CN107987098B - Method for reducing content of polychlorinated biphenyl in diphenyldimethoxysilane - Google Patents
Method for reducing content of polychlorinated biphenyl in diphenyldimethoxysilane Download PDFInfo
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- CN107987098B CN107987098B CN201711237216.XA CN201711237216A CN107987098B CN 107987098 B CN107987098 B CN 107987098B CN 201711237216 A CN201711237216 A CN 201711237216A CN 107987098 B CN107987098 B CN 107987098B
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- polychlorinated biphenyl
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- diphenyldimethoxysilane
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- 150000003071 polychlorinated biphenyls Chemical group 0.000 title claims abstract description 46
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 abstract description 25
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000001632 sodium acetate Substances 0.000 abstract description 4
- 235000017281 sodium acetate Nutrition 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 230000006378 damage Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 210000000987 immune system Anatomy 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 210000000577 adipose tissue Anatomy 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal alkoxide Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- QLLINCWWWZHEMD-UHFFFAOYSA-N dichloro-phenoxy-phenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)OC1=CC=CC=C1 QLLINCWWWZHEMD-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to a method for reducing the content of polychlorinated biphenyl in diphenyldimethoxysilane, which comprises the following steps: s1, adding metal sodium into diphenyl dimethoxysilane containing polychlorinated biphenyl, stirring for 5-6 hours under the condition of heat preservation and oil bath at the temperature of 100-105 ℃, and cooling to room temperature; s2, adjusting the pH value of the system to 6-8 by using organic acid; s3, filtering and rectifying to obtain the diphenyl dimethoxy silane product. The invention adopts the technical scheme that the method has the advantages that: the metal sodium can be in a molten state at the temperature of 100-105 ℃, and has high enough activity, so that the metal sodium can easily react with chlorine in the polychlorinated biphenyl; the acid for adjusting the pH value of the system is acetic acid, the formed salt is sodium acetate, and the product loss caused by the destruction of the diphenyl dimethoxysilane product in the subsequent rectification process can be avoided; the generated by-product sodium chloride or sodium acetate is not dissolved in a reaction system, is easy to remove by filtration, and has simple industrial operation.
Description
Technical Field
The invention relates to a method for reducing the content of polychlorinated biphenyl in diphenyldimethoxysilane, wherein the diphenyldimethoxysilane is prepared by a diphenyl dichlorosilane hydrolysis method.
Background
Polychlorinated biphenyls (PCBs) are one of the most harmful pollutants to the human environment at present, belong to carcinogenic substances, are very easy to dissolve in fat, and are easily absorbed and accumulated by human adipose tissues, so that diseases of the brain, the skin and the viscera are caused, and the nervous system, the reproductive system and the immune system are influenced. As early as 1991, the energy department and the environmental protection agency of China issued documents to strictly control the use and treatment of products and wastes containing PCBs, the products containing more than 50ppm of polychlorinated biphenyl must be treated. PCBs are listed in category 47 hazardous wastes listed in the national hazardous wastes bibliography issued on 4.1.1998. On 23.5.2001, representatives of 127 countries and regions, including the Chinese government, signed the Stockholm convention aimed at strictly banning or restricting the use of 12 Persistent Organic Pollutants (POPs) of which PCBs were a class of substances once used in large quantities, and it has been found that the reproductive decline and suppression of the immune system in humans and many wild animals are associated with polychlorinated biphenyls (PCBs), which are also the basic substances for the production of strong carcinogens, Dioxins (Dioxins).
The diphenyl dimethoxysilane is an important organic silicon compound, can be used for producing phenyl silicone oil, phenyl silicone resin and phenyl silicone rubber, and has very important value for high and new industries and defense industries. The traditional method for synthesizing the diphenyldimethoxysilane is prepared by utilizing the hydrolysis reaction of diphenyldichlorosilane, and the diphenyldichlorosilane is obtained by a direct method (chlorobenzene and silicon powder are directly synthesized under the catalysis of a catalyst) and a thermal condensation method (chlorobenzene and chlorosilane are thermally condensed at high temperature), a large amount of polychlorinated biphenyl byproducts are generated by the production method, and the polychlorinated biphenyl is difficult to directly remove once produced, so that the polychlorinated biphenyl can be finally embodied in a diphenyldimethoxysilane product. The application range of the diphenyl dimethoxysilane product is influenced by the high content of inorganic chlorine or polychlorinated biphenyl, and the diphenyl dimethoxysilane product cannot be used in some high-end fields. While the addition of an alkali metal compound of an alcohol can remove inorganic chlorine in the diphenyldimethoxysilane product, it is not effective for polychlorinated biphenyl. Therefore, it is especially necessary to find a method for reducing the content of polychlorinated biphenyl in the diphenyldimethoxysilane.
Various methods have been reported in the literature for processing polychlorinated biphenyls. For example, patent US4623464 adopts a method of combining physical chemistry and biological treatment to remove polychlorinated biphenyl in wastewater; US5746926 adopts a hydrothermal oxidation method to dechlorinate polychlorinated biphenyl, the reaction is carried out at 300-400 ℃ and 20-400 atm by taking a sodium carbonate aqueous solution as a medium, dechlorination conditions are harsh, and industrial treatment is difficult. US5185488 uses sodium or calcium metal as a reducing agent to dechlorinate polychlorinated biphenyls in transformer oil, but low carbon alcohol (methanol) must be added, and the amount of the metal reducing agent used is 30-40 times of the chlorine content in the system. CN1470300 reports a method for treating polychlorinated biphenyl in transformer oil by using a high-activity nano-scale alkali metal hydride synthesized by a complex catalytic method as a reducing agent and a transition metal compound as a reaction promoter. CN1016142 reports a method for destroying organic halogenated products such as polychlorinated biphenyl in organic oil or mineral oil at 250-290 ℃ by using powdery sodium methoxide. EP99951 reports the treatment of polychlorinated biphenyls in insulating oil with dispersible granular sodium at 110-130 ℃. The method needs to prepare fine dispersible sodium particles in advance, more than 80 percent of the sodium particles need to be smaller than 10 mu m in particle size, and otherwise, the treatment effect is not realized; in addition, the conditions are severe in order to recover unreacted sodium by centrifugation.
Because the siloxane bond in the diphenyldimethoxysilane is relatively active, the product can be subjected to alkaline hydrolytic condensation under the action of alkali metal alkoxide (such as sodium methoxide) at high temperature, so that the product loss is large, and industrialization is difficult to realize. Therefore, none of the above methods is suitable for treating polychlorinated biphenyl in diphenyldimethoxysilane.
Disclosure of Invention
The invention aims to provide a method for removing polychlorinated biphenyl in diphenyldimethoxysilane under mild conditions through simple operation, which can improve the product quality and widen the application field of the product.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for reducing the content of polychlorinated biphenyl in a diphenyldimethoxysilane product comprises the following steps:
s1, adding metal sodium into diphenyl dimethoxysilane containing polychlorinated biphenyl, stirring for 5-6 hours under the condition of heat preservation and oil bath at the temperature of 100-105 ℃, and cooling to room temperature;
s2, adjusting the pH value of the system to 6-8 by using organic acid;
s3, filtering and rectifying to obtain the diphenyl dimethoxy silane product.
According to the scheme, the addition amount of the metal sodium is 2-10 times of the amount (calculated by chlorine) of the polychlorinated biphenyl, and the metal sodium is calculated by mole.
According to the scheme, the addition amount of the metal sodium is 5 times and moles of the polychlorinated biphenyl (calculated by chlorine).
According to the scheme, the organic acid in the step S2 is acetic acid.
According to the scheme, the diphenyl dimethoxysilane is prepared by hydrolyzing diphenyl dichlorosilanol and is subjected to preliminary dechlorination treatment.
According to the scheme, the content of polychlorinated biphenyl in the diphenyldimethoxysilane product obtained in the step S3 is reduced to be less than 5ppm (calculated by chlorine).
According to the scheme, the pH value in the step S3 is 6.5-7.5.
The content of polychlorinated biphenyl of the diphenyl dimethoxy silane product treated by the scheme is reduced to below 5ppm (calculated by chlorine).
The invention adopts the technical scheme that the method has the advantages that: the metal sodium can be in a molten state at the temperature of 100-105 ℃, and has high enough activity, so that the metal sodium can easily react with chlorine in the polychlorinated biphenyl; the acid for adjusting the pH value of the system is acetic acid, the formed salt is sodium acetate, and the product loss caused by the destruction of the diphenyl dimethoxysilane product in the subsequent rectification process can be avoided; the generated by-product sodium chloride or sodium acetate is not dissolved in a reaction system, is easy to remove by filtration, and has simple industrial operation.
Detailed Description
The following examples are further illustrative of the present invention. The present invention includes, but is not limited to, the following examples.
Example 1
285.3g of diphenyldimethoxysilane (diphenyldimethoxysilane is prepared by a diphenyldichlorosilanolysis method and is subjected to preliminary dechlorination treatment, the content of polychlorinated biphenyl is 386ppm (0.003mol) in terms of chlorine, 0.35g (0.015mol) of metal sodium is added, the mixture is stirred for 5 hours at 105 ℃ in an oil bath, and then cooled, and acetic acid is slowly added dropwise while stirring until the pH value of the system is 6.8. Filtering, removing sodium salt, rectifying the filtrate to obtain 236.8g of product diphenyldimethoxysilane, and analyzing and detecting the polychlorinated biphenyl content (calculated by chlorine) in the product to be 2.91 ppm.
Example 2
265g of diphenyldimethoxysilane (the diphenyldimethoxysilane is prepared by a diphenyldichlorosilanolysis method and is subjected to preliminary dechlorination treatment, the content of polychlorinated biphenyl is 293ppm (0.002mol) calculated by chlorine), 0.32g (0.014mol) of metal sodium is added, the mixture is heated in an oil bath at 105 ℃ for 5 hours, acetic acid is slowly added dropwise while stirring after cooling until the pH value of the system is 7.2, the product is filtered, sodium salt is removed, the filtrate is rectified to obtain 217.3g of product diphenyldimethoxysilane, and the content of polychlorinated biphenyl (calculated by chlorine) in the product is analyzed and detected to be 1.04 ppm.
Claims (3)
1. A method for reducing the content of polychlorinated biphenyl in a diphenyldimethoxysilane product comprises the following steps:
s1, adding metal sodium into diphenyl dimethoxysilane containing polychlorinated biphenyl, stirring for 5-6 hours under the condition of heat preservation and oil bath at the temperature of 100-105 ℃, and cooling to room temperature; the addition amount of the metal sodium is 2-10 times of the amount of the polychlorinated biphenyl counted by chlorine, and the metal sodium is counted by mol;
s2, adjusting the pH value of the system to 6-8 by using organic acid; the organic acid is acetic acid;
s3, filtering and rectifying to obtain the diphenyl dimethoxy silane product.
2. The method for reducing the content of polychlorinated biphenyl in the diphenyldimethoxysilane product as claimed in claim 1, wherein the method comprises the following steps: the content of polychlorinated biphenyl in the diphenyldimethoxysilane product obtained in the step S3 is reduced to be below 5ppm in terms of chlorine.
3. The method for reducing the content of polychlorinated biphenyl in the diphenyldimethoxysilane product as claimed in claim 1, wherein the method comprises the following steps: the pH value of the step S2 is 6.5-7.5.
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| CN109336919A (en) * | 2018-11-02 | 2019-02-15 | 辽宁新邦新材料有限公司 | The purification process and device of the precursor material of organosilicon material |
| CN111072715A (en) * | 2019-12-31 | 2020-04-28 | 仙桃市格瑞化学工业有限公司 | Preparation method of bis (phenylcyclosiloxane) |
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| US6984767B2 (en) * | 2002-04-23 | 2006-01-10 | Sonic Environmental Solutions Inc. | Sonication treatment of polychlorinated biphenyl contaminated media |
| KR20070073679A (en) * | 2007-06-07 | 2007-07-10 | 전정구 | Method and potable type equipment for treatment of polychlorinated biphenyls in wasted insulation oil |
| JP2013056063A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
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