CN104693226A - Method for recovering organic silicon monomer from silicone rubber wastes - Google Patents
Method for recovering organic silicon monomer from silicone rubber wastes Download PDFInfo
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- CN104693226A CN104693226A CN201510072993.8A CN201510072993A CN104693226A CN 104693226 A CN104693226 A CN 104693226A CN 201510072993 A CN201510072993 A CN 201510072993A CN 104693226 A CN104693226 A CN 104693226A
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Abstract
The invention discloses a method for recovering an organic silicon monomer from silicone rubber waste. The method comprises the following steps: adding a composite catalyst into the silicone rubber waste in the atmosphere of normal-pressure air, and carrying out catalytic cracking reaction at the temperature of 350-640 DEG C to generate crude DMC (dimethylcyclosiloxane) oil; adding a water-soluble oxidizing agent into the crude DMC oil to remove allochromatic impurities; taking a part of oxidized crude DMC oil, adding a composite catalyst into the oxidized crude DMC oil, refluxing at normal pressure and the temperature of 120-210 DEG C for 5-7 hours to obtain reaction mother liquor, feeding the left oxidized crude DMC oil continuously with a pump, mixing the left oxidized crude DMC oil with the reaction mother liquor, and carrying out reaction at the temperature of 185-250 DEG C to obtain refined DMC oil; and rectifying the refined DMC oil and separating to obtain the organic silicon monomer. The process disclosed by the invention has the advantages of simple production procedure, good catalyst efficiency, high recovered product purity, continuous production and good economic benefit.
Description
Technical field
The present invention relates to the chemical comprehensive utilization of silicone rubber, particularly relate to a kind of method adopting composite catalyst pyrolytic silicon rubber waste recovery organosilane monomer.
Background technology
Organosilicon chemistry goods, as silicon rubber, silicone oil etc., more and more large trend is had in the application in manufacture field, the industry such as all act buildings, electronics, weaving, space flight, all need to use organosilicon chemistry goods, and along with the development of domestic construction industry, communication electronics industry, demand significantly increases especially.At present, only the silastic press key factory in Guangdong Province is just more than 100, and the conservative estimation of silicon rubber starting material annual requirement, more than 8,000 ton, has a large amount of wastes and waste product to be thrown aside every year, both caused the wasting of resources, again serious environment pollution.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of method reclaiming organosilane monomer from silicone rubber, make derelict silicon rubber scrap stock and waste product obtain appropriate utilization
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
From silicone rubber, reclaim a method for organosilane monomer, its step comprises:
(1) under atmospheric air, add composite catalyst in silicone rubber, at 350 ~ 640 DEG C, catalytic pyrolysis generates organosilicon hybrid ring body (DMC) slightly oil;
(2) 3 ~ 5 hours are processed add water-soluble oxidizers 85 ~ 120 DEG C in the thick oil of DMC at, removing variable color impurity;
(3) DMC getting partial oxidation process is slightly oily, add composite catalyst normal pressure 120 ~ 210 DEG C backflow 5 ~ 7 hours, as reaction mother liquor, the thick oil pump continous way charging of other DMC and reaction mother liquor mix, at 185 ~ 250 DEG C, carry out reaggregation, re-constituted, heavy scission reaction, obtain DMC essential oil;
(4) DMC essential oil obtains organosilane monomer through rectifying separation.
Further, step (1) described composite catalyst accounts for 8 ~ 12wt% of silicone rubber total amount, and catalytic pyrolysis temperature is 350 ~ 550 DEG C.
Further, described composite catalyst is made up of alkaline catalysts, antioxidant, interfacial agent and water, and wherein alkaline catalysts accounts for 25 ~ 35wt%; Antioxidant accounts for 5 ~ 9wt%; Interfacial agent accounts for 2 ~ 6wt%; Water accounts for 50 ~ 68wt%.
Described alkaline catalysts is selected from potassium hydroxide (KOH), sodium hydroxide (NaOH) or cesium hydroxide (CsOH);
Described antioxidant is selected from iron(ic) chloride (FeCl
3), cupric chloride (CuCl
2), ironic hydroxide (Fe (OH)
3) or other transition metal oxides, oxyhydroxide;
Described interfacial agent is selected from C
12~ C
24anionic sodium salt or non-ionic interfacial agent.
Further, be 6 ~ 11wt% in described step (2) water soluble oxidized agent concentration, it is 12 ~ 20wt% that described water-soluble oxidizers accounts for the thick oil quality ratio of DMC.Described water-soluble oxidizers is selected from hydrogen peroxide (H
2o
2), potassium permanganate (KMnO
4) or potassium perchlorate (KClO
4).
Further, the organosilane monomer described in step (4) comprises hexamethyldisiloxane (M
2), octamethyltrisiloxane (MDM), decamethyl tetrasiloxane (MD
2m), hexam ethylcyclotrisiloxane (D
3), octamethylcyclotetrasiloxane (D
4), decamethyl five siloxanes (D
5), ten dimethyl six siloxanes (D
6).
The cleavage method of silicone rubber, existing patent adopts Pintsch process (350 ~ 750 DEG C) and catalytic pyrolysis (120 ~ 300 DEG C), the present invention adopts composite catalyst, its major ingredient is catalyzer, antioxidant and interfacial agent, the cracking production DMC being applied to silicon rubber is slightly oily, and the thick oily purifying of DMC becomes in DMC essential oil, the feature of catalyzer of the present invention is: introduced by antioxidant in alkaline catalysts, with ferric iron Fe (III) compound F 17-hydroxy-corticosterone e
2o
3for example, more than the 160 DEG C oxygenizements that can suppress silicon rubber, but do not affect Degradation, can obtain DMC slightly oily.General cracking process all has oxidation free radical reaction, produces inflammable gas, as H
2, CH
4, CO etc., and Fe (III) antioxidant can Mulberry Extract electronics, forms Fe (II) compound, interrupts free radical chain reactions, thus increase the security of industrial production.Fe (II) again be oxidized into Fe (III) compound in atmosphere, for regenerative antioxidant, because oxygenizement is suppressed, silicon rubber is when heating, degree of crosslinking does not increase, and does not produce coking phenomenon, and catalytic degradation reaction 300 ~ 550 DEG C is evenly smooth and easy, its lysis efficiency and speed all can improve, and impurity phase is to minimizing simultaneously.
Compared with prior art; advantage of the present invention comprises: the present invention has explained hereafter and simplifies; catalyst efficiency is good; recovery product purity is high, and continous way is produced, good in economic efficiency advantage; not only solve the problem that silicone rubber is recycled; simultaneously the secondary pollutant that produces of process of the present invention is little, and having industry security and environmental protection property concurrently, is the excellent process that silicone rubber reclaims organosilane monomer.
Embodiment
In view of deficiency of the prior art, inventor, through studying for a long period of time and putting into practice in a large number, is proposed technical scheme of the present invention.To be further explained this technical scheme, its implementation process and principle etc. as follows.
Below in conjunction with embodiment, the present invention is described in further detail.
embodiment 1
100 kilograms of distilled water are put into 200 liter tempering tanks, again 55 kilograms of potassium hydroxide are slowly dissolved in distilled water, after having dissolved, put into 5 kilogram of ten acid dimethyl sodium interfacial agent, be uniformly mixed uniformly solution, slowly instill the iron(ic) chloride saturated solution of 10 kilograms, stir after 1.5 hours in room temperature, take out and pour ball mill grinding into obtain Fe composite catalyst for subsequent use.By 100 kilograms of silicone rubbers, after washing cuts into and is less than 2 × 2 × 2cm size, add 8 kilograms of Fe composite catalysts, after stirring in advance, in direct input multitube reactive tank, groove is heated up under normal pressure, carries out catalytic pyrolysis, when temperature reaches 350 DEG C, start have cracking to produce, when temperature rises to 400 ~ 450 DEG C, a large amount of product produces and gets off through condensation, outlet temperature to 500 ~ 600 DEG C, react after 180 minutes, obtain 60 kilograms of thick organosilicon hybrid ring bodies (DMC), this mixed methylcyclosiloxane is taken out, drop in 300 liter washing baths, add 5 kilogram of 6% aqueous hydrogen peroxide solution, stir and be warmed up to 100 DEG C and carry out oxide treatment, after 1 ~ 2 hour, be cooled to 70 DEG C, put into 50 kilograms of distilled water, wash, stir 60 minutes, stop stirring, stratification, take out oil reservoir and drop into 300 liter reactive tanks, add 3 kilograms of Fe composite catalysts, add 100CS silicone oil 5 kilograms again, stir, be warming up to 150 DEG C of stirrings and carry out ring-opening polymerization in 6 hours, and after loop chain balance, temperature rises to 200 ~ 240 DEG C and distills out 50 kilograms of organosilicon hybrid ring body (DMC) treated oils.
DMC essential oil obtains through rectifying separation:
| M 2 | MDM | MD 2 M | D 3 | D 4 | D 5 | D 6 |
| 5.7％ | 9.8％ | 2.2％ | 15.6％ | 58.83％ | 7.5％ | 0.42％ |
| 3.4Kg | 5.9Kg | 1.3Kg | 9.35Kg | 35.3Kg | 4.5Kg | 0.25Kg |
embodiment 2
100 kilograms of distilled water are put into 200 liter tempering tanks, again 55 kilograms of sodium hydroxide are slowly dissolved in distilled water, after having dissolved, put into 5 kilogram of ten acid dimethyl sodium interfacial agent, be uniformly mixed uniformly solution, slowly instill the cupric chloride saturated solution of 10 kilograms, stir after 2 hours in room temperature, take out and pour ball mill grinding into obtain Cu composite catalyst for subsequent use.By 100 kilograms of silicone rubbers, after washing cuts into and is less than 2 × 2 × 2cm size, add 5 kilograms of Cu composite catalysts, after stirring in advance, in direct input multitube reactive tank, groove is heated up under normal pressure, carries out catalytic pyrolysis, when temperature reaches 350 DEG C, start have cracking to produce, when temperature rises to 400 ~ 450 DEG C, a large amount of product produces and gets off through condensation, outlet temperature to 500 ~ 600 DEG C, react after 180 minutes, obtain 60 kilograms of thick organosilicon hybrid ring bodies (DMC), this mixed methylcyclosiloxane is taken out, drop in 300 liter washing baths, add 5.5 kilogram of 5% aqueous hydrogen peroxide solution, stir and be warmed up to 100 DEG C and carry out oxide treatment, after 1 ~ 2 hour, be cooled to 70 DEG C, put into 50 kilograms of distilled water, wash, stir 60 minutes, stop stirring, stratification, take out oil reservoir and drop into 300 liter reactive tanks, add 2.5 kilograms of Cu composite catalysts, add 80CS silicone oil 5 kilograms again, stir, be warming up to 155 DEG C of stirrings and carry out ring-opening polymerization in 6 hours, and after loop chain balance, temperature rises to 200 ~ 240 DEG C, by the mixed methylcyclosiloxane pump continuously feeding of oxide treatment complete ground, with 50 kilograms of dischargings per hour, and control discharging/charge proportion and maintain between 0.85 ~ 0.95, distillating product is DMC treated oil, its composition is as follows:
Should be appreciated that above-described embodiment is only and technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (7)
1. from silicone rubber, reclaim a method for organosilane monomer, it is characterized in that its step comprises:
(1) under atmospheric air, add composite catalyst in silicone rubber, at 350 ~ 640 DEG C, catalytic pyrolysis generates organosilicon hybrid ring body (DMC) slightly oil;
(2) 3 ~ 5 hours are processed add water-soluble oxidizers 85 ~ 130 DEG C in the thick oil of DMC at, removing variable color impurity;
(3) DMC getting partial oxidation process is slightly oily, add composite catalyst normal pressure 120 ~ 210 DEG C backflow 5 ~ 7 hours, as reaction mother liquor, the thick oil pump continous way charging of other DMC and reaction mother liquor mix, at 185 ~ 250 DEG C, carry out reaggregation, re-constituted, heavy scission reaction, obtain DMC essential oil;
(4) DMC essential oil obtains organosilane monomer through rectifying separation.
2. the method reclaiming organosilane monomer from silicone rubber according to claim 1, it is characterized in that step (1) described composite catalyst accounts for 8 ~ 12wt% of silicone rubber total amount, catalytic pyrolysis temperature is 350 ~ 550 DEG C.
3. the method reclaiming silicon monomer from silicone rubber according to claim 1 and 2, is characterized in that: described composite catalyst is made up of alkaline catalysts, antioxidant, interfacial agent and water, and wherein alkaline catalysts accounts for 25 ~ 35wt%; Antioxidant accounts for 5 ~ 9wt%; Interfacial agent accounts for 2 ~ 6wt%; Water accounts for 50 ~ 68wt%.
4. the method reclaiming silicon monomer from silicone rubber according to claim 3, is characterized in that: described alkaline catalysts is selected from potassium hydroxide (KOH), sodium hydroxide (NaOH) or cesium hydroxide (CsOH);
Described antioxidant is selected from iron(ic) chloride (FeCl
3), cupric chloride (CuCl
2), ironic hydroxide (Fe (OH)
3) or other transition metal oxides, oxyhydroxide;
Described interfacial agent is selected from C
12~ C
24anionic sodium salt or non-ionic interfacial agent.
5. the method reclaiming organosilane monomer from silicone rubber according to claim 1, is characterized in that described step (2) water soluble oxidized agent concentration is 6 ~ 11wt%, and it is 12 ~ 20wt% that described water-soluble oxidizers accounts for the thick oil quality ratio of DMC.
6. the method reclaiming organosilane monomer from silicone rubber according to claim 5, is characterized in that described water-soluble oxidizers is selected from hydrogen peroxide (H
2o
2), potassium permanganate (KMnO
4) or potassium perchlorate (KClO
4).
7. the method reclaiming organosilane monomer from silicone rubber according to claim 1, is characterized in that the organosilane monomer described in step (4) comprises hexamethyldisiloxane (M
2), octamethyltrisiloxane (MDM), decamethyl tetrasiloxane (MD
2m), hexam ethylcyclotrisiloxane (D
3), octamethylcyclotetrasiloxane (D
4), decamethyl five siloxanes (D
5), ten dimethyl six siloxanes (D
6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510072993.8A CN104693226A (en) | 2015-02-12 | 2015-02-12 | Method for recovering organic silicon monomer from silicone rubber wastes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510072993.8A CN104693226A (en) | 2015-02-12 | 2015-02-12 | Method for recovering organic silicon monomer from silicone rubber wastes |
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| Publication Number | Publication Date |
|---|---|
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ID=53340817
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061490A (en) * | 2015-08-19 | 2015-11-18 | 湖北兴瑞化工有限公司 | Method for reducing content of impurities in organosilicone DMC |
| CN107658456A (en) * | 2017-09-27 | 2018-02-02 | 杨小旭 | The method and lithium battery of lithium battery energy storage battery material are prepared using silicon chip cutting waste material |
| CN107778326A (en) * | 2016-08-29 | 2018-03-09 | 枣阳市金鹏化工有限公司 | Useless silica gel production DMC method |
| CN116355008A (en) * | 2023-04-06 | 2023-06-30 | 江门市江业豪硅材料有限公司 | Treatment process for recycling silicone rubber |
-
2015
- 2015-02-12 CN CN201510072993.8A patent/CN104693226A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061490A (en) * | 2015-08-19 | 2015-11-18 | 湖北兴瑞化工有限公司 | Method for reducing content of impurities in organosilicone DMC |
| CN105061490B (en) * | 2015-08-19 | 2017-10-27 | 湖北兴瑞化工有限公司 | A kind of method for reducing impurity content in organosilicon DMC |
| CN107778326A (en) * | 2016-08-29 | 2018-03-09 | 枣阳市金鹏化工有限公司 | Useless silica gel production DMC method |
| CN107658456A (en) * | 2017-09-27 | 2018-02-02 | 杨小旭 | The method and lithium battery of lithium battery energy storage battery material are prepared using silicon chip cutting waste material |
| CN107658456B (en) * | 2017-09-27 | 2020-04-28 | 杨小旭 | Method for preparing lithium battery energy storage material by using silicon wafer cutting waste and lithium battery |
| CN116355008A (en) * | 2023-04-06 | 2023-06-30 | 江门市江业豪硅材料有限公司 | Treatment process for recycling silicone rubber |
| CN116355008B (en) * | 2023-04-06 | 2024-01-05 | 江门市江业豪硅材料有限公司 | Treatment process for recycling silicone rubber |
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Application publication date: 20150610 |