CN114524408A - Environment-friendly comprehensive recycling method of organic silicon pulp residues - Google Patents
Environment-friendly comprehensive recycling method of organic silicon pulp residues Download PDFInfo
- Publication number
- CN114524408A CN114524408A CN202210134730.5A CN202210134730A CN114524408A CN 114524408 A CN114524408 A CN 114524408A CN 202210134730 A CN202210134730 A CN 202210134730A CN 114524408 A CN114524408 A CN 114524408A
- Authority
- CN
- China
- Prior art keywords
- residue
- extraction
- slag
- reaction kettle
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000010703 silicon Substances 0.000 title claims abstract description 87
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 95
- 238000000605 extraction Methods 0.000 claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001257 hydrogen Substances 0.000 claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 56
- 239000002002 slurry Substances 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 238000004062 sedimentation Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 11
- 238000004537 pulping Methods 0.000 claims abstract description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001385 heavy metal Chemical group 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 124
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000005046 Chlorosilane Substances 0.000 claims description 21
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 21
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 16
- 239000002910 solid waste Substances 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 239000008247 solid mixture Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims 2
- 239000002699 waste material Substances 0.000 abstract description 22
- 238000011282 treatment Methods 0.000 abstract description 18
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 13
- 239000000446 fuel Substances 0.000 abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 16
- 239000010802 sludge Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 6
- -1 chlorine radicals Chemical group 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Combustion & Propulsion (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a green comprehensive recycling method of organic silicon slurry residues. The current direct method is the only industrial production method of methyl chlorosilane monomers, and the production process produces about 2 to 5 percent of waste residue slurry as a byproduct. The invention carries out the innocent treatment of the exhibition waste slag slurry by a series of comprehensive separation and treatment methods. The invention is based on a hydrolysis method, combines high-efficiency pretreatment methods such as sedimentation, reduced pressure distillation, ball milling, pulping and the like, and then carries out a series of regeneration comprehensive utilization treatments such as hydrogen extraction, filtration, slag washing, copper extraction and the like, thereby achieving the high-efficiency harmless treatment of the organic silicon waste residue. The residue after the treatment by the method is washed and neutralized by calcium oxide, the residual amount is only about 10 percent of the weight of the slurry residue, no chlorine radical and heavy metal residue exist, the carbon content is 30 to 50 percent, and the residue can be used for building and thermal power fuel and can be reused. And simultaneously, recycled products of water glass and copper sulfate are obtained through comprehensive treatment, so that the waste of raw materials and the pressure of waste treatment are reduced, and the method has obvious environment-friendly significance and economic significance.
Description
Technical Field
The invention relates to the technical field of organic silicon waste residue treatment, in particular to a green comprehensive recycling method of organic silicon slurry residue.
Background
The organic silicon material is a novel material which cannot be replaced by modern high-technology industry, and more than 90% of products are derived from methyl chlorosilane monomers. The current direct method is the only industrial production method of methyl chlorosilane monomers, and the production process produces about 2 to 5 percent of waste residue slurry as a byproduct.
In recent years, the organic silicon production capacity is continuously expanded, the waste residue slurry seriously restricts the healthy development of the industry, and the resource treatment is urgent. The methyl chlorosilane monomer is generated by the catalytic reaction of silicon powder and chloromethane in a fluidized bed, most of the silicon powder in the reaction mixture is removed by a cyclone separator, the reaction mixture enters a washing tower for dust removal, and waste residue slurry is discharged from the bottom of the washing tower. The waste residue slurry contains organic chlorosilane with high boiling point, silicon powder, copper powder and other substances. The content of the waste residue slurry is 20-70%, the waste residue slurry is mainly organic chlorosilane with a large boiling point, the organic chlorosilane is easy to hydrolyze, and a large amount of acid mist is generated after the organic chlorosilane is exposed to air, so that the environment is polluted. The waste slag slurry has poor fluidity, has abrasion and corrosion resistance, is easy to block pipelines and equipment, and has small solid particle size, large specific surface area, high activity, easy spontaneous combustion and large utilization difficulty.
In the production process of organic silicon, a certain amount of organic silicon waste is generated, and because the components are complex and easy to hydrolyze, the cost for extracting useful components from waste liquid by adopting methods such as direct simple rectification and the like is higher. Some researchers use simple hydrolysis treatment, but a large amount of HCl is generated in the hydrolysis process, and the hydrolysis condition is difficult to control. The solid substances generated by hydrolysis are not fully utilized, so the treatment and resource utilization of the organic silicon waste are the problems to be solved in the organic silicon industry.
Disclosure of Invention
The invention aims to provide a green comprehensive recycling method of organic silicon slurry residues. A technical method for green comprehensive utilization of waste residue slurry generated in the organic silicon synthesis process realizes efficient treatment of waste and recycling of byproducts.
The technical scheme adopted by the invention for solving the technical problems is as follows:
step 1, pretreating pulp slag:
extracting the upper layer of high-boiling-point chlorosilane by simple sedimentation separation; or vacuum distilling to 150-180 deg.c to obtain high boiling point chlorosilane; the residue black slag is hydrolyzed and can enter the crushing process.
The content of high-boiling-point substances in the black slag obtained by the sedimentation separation is controlled to be 10-25%, and the content of high-boiling-point substances in the black slag obtained by the vacuum distillation is controlled to be 5-7%.
And 2, crushing the pretreated black slag.
Among the widely available mechanical crushing methods, ball milling is the most preferred choice for crushing the hydrolysis sludge. During the ball milling process, a certain amount of water is added into the black slag, and the water addition amount is 50-300% of the dry weight of the black slag. And performing ball milling to obtain mixed crushed slurry slag. The size of the crushed black slag is 200 meshes to 1 mesh, and preferably 20 meshes to 40 meshes.
And 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and pumping to the reaction kettle. The mass ratio of the crushed pulp to the water is 1: 0.5-1: 100, preferably 1: 1-1: 5.
And 4, pumping the pulped pulp residue to a reaction kettle for reaction. Nitrogen was used to replace the oxygen content in the autoclave before feeding to below 1%. The mass ratio of the slurry residue to the caustic soda in the reaction kettle is 1: 0.1-1: 10, preferably 1: 0.8-1: 2. The reaction temperature is 5-120 deg.C, preferably 40-60 deg.C.
And 5, after the slurry slag and the caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen. The hydrogen is led out from the upper part of the reaction kettle, dehydrated, pressurized, catalytically combusted and deoxidized, and then pressed into a hydrogen storage tank.
During the reaction of extracting hydrogen and silicon, the generated hydrogen is partially used for reducing the metallic silicon.
And 6, after the hydrogen extraction and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle, wherein the filtrate is water glass. The solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is about 10-30%.
And 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two. And heating the reaction kettle to perform oxidation copper extraction. The reaction temperature for extracting copper is 20-120 ℃, and the optimal reaction temperature is 60-90 ℃. When the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
And 8, washing and neutralizing residues after copper extraction reaction by calcium oxide, wherein the residual solid waste is only 10-12% of the weight of the original slurry residue, and the residues have no chlorine radical and heavy metal residue and 30-50% of carbon content, and can be used for building and thermal power fuels and reused.
The invention has the following beneficial effects:
the invention is based on a hydrolysis method, combines high-efficiency pretreatment methods such as sedimentation, reduced pressure distillation, ball milling, pulping and the like, and then carries out a series of regeneration comprehensive utilization treatments such as hydrogen extraction, filtration, slag washing, copper extraction and the like, thereby achieving the high-efficiency harmless treatment of the organic silicon waste residue. The residue after the treatment by the method is washed and neutralized by calcium oxide, the residual amount is only 7-12% of the weight of the pulp residue, no chlorine radical and heavy metal residue exist, the carbon content is 30-50%, and the residue can be used for building and thermal power fuel for reutilization. And simultaneously, recycled products of water glass and copper sulfate are obtained through comprehensive treatment, so that the waste of raw materials and the pressure of waste treatment are reduced, and the method has obvious environment-friendly significance and economic significance.
Detailed Description
The present invention will be further described with reference to the following examples.
The invention provides a green comprehensive recycling method of organic silicon slurry residues. The high-efficiency treatment of wastes and the recycling of byproducts are realized by the procedures of pretreating, crushing, pulping, extracting hydrogen to produce water glass, filtering, washing slag, extracting copper and the like on pulp slag.
Example 1
Step 1, pretreating pulp slag:
extracting the upper layer of high-boiling-point chlorosilane by simple sedimentation separation; or distilling under reduced pressure at 150 deg.C to obtain high-boiling-point chlorosilane; the residue black slag is hydrolyzed and can enter the crushing process.
The content of high-boiling-point substances in the black slag obtained by the sedimentation separation is controlled to be 10 percent, and the content of the high-boiling-point substances in the black slag obtained by the vacuum distillation is controlled to be 5 percent.
And 2, crushing the pretreated black slag.
Among the widely available mechanical crushing methods, ball milling is the most preferred choice for crushing the hydrolysis sludge. During the ball milling process, a certain amount of water is added into the black slag, and the water addition amount is 50% of the dry weight of the black slag. And performing ball milling to obtain mixed crushed slurry slag. The size of the crushed black slag is 20 meshes.
And 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and pumping to the reaction kettle. The mass ratio of the crushed pulp residue to the water is 1:1.
And 4, pumping the pulped pulp residue to a reaction kettle for reaction. Nitrogen was used to replace the feed to make the oxygen content in the reactor less than 1%. The mass ratio of the slurry residue to the caustic soda in the reaction kettle is 1:0.8, and the reaction temperature is 40 ℃.
And 5, after the slurry slag and the caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen. The hydrogen is led out from the upper part of the reaction kettle, dehydrated, pressurized, catalytically combusted and deoxidized, and then pressed into a hydrogen storage tank.
During the reaction of extracting hydrogen and silicon, the generated hydrogen is partially used for reducing the metallic silicon.
And 6, after the hydrogen extraction and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle, wherein the filtrate is water glass. The solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is about 10%.
And 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two. And heating the reaction kettle to perform oxidation copper extraction. The reaction temperature for extracting copper is 60 ℃. When the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
And 8, washing and neutralizing residues after copper extraction reaction by calcium oxide, wherein the residual solid waste is only 10% of the weight of the original slurry residue, and the residues have no chlorine radicals and heavy metal residues, have a carbon content of 30%, and can be used for building and thermal power fuels and be reused.
Example 2
Step 1, pretreating pulp slag:
extracting the upper layer of high-boiling-point chlorosilane by simple sedimentation separation; or vacuum distilling high boiling point chlorosilane at 160 deg.c; the residue black slag is hydrolyzed and can enter the crushing process.
The content of high-boiling-point substances in the black slag obtained by the sedimentation separation is controlled to be 20 percent, and the content of the high-boiling-point substances in the black slag obtained by the vacuum distillation is controlled to be 6 percent.
And 2, crushing the pretreated black slag.
Among the widely available mechanical crushing methods, ball milling is the most preferred choice for crushing the hydrolysis sludge. During the ball milling process, a certain amount of water is added into the black slag, and the water addition amount is 100 percent of the dry weight of the black slag. And performing ball milling to obtain mixed crushed slurry slag. The size of the crushed black slag is 25 meshes.
And 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and pumping to the reaction kettle. The mass ratio of the crushed pulp residue to the water is 1: 1.2.
And 4, pumping the pulped pulp residue to a reaction kettle for reaction. Nitrogen was used to replace the feed to make the oxygen content in the reactor less than 1%. The mass ratio of the slurry residue to the caustic soda in the reaction kettle is 1:1, and the reaction temperature is 45 ℃.
And 5, after the slurry slag and the caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen. The hydrogen is led out from the upper part of the reaction kettle, dehydrated, pressurized, catalytically combusted and deoxidized, and then pressed into a hydrogen storage tank.
During the reaction of extracting hydrogen and silicon, the generated hydrogen is partially used for reducing the metallic silicon.
And 6, after the hydrogen extraction and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle, wherein the filtrate is water glass. The solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is about 15%.
And 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two. And heating the reaction kettle to perform oxidation copper extraction. The reaction temperature for extracting copper is 65 ℃. When the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
And 8, washing and neutralizing residues after copper extraction reaction by calcium oxide, wherein the residual solid waste is only 11% of the weight of the original slurry residue, and the residual solid waste has no chlorine radical and heavy metal residue and has a carbon content of 35%, and can be used for building and thermal power fuels and reused.
Example 3
Step 1, pretreating pulp slag:
extracting the upper layer of high-boiling-point chlorosilane by simple sedimentation separation; or vacuum distilling high boiling point chlorosilane at 160 deg.c; the residue black slag is hydrolyzed and can enter the crushing process.
The content of high-boiling-point substances in the black slag obtained by the sedimentation separation is controlled to be 20 percent, and the content of the high-boiling-point substances in the black slag obtained by the vacuum distillation is controlled to be 6.5 percent.
And 2, crushing the pretreated black slag.
Among the widely available mechanical crushing methods, ball milling is the most preferred choice for crushing the hydrolysis sludge. During the ball milling process, a certain amount of water is added into the black slag, and the water addition amount is 150% of the dry weight of the black slag. And performing ball milling to obtain mixed crushed slurry slag. The size of the crushed black slag is 30 meshes.
And 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and pumping to the reaction kettle. The mass ratio of the crushed pulp residue to the water is 1: 1.3.
And 4, pumping the pulped pulp residue to a reaction kettle for reaction. Nitrogen was used to replace the feed to make the oxygen content in the reactor less than 1%. The mass ratio of the slurry residue to the caustic soda in the reaction kettle is 1:2, and the reaction temperature is 50 ℃.
And 5, after the slurry slag and the caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen. The hydrogen is led out from the upper part of the reaction kettle, dehydrated, pressurized, catalytically combusted and deoxidized, and then pressed into a hydrogen storage tank.
During the reaction of extracting hydrogen and silicon, the generated hydrogen is partially used for reducing the metallic silicon.
And 6, after the hydrogen extraction and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle, wherein the filtrate is water glass. The solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is about 25%.
And 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two. And heating the reaction kettle to perform oxidation copper extraction. The reaction temperature for extracting copper is 75 ℃. When the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
And 8, washing and neutralizing residues after copper extraction reaction by using calcium oxide, wherein the residual solid waste is only 11 percent of the weight of the original slurry residue, and the residual solid waste has no chlorine radicals and heavy metal residues, has a carbon content of 45 percent, can be used for building and thermal power fuels, and can be reused.
Example 4
Step 1, pretreating pulp slag:
extracting the upper layer of high-boiling-point chlorosilane by simple sedimentation separation; or vacuum distilling high boiling point chlorosilane at 170 deg.c to obtain chlorosilane product; the residue black slag is hydrolyzed and can enter the crushing process.
The content of high-boiling-point substances in the black slag obtained by the sedimentation separation is controlled to be 20 percent, and the content of the high-boiling-point substances in the black slag obtained by the reduced pressure distillation is controlled to be 7 percent.
And 2, crushing the pretreated black slag.
Among the widely available mechanical crushing methods, ball milling is the most preferred choice for crushing the hydrolysis sludge. During the ball milling process, a certain amount of water is added into the black slag, and the water addition amount is 200% of the dry weight of the black slag. And performing ball milling to obtain mixed crushed slurry slag. The size of the crushed black slag is 35 meshes.
And 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and pumping to the reaction kettle. The mass ratio of the crushed pulp residue to the water is 1: 1.25.
And 4, pumping the pulped pulp residue to a reaction kettle for reaction. Nitrogen was used to replace the feed to make the oxygen content in the reactor less than 1%. The mass ratio of the slurry residue to the caustic soda in the reaction kettle is 1:1, and the reaction temperature is 55 ℃.
And 5, after the slurry slag and the caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen. The hydrogen is led out from the upper part of the reaction kettle, dehydrated, pressurized, catalytically combusted and deoxidized, and then pressed into a hydrogen storage tank.
During the reaction of extracting hydrogen and silicon, the generated hydrogen is partially used for reducing the metallic silicon.
And 6, after the hydrogen and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle, wherein the filtrate is water glass. The solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is about 25%.
And 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two. And heating the reaction kettle to perform oxidation copper extraction. The reaction temperature for extracting copper is 80 ℃. When the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
And 8, washing and neutralizing residues after copper extraction reaction by calcium oxide, wherein the residual solid waste is only 10% of the weight of the original slurry residue, and the residual solid waste has no chlorine radical and heavy metal residue and has a carbon content of 45%, so that the residual solid waste can be used for building and thermal power fuels and can be reused.
Example 5
Step 1, pretreating pulp slag:
extracting the upper layer of high-boiling-point chlorosilane by simple sedimentation separation; or vacuum distilling at 177 deg.C to obtain high-boiling chlorosilane; the residue black slag is hydrolyzed and can enter the crushing process.
The content of high-boiling-point substances in the black slag obtained by the sedimentation separation is controlled to be 23 percent, and the content of the high-boiling-point substances in the black slag obtained by the vacuum distillation is controlled to be 7 percent.
And 2, crushing the pretreated black slag.
Among the widely available mechanical crushing methods, ball milling is the most preferred choice for crushing the hydrolysis sludge. During the ball milling process, a certain amount of water is added into the black slag, and the water addition amount is 250% of the dry weight of the black slag. And performing ball milling to obtain mixed crushed slurry slag. The size of the crushed black slag is 40 meshes.
And 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and pumping to the reaction kettle. The mass ratio of the crushed pulp residue to the water is 1: 1.35.
And 4, pumping the pulped pulp residue to a reaction kettle for reaction. Nitrogen was used to replace the feed to make the oxygen content in the reactor less than 1%. The mass ratio of the slurry residue to the caustic soda in the reaction kettle is 1:1.2, and the reaction temperature is 52 ℃.
And 5, after the slurry slag and the caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen. The hydrogen is led out from the upper part of the reaction kettle, dehydrated, pressurized, catalytically combusted and deoxidized, and then pressed into a hydrogen storage tank.
During the reaction of extracting hydrogen and silicon, the generated hydrogen is partially used for reducing the metallic silicon.
And 6, after the hydrogen extraction and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle, wherein the filtrate is water glass. The solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is about 28%.
And 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two. And heating the reaction kettle to perform oxidation copper extraction. The reaction temperature for extracting copper is 80 ℃. When the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
And 8, washing and neutralizing residues after copper extraction reaction by calcium oxide, wherein the residual solid waste is only 10% of the weight of the original slurry residue, and the residues have no chlorine radicals and heavy metal residues, have 48% of carbon content, can be used for building and thermal power fuels, and can be reused.
Example 6
Step 1, pretreating pulp slag:
extracting the upper layer of high-boiling-point chlorosilane by simple sedimentation separation; or distilling under reduced pressure at 180 deg.C to obtain high-boiling chlorosilane; the residue black slag is hydrolyzed and can enter the crushing process.
The content of high-boiling-point substances in the black slag obtained by the sedimentation separation is controlled to be 25 percent, and the content of the high-boiling-point substances in the black slag obtained by the vacuum distillation is controlled to be 7 percent.
And 2, crushing the pretreated black slag.
Among the widely available mechanical crushing methods, ball milling is the most preferred choice for crushing the hydrolysis sludge. During the ball milling process, a certain amount of water is added into the black slag, and the water addition amount is 300 percent of the dry weight of the black slag. And performing ball milling to obtain mixed crushed slurry slag. The size of the crushed black slag is 40 meshes.
And 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and pumping to the reaction kettle. The mass ratio of the crushed pulp residue to the water is 1: 1.5.
And 4, pumping the pulped pulp residue to a reaction kettle for reaction. Nitrogen was used to replace the feed to make the oxygen content in the reactor less than 1%. The mass ratio of the slurry slag to the caustic soda in the reaction kettle is 1:1.2, and the reaction temperature is 60 ℃.
And 5, after the slurry slag and the caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen. The hydrogen is led out from the upper part of the reaction kettle, dehydrated, pressurized, catalytically combusted and deoxidized, and then pressed into a hydrogen storage tank.
During the reaction of extracting hydrogen and silicon, the generated hydrogen is partially used for reducing the metallic silicon.
And 6, after the hydrogen extraction and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle, wherein the filtrate is water glass. The solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is about 30%.
And 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two. And heating the reaction kettle to perform oxidation copper extraction. The reaction temperature for extracting copper is 90 ℃. When the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
And 8, washing and neutralizing residues after copper extraction reaction by calcium oxide, wherein the residual solid waste is only 10% of the weight of the original slurry residue, and the residues have no chlorine radicals and heavy metal residues, have a carbon content of 50%, and can be used for building and thermal power fuels and be reused.
Having described in detail and by way of example in the examples section herein specific embodiments of the invention,
various modifications and alternatives may be devised. It should be understood, however, that there is no intention to limit the invention to the specific forms disclosed. Rather, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the following appended claims.
Claims (9)
1. A green comprehensive recycling method of organic silicon slurry residues is characterized by comprising the following steps:
step 1, pretreating pulp slag:
step 2, crushing the pretreated black slag;
step 3, pulping the crushed pulp slag and water by using mechanical stirring equipment, and then pumping to a reaction kettle;
step 4, pumping the pulped pulp residue to a reaction kettle for reaction;
step 5, after the slurry slag and caustic soda are subjected to hydrogen extraction and silicon extraction in the reaction kettle, generating metal silicon and hydrogen;
step 6, after the hydrogen extraction and silicon extraction reaction is finished, filtering the residual liquid-solid mixture in the reaction kettle;
step 7, adding the filtered silicon extraction residue into a reaction kettle filled with dilute sulfuric acid, and introducing oxygen or air or a mixture of the two; heating the reaction kettle to perform oxidation copper extraction;
and 8, washing and neutralizing residues obtained after the copper extraction reaction by using calcium oxide, and collecting residual solid waste.
2. The method for comprehensively recycling the organic silicon pulp residue in a green manner according to claim 1, characterized in that the pulp residue is pretreated in the step 1 by adopting sedimentation separation, and chlorosilane with high boiling point at the upper layer is extracted; hydrolyzing the residue black slag, and performing a crushing process; the content of high-boiling residues in the black residues obtained by settling separation is controlled to be 10-25%.
3. The method for comprehensively recycling the organic silicon pulp residue in the green environment according to claim 1, characterized in that the pulp residue is pretreated by reduced pressure distillation, and high-boiling chlorosilane is distilled out under reduced pressure at 150-180 ℃; hydrolyzing the residual black slag, and performing a crushing process; the content of high-boiling residues in the black residues obtained by reduced pressure distillation is controlled to be 5-7 percent.
4. The method for comprehensively recycling the organic silicon pulp residue in the green color according to the claim 1, the claim 2 or the claim 3, wherein the step 2 comprises the steps of crushing the pretreated black residue, and selecting a ball milling method for crushing the hydrolyzed pulp residue; in the ball milling process, adding a certain amount of water into the black slag, wherein the water addition amount is 50-300% of the dry weight of the black slag; and performing ball milling to obtain mixed crushed slurry slag, wherein the size of the crushed black slag is 20-40 meshes.
5. The green comprehensive recycling method of the organic silicon pulp residue according to claim 1, 2 or 3, characterized in that the mass ratio of the crushed pulp residue in the step 3 to the water is 1:1 to 1: 5.
6. The method for comprehensively recycling the organic silicon pulp residue in green according to the claim 1, the claim 2 or the claim 3, characterized in that the pulped pulp residue in the step 4 is pumped to a reaction kettle for reaction; replacing the feed with nitrogen until the oxygen content in the reaction kettle is lower than 1%; the mass ratio of the slurry slag to the caustic soda in the reaction kettle is 1: 0.8-1: 2; the reaction temperature is 40-60 ℃.
7. The green comprehensive recycling method of the organic silicon slurry residue according to claim 1, 2 or 3, characterized in that after the slurry residue and caustic soda are subjected to hydrogen extraction and silicon extraction in a reaction kettle, the residual liquid-solid mixture in the reaction kettle is filtered, and the filtrate is water glass; the solid phase is silicon extraction residue, and the copper content of the silicon extraction residue is 10-30%.
8. The green comprehensive recycling method of the organic silicon slurry residue according to claim 1, 2 or 3, characterized in that the reaction temperature of copper extraction in the step 7 is 60-90 ℃; when the copper extraction reaction is finished, the residue is filtered, and the filtrate is copper sulfate.
9. The method for comprehensively recycling the organic silicon pulp residue in the green environment according to the claim 1, the claim 2 or the claim 3, which is characterized in that the residual solid waste in the step 8 is only 7 to 12 percent of the weight of the original pulp residue, no chlorine radicals and heavy metal residues exist, and the carbon content is 30 to 50 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210134730.5A CN114524408A (en) | 2022-02-14 | 2022-02-14 | Environment-friendly comprehensive recycling method of organic silicon pulp residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210134730.5A CN114524408A (en) | 2022-02-14 | 2022-02-14 | Environment-friendly comprehensive recycling method of organic silicon pulp residues |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114524408A true CN114524408A (en) | 2022-05-24 |
Family
ID=81623727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210134730.5A Pending CN114524408A (en) | 2022-02-14 | 2022-02-14 | Environment-friendly comprehensive recycling method of organic silicon pulp residues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114524408A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4205980A1 (en) * | 1992-02-27 | 1993-09-02 | Nuenchritz Chemie Gmbh | Processing of chloro-silane synthesis residues - by non-oxidative treatment with sulphuric acid |
| WO1995026926A1 (en) * | 1994-03-30 | 1995-10-12 | Elkem A/S | Method for upgrading of silicon-containing residues obtained after leaching of copper-containing residues from chlorosilane synthesis |
| 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 |
| CN104909400A (en) * | 2014-03-13 | 2015-09-16 | 四川瑞能硅材料有限公司 | Treatment system and treatment method of chlorosilane slurry raffinate |
| CN105858602A (en) * | 2016-04-08 | 2016-08-17 | 北京科技大学 | Polycrystalline silicon cutting waste material treatment method |
| CN107628623A (en) * | 2017-09-29 | 2018-01-26 | 四川绿源聚能环保科技有限责任公司 | A kind of method for handling chlorosilane slurry raffinate |
| CN108821300A (en) * | 2018-08-06 | 2018-11-16 | 东北大学 | One kind preparing CaSiO by discarded silicon slag3Method |
| CN113582183A (en) * | 2021-08-26 | 2021-11-02 | 枣阳市一鸣化工有限公司 | Treatment method and treatment system for organic silicon waste residue slurry |
-
2022
- 2022-02-14 CN CN202210134730.5A patent/CN114524408A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4205980A1 (en) * | 1992-02-27 | 1993-09-02 | Nuenchritz Chemie Gmbh | Processing of chloro-silane synthesis residues - by non-oxidative treatment with sulphuric acid |
| WO1995026926A1 (en) * | 1994-03-30 | 1995-10-12 | Elkem A/S | Method for upgrading of silicon-containing residues obtained after leaching of copper-containing residues from chlorosilane synthesis |
| 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 |
| CN104909400A (en) * | 2014-03-13 | 2015-09-16 | 四川瑞能硅材料有限公司 | Treatment system and treatment method of chlorosilane slurry raffinate |
| CN105858602A (en) * | 2016-04-08 | 2016-08-17 | 北京科技大学 | Polycrystalline silicon cutting waste material treatment method |
| CN107628623A (en) * | 2017-09-29 | 2018-01-26 | 四川绿源聚能环保科技有限责任公司 | A kind of method for handling chlorosilane slurry raffinate |
| CN108821300A (en) * | 2018-08-06 | 2018-11-16 | 东北大学 | One kind preparing CaSiO by discarded silicon slag3Method |
| CN113582183A (en) * | 2021-08-26 | 2021-11-02 | 枣阳市一鸣化工有限公司 | Treatment method and treatment system for organic silicon waste residue slurry |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585860A (en) | Method performing microwave pyrolysis on garbage | |
| CN112250559B (en) | Recycling process of chloro pivaloyl chloride raffinate | |
| CN114524408A (en) | Environment-friendly comprehensive recycling method of organic silicon pulp residues | |
| CN106077037A (en) | A kind of method of ultrasonic assistant flotation pressurized acid leaching synthetical recovery aluminum electrolysis waste cathode carbon block | |
| CN101486490B (en) | Preparation of refined zirconium tetrachloride | |
| CN214830137U (en) | Low-quality transformer oil recycling system | |
| CN113860315B (en) | Method for purifying waste obtained by extracting copper from organic silicon waste residue slurry | |
| CN1260326C (en) | Pressurized gasifying process of polynary slurry | |
| CN113956219A (en) | Process flow for producing furfural from papermaking wastewater | |
| CN113755250A (en) | Treatment process of biodiesel byproduct crude glycerol containing solid base catalyst | |
| CN113201365A (en) | Low-quality transformer oil recycling system and recycling method thereof | |
| CN114057584A (en) | Method for reducing tar in aniline system | |
| KR20210089005A (en) | Manufacturing method of microorganism energy source from wasted glycerin's recycling process | |
| CN111018665A (en) | Method for recycling trichloropropane in epichlorohydrin heavy component | |
| CN113087735A (en) | Method for recycling chlorosilane slag slurry and production system thereof | |
| CN211035832U (en) | Suspension bed hydrogenation residue processing system | |
| CN112574806B (en) | Method for treating waste lubricating oil by refining enterprise | |
| CN212560050U (en) | Device for producing glycol diacrylate by using low-concentration ethylene glycol | |
| CN113996280B (en) | Solid base catalyst for hydrolyzing TDI tar residues and application thereof | |
| CN112707559B (en) | Treatment method of titanium-containing distillation raffinate | |
| CN117801881B (en) | Pretreatment method for waste grease | |
| CN111204745B (en) | Process and system for producing calcium chloride dihydrate and graphene by using chlor-alkali hydrochloric acid | |
| CN101798522B (en) | Deacidification method of acid sludge oil | |
| CN102351896A (en) | Method for producing dibutyl phosphate by comprehensively using three wastes in production process | |
| CN110963965B (en) | Recycling method of waste residue in antioxidant AW production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |