percentages stated in the present invention are mass percentages unless otherwise indicated.
Claims (2)
1. A recovery processing method of white precipitate of methyl tin mercaptide is characterized by comprising the following steps:
(1) Pretreatment: adding hydrochloric acid into a reaction kettle, starting stirring, and then adding a thiolmethyl tin oxide-color precipitate for acidolysis reaction, wherein the mass ratio of the hydrochloric acid to the white precipitate is 1: (0.5-2.0), standing for phase separation after the precipitated substances are completely dissolved, and obtaining an organic phase A substance and a water phase B substance; the substance A is methyl tin mercaptide product mixed in the original white precipitate substance, and isooctyl thioglycolate obtained by acidolysis reaction, and the substance B is methyl tin chloride aqueous solution converted by white precipitate;
(2) Recycling: adding aqueous solution of methyl tin chloride and isooctyl thioglycolate into another reaction kettle, wherein the molar ratio of chloride ions of the aqueous solution of methyl tin chloride to isooctyl thioglycolate is 1: (1.04-1.1), starting stirring, then adding the substance A or the substance B or the mixture of the substance A and the substance B, slowly dripping ammonia water for neutralization, and obtaining a reaction end point when the pH value reaches 7.0-9.0; after the reaction is finished, standing for phase separation, taking an organic phase for water washing, carrying out phase separation, and finally carrying out reduced pressure distillation and filtration on the organic phase to finish recovery of white precipitate substances, thereby obtaining a colorless and transparent methyl tin mercaptide plastic heat stabilizer product.
2. The method for recycling white precipitate of tin methyl mercaptide according to claim 1, wherein in the step (2), the amount of the substance a or the substance B added, or the total amount of the substances a and B added is 3% -10% of the mass of the aqueous solution of tin methyl chloride.
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