CN106623370B - Organic silicon slurry slag treatment process and system - Google Patents
Organic silicon slurry slag treatment process and system Download PDFInfo
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- CN106623370B CN106623370B CN201710038176.XA CN201710038176A CN106623370B CN 106623370 B CN106623370 B CN 106623370B CN 201710038176 A CN201710038176 A CN 201710038176A CN 106623370 B CN106623370 B CN 106623370B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 66
- 239000010703 silicon Substances 0.000 title claims abstract description 66
- 239000002002 slurry Substances 0.000 title claims abstract description 54
- 239000002893 slag Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 claims abstract description 71
- 239000010949 copper Substances 0.000 claims abstract description 71
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 56
- 230000007062 hydrolysis Effects 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 28
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 238000011001 backwashing Methods 0.000 claims abstract description 25
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 12
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229960002089 ferrous chloride Drugs 0.000 claims description 24
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 24
- 239000002918 waste heat Substances 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 238000011084 recovery Methods 0.000 claims description 21
- 238000003825 pressing Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000003595 mist Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 24
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 238000009835 boiling Methods 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JTBAMRDUGCDKMS-UHFFFAOYSA-N dichloro-[dichloro(methyl)silyl]-methylsilane Chemical compound C[Si](Cl)(Cl)[Si](C)(Cl)Cl JTBAMRDUGCDKMS-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine group Chemical group C(CCC)N(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to an organic silicon slurry residue treatment process, which comprises the following steps: disilane hydrolysis, copper chloride leaching, squeezing backwashing, copper replacement, silicon slag roasting and tail gas treatment, the invention effectively utilizes the hydrogen chloride gas generated by hydrolysis, so that the hydrogen chloride gas has zero discharge, a stirring reaction kettle is adopted for stirring and leaching, the leaching rate of copper is up to 99%, the copper content of sponge copper is more than 70%, the ferric chloride content is controlled to be more than 30%, the economic value is improved, hydrolysis slag is roasted through a rotary kiln, the silicon oxide content is more than 98%, the whole process route has no waste water and waste residue discharge, the waste gas is only carbon dioxide, the harm to the environment is reduced to the minimum, the products are metallic copper and silicon powder, and the economic value is high; the whole process has zero discharge of waste water and waste residue, obvious environmental benefit, low requirements on the material and strength of equipment because hydrolysis and leaching are carried out under normal pressure at the temperature of lower than 90 ℃, the roasting temperature of the rotary kiln is 500-850 ℃, and the requirement on the material of the rotary kiln is not high because silicon powder does not contain corrosive hydrogen chloride.
Description
Technical Field
The invention relates to a process and equipment for treating organic silicon pulp slag, belonging to the technical field of organic silicon pulp slag treatment.
Background
In the production process of methyl chlorosilane, the synthesized methyl chlorosilane mixture is subjected to wet dust removal by using a high-boiling byproduct of the methyl chlorosilane, and a dark brown slurry liquid-solid mixture is produced. The mixture contains high boiling point substance as main component, mainly 1, 2-dimethyl tetrachloro disilane, etc. and contains small amount of copper, and the total copper content is 1.5-5%. This mixture is referred to as organosilicon sludge for short.
The organosilicon slurry residue contains a large amount of high boiling point by-products of methyl chlorosilane, and generates hydrogen chloride gas when meeting water to form acid mist, thereby polluting the environment. Meanwhile, the organic silicon pulp residue contains copper and has certain economic value.
Chinese patent document CN 2010106071036 discloses an organic silicon slurry residue treatment process, wherein the organic silicon slurry residue is treated by lime water, hydrogen chloride gas generated by hydrolysis of the organic silicon slurry residue is neutralized by lime water, and environmental pollution is effectively reduced. And selling the hydrolyzed slag. The method can solve the problem of pollution caused by hydrogen chloride gas released by hydrolysis of the organic silicon slurry residues in water, but has the main defects that the hydrolysis residues are mixed with a large amount of lime, the direct sale economic benefit is low, more working procedures are added for recovering silicon and copper in the hydrolysis residues in the next step, and more cost is consumed.
CN2011201691564 discloses a special incineration device for slurry residue generated in an organic silicon production process, which adopts an incineration method to treat organic silicon slurry residue, can effectively recover hydrogen chloride gas, but silicon and copper in a product are mixed together, and are not effectively separated. Meanwhile, high-temperature hydrogen chloride gas generated in the incineration process has great corrosion to equipment, the incineration equipment and a pipeline system are required to have high corrosion resistance, the equipment loss and investment are great, silicon and copper are not effectively separated, the equipment investment is high, and the application and popularization significance is not realized.
Chinese patent document CN102180605A discloses a comprehensive treatment process of organosilicon production waste slurry and slag, which is to pump the discharged water from a sewage station into a lime pool by a pump, dissolve the lime added from the outside into lime water, and the pH value of the lime water is more than or equal to 11. The lime water is pumped into a slurry residue treatment reactor through a slurry pump; then nitrogen is added into the slurry slag tank to be punched to 0.03MP, and the slurry slag is pressed into a slurry slag treatment reactor to react.
CN1618840 discloses a method for treating waste residue slurry in the process of synthesizing organosilicon monomers, which comprises the following steps: (A) Separating 90% of high-boiling residues from waste residue slurry in the synthesis of the organic silicon monomer by a centrifugal gravity settling centrifuge, and using the high-boiling residues for cracking and other purposes; (B) Hydrolyzing the centrifuged high-viscosity waste residue slurry in a hydrolysis kettle, wherein the hydrolysis medium is 70% sulfuric acid solution; (C) A small amount of hydrogen chloride gas containing siloxane is separated out from the liquid phase; (D) And (4) carrying out liquid-solid separation on the hydrolysate, discharging the solid hydrolysate, and carrying out subsequent treatment on the liquid phase to recover copper.
CN101659672A discloses a method for cracking treatment of organic silicon waste residue slurry, which comprises adding high-boiling substances with the same mass into a liquid-solid mixture with the solid content of the organic silicon waste residue slurry of 20% to prepare a cracking raw material solution; the catalyst is tributylamine, the cracking reaction temperature is 80-160 ℃, HCl gas is introduced, the feeding speed of hydrogen chloride and the mixed liquid ratio of the raw materials are 1: 1.05-1: 1.12; the slag slurry with the solid content of 20 percent is matched with a high-boiling-point substance for use, the product monosilane is directly separated in the cracking process, the conversion rate is over 70 percent, the selectivity of dimethyldichlorosilane is more than 35 percent, the selectivity of monomethylhydrosilane is more than 40 percent, and the cracked slag has certain fluidity and can be further processed.
CN102390860B discloses an environment-friendly treatment method and device for organic silicon slag slurry, wherein the organic silicon slag slurry is cooled and then is introduced into a closed hydrolysis tank filled with alkaline solution, high-boiling substances in the slag slurry react with alkaline water under stirring to generate neutral or alkaline granular hydrolysate, the neutral or alkaline granular hydrolysate is collected to the bottom of the hydrolysis tank and is collected, and the flocculent copper hydroxide precipitate generated by the reaction flows out from an upper overflow port of the closed hydrolysis tank along with the aqueous solution.
CN103550902A discloses an environment-friendly process for hydrolysis regeneration of organic silicon pulp residue, and the invention discloses an environment-friendly process for hydrolysis regeneration of organic silicon pulp residue, alkaline water is pumped into a tee joint of a tubular reactor through a high-pressure water pump, and the organic silicon pulp residue is pumped into an inner tube in the tee joint of the tubular reactor through a diaphragm air pump; the alkaline water and the organic silicon pulp residue enter a straight pipe of the tubular reactor in a forward direction for reaction, after the reaction is finished, the hydrolysate of the organic silicon pulp residue is brought into a ground groove through the alkaline water, and after incompletely reacted residues and water generated by the reaction are separated by a grid separation plate, the water is recycled; the hydrolysate of the organic silicon pulp residue is subjected to the next reaction procedure.
The method has the advantages of complex process, high treatment cost, small treatment amount, easy generation of other pollution sources, incapability of really realizing harmless treatment and limitation on the development of the organic silicon industry.
Disclosure of Invention
Aiming at the defects of the existing organosilicon slurry-residue treatment technology, the invention provides an organosilicon slurry-residue treatment process which effectively utilizes hydrogen chloride, effectively separates silicon and copper and has low requirements on equipment, and also provides a system for realizing the process.
The organic silicon slurry slag treatment process comprises disilane hydrolysis, copper chloride leaching, squeezing backwashing, copper replacement, silicon slag roasting and tail gas treatment, and comprises the following specific steps of:
(1) And (3) hydrolyzing disilane:
mixing the organic silicon slurry residue and water according to the mass ratio of 1-2 for hydrolysis reaction for 10-60 minutes, absorbing acid mist generated in hydrolysis, and absorbing hydrochloric acid for later use;
(2) Leaching copper chloride:
maintaining the hydrolysis liquid level stable, supplementing a proper amount of hydrochloric acid after discharging the hydrolyzed slurry, maintaining the pH value at 0.5-2.0, stirring for reacting for 1-8 hours at the stirring temperature of 40-90 ℃ and the stirring speed of 80-100 revolutions per minute (rpm), sampling and detecting the dissolution rate of copper in the slag, and stopping the reaction when the leaching rate of the copper reaches more than 99%;
(3) Squeezing and backwashing:
carrying out filter pressing on the slurry after leaching the copper chloride, wherein the pressing pressure is 5-8Mpa, introducing clear water for backwashing after pressing, stopping backwashing when the content of copper ions in the washing water is detected to be less than 0.05g/l, and roasting the silicon slag after backwashing; the solution after filter pressing is sent to a copper replacement process, and washing water is returned to the step (1) (disilane hydrolysis) to be used as organic silicon slurry residue mixed water;
(4) Copper replacement:
carrying out sponge copper placement on the filter-pressed copper-containing solution in the step (3), adding iron powder for replacement, filtering and separating the replaced slurry to obtain sponge copper and a ferrous chloride solution, wherein the copper content of the sponge copper is more than 70%, carrying out ferrous chloride concentration oxidation on the ferrous chloride solution, firstly adding hydrogen peroxide or sodium chlorate for oxidation, detecting that more than 99% of ferrous iron is oxidized into ferric iron, finishing oxidation, and heating to evaporate water until the mass content of ferric chloride is more than 38%;
(5) Roasting the silicon slag:
controlling the roasting temperature of the silicon slag after the back washing to be 500-850 ℃, controlling the roasting time to be 30-90 minutes, and oxidizing the hydrolyzed silicon-containing products (silanol and the like) to generate silicon powder;
(6) Tail gas treatment:
recovering the waste heat of tail gas generated by roasting the silicon slag, wherein the recovered heat is used for heating the slurry in the step (2) to improve the temperature of agitation leaching, or is used for concentrating and oxidizing ferrous chloride in the step (4) to concentrate a ferrous chloride solution; and collecting dust for tail gas after waste heat recovery.
The organic silicon slurry slag treatment system for realizing the process adopts the following technical scheme:
this system, including hydrolysis tank, stirred tank reactor, plate and frame filter press, sponge copper replacement groove and rotary kiln, the hydrolysis tank passes through the pipeline and is connected with stirred tank reactor, and stirred tank reactor passes through the pipeline and the pump is connected with plate and frame filter press, and plate and frame filter press's filtrating mouth passes through the pipeline and is connected with sponge copper replacement groove, is connected with the concentrated oxidation unit of ferrous chloride on the sponge copper replacement groove, and plate and frame filter press's filter residue mouth passes through band conveyer and is connected with the rotary kiln.
The upper part of the hydrolysis tank is connected with an acid mist absorption tower which is respectively connected with an alkali liquor absorption tower and a hydrochloric acid storage tank and is used for realizing the recovery of hydrogen chloride and the thorough removal of residual hydrogen chloride, thereby achieving the zero emission of hydrogen chloride gas. The hydrochloric acid storage tank is connected with the hydrolysis tank, and hydrogen chloride is recycled.
The rotary kiln is connected with a waste heat recovery device, and the waste heat recovery device is connected with the stirring reaction kettle. The waste heat recovery device is connected with the ferrous chloride concentration and oxidation device. The waste heat recovery device is also connected with a bag dust collector. The waste heat recovery device can fully utilize the excessive and underutilized heat, thereby improving the benefit.
The ferric chloride concentration oxidation device is a stirring evaporation kettle.
The method effectively utilizes the hydrogen chloride gas generated by hydrolysis, so that the zero emission of the hydrogen chloride gas is realized. The leaching rate of copper is up to 99 percent by adopting stirring leaching and controlling the temperature and the PH value of the solution. The copper content of the sponge copper is more than 70%, and the content of the byproduct ferric chloride is controlled to be more than 30%, so that the sponge copper can be sold, and the economic value is improved. And roasting the hydrolysis residues, wherein the roasted product is silicon powder, the content of silicon oxide is more than 98%, and the silicon powder can be directly sold to building material companies for use.
The method can reasonably separate silicon and copper in the organic silicon slurry slag, effectively utilizes hydrogen chloride gas generated by hydrolysis, has no wastewater and waste slag discharge in the whole process route, and only uses carbon dioxide roasted by a rotary kiln as waste gas. The harm to the environment is reduced to the minimum, the products are metal copper and silicon powder, the products can be sold, and the economic value is high; the whole process flow adopts pipeline conveying and belt conveying, so that the production efficiency is high; the whole process has zero discharge of waste water and waste residue, obvious environmental benefit, simple equipment and low cost; the hydrolysis and leaching are carried out under normal pressure at the temperature lower than 90 ℃, the requirements on the material and strength of equipment are not high, the roasting temperature is 500-850 ℃, and the requirements on the material of a rotary kiln are not high because silicon powder does not contain corrosive hydrogen chloride.
Drawings
FIG. 1 is a schematic structural diagram of an organosilicon slurry-residue treatment system according to the invention.
In the figure: 1. the device comprises a hydrolysis tank, 2 stirring reaction kettles, 3 a plate-and-frame filter press, 4 sponge copper replacement tanks, 5 rotary kilns, 6 pumps, 7 ferrous chloride concentration and oxidation devices, 8 belt conveyors, 9 acid mist absorption towers, 10 alkali liquor absorption towers, 11 waste heat recovery devices, 12 cloth bag dust collectors, 13 sponge copper collecting tanks, 14 silicon powder collecting tanks and 15 hydrochloric acid storage tanks.
Detailed Description
As shown in figure 1, the organic silicon slurry slag treatment system comprises a hydrolysis tank 1, a stirring reaction kettle 2, a plate-and-frame filter press 3, a sponge copper replacement tank 4 and a rotary kiln 5.
The hydrolysis tank 1 is connected with the stirring reaction kettle 2 through a pipeline. The stirring reaction kettle 2 is connected with the plate-and-frame filter press 3 through a pipeline, and a pump 6 is arranged on the pipeline. The filtrate port of the plate-and-frame filter press 3 is connected with the sponge copper replacement tank 4 through a pipeline. The sponge copper replacement tank 4 is connected with a ferrous chloride concentration oxidation device 7 and a sponge copper collecting tank 13, and the ferric chloride concentration oxidation device 7 is a stirring evaporation kettle.
The filter residue port of the plate-and-frame filter press 3 is connected with the rotary kiln 5 through a belt conveyor 8, and the rotary kiln 5 is connected with the silicon powder collecting tank 14. The rotary kiln 5 is connected with a waste heat recovery device 11, and the waste heat recovery device 11 is connected with the stirring reaction kettle 2. The waste heat recovery device 11 is also connected with the ferrous chloride concentration and oxidation device 7 and the bag dust collector 12. The waste heat recovery device 11 adopts a cooling water circulation pipeline. The waste heat recovery device 11 makes full use of the excessive and underutilized heat, and improves the benefit.
The upper part of the hydrolysis tank 1 is connected with an acid mist absorption tower 9, and the acid mist absorption tower 9 is respectively connected with an alkali liquor absorption tower 10 and a hydrochloric acid storage tank 15, so that the hydrogen chloride recovery and the complete removal of residual hydrogen chloride are realized, and the zero emission of hydrogen chloride gas is realized. The hydrochloric acid storage tank 15 is connected to the hydrolysis tank 1 to reuse hydrogen chloride.
The process of the system for treating the organic silicon slurry slag comprises disilane hydrolysis, copper chloride leaching, squeezing backwashing, copper replacement, silicon slag roasting and tail gas treatment.
(1) Disilane hydrolysis
Adding the organic silicon slurry residue and water into a hydrolysis tank 1 according to the mass ratio of 1-2 for reaction for 10-60 minutes, absorbing acid mist generated in the hydrolysis tank 1 by an acid mist absorption tower 9, and allowing the absorbed hydrochloric acid to flow into a hydrochloric acid storage tank 15 for later use.
(2) Copper chloride leaching
The bottom of the adjusting hydrolysis tank 1 is provided with a valve to keep the liquid level in the hydrolysis tank 1 stable. Discharging the slurry in the hydrolysis tank 1 to a stirring reaction kettle 2, supplementing a proper amount of hydrochloric acid, and keeping the pH value of the solution at 0.5-2.0, wherein the hydrochloric acid can be supplemented by the absorbed hydrochloric acid. Stirring and reacting for 1-8 hours, wherein the solution temperature is 40-90 ℃, the stirring speed is 80-100rpm, sampling is carried out to detect the dissolution rate of copper in the slag, and the reaction is stopped when the leaching rate of copper reaches more than 99 percent.
(3) Squeeze backwash
Pumping the slurry after the leaching reaction into a backwashing plate-and-frame filter press 3, pressing at 5-8Mpa, introducing clear water for backwashing after pressing, stopping backwashing when the washing water contains less than 0.05g/l of copper ions through detection, and delivering the silicon slag after backwashing to a rotary kiln 5 for roasting. And (3) delivering the solution subjected to filter pressing to a copper replacement process, and returning the washing water to the disilane hydrolysis process in the step (1) for mixing with the organic silicon slurry residue.
(4) Copper replacement
The filter-pressed copper-containing solution is sent to the sponge copper replacement tank 4, the iron powder replacement is added, the slurry after replacement is filtered and separated to obtain sponge copper and ferrous chloride solution, the sponge copper-containing is more than 70%, the ferrous chloride solution flows into the ferrous chloride concentration oxidation device 7 (namely, the stirring and evaporation kettle), hydrogen peroxide or sodium chlorate is added firstly for oxidation, after the more than 99% oxidation of detection bivalent iron is ferric iron, the oxidation is ended, the water is evaporated again, and the design index is reached: the mass content of ferric trichloride is more than 38 percent.
(5) Roasting of silicon slag
Conveying the silicon slag after the back washing to a rotary kiln 5 by a belt for roasting, controlling the roasting temperature at 500-850 ℃, controlling the roasting time at 30-90 minutes, and oxidizing the hydrolyzed silicon-containing products, namely silanol and the like to generate silicon powder.
(6) Tail gas treatment
The tail gas waste heat of the rotary kiln 5 is recovered by a waste heat recovery device 11 (cooling water circulation pipeline), cooling water is heated by tail gas, and heat is collected by the cooling water and is introduced into the stirring reaction kettle 2 to improve the temperature of stirring leaching or is introduced into a ferrous chloride concentration oxidation device 7 to be used for concentrating a ferrous chloride solution. The tail gas after waste heat recovery is collected by a bag collector 12.
Specific examples of the above process are given below.
Example 1
(1) Hydrolysis of disilane: 1 ton of organic silicon slurry residue and 2 tons of water are added into the hydrolysis tank 1 for reaction for 60 minutes.
(2) Leaching copper chloride: keeping the liquid level of the hydrolysis tank stable at about 80%, discharging the slurry of the hydrolysis tank to a stirring reaction kettle, supplementing a proper amount of hydrochloric acid, adjusting the pH value of the solution to 0.5, the temperature of the solution to 40 ℃, the stirring speed to 100rpm, starting stirring to continue reacting for 4 hours, sampling and detecting the dissolution rate of copper in the slag, and stopping the reaction when the leaching rate of the copper reaches 99%.
(3) Squeezing and backwashing: pumping the slurry after the leaching reaction into a backwashing plate and frame filter press 3, pressing at 6Mpa, introducing clear water for backwashing after pressing, stopping backwashing when the washing water contains less than 0.05g/l of copper ions after detection, and delivering the silicon slag after backwashing to a rotary kiln for roasting.
(4) Copper replacement: the solution after filter pressing is sent to a copper replacement process, and the washing water is returned to the disilane hydrolysis process for use. And adding iron powder into the filter-pressed copper-containing solution for replacement, and filtering and separating the replaced slurry to obtain a sponge copper and ferrous chloride solution, wherein the copper content of the sponge copper is more than 70% (namely 42.43 kg).
(5) Roasting the silicon slag: the roasting temperature of the silicon slag after the back washing is 750 ℃, the roasting time is 50 minutes, and the hydrolyzed silicon-containing products, such as silanol and the like, are oxidized to generate silicon powder (309.3 kg, the content is 97%).
Example 2
This example was conducted in the same manner as in example 1 except that 1 ton of the silicone sludge and 1.5 tons of water were charged into the hydrolysis tank 1 and reacted for 30 minutes.
In the copper chloride leaching step, the pH value of the solution is 1.5, the temperature of the solution is 70 ℃, the stirring speed is 80rpm, the stirring reaction time is 8 hours, and the final yield of the sponge copper is 42.21 kg.
Example 3
This example was conducted in the same manner as in example 1 except that 1 ton of the silicone sludge and 1 ton of water were charged into the hydrolysis tank 1 and reacted for 10 minutes.
The leaching rate of copper in the copper chloride leaching step is 99.5%, the pH value of the solution is controlled to be 2, the temperature of the reaction solution is 90 ℃, the stirring speed is 100rpm, and the reaction time is 1 hour. Finally, 42.64 kg of sponge copper is produced by 1 ton of organic silicon slurry slag.
Example 4
The parameters of this example are substantially the same as those of example 1, except that the calcination temperature in the silica slag calcination step is 500 ℃, and 302 kg of silica powder is produced.
Example 5
The parameters of this example are substantially the same as those of example 1, except that the roasting temperature in the roasting step of the silica slag is 850 ℃ to produce 317.5 kg of silica powder.
Claims (3)
1. An organic silicon slurry slag treatment process is characterized by comprising disilane hydrolysis, copper chloride leaching, squeezing backwashing, copper replacement, silicon slag roasting and tail gas treatment, and comprises the following specific steps:
(1) And (3) hydrolyzing disilane:
mixing the organic silicon slurry residue and water according to the mass ratio of 1-2, carrying out hydrolysis reaction for 10-60 minutes, absorbing acid mist generated in hydrolysis, and keeping the absorbed hydrochloric acid for later use;
(2) Leaching copper chloride:
keeping the hydrolysis liquid level stable, supplementing a proper amount of hydrochloric acid after discharging the hydrolyzed slurry, keeping the pH value at 0.5-2.0, stirring for reacting for 1-8 hours at the stirring temperature of 40-90 ℃ and the stirring speed of 80-100 r/min, sampling and detecting the dissolution rate of copper in the slag, and stopping the reaction when the leaching rate of copper reaches more than 99%;
(3) Squeezing and backwashing:
carrying out filter pressing on the slurry after leaching the copper chloride, wherein the pressing pressure is 5-8Mpa, introducing clear water for backwashing after pressing, stopping backwashing when the content of copper ions in the washing water is detected to be less than 0.05g/l, and roasting the silicon slag after backwashing; the solution after filter pressing is sent to a copper replacement process, and the washing water is returned to the step (1) to be used as the mixed water of the organic silicon slurry residue;
(4) Copper replacement:
carrying out sponge copper placement on the copper-containing solution subjected to filter pressing in the step (3), adding iron powder for replacement, filtering and separating the replaced slurry to obtain sponge copper and a ferrous chloride solution, wherein the copper content of the sponge copper is more than 70%, carrying out ferrous chloride concentration oxidation on the ferrous chloride solution, firstly adding hydrogen peroxide or sodium chlorate for oxidation, detecting that more than 99% of bivalent iron is oxidized into trivalent iron, finishing oxidation, and then heating to evaporate water until the mass content of ferric trichloride is more than 38%;
(5) Roasting the silicon slag:
controlling the roasting temperature of the silicon slag after the back washing to be 500-850 ℃, controlling the roasting time to be 30-90 minutes, and oxidizing the hydrolyzed silicon-containing product to generate silicon powder;
(6) Tail gas treatment:
recovering the waste heat of tail gas generated by roasting the silicon slag, wherein the recovered heat is used for heating the slurry in the step (2) to improve the temperature of agitation leaching, or is used for concentrating and oxidizing ferrous chloride in the step (4) to concentrate a ferrous chloride solution; and collecting dust for tail gas after waste heat recovery.
2. An organic silicon thick liquid sediment processing system, characterized by: the device comprises a hydrolysis tank, a stirring reaction kettle, a plate-and-frame filter press, a sponge copper replacement tank and a rotary kiln, wherein the hydrolysis tank is connected with the stirring reaction kettle through a pipeline, the stirring reaction kettle is connected with the plate-and-frame filter press through a pipeline and a pump, a filtrate port of the plate-and-frame filter press is connected with the sponge copper replacement tank through a pipeline, a ferrous chloride concentration and oxidation device is connected onto the sponge copper replacement tank, and a filter residue port of the plate-and-frame filter press is connected with the rotary kiln through a belt conveyor;
the upper part of the hydrolysis tank is connected with an acid mist absorption tower, and the acid mist absorption tower is respectively connected with an alkali liquor absorption tower and a hydrochloric acid storage tank; the hydrochloric acid storage tank is connected with the hydrolysis tank;
the rotary kiln is connected with a waste heat recovery device, and the waste heat recovery device is connected with the stirring reaction kettle; the waste heat recovery device is connected with the ferrous chloride concentration and oxidation device, and the waste heat recovery device is also connected with the bag dust collector.
3. The silicone sludge treatment system of claim 2 wherein: the ferrous chloride concentration and oxidation device is a stirring evaporation kettle.
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| 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 |
| CN115475825B (en) * | 2022-09-29 | 2023-06-27 | 鲁西化工集团股份有限公司硅化工分公司 | Organosilicon slurry residue treatment process |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108929A (en) * | 1986-12-26 | 1988-07-13 | 南通市第十三中学校办工厂 | The treatment process of waste cuprous chloride solution |
| JP2006281413A (en) * | 2005-04-04 | 2006-10-19 | Sharp Corp | Collecting method of silicone containing material |
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN202877217U (en) * | 2012-09-29 | 2013-04-17 | 山东金岭化学有限公司 | Organic silicon slurry residue hydrolytic treatment device |
| CN103555951A (en) * | 2013-10-23 | 2014-02-05 | 泸州北方化学工业有限公司 | Method for extracting copper from organic silicon scrap |
| CN103936081A (en) * | 2013-01-21 | 2014-07-23 | 解付兵 | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid |
| CN104740986A (en) * | 2013-12-27 | 2015-07-01 | 江苏立宇环境科技有限公司 | Hydrolysis treatment process for organosilicon slurry residue |
| CN105087939A (en) * | 2015-08-19 | 2015-11-25 | 杭州泰谱环境科技有限公司 | System for recycling copper in organic silicon waste residue slurry and recycling method for system |
| CN207723171U (en) * | 2017-01-18 | 2018-08-14 | 李鹏 | A kind of organic silicon slurry slag processing system |
-
2017
- 2017-01-18 CN CN201710038176.XA patent/CN106623370B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108929A (en) * | 1986-12-26 | 1988-07-13 | 南通市第十三中学校办工厂 | The treatment process of waste cuprous chloride solution |
| JP2006281413A (en) * | 2005-04-04 | 2006-10-19 | Sharp Corp | Collecting method of silicone containing material |
| CN202877217U (en) * | 2012-09-29 | 2013-04-17 | 山东金岭化学有限公司 | Organic silicon slurry residue hydrolytic treatment device |
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN103936081A (en) * | 2013-01-21 | 2014-07-23 | 解付兵 | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid |
| CN103555951A (en) * | 2013-10-23 | 2014-02-05 | 泸州北方化学工业有限公司 | Method for extracting copper from organic silicon scrap |
| CN104740986A (en) * | 2013-12-27 | 2015-07-01 | 江苏立宇环境科技有限公司 | Hydrolysis treatment process for organosilicon slurry residue |
| CN105087939A (en) * | 2015-08-19 | 2015-11-25 | 杭州泰谱环境科技有限公司 | System for recycling copper in organic silicon waste residue slurry and recycling method for system |
| CN207723171U (en) * | 2017-01-18 | 2018-08-14 | 李鹏 | A kind of organic silicon slurry slag processing system |
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