CN101209842B - Method for producing white carbon black and simultaneously recycling product from by-product of organosilicon reaction - Google Patents
Method for producing white carbon black and simultaneously recycling product from by-product of organosilicon reaction Download PDFInfo
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- CN101209842B CN101209842B CN2006101715863A CN200610171586A CN101209842B CN 101209842 B CN101209842 B CN 101209842B CN 2006101715863 A CN2006101715863 A CN 2006101715863A CN 200610171586 A CN200610171586 A CN 200610171586A CN 101209842 B CN101209842 B CN 101209842B
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Abstract
The invention relates to a comprehensive recycling technology. A colloidal or suspended granular byproduct generated from organosilicon reaction is treated with alkalization, and a solution silicate solution is obtained. A product of a recovery system is extracted by using organic solvent and the pH value of the solution adjusted by using silicate solution; a silicon oxide precipitation is obtained; finally, a white carbon black is obtained through post treatment process. The invention not only turns the byproduct of organosilicon reaction into a white carbon black, but also recycles part of products wrapped in the recycled byproduct, thus improving the total yield of the reaction.
Description
Technical field
The invention belongs to the recycle and the comprehensive recovery technology field that produce waste.
Background technology
White carbon black is a white, water insoluble, high temperature resistant, do not burn, pollution-free, have good electrical insulating property, a porousness, have purposes widely at numerous areas such as rubber, paint, coating, plastics, papermaking, medicine, fire-fighting, daily use chemicals, food and chemical industry, have huge potentiality to be exploited and vast potential for future development.The production technique of white carbon black mainly is the precipitator method and vapor phase process, is to utilize natural siliceous sand to make water glass, makes white carbon black then.Present production technique is the production cost height not only, and needs to consume a large amount of quartz sand resources, makes white carbon black production industry become the resource-hungry industry.In view of this, existing many investigators redirect to sight in the technical renovation field that utilizes other resources to produce white carbon black.According to existing report, other resources comprise rice hull ash (CN1762802 introduce be the white carbon black of feedstock production with the rice hull ash), diatomite (" Sichuan chemical industry " first phase in 1997 the 8th page of introduction be the white carbon black of raw material production with diatomite), kaolin (" chemistry world " the 198th page of introduction in 1988 be the white carbon black of feedstock production with kaolin), clay (" nonmetalliferous ore " first phase in 1999 the 17th page of introduction be the white carbon black of feedstock production) with Hainaut stone clay, swelling soil (" Qiqihar College of Light Industry journal " fourth phase in 1993 the 64th page of introduction be the white carbon black of raw material system with the swelling soil) or the like, it is molten generally to pass through alkali, filter, the solution adjust pH, ageing, filter, pulverize, multiple working procedures such as thermal treatment.Though these technologies can avoid using the problem of natural siliceous sand to a great extent, but because silicone content is low in these raw materials, need more other consumptions of raw materials, more operational ton and more waste residue, discharging of waste liquid, from the big angle of producing of entire societyization, be not best selection.
Organosilane is the key of modern organosilicon industry, obtains general application (" organosilicon synthesis technique and product application ", the loose people of good fortune, Wang Yilu write Chemical Industry Press, version in 2000) in modern society's all respects.Part organosilane wherein, as organic halosilanes, organohydrogensilicon alkane, organoalkoxysilane, organic amino silane etc., when participating in the application of each side such as chemical industry, material, medicine, the energy and reaction as basic material, form easily the glue of various reactions or the by product of suspended particle shape, not only cause reaction treatment difficulty and can be because glue or suspended particle shape form reduce yield to the parcel of product easily.The by product main component of these glues or suspended particle shape is silicic acid and silicon oxide, and stable in properties is not easy to remove, and on the general industry is it is filtered the back high temperature incineration, produces white carbon black.Not only need a large amount of energy, and owing to be enclosed with a large amount of products, after burning, the product of parcel is burnt, and produces a large amount of wastes simultaneously.In addition, because parcel, the white carbon black of generation is second-rate, also can produce a large amount of secondary pollutions in burning process.There is not appropriate means to address this problem at present as yet.
The present invention just provides a kind of comprehensive reutilization technology, utilizes the glue of reaction generation or the by product of suspended particle shape, it is changed into products such as white carbon black or silica gel, reclaims the portioned product that wraps up in the by product simultaneously, improves overall yield of reaction.
Summary of the invention
In order to realize utilizing the glue of organosilicon reaction generation or the by product of suspended particle shape to change products such as white carbon black or silica gel into, reclaim the portioned product that wraps up in the by product simultaneously, improve the target of overall yield of reaction, technical scheme provided by the invention is:
The glue that organosilicon reaction is produced or the by product of suspended particle shape, if or reaction product insensitive and good dissolving ability can be arranged in organic solvent to alkali, directly use unsegregated reaction mixture, carry out alkalinisation treatment; Take out reaction product with organic solvent extracting, obtain the silicate solutions of solution shape; Regulate the pH value of silicate solutions, obtain silicon oxide precipitation; Drying or calcination silicon oxide precipitation obtain white carbon black.Specific embodiment is:
With behind the organosilicon reaction from the by product of isolated glue of system or suspended particle shape, if reaction product is insensitive and good dissolving ability can be arranged in organic solvent to alkali, can directly use reaction mixture (be product do not separate handle) with byproduct, alkali and water drop in the reactor according to certain ratio and react, alkali comprises sodium hydroxide, in the potassium hydroxide one or both, or replace described alkali with in yellow soda ash, the salt of wormwood one or both.Silicon feeds intake: the alkali mol ratio is 1.0～6.0, preferred 1.5～3.0.Amount of water, the concentration of guarantee system mesosilicic acid salts solution in system is 1～40%, preferred 5～20%.React completely back pH value of solution value greater than 9, be preferably greater than 10 less than 14.
2. the organosilicon by product is meant organic halosilanes, organosilicons such as organohydrogensilicon alkane or organoalkoxysilane participate in the by product of reaction back system, wherein organic halosilanes, organohydrogensilicon alkane or organoalkoxysilane comprise silicon tetrafluoride, silicon tetrachloride, trichlorosilane, dichloro hydrogen silicon, trichloromethyl silane, dichloro methyl silane, dichloromethyl hydrogen silicon, trichlorophenyl silane, tetramethoxy-silicane, tetraethoxysilane, the trimethoxy chlorosilane, the dimethoxy dichlorosilane, the triethoxy chlorosilane, the diethoxy dichlorosilane, trimethoxy hydrogen silicon or triethoxy hydrogen silicon etc.
3. the treatment temp of alkalinisation treatment is 80～130 ℃, preferred 90～110 ℃.Processing pressure is 0.06～0.3MPa, preferred 0.09～0.15MPa.Treatment time is 10 minutes～8 hours, preferred 30 minutes～2 hours.After reaction is finished, obtain clarifying silicate solutions.Under the partial condition, have small amount of precipitate or insolubles, can obtain settled solution by filtration or press filtration, in order to the operation of back.
4. add water-insoluble organic solvent in reactor, stir, extract product, extraction liquid obtains the product that output improves through handling.Because the glue of beginning or suspended particle shape by product product adsorbed and parcel has been released, compares reaction yield and can improve 5～20% and do not wait.Simultaneously the organic constituent content in the aqueous phase solution seldom can directly be used for fully and operates with any other hardly.Extraction is selected from tetracol phenixin, trichloromethane, methylene dichloride, trieline, tetrachloroethane, dimethylbenzene, benzene, toluene, sherwood oil, diesel oil, kerosene, gasoline, hexane, heptane, octane, ether or butyl ether etc. with organic solvent, preferred tetrachloroethane, toluene or sherwood oil.
5. the pH value of regulating aqueous silicate solution with acidic substance is reduced to 8～11 scopes, and is preferred 8.5～10.5, with generation silicon oxide crystal seed.The seeded growth time kept 10 minutes～24 hours, preferred 2～8 hours.Temperature of reaction is 50～100 ℃, preferred 70～80 ℃.Acidic substance are mineral acid, organic acid, sour gas or other some acidic substance, comprise hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, carbonic acid gas, sulfurous gas or sulphur trioxide etc., preferred hydrochloric acid, sulfuric acid or carbonic acid gas.
6. to acidity, promptly the pH value was less than 6 with the pH value of acidic substance regulator solution in continuation after the silicon oxide crystal seed produced and finishes, and maintenance system acidity guarantees growth of silicon oxide 10 minutes～24 hours, preferred 2～8 hours, obtained a large amount of oxidizing aqueous silicon precipitations.
7. silicon oxide precipitation promptly obtains the various white carbon blacks that need performance through filtration, washing, making beating, defibrination after drying, oven dry or calcination, packing.In most cases only need dry getting final product to white carbon black operation,, can save a large amount of energy generally without high temperature sintering by silicon oxide precipitation.
8. in order to obtain the white carbon black of various performances, as amorphous white carbon black and nano white carbon black etc., generally in the 5th step, promptly before regulating pH value step, add some functional agents toward system with acidic substance, with the form and the structure of regulating oxidizing aqueous silicon, thereby obtain the white carbon black of various performances at last.Described functional agent is selected from one or more in sodium sulfate, mahogany acid, amino dodecane, methyl alcohol, ethanol, ethylene glycol, glycol ether, polyoxyethylene glycol, Soxylat A 25-7, organoalkoxysilane, alkyl chlorosilane, trolamine, diethanolamine, hexahydroaniline, the tetraethoxy etc.
Below mode by concrete enforcement technical scheme of the present invention is described in further detail, be limitation of the present invention but should not be construed as.
Embodiment
Embodiment 1
Trichlorosilane reduces triphenylphosphinc oxide under the condition that is added with the sour agent of prisoner, obtain triphenyl phosphorus, and solvent is a toluene.Obtain mashed prod after having reacted, thickness and be not easy liquid-solid separation.Get this mashed prod 1000 grams, interior siliceous 100 grams add sodium hydroxide 50 grams, 500 milliliters in water, heated and stirred reaction.Spend stirring reactions 2 hours 110, cooling back separatory, water toluene extracting and washing 3 times, each 100 milliliters.Obtain product behind the toluene phase evaporate to dryness, yield improves 10～20%.Water is warmed up to 80 ℃, with 10M salt acid for adjusting pH value to 9, keeps 8 hours.Continue to add acid, regulate pH value to 3, the time is 8 hours, obtains a large amount of oxidizing aqueous silicon.Oxidizing aqueous silicon is through obtaining deposition white carbon black 180 grams after filtering, wash, pull an oar, drying.
Embodiment 2
The trimethoxy chlorosilane generates alkyl trimethoxysilane with the alkyl olefine reaction under the chloroplatinic acid-catalysis effect, after reaction is finished, steam to remove and reclaim behind the superfluous trimethoxy chlorosilane that distillation obtains product under high vacuum condition, and remaining is thick by product.Get this mashed prod 1000 grams, interior siliceous 300 grams add yellow soda ash 500 grams, 3000 milliliters in water, heated and stirred reaction.Spend stirring reactions 8 hours 100, cooling back separatory, water tetrachloroethane extracting and washing 3 times, each 300 milliliters.Obtain alkyl alkene 50～100 grams behind the tetrachloroethane phase evaporate to dryness.Water is warmed up to 50 ℃, feeds carbon dioxide and regulates pH value to 8, keeps 4 hours.Continue to feed carbon dioxide, regulate pH value to 5, the time is 24 hours, obtains a large amount of oxidizing aqueous silicon.Oxidizing aqueous silicon is through filtering, obtaining amorphous white carbon black 300～500 grams after the washing, making beating, oven dry, 600 ℃ of calcinations.
Embodiment 3
Silicon tetrachloride and dehydrated alcohol reaction generate tetraethyl orthosilicate, and product and superfluous raw material obtain jelly after steaming and removing.Get this jelly 1000 grams, interior siliceous 200 grams add salt of wormwood 400 grams, 3000 milliliters in water, heated and stirred reaction.Spend stirring reactions 1 hour 80, water washed with dichloromethane 3 times of cooling back, each 100 milliliters.Water is warmed up to 60 ℃ after filtering, and adds poly----ethylene glycol, trimethylchlorosilane and protective material---sodium sulfate and tetraethoxy of dispersion agent of appropriate amount, stirs fast, slowly drips vinegar acid for adjusting pH value to 9.5, keeps 4 hours.Continue slowly to drip vinegar acid for adjusting pH value to 5, the time is 24 hours, obtains the moisture nano silicon oxide of suspension.Oxidizing aqueous silicon removes by filter the oxidizing aqueous silicon of volume particle size, liquid phase obtains nano white carbon black 200～400 grams through lyophilize or spraying drying.
Claims (9)
1. method by the white carbon black of organosilicon reaction by-product production, it is characterized in that: with the glue of organosilicon reaction generation or the by product of suspended particle shape, if or reaction product is insensitive and good dissolving ability arranged in organic solvent to alkali, directly use unsegregated reaction mixture, drop in the reactor according to certain ratio with alkali and water and to react, alkali comprises one or both in sodium hydroxide, the potassium hydroxide, thereby carries out alkalinisation treatment; Go out reaction product with above-mentioned organic solvent extraction, obtain silicate solutions; Regulate the pH value of silicate solutions, obtain silicon oxide precipitation; Drying or calcination silicon oxide precipitation obtain white carbon black; Wherein, described organosilicon is meant organic halosilanes, organohydrogensilicon alkane or organoalkoxysilane.
2. a kind of method by the white carbon black of organosilicon reaction by-product production according to claim 1 is characterized in that: described organic halosilanes, organohydrogensilicon alkane or organoalkoxysilane comprise silicon tetrafluoride, silicon tetrachloride, trichlorosilane, dichloro hydrogen silicon, trichloromethyl silane, dichloro methyl silane, dichloromethyl hydrogen silicon, trichlorophenyl silane, tetramethoxy-silicane, tetraethoxysilane, trimethoxy chlorosilane, dimethoxy dichlorosilane, triethoxy chlorosilane, diethoxy dichlorosilane, trimethoxy hydrogen silicon or triethoxy hydrogen silicon.
3. a kind of method by the white carbon black of organosilicon reaction by-product production according to claim 1 is characterized in that: replace described alkali with in yellow soda ash, the salt of wormwood one or both.
4. a kind of method by the white carbon black of organosilicon reaction by-product production according to claim 1 is characterized in that: the treatment temp of alkalinisation treatment is 80～130 ℃; Processing pressure is 0.06～0.3MPa; Treatment time is 10 minutes～8 hours.
5. a kind of method by the white carbon black of organosilicon reaction by-product production according to claim 1 is characterized in that: silicon: the alkali mol ratio is 1.0～6.0.
6. a kind of method by the white carbon black of organosilicon reaction by-product production according to claim 1 is characterized in that: extraction is selected from tetracol phenixin, trichloromethane, methylene dichloride, trieline, tetrachloroethane, dimethylbenzene, benzene, toluene, sherwood oil, diesel oil, kerosene, gasoline, hexane, heptane, octane, ether or butyl ether with organic solvent.
7. a kind of method by the white carbon black of organosilicon reaction by-product production according to claim 1 is characterized in that: pH value to 8～11 scopes of regulating silicate solutions with acidic substance.
8. a kind of method according to claim 1 by the white carbon black of organosilicon reaction by-product production, it is characterized in that: in order to obtain the white carbon black of various performances, before regulating pH value step, add some functional agents toward system with acidic substance, with the form and the structure of regulating oxidizing aqueous silicon, thereby obtain the white carbon black of various performances at last.
9. a kind of method by the white carbon black of organosilicon reaction by-product production according to claim 8, it is characterized in that: described functional agent is selected from one or more in sodium sulfate, mahogany acid, amino dodecane, methyl alcohol, ethanol, ethylene glycol, glycol ether, polyoxyethylene glycol, Soxylat A 25-7, organoalkoxysilane, alkyl chlorosilane, trolamine, diethanolamine, hexahydroaniline, the tetraethoxy.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7897125B1 (en) * | 2009-08-14 | 2011-03-01 | Vithal Revankar | Silicon tetrafluoride byproduct separation process |
| CN102092721B (en) * | 2010-11-24 | 2012-10-31 | 陈君华 | Method for preparing nanoscale white carbon black through sulfuric acid precipitation method |
| CN102604154B (en) * | 2012-02-27 | 2013-08-14 | 周其强 | Application of polysilicon waste material in preparing rubber-modified masterbatch |
| CN106744989A (en) * | 2016-12-22 | 2017-05-31 | 上海至正道化高分子材料股份有限公司 | A kind of one-step method silanes liquid post-processing approach |
| CN107055559A (en) * | 2017-01-25 | 2017-08-18 | 湖北新蓝天新材料股份有限公司 | A kind of method for treating waste liquid of Direct Synthesis of Trialkoxysilane monomer |
| CN108659580B (en) * | 2018-04-03 | 2019-11-08 | 中国科学院化学研究所 | A kind of apparatus and method of the organic silicon byproduct processing filler with silica structure |
| CN112236391B (en) * | 2019-03-05 | 2023-06-02 | 瓦克化学股份公司 | Recovery of materials containing organosilicon compounds |
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| CN1096524A (en) * | 1993-06-18 | 1994-12-21 | 鞍山钢铁学院 | A kind of method of producing white carbon black |
| CN1686791A (en) * | 2005-03-28 | 2005-10-26 | 广州吉必时科技实业有限公司 | Technique of energy saving vapor phase process in high efficiency for synthesizing carbon white |
| CN1810641A (en) * | 2006-01-10 | 2006-08-02 | 广州市康明硅橡胶科技有限公司 | Comprehensive utilization process of cracked waste silicone rubber cinder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096524A (en) * | 1993-06-18 | 1994-12-21 | 鞍山钢铁学院 | A kind of method of producing white carbon black |
| CN1686791A (en) * | 2005-03-28 | 2005-10-26 | 广州吉必时科技实业有限公司 | Technique of energy saving vapor phase process in high efficiency for synthesizing carbon white |
| CN1810641A (en) * | 2006-01-10 | 2006-08-02 | 广州市康明硅橡胶科技有限公司 | Comprehensive utilization process of cracked waste silicone rubber cinder |
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Assignee: Beijing Jin Yuan Xinhua Environmental Technology Co., Ltd. Assignor: Beijing CHARNA Chemicals Ltd. Contract record no.: 2011110000126 Denomination of invention: Method for producing white carbon black and simultaneously recycling product from by-product of organosilicon reaction Granted publication date: 20100630 License type: Exclusive License Open date: 20080702 Record date: 20110802 |
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