CN112707930A - Method for recovering high-boiling-point substances in organic silicon slurry slag - Google Patents
Method for recovering high-boiling-point substances in organic silicon slurry slag Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 57
- 239000002893 slag Substances 0.000 title claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 22
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- 238000009835 boiling Methods 0.000 claims abstract description 99
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- 238000011084 recovery Methods 0.000 claims abstract description 51
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- 238000004821 distillation Methods 0.000 claims description 22
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- 239000002826 coolant Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 239000002918 waste heat Substances 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 abstract description 8
- 230000008020 evaporation Effects 0.000 abstract description 7
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- 230000008901 benefit Effects 0.000 abstract description 2
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- 238000012360 testing method Methods 0.000 description 8
- 239000011863 silicon-based powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
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- 239000005046 Chlorosilane Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- DMZWVCJEOLBQCZ-UHFFFAOYSA-N chloro(ethenyl)silane Chemical compound Cl[SiH2]C=C DMZWVCJEOLBQCZ-UHFFFAOYSA-N 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07F7/12—Organo silicon halides
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for recovering high-boiling-point substances in organic silicon slurry residues. By adding the high-boiling point inert oil, the heating uniformity is improved, the high-boiling point substances are separated in an evaporation mode, the recovery rate of the high-boiling point substances in the slurry slag is improved, the economic benefit is improved, the amount of the slurry slag to be treated is reduced, the amount of sewage generated by harmless treatment of the slurry slag is reduced, and the method is environment-friendly. The high boiling point inert oil is used as an intermediate medium, so that the fluidity of the slurry slag is improved, and the blockage of a discharge pipeline by solids in the slurry slag is avoided.
Description
Technical Field
The invention relates to the technical field of organic silicon, in particular to a method for recovering high-boiling-point substances in slurry slag in the organic silicon industry.
Background
The organic silicon is a novel chemical product with excellent performance and wide application, and can be widely applied to the living fields of textiles, automobiles, buildings, electronics, cosmetics and the like and the special fields of national defense and the like. A plurality of organic silicon products mainly come from a direct method monomer synthesis device, and the general process flow is as follows: liquid phase chlorosilane is gasified by a vaporizer after being metered, heated by a superheater and then enters a fluidized bed through a distribution plate, silicon powder and a catalyst are mixed and then enter the fluidized bed through a fluidized bed feeding port, the reaction is started by heating heat conduction oil, and after the reaction is normal, the reaction heat release is taken away by cold conduction oil. In order to maintain the fluidized bed level and reaction, silicon powder and catalyst are required to be supplemented continuously. Synthetic gas (which is reaction product silane, unreacted chloromethane, fine silicon powder and a catalyst) enters a cyclone system through the top of a fluidized bed, the synthetic gas of the fluidized bed reactor carries fine powder, large-particle fine powder is captured through the cyclone separation system, then heavy components in chlorosilane are further separated through a washing tower system, and the heavy components comprise the fine powder which is not captured by the cyclone system and high-boiling-point silane. And evaporating the heavy component by flash evaporation and other evaporation treatments to evaporate the light component, extracting partial silane, and commonly referring the rest part as silane slurry residue. The silane slurry slag is a solid-liquid mixture, and mainly comprises high-boiling-point substances, fine silicon powder and fine catalysts (Cu, Zn, Sn and the like), wherein the main components of the high-boiling-point substances are high-boiling-point chlorosilane.
Usually, the part of the slurry residue is distilled to recover high boiling point substances (boiling point >160 ℃) and then the slurry residue which cannot be recovered is subjected to further harmless treatment by hydrolysis and the like. Since the slurry slag is directly discharged from the monomer organosilicon reactor, activated fine silicon powder and fine catalysts (Cu, Zn, Sn and the like) are contained, and when the slurry slag meets air, the ignition risk exists, and solid substances easily block a discharge pipeline.
CN107501315A discloses a method and a device for treating organic silicon slurry slag, which adopt a high-temperature evaporation and nitrogen fluidization mode to recover high-boiling residues; however, the slurry slag contains fine silicon powder and a catalyst, so that the fluidization distribution plate is easy to block; under the high temperature condition, higher requirements are put forward on the selection of the filter and the selection of the filter bag, the equipment is expensive, and the popularization and the implementation are not facilitated. CN107501315A is the common idea of the recovery treatment of organosilicon slurry slag in the industry at present, namely, the recovery of high economic substances in the slurry slag is improved by increasing the temperature of the flash evaporation or distillation of the slurry slag, but the method has the defects that the solid on a flash tank or a distillation still is caked or blocks a pipeline, and the caked solid can seriously threaten the safety of equipment and process. If excessive distillation of the sludge is to be prevented, which threatens production safety, the proper liquid phase component needs to be deliberately retained, which in turn leads to the loss of high economic substances.
Disclosure of Invention
The invention provides a method for recovering high-boiling-point substances in organic silicon slurry residues, which aims to effectively recover the high-boiling-point substances in the slurry residues (the main components are high-boiling-point chlorosilane, such as methyl chlorosilane, vinyl chlorosilane, methyl chloroethyl silane and the like, which are high economic substances), reduce the sewage discharge amount of harmless treatment of the slurry residues and avoid the production safety problem caused by excessive distillation in the traditional treatment process.
The purpose of the invention is realized by the following technical scheme:
a method for recovering high-boiling-point substances from organic silicon slurry residues comprises the steps of adding high-boiling-point inert oil into the organic silicon slurry residues, and distilling to recover the high-boiling-point substances.
The organic silicon slurry residue or slurry residue for short in the invention refers to the heavy component separated from synthesis gas generated in monomer organic silicon synthesis through a final washing device, and the heavy component is evaporated to remove the light component and the rest. The catalyst is a solid-liquid mixture, and mainly comprises high-boiling-point substances, fine silicon powder and fine catalysts (Cu, Zn, Sn and the like), wherein the main components of the high-boiling-point substances are high-boiling-point chlorosilane.
The organic silicon slurry residue contains metals for catalysts such as copper and/or zinc, and has a certain cracking catalysis effect at high temperature, so according to the invention, the high-boiling point inert oil refers to an oil product with a flash point of more than 210 ℃ at normal pressure and capable of resisting high-temperature cracking, such as: dimethyl silicone oil with flash point of 280 ℃ under normal pressure; or alkylbenzene type heat conducting oil L-QC, L-QD and the like. In one embodiment of the invention, the high boiling inert oil is dimethicone having a flash point of 280 ℃ at atmospheric pressure.
According to the invention, when distilling and recovering the high-boiling substance, normal pressure distillation or low pressure distillation can be adopted, and the temperature of distilling and recovering the high-boiling substance is controlled between 150 ℃ and 250 ℃ according to the used pressure. In order to prevent the cracking of the high-boiling point inert oil at high temperature, the distillation is preferably carried out under negative pressure, the absolute pressure is 0.01 MpaA-0.08 MpaA, and the distillation temperature is 150-220 ℃.
According to the present invention, the slurry residue after the high boiling point substance is distilled off (hereinafter also referred to as "slurry residue after high boiling point removal" for convenience of description) is discharged out of the slurry residue recovery apparatus together with the high boiling point inert oil, and after the solid-liquid separation treatment, the recovered high boiling point inert oil and the slurry residue solid after high boiling point removal are obtained, respectively.
According to the invention, the recovered high-boiling point inert oil can be recycled to the slurry-residue recovery device for distillation recovery of high-boiling residues of the slurry-residue.
According to the present invention, it is preferable that the temperature of the mixture of the high boiling point inert oil and the high boiling point removed sludge discharged from the sludge recovering apparatus is lowered by the heat exchanger before the solid-liquid separation treatment. In order to incorporate the subsequent solid-liquid separation method and apparatus, the temperature of the mixture is preferably lowered to 80 ℃ or lower, more preferably 50 ℃ or lower. Because the pulp residue is easy to be hydrolyzed in the air to generate combustible containing hydrogen chloride gas, the temperature is reduced, not only can the filtration equipment be conveniently selected, but also the spontaneous combustion risk when solid residue is discharged can be effectively reduced.
According to the invention, the temperature of the high-boiling point inert oil entering the slurry-residue recovery device is heated by the heat exchange device.
In one embodiment of the invention, the temperature of the mixture is gradually reduced using two heat exchange means, namely a heat exchange means for the first mixture and a heat exchange means for the second mixture.
According to the present invention, it is preferable that the heat exchanger for the first mixture for reducing the temperature of the mixture and the heat exchanger for heating the high boiling point inert oil be the same apparatus, that is, the high boiling point inert oil is heated by the waste heat of the mixture, and the temperature of the mixture is reduced by the high boiling point inert oil, thereby achieving the effect of improving the overall energy efficiency.
According to the present invention, it is preferable that the heat exchange means for the second mixture use cooling water as a cooling medium.
According to the present invention, the solid-liquid separation can be performed by conventional separation methods known in the art, including but not limited to pressure filtration, centrifugation, suction filtration, and the like. The solid content in the organic silicon slurry residue is about 20-30%, so the solid residue discharge amount and the discharge frequency are higher, and in the preferred embodiment of the invention, the solid-liquid separation is carried out by adopting filter pressing.
According to the present invention, the distilled high boiling substance can be condensed and recovered, and then used in other processes, for example, rectification as a final product.
According to the invention, the volume of high-boiling inert oil used in the process is greater than the volume of the sludge. In one embodiment of the invention, after the high boiling point inert oil and the slurry slag are added into the slurry slag recovery device, the liquid level of the slurry slag recovery device is controlled to be 35-85% of the volume of the whole device, and when the liquid level is lower than the liquid level, new high boiling point inert oil is supplemented into the system. The liquid level is controlled in a reasonable range to prevent caking and blockage of pipelines and equipment, the solid content in the organic silicon slurry residue is about 20-30%, and the liquid level can be controlled in the range to effectively prevent caking and blockage of the pipelines and the equipment, so that the stable operation of a system is facilitated.
According to the invention, in the slurry slag recovery device, the stirring speed of the slurry slag is controlled at 190-500 rpm. Solid matter in the slurry slag is easy to sink and agglomerate at the bottom at the too low rotating speed, and equipment is abraded at the too high rotating speed, so that the service life of the equipment is influenced.
The present invention further provides an apparatus for use in the aforementioned method, comprising: a slurry and slag recovery device, a heat exchange device for the first mixture, a solid-liquid separation device and connecting pipelines among the devices.
According to the invention, the distillation of high-boiling-point substances in the organic silicon slurry residue is carried out in the slurry residue recovery device, the top of the slurry residue recovery device is respectively provided with a slurry residue inlet, a high-boiling-point inert oil inlet and a high-boiling-point substance outlet, and the bottom of the slurry residue recovery device is connected with a heat exchange device for a first mixture through a pipeline. The slurry-residue recovery device is provided with a stirring structure, and the stirring structure is used for stirring the slurry residues and the high-boiling point inert oil added into the slurry-residue recovery device, so that the slurry residues and the high-boiling point inert oil are uniformly mixed, and solid substances in the slurry residues are prevented from sinking. In one embodiment of the invention, the slurry-residue recovery device is a jacketed slurry-residue flash tank, the outer wall of the slurry-residue recovery device is provided with a heat-conducting oil jacket, a heat-conducting oil inlet and a heat-conducting oil outlet, and the slurry-residue recovery device is heated by the heat-conducting oil to distill high-boiling residues.
According to the invention, the heat exchange device for the first mixture is used for reducing the temperature of the mixture of the high-boiling point inert oil and the high-boiling point slurry residue discharged from the bottom of the slurry residue recovery device.
According to the invention, the first mixture is connected with a solid-liquid separation device by a heat exchange device, and the solid-liquid separation device separates the cooled and cooled high-boiling-point removed slurry residue from the high-boiling-point inert oil mixture to obtain separated high-boiling-point inert oil and high-boiling-point removed slurry residue solids. In one embodiment of the invention, the solid-liquid separation device is a filter press.
The device further comprises a heat exchange device for high-boiling point inert oil, and the heat exchange device is arranged on a connecting pipeline of the solid-liquid separation device and the slurry residue recovery device. And the high-boiling point inert oil separated by the solid-liquid separation device is preheated by a heat exchange device through the high-boiling point inert oil and sent to a slurry residue recovery device for recycling.
The apparatus further comprises a high boiling point inert oil storage device on a connection line between the solid-liquid separation device and the heat exchange device for high boiling point inert oil. The separated high boiling point inert oil and the added high boiling point inert oil can both enter a high boiling point inert oil storage device for storage, the output high boiling point inert oil is preheated by a heat exchange device through the high boiling point inert oil, and then a slurry residue recovery device is added.
In one embodiment of the present invention, in order to improve the overall energy efficiency, the heat exchange device for the first mixture and the heat exchange device for the high-boiling point inert oil are the same heat exchange device, the mixture of the high-boiling point inert oil discharged from the slurry residue recovery device and the slurry residue after high removal is used as a heating medium, the high-boiling point inert oil to be fed into the slurry residue recovery device is used as a cooling medium, the high-boiling point inert oil is heated by using the waste heat of the mixture, and the temperature of the mixture is reduced by using the high-boiling point inert oil.
In one embodiment of the present invention, the apparatus further comprises a heat exchange means for the second mixture, the heat exchange means for the second mixture being located in the line connecting the heat exchange means for the first mixture and the solid-liquid separation means, and cooperating with the heat exchange means for the first mixture to gradually lower the temperature of the mixture. In one embodiment of the present invention, the cooling medium of the heat exchange device for the second mixture is cooling water.
The device further comprises a buffer device which is arranged on a connecting pipeline of the heat exchange device for the mixture and the solid-liquid separation device and is used for receiving the cooled high-boiling point inert oil and the slurry-residue mixture after being subjected to high-boiling point removal. The number thereof may be one or more. It may be located entirely after the heat exchange means and before the solid-liquid separation means. When the first and second mixture heat exchange means are present, they may be located between the first and second mixture heat exchange means and between the second mixture heat exchange means and the solid-liquid separation device, respectively, or may be located entirely between the first and second mixture heat exchange means, or may be located entirely between the second mixture heat exchange means and the solid-liquid separation device. In one embodiment of the present invention, the number of the buffer devices is 1, and the buffer devices are located after the heat exchange device and before the solid-liquid separation device. In another embodiment of the present invention, the number of the buffering means is 2, one is located between the heat exchanging means for the first and second mixtures, and one is located between the heat exchanging means for the second mixture and the solid-liquid separating means. In a further embodiment of the invention, the number of said buffer means is 2, all located between the heat exchange means for the first and second mixtures. In still another embodiment of the present invention, the number of the buffer means is 2, and all of the buffer means are located between the heat exchange means for the second mixture and the solid-liquid separation means.
The device further comprises a high-boiling-point substance condensing device which is positioned behind a high-boiling-point substance discharge port of the slurry residue recovery device and condenses the distilled high-boiling-point substance. In one embodiment of the present invention, the condensing means uses cooling water as a cooling medium.
The device further comprises a high-boiling-point substance recovery device which is positioned behind the high-boiling-point substance condensation device and used for collecting and storing the condensed high-boiling-point substance.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the heating uniformity is improved by adding high-boiling point inert oil, the separation of high-boiling point substances by an evaporation mode is facilitated, the recovery rate of substances with high economic value (such as methyl chlorosilane, vinyl chlorosilane, methyl chloroethyl silane and the like) is ensured, and the economic benefit is improved.
And secondly, because the substances with high economic value are effectively recovered, the amount of the slurry and the slag which are finally required to be treated is reduced, and further, the amount of sewage for harmless treatment of the slurry and the slag is reduced, so that the method is environment-friendly.
And thirdly, because high-boiling point inert oil such as silicone oil is used as an intermediate medium, the fluidity of the slurry slag is improved, the hazards of solid wall formation, pipeline blockage and the like in the residual slurry slag caused by excessive recovery of high-economic substances are avoided, and the aims of improving the recovery utilization rate of the high-economic substances and effectively avoiding the hazards of solid wall formation or pipeline blockage to distillation equipment or flash evaporation equipment are achieved.
Description of the drawings:
FIG. 1: the connection of the devices used in the embodiments of the present invention and the process flow are schematic. In the figure: 1. slurry-slag recovery device-jacketed slurry-slag flash tank; 2. a high-boiling-point substance condenser; 3. a high-boiling residue recovery tank; 4. a vacuum pump; 5. a heat exchanger for the first mixture; 6. a heat exchanger for the second mixture; 7. a buffer tank; 8. a circulation pump; 9. and (4) a filter press.
The specific implementation mode is as follows:
according to the equipment device and the flow schematic diagram shown in figure 1, the high-boiling-point substances in the organic silicon slurry slag are recovered.
Organosilicon thick liquid sediment passes through thick liquid sediment entry, and silicone oil passes through the silicone oil entry and adds to jacketed thick liquid sediment flash tank 1, and the stirring rake in the flash tank stirs thick liquid sediment and silicone oil and mixes, and the flash tank adopts the conduction oil to heat in order to distill the high boiling thing. The distilled high-boiling substance is discharged from an outlet at the top of the flash tank 1, is subjected to condensation treatment by a high-boiling substance condenser 2, and enters a high-boiling substance recovery tank 3. The recovered high-boiling residues can be mixed with a crude siloxane product and enter a rectification unit for purification step by step, and finally a qualified product is generated, so that the aims of effectively separating slurry and slag and recovering the product are fulfilled, and the production operation cost is reduced.
The slurry residue after the high-boiling-point substances are removed by steaming is a mixture formed by 'slurry residue after the high-boiling-point substances are removed' and silicon oil, the mixture is discharged out of the flash tank 1 from the bottom of the flash tank 1, the mixture is sent into a heat exchanger 5 for a first mixture through a pipeline, then enters a heat exchanger 6 for a second mixture, is cooled and then enters a buffer tank 7, and is sent into a filter press 9 under the action of a circulating pump 8. And the filter press 9 separates the pulp residue solid and the silicone oil after the height removal, the separated silicone oil is sent to the heat exchanger 5 for the first mixture, and the preheated silicone oil enters the flash tank for recycling from the top silicone oil inlet of the flash tank 1.
Both the high-boiling substance condenser 2 and the second mixture heat exchanger 6 use cooling water as a cooling medium. The first mixture uses the heat exchanger 5 to heat the silicone oil by using the residual heat of the mixture and reduce the temperature of the mixture by using the silicone oil, wherein the mixture of the silicone oil discharged from the flash tank 1 and the pulp residue after the flash tank is heightened is used as a heating medium, the silicone oil to be input into the flash tank 1 is used as a cooling medium.
The effect of the method for recovering high-boiling components from silicone sludge according to the present invention will be described in further detail with reference to the following specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples are either commercially available or may be prepared by known methods or derived from by-products of upstream processing routes.
Example (b): verification of effect of distillation recovery of high-boiling-point substances in slurry slag by adopting high-boiling-point inert oil
According to the volume ratio of the silicone oil to the pulp residue of 2:1, 500ml of inert silicone oil (Lanxingsanhuo organosilicon dimethyl silicone oil V100) is firstly added into a 2L four-neck flask, about 240ml of pulp residue (about 360g) is slowly added, a temperature-controlled electric heating jacket is adopted for heating, a vacuum pump is adopted for heating and vacuum negative pressure distillation at the stirring speed of 190rpm, a condensing tube is adopted at the tail part for recovering the fraction, and 190ml of fraction is collected in total.
The experimental conditions were as follows:
| condition | Test 1 | |
|
Test 4 | |
Test 6 |
| Heating temperature/. degree.C | 150 | 170 | 190 | 210 | 220 | 220 |
| Residence time/min | 20 | 20 | 60 | 60 | 60 | 30 |
| Absolutepressure/MPaA | 0.04 | 0.03 | 0.03 | 0.03 | 0.03 | 0.07 |
| Fraction collection speed (drops/sec) | 1.5 | 2 | 2 | 1 | 1.5 | 1 |
The mixture of the silicone oil and the pulp residue after the height removal is obtained after each test, wherein the effect of separating the silicone oil from the solid in the pulp residue after the height removal is shown as follows:
| 600 mesh | 400 mesh | 300 mesh | 300 mesh + filter aid | |
| Speed of filtration | Hardly filtered | 40ml/h | 50ml/h | 100ml/h |
Taking the fraction obtained in test 3 as an example, the analytical data of the fraction are as follows:
| name of physical distribution | Mass percent (%) |
| CH3SiCl3 | 0.004838 |
| C2H6SiCl2 | 0.008634 |
| C3H9SiCl | 0.003031 |
| C4H12Si | 0.043425 |
| CH2＝CHSiCl2CH3 | 0.024605 |
| CH3CH2-SiCl3 | 0.022784 |
| CH3CH2-SiCl2CH2CH3 | 0.051541 |
| C6H5SiCl3 | 0.037029 |
| (CH3)2ClSi-Si-Cl2CH3 | 0.178747 |
| CH3Cl2Si-Si-Cl2CH3 | 0.207195 |
| (CH3)2ClSi-Si-Cl(CH3)2 | 0.060566 |
| (CH3)2ClSi-CH2-Si-Cl(CH3)2 | 0.033622 |
| CH3Cl2Si-CH2-Si-Cl(CH3)2 | 0.083987 |
| (CH3)2ClSi-O-Si-Cl(CH3)2 | 0.073861 |
| (CH3)2ClSi-O-Si-Cl2CH3 | 0.035086 |
| Cl3Si-Si-Cl3 | 0.061003 |
| Others | 0.069812 |
| Silicone oil (V100) | 0 |
From the above experiment and results, it can be seen that the fraction does not contain silicone oil, and the silicone oil can be smoothly filtered and separated from the solids in the slurry residue after the height removal, and can be recycled through separation. Through detection of the separated silicone oil, the silicone oil is confirmed to be not cracked at the distillation temperature, and although the silicone oil contains a small amount of components in the slurry residue, the cyclic use of the silicone oil in the process method is not influenced.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recovering high-boiling-point substances in organic silicon slurry residues is characterized in that high-boiling-point inert oil is added into the organic silicon slurry residues and is distilled to recover the high-boiling-point substances, wherein the high-boiling-point inert oil is an oil product with a flash point higher than 210 ℃ under normal pressure, and preferably one or a mixture of more than two of dimethyl silicone oil with a flash point of 280 ℃ under normal pressure, alkylbenzene type heat conduction oil L-QC and alkylbenzene type heat conduction oil L-QD.
2. The method of claim 1, wherein in the distillation recovery of the high boiling substance, atmospheric distillation or low pressure distillation is used, and the temperature of the high boiling substance recovered by distillation is controlled to be between 150 ℃ and 250 ℃ according to the pressure used; preferably, the distillation is carried out under the negative pressure, the absolute pressure is 0.01MpaA to 0.08MpaA, and the distillation temperature is 150-220 ℃.
3. The method of claim 1 or 2, wherein the volume of high boiling inert oil is greater than the volume of sludge; preferably, after the high-boiling point inert oil and the slurry slag are added, the liquid level of the slurry slag recovery device is controlled to be 35-85% of the volume of the whole device.
4. The method according to any one of claims 1 to 3, wherein the slurry residue after the high boiling point substance is distilled off is slurry residue after the high boiling point substance is removed, and a mixture formed by the slurry residue and the high boiling point inert oil is subjected to solid-liquid separation treatment to obtain recovered high boiling point inert oil and slurry residue solid after the high boiling point inert oil is removed;
preferably, the recovered high-boiling point inert oil is recycled for distillation recovery of slurry residue high-boiling point substances;
preferably, before the solid-liquid separation treatment, the temperature of the mixture of the high-boiling point inert oil and the slurry residue after the high-boiling point inert oil is removed is reduced by a heat exchange device; preferably the temperature of the mixture is reduced to below 80 ℃; preferably, the temperature of the mixture is gradually reduced using a heat exchange means for the first mixture and a heat exchange means for the second mixture connected in series.
5. The method of claim 4, wherein the temperature of the high boiling point inert oil recovered for the distillation of the slurry residue high boiling point substance is heated by a heat exchange device; preferably, the heat exchange device for the first mixture for reducing the temperature of the mixture and the heat exchange device for heating the high-boiling inert oil are the same device, the high-boiling inert oil is heated by using the waste heat of the mixture, and the temperature of the mixture is reduced by using the high-boiling inert oil.
6. Apparatus for use in the method of any one of claims 1 to 5, characterised in that it comprises: a slurry-residue recovery device, a heat exchange device for the first mixture, a solid-liquid separation device and connecting pipelines among the devices;
distilling high-boiling-point substances in the organic silicon slurry residues in the slurry residue recovery device, wherein the top of the slurry residue recovery device is respectively provided with a slurry residue inlet, a high-boiling-point inert oil inlet and a high-boiling-point substance outlet, and the bottom of the slurry residue recovery device is connected with a first mixture heat exchange device through a pipeline; the heat exchange device for the first mixture is used for reducing the temperature of the mixture of the high-boiling point inert oil and the high-boiling point removed slurry slag discharged from the bottom of the slurry slag recovery device; the first mixture is connected with a solid-liquid separation device by a heat exchange device, and the solid-liquid separation device separates cooled high-boiling point inert oil from high-boiling point removed slurry slag;
preferably, the system further comprises a heat exchange device for the high-boiling-point inert oil, wherein the heat exchange device is arranged on a connecting pipeline between the solid-liquid separation device and the slurry residue recovery device, the high-boiling-point inert oil separated by the solid-liquid separation device is preheated by the heat exchange device for the high-boiling-point inert oil, and is sent to the slurry residue recovery device for recycling;
preferably, the heat exchange device for the first mixture and the heat exchange device for the high-boiling point inert oil are the same heat exchange device, the mixture of the high-boiling point inert oil discharged by the slurry-residue recovery device and the slurry residue after high removal is used as a heating medium, the high-boiling point inert oil to be input into the slurry-residue recovery device is used as a cooling medium, the high-boiling point inert oil is heated by using the waste heat of the mixture, and the temperature of the mixture is reduced by using the high-boiling point inert oil.
7. The apparatus as claimed in claim 6, further comprising a high boiling point inert oil storage device, wherein the high boiling point inert oil and/or the additional high boiling point inert oil separated from the solid-liquid separation device and the high boiling point inert oil storage device are connected with each other by the heat exchange device, and the high boiling point inert oil and/or the additional high boiling point inert oil are/is stored in the high boiling point inert oil storage device, and then is output, preheated by the heat exchange device for the high boiling point inert oil, and then added into the slurry residue recovery device.
8. The apparatus of claim 6 or 7, further comprising heat exchange means for the second mixture, said heat exchange means for the second mixture being located in the line connecting the heat exchange means for the first mixture and the solid-liquid separation means, and cooperating with the heat exchange means for the first mixture to gradually reduce the temperature of the mixture.
9. The apparatus according to any one of claims 6 to 8, further comprising a buffer means on a connecting line between the heat exchange means for the mixture and the solid-liquid separation means for receiving the cooled high boiling inert oil and the degritted slurry mixture;
preferably, the number of the buffer devices is 1, and the buffer devices are positioned after the heat exchange device and before the solid-liquid separation device;
preferably, the number of the buffer devices is 2, one is positioned between the heat exchange device for the first mixture and the heat exchange device for the second mixture, and the other is positioned between the heat exchange device for the second mixture and the solid-liquid separation device.
10. The apparatus according to any one of claims 6 to 9, wherein the sludge recovery apparatus has an agitation structure that agitates the sludge and the high boiling point inert oil added to the sludge recovery apparatus;
preferably, the slurry residue recovery device is a jacket type slurry residue flash tank, and the outer wall of the slurry residue recovery device is provided with a heat conduction oil jacket, a heat conduction oil inlet and a heat conduction oil outlet;
preferably, the solid-liquid separation device is a filter press.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307974A (en) * | 2021-06-21 | 2021-08-27 | 江西蓝星星火有机硅有限公司 | Method for rapidly recovering hydrogen-containing silicone oil in acid |
| CN114292288A (en) * | 2021-12-13 | 2022-04-08 | 华陆工程科技有限责任公司 | Method for treating synthetic reaction slurry in production of methyl silicate by directly synthesizing silicon powder |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3824335A1 (en) * | 1988-07-18 | 1989-09-21 | Gao Ges Automation Org | Ink jet printer and method of protecting the ink of an ink jet printer against drying up |
| CN101380597A (en) * | 2008-10-23 | 2009-03-11 | 广州有色金属研究院 | Method for removing landification dead catalyst oiliness material |
| CN103553051A (en) * | 2013-10-29 | 2014-02-05 | 泸州北方化学工业有限公司 | Method for separating solids from liquid of dregs in production process of organic silicon |
| CN105037414A (en) * | 2015-07-29 | 2015-11-11 | 湖北兴瑞化工有限公司 | Method and device for recovering efficient high-boiling substance from organic silicon residue slurry |
| CN106220666A (en) * | 2016-07-18 | 2016-12-14 | 聊城市鲁西化工工程设计有限责任公司 | The processing system of a kind of organic silicon slurry slag and processing method |
| CN109134527A (en) * | 2018-09-07 | 2019-01-04 | 江西蓝星星火有机硅有限公司 | A kind of scrubber system and its application in separation methyl chlorosilane monomer |
| CN210613092U (en) * | 2019-05-14 | 2020-05-26 | 黄山新力油墨科技有限公司 | A solvent recovery unit for single solvent printing ink of intaglio plastics |
-
2021
- 2021-01-04 CN CN202110004913.0A patent/CN112707930A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3824335A1 (en) * | 1988-07-18 | 1989-09-21 | Gao Ges Automation Org | Ink jet printer and method of protecting the ink of an ink jet printer against drying up |
| CN101380597A (en) * | 2008-10-23 | 2009-03-11 | 广州有色金属研究院 | Method for removing landification dead catalyst oiliness material |
| CN103553051A (en) * | 2013-10-29 | 2014-02-05 | 泸州北方化学工业有限公司 | Method for separating solids from liquid of dregs in production process of organic silicon |
| CN105037414A (en) * | 2015-07-29 | 2015-11-11 | 湖北兴瑞化工有限公司 | Method and device for recovering efficient high-boiling substance from organic silicon residue slurry |
| CN106220666A (en) * | 2016-07-18 | 2016-12-14 | 聊城市鲁西化工工程设计有限责任公司 | The processing system of a kind of organic silicon slurry slag and processing method |
| CN109134527A (en) * | 2018-09-07 | 2019-01-04 | 江西蓝星星火有机硅有限公司 | A kind of scrubber system and its application in separation methyl chlorosilane monomer |
| CN210613092U (en) * | 2019-05-14 | 2020-05-26 | 黄山新力油墨科技有限公司 | A solvent recovery unit for single solvent printing ink of intaglio plastics |
Non-Patent Citations (3)
| Title |
|---|
| 刘芳，等: "多晶硅生产过程中的硅渣浆处理", 《广东化工》 * |
| 天津海关: "《疑难商品归类解析》", 30 September 2014, 中国海关出版社 * |
| 马义虎: "多晶硅生产过程中硅渣浆的处理", 《环球市场》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307974A (en) * | 2021-06-21 | 2021-08-27 | 江西蓝星星火有机硅有限公司 | Method for rapidly recovering hydrogen-containing silicone oil in acid |
| CN114292288A (en) * | 2021-12-13 | 2022-04-08 | 华陆工程科技有限责任公司 | Method for treating synthetic reaction slurry in production of methyl silicate by directly synthesizing silicon powder |
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