CN102603788B - Method for recycling organotin from organotin distillation waste materials - Google Patents
Method for recycling organotin from organotin distillation waste materials Download PDFInfo
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- CN102603788B CN102603788B CN201110420346.3A CN201110420346A CN102603788B CN 102603788 B CN102603788 B CN 102603788B CN 201110420346 A CN201110420346 A CN 201110420346A CN 102603788 B CN102603788 B CN 102603788B
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- ethyl hexyl
- hexyl ethanoate
- dimethyl dimercapto
- ethanoate tin
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- 238000004821 distillation Methods 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004064 recycling Methods 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 19
- -1 dimethyl dimercapto 2-ethyl hexyl ethanoate tin Chemical compound 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000011368 organic material Substances 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 25
- 239000012043 crude product Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 10
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- 238000006482 condensation reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 10
- MWTNHBHKLRBECL-UHFFFAOYSA-N 4-methyltrithiole Chemical compound CC1=CSSS1 MWTNHBHKLRBECL-UHFFFAOYSA-N 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- RZBBHEJLECUBJT-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylacetate Chemical class CC(C)CCCCCOC(=O)CS RZBBHEJLECUBJT-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical group C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 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 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for recycling organotin from organotin distillation waste materials. The method comprises the steps of carrying out a condensation reaction on waste materials generated by organotin distillation and an organotin midbody so as to obtain coarse products, distilling, and cooling so as to obtain the organotin. According to the method, organic impurities generated in the organotin distillation process can become organotin products again, so that the material waste is reduced, the environment pollution is reduced, and good economic and social benefits are realized.
Description
Technical field
The present invention relates to fine chemistry industry production field, be specifically related to a kind of method reclaiming organotin from organotin distillation waste material.
Background technology
Organo-tin het stabilizer is the important fine chemicals of a class, is the excellent raw material preparing polyvinyl chloride (P VC) plastics thermo-stabilizer.Along with the quick growth of the organo-tin het stabilizer market requirement, the output of organotin progressively promotes, and containing a large amount of ester compounds and lower boiling organic impurity in the organic waste materials of generation, smell is large, affects social environment.
Traditional waste disposal mode be by waste water through neutralization after again through COD oxide treatment, alkaline hydrolysis burning disposal, complex disposal process, has a large amount of carbonic acid gas to produce after burning disposal, the inadaptable low carbonization environmental protection concept advocated at present, and treatment operating costs is higher.
Research as the various methods of the environmental protection treatment of organotin more and more comes into one's own, and needs to provide a kind of technique simple, can reclaim large-tonnage product after process, the low and method that efficiency is high of processing cost.
Summary of the invention
The present invention is directed to the shortcoming of existing organotin organic waste materials process field deficiency, provide a kind of process recoverying and utilizing method newly, not only saved production cost, also reduced environmental pollution.The economic and social benefit brought.
The object of the present invention is achieved like this: a kind of method reclaiming organotin from organotin distillation waste material, comprises the steps:
Organotin distillation waste material and organotin intermediate carry out condensation reaction, obtain crude product, and distillation, cooling, obtain organotin.
Described organotin distillation waste material and organotin intermediate carry out condensation reaction, and be that the chlorion contained in the sulfydryl and organotin intermediate contained in organotin reacts, the mol ratio of sulfydryl and chlorion is 1-1.5: 1.
Preferably, the mol ratio of described sulfydryl and chlorion is 1: 1.(molecular weight of described sulfydryl is 33)
Described organotin distillation waste material is preparing organotin if dimethyl dimercapto 2-ethyl hexyl ethanoate tin, monomethyl tri-thiol 2-ethyl hexyl ethanoate tin or methyl are against in ester tin process, the waste material distilled out, containing organism such as isooctyl alcohol, Thiovanic acid, isooctyl mercaptoacetates in this organotin distillation waste material;
Described organotin intermediate is monomethyl tin trichloride or dimethyltin chloride.
Particularly, the method reclaiming organotin from organotin distillation waste material provided by the invention comprises the following steps:
1) washing of organotin distillation waste material is purified: organotin is distilled waste material and leave standstill 4 ~ 6 hours, directly remove water layer after layering, reclaim organic materials; Again organic materials is added water according to the ratio that volume ratio is 1: 2-4 and wash, leave standstill 2-3 hour, after layering, remove water layer, reclaim organic materials;
2) condensation reaction: 20-70 DEG C, normal pressure, weak base effect condition under by washing after organic materials and organotin intermediate carry out condensation reaction, reaction after product is washed, remove water layer after leaving standstill 2 ~ 3 little layereds, obtain the crude product of organotin;
3) distill 2-3 hour vacuumizing under (50-300Pa), 70-90 DEG C condition, then temperature control distills 3-4 hour under the condition of 120-130 DEG C, cooling, obtains organotin.
Wherein,
Described step 1) in the volume ratio of organic materials and water be 1: 2-4;
Step 2) described in normal pressure refer to 0-0.05Mpa;
Described weak base is organic or inorganic weak base, is specially sodium bicarbonate, ammoniacal liquor, sodium carbonate, bicarbonate of ammonia or volatile salt;
Described organotin is: dimethyl dimercapto 2-ethyl hexyl ethanoate tin, monomethyl tri-thiol 2-ethyl hexyl ethanoate tin or methyl are against ester tin.
The principle reclaiming organotin from the distillation waste material preparing organotin provided by the invention:
Organotin is distilled waste material by stratification, remove water layer, washing again, then leave standstill, is to remove the soluble organic salts produced in organotin still-process;
Organotin distillation waste material and organotin intermediate condensation reaction are in order to the isooctyl alcohol in waste material, Thiovanic acid, isooctyl mercaptoacetate and organotin intermediate are carried out condensation reaction, and generate organotin, its reaction equation is as follows:
HSCH
2cOOH (Thiovanic acid)+C
8h
17oH (isooctyl alcohol)=HSCH
2cOOC
8h
17(isooctyl mercaptoacetate)+H
2o;
(CH
3)
2snCl
2(dimethyltin chloride)+2HSCH
2cOOC
8h
17(isooctyl mercaptoacetate)=(CH
3)
2sn (SCH
2cOOC
8h
17)
2(dimethyl dimercapto 2-ethyl hexyl ethanoate tin)+2HCl;
CH
3snCl
3(monomethyl tin trichloride)+3HSCH
2cOOC
8h
17(thiol esters)=CH
3sn (SCH
2cOOC
8h
17)
3(monomethyl tri-thiol 2-ethyl hexyl ethanoate tin)+3HCl.
The Application way of organotin distillation waste material provided by the invention has the following advantages:
1, the invention reside in the organic impurity produced in organotin still-process is become organotin product again, decrease material waste and environmental pollution, there is good economic benefit, social benefit and environmental protection concept.
2, the present invention changes traditional waste water treatment process, and processing costs is low, simple operation, has good operability.
3, provided by the invention from organotin distillation waste material, to reclaim the organotin purity obtained high, can re-use.
Accompanying drawing explanation
Fig. 1: the process flow sheet reclaiming organotin from organotin distillation waste material;
Fig. 2: record with LC-10AT liquid chromatograph: the content of sulfydryl in dimethyl dimercapto 2-ethyl hexyl ethanoate tin Distillation recovery waste material;
Fig. 3: the purity of the dimethyl dimercapto 2-ethyl hexyl ethanoate tin product obtained with the recovery that LC-10AT liquid chromatograph records.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1: the method (process flow sheet is shown in Fig. 1) reclaiming dimethyl dimercapto 2-ethyl hexyl ethanoate tin from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin
1, after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, the water then adding organic materials 2 times of volumes is washed, and after leaving standstill 3 little layereds, removes water layer, reclaims organic materials, for subsequent use;
2, have agitator, condenser, thermometer 1000ml there-necked flask in, (sulfhydryl content is 56.8% to the dimethyl dimercapto 2-ethyl hexyl ethanoate tin distillation waste material 204g reclaimed after adding washing, detect with LC-10AT liquid chromatograph, lower same), dimethyltin chloride 95ml (chlorine ion concentration is 6.0Mol/L), mass concentration is the ammoniacal liquor 166g of 11%, under agitation, control temperature is 35 DEG C, react after 2.5 hours and leave standstill 2 hours, remove water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3, crude product is at 90.55kPa, 3 hours are incubated under the condition of 75 DEG C, promoting temperature again controls 125 DEG C of underpressure distillation 3.5 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 154.5g, quality product purity is 97.62% (detection of purity LC-10AT liquid chromatograph), in the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin, yield 98.02%.
4, illustrate:
1) sulfydryl in the dimethyl dimercapto 2-ethyl hexyl ethanoate tin distillation waste material reclaimed after washing is detected, carry out with LC-10AT liquid chromatograph.
Table 1: sulfhydryl content in organotin distillation waste material after washing
| Peak number | Retention time | Peak height | Peak area | Concentration (%) |
| 1 | 0.213 | 53 | 128.8 | 0.0337 |
| 2 | 0.480 | 343 | 1772.7 | 0.4640 |
| 3 | 0.580 | 57664 | 212083.2 | 55.5158 |
| 4 | 0.800 | 2144 | 12274.9 | 3.2131 |
| 5 | 1.687 | 1222 | 11039.9 | 2.8899 |
| 6 | 2.333 | 12392 | 144723.8 | 37.8835 |
| Add up to | 73818 | 382023.4 | 100.0000 |
Result is as shown in Figure 2 and Table 1: sulfhydryl content is 56.8%.
2) quality product, detects with LC-10AT liquid chromatograph.
Table 2: the purity of organotin in finished product
| Peak number | Retention time | Peak area | Peak height | Area (%) | Highly (%) |
| 1 | 9.549 | 9248227 | 710677 | 98.549 | 98.944 |
| 2 | 21.461 | 136213 | 7587 | 1.451 | 1.056 |
| Add up to | 9384440 | 718264 | 100.000 | 100.000 |
Result is as shown in figure 3 and table 2: the purity of the middle the finished product of embodiment 1 is 97.62%.
Embodiment 2: the method reclaiming dimethyl dimercapto 2-ethyl hexyl ethanoate tin from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin
1, after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, the water then adding organic materials 2 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaims organic materials, for subsequent use;
2, have agitator, condenser, thermometer 1000ml there-necked flask in, (method is with embodiment 1 for the dimethyl dimercapto 2-ethyl hexyl ethanoate tin Distillation recovery material 205g reclaimed after adding washing, under with sulfhydryl content 57.8%), dimethyltin chloride 96.5ml (chlorine ion concentration is 6.0Mol/L), mass concentration is the ammoniacal liquor 169g of 11%, under agitation, control temperature is 40 DEG C, react after 3 hours and leave standstill 3 hours, remove water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3, crude product is at 90.59kPa, 3 hours are incubated under the condition of 80 DEG C, promoting temperature again controls 126 DEG C of underpressure distillation 3.5 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 158.04g, quality product purity is that 97.59% (detection method is with embodiment 1, lower same), in dimethyl dimercapto 2-ethyl hexyl ethanoate tin distillation waste material, yield 98.05%.
Embodiment 3: the method reclaiming dimethyl dimercapto 2-ethyl hexyl ethanoate tin from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin
1, after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, the water then adding organic materials 2 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaims organic materials, for subsequent use;
2, have agitator, condenser, thermometer 1000ml there-necked flask in, dimethyl dimercapto 2-ethyl hexyl ethanoate tin Distillation recovery material 203.5g (sulfhydryl content 59.8%) reclaimed after adding washing, dimethyltin chloride 98ml (chlorine ion concentration is 6.0Mol/L), mass concentration is the ammoniacal liquor 172g of 11%, under agitation, control temperature is 45 DEG C, reacts after 2.5 hours and leaves standstill removal water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3, crude product is at 150kPa, 3 hours are incubated under the condition of 90 DEG C, promoting temperature again controls 123 DEG C of underpressure distillation 4 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 160.79g, quality product purity is 98.47%, in dimethyl dimercapto 2-ethyl hexyl ethanoate tin distillation waste material, yield 97.13%.
Embodiment 4: the method reclaiming dimethyl dimercapto 2-ethyl hexyl ethanoate tin from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin
1, after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, the water then adding organic materials 3 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaims organic materials, for subsequent use;
2, have agitator, condenser, thermometer 1000ml there-necked flask in, dimethyl dimercapto 2-ethyl hexyl ethanoate tin Distillation recovery material 204g (sulfhydryl content 59.8%) reclaimed after adding washing, dimethyltin chloride 100ml (chlorine ion concentration is 6.0Mol/L), mass concentration is the ammoniacal liquor 190g of 11%, under agitation, control temperature is 50 DEG C, reacts after 2.5 hours and leaves standstill removal water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3, crude product is at 50kPa, 3 hours are incubated under the condition of 90 DEG C, promoting temperature again controls 123 DEG C of underpressure distillation 4 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 163.5g, quality product purity is 97.11%, in dimethyl dimercapto 2-ethyl hexyl ethanoate tin distillation waste material, yield 98.52%.
Embodiment 5: the method reclaiming dimethyl dimercapto 2-ethyl hexyl ethanoate tin from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin
1, after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, the water then adding organic materials 3 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaims organic materials, for subsequent use;
2, have agitator, condenser, thermometer 1000ml there-necked flask in, dimethyl dimercapto 2-ethyl hexyl ethanoate tin Distillation recovery material 204g (sulfhydryl content 59.8%) reclaimed after adding washing, dimethyltin chloride 95ml (chlorine ion concentration is 6.0Mol/L), mass concentration is the ammoniacal liquor 181g of 11%, under agitation, control temperature is 50 DEG C, reacts after 2.5 hours and leaves standstill removal water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3, crude product is at 50kPa, 3 hours are incubated under the condition of 90 DEG C, promoting temperature again controls 123 DEG C of underpressure distillation 4 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 158.2g, quality product purity is 98.96%, in sulphur dimethyl dimercapto 2-ethyl hexyl ethanoate tin distillation waste material, yield 95.3%.
Embodiment 6: the method reclaiming monomethyl tri-thiol 2-ethyl hexyl ethanoate tin from the distillation waste material of monomethyl tri-thiol 2-ethyl hexyl ethanoate tin
1, after the distillation waste material of monomethyl tri-thiol 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, the water then adding organic materials 2.5 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaims organic materials, for subsequent use;
2, have agitator, condenser, thermometer 1000ml there-necked flask in, monomethyl tri-thiol 2-ethyl hexyl ethanoate tin Distillation recovery material 204g (sulfhydryl content 59.8%) reclaimed after adding washing, monomethyl tin trichloride 95ml (chlorine ion concentration is 6.0Mol/L), mass concentration is the ammoniacal liquor 181g of 11%, under agitation, control temperature is 50 DEG C, reacts after 2.5 hours and leaves standstill removal water layer, obtain monomethyl tri-thiol 2-ethyl hexyl ethanoate tin crude product;
3, crude product is at 50kPa, 3 hours are incubated under the condition of 90 DEG C, promoting temperature again controls 123 DEG C of underpressure distillation 4 hours, obtain product monomethyl tri-thiol 2-ethyl hexyl ethanoate tin 140.1g, quality product purity is 99.06%, in monomethyl tri-thiol 2-ethyl hexyl ethanoate tin distillation waste material, yield 94.6%.
Embodiment 7: reclaim the method for methyl against ester tin from methyl against the distillation waste material of ester tin
1, left standstill after 5 little layereds by the distillation waste material of methyl against ester tin, remove water layer, obtain organic materials, the water then adding organic materials 2.5 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaims organic materials, for subsequent use;
2, have agitator, condenser, thermometer 1000ml there-necked flask in, the methyl reclaimed after adding washing is against ester tin Distillation recovery material 204g (sulfhydryl content 59.8%), monomethyl tin trichloride 95ml (chlorine ion concentration is 6.0Mol/L), mass concentration is the ammoniacal liquor 181g of 11%, under agitation, control temperature is 50 DEG C, reacts after 2.5 hours and leaves standstill removal water layer, obtain methyl against ester tin crude product;
3, crude product is at 50kPa, and be incubated 3 hours under the condition of 90 DEG C, then promote temperature and control 123 DEG C of underpressure distillation 4 hours, obtain product methyl against ester tin 142.6g, quality product purity is 99.12%, in methyl against ester tin distillation waste material, and yield 94.3%.
Comparative example 1: the detection of the organotin reclaimed in embodiment
1, laboratory apparatus: XSS-300 torque rheometer.
2, experimental formula: 100gDG-800 type PVC resin powder, 0.4g solid paraffin, 1gACR (processing aids acrylic resin), 4gMBS (MBS copolymerization anti-impact modifier), 0.8g fatty acid pentaerythritol ester, 1g reclaimed materials dimethyl dimercapto 2-ethyl hexyl ethanoate tin stablizer.
3, experimental technique: stir 20s on mixer, weighs 65g in weighing cup.Treat that torque rheometer temperature-stable can start to carry out rheometer experiment, material is pressed in kneading device, the time shown on rheometer software starts with tweezers gripping in kneading device a little PVC melt when arriving 3min, putting into pliers compressing tablet groove and compressing rapidly pliers makes melt cooling shaping, remove around circular print with scissors and overflow rim charge, get a defective material at interval of 2min afterwards.Experiment is stopped after getting sheet to 15min.Experiment gained print is put on color difference meter and measures, by surveyed L, A.B value record in Microsoft Excel.Aforesaid operations is repeated to thiol methyl tin SW-977 (market hit product), is recycled the colour of material dimethyl dimercapto 2-ethyl hexyl ethanoate tin and SW-977.
Table 3 is rheometer data, and table 4 is colour table.
Table 3: rheological data table
| Sample | Minimal torque (Nm) | Peak torque (Nm) | Balancing torque (Nm) | Fusion time (S) | Material temperature (DEG C) |
| Reclaimed materials methyl tin | 37.9 | 40.6 | 17.1 | 25.8 | 193.6 |
| SW-977 | 37.2 | 40.2 | 17.2 | 26.3 | 194.2 |
Table 4: colour table
By the less stability of B value this foundation better, as can be seen from table 1,2 results: each side data of reclaimed materials methyl tin all maintain an equal level with SW-977.
In like manner, reclaim the organotin obtained test 2-6 in all the other embodiments, each side data also maintain an equal level with SW-977.
4, conclusion: provided by the invention to reclaim the organotin purity obtained high from organotin distillation waste material.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (3)
1. from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin, reclaim the method for dimethyl dimercapto 2-ethyl hexyl ethanoate tin, the method comprises the following steps:
1), after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, then the water adding organic materials 3 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaim organic materials, for subsequent use;
2) have agitator, condenser, thermometer 1000ml there-necked flask in, the dimethyl dimercapto 2-ethyl hexyl ethanoate tin Distillation recovery material 204g reclaimed after adding washing, sulfhydryl content 59.8%, dimethyltin chloride 100ml, chlorine ion concentration is 6.0Mol/L, and mass concentration is the ammoniacal liquor 190g of 11%, under agitation, control temperature is 50 DEG C, reacts after 2.5 hours and leaves standstill removal water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3) crude product is at 50kPa, is incubated 3 hours, then promotes temperature and control 123 DEG C of underpressure distillation 4 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 163.5g under the condition of 90 DEG C.
2. from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin, reclaim a method for dimethyl dimercapto 2-ethyl hexyl ethanoate tin, the method comprises the following steps:
1), after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, then the water adding organic materials 2 times of volumes is washed, and after leaving standstill 3 little layereds, removes water layer, reclaim organic materials, for subsequent use;
2) have agitator, condenser, thermometer 1000ml there-necked flask in, dimethyl dimercapto 2-ethyl hexyl ethanoate tin distillation waste material 204g (sulfhydryl content is 56.8%) reclaimed after adding washing, dimethyltin chloride 95ml, chlorine ion concentration is 6.0Mol/L, and mass concentration is the ammoniacal liquor 166g of 11%, under agitation, control temperature is 35 DEG C, react after 2.5 hours and leave standstill 2 hours, remove water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3) crude product is at 90.55kPa, is incubated 3 hours, then promotes temperature and control 125 DEG C of underpressure distillation 3.5 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 154.5g under the condition of 75 DEG C.
3. from the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin, reclaim a method for dimethyl dimercapto 2-ethyl hexyl ethanoate tin, the method comprises the following steps:
1), after the distillation waste material of dimethyl dimercapto 2-ethyl hexyl ethanoate tin being left standstill 5 little layereds, remove water layer, obtain organic materials, then the water adding organic materials 2 times of volumes is washed, and after leaving standstill 4 little layereds, removes water layer, reclaim organic materials, for subsequent use;
2) have agitator, condenser, thermometer 1000ml there-necked flask in, dimethyl dimercapto 2-ethyl hexyl ethanoate tin Distillation recovery material 205g (sulfhydryl content is 57.8%) reclaimed after adding washing, dimethyltin chloride 96.5ml, chlorine ion concentration is 6.0Mol/L, and mass concentration is the ammoniacal liquor 169g of 11%, under agitation, control temperature is 40 DEG C, react after 3 hours and leave standstill 3 hours, remove water layer, obtain dimethyl dimercapto 2-ethyl hexyl ethanoate tin crude product;
3) crude product is at 90.59kPa, is incubated 3 hours, then promotes temperature and control 126 DEG C of underpressure distillation 3.5 hours, obtain product dimethyl dimercapto 2-ethyl hexyl ethanoate tin 158.04g under the condition of 80 DEG C.
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