CN113582183A - Treatment method and treatment system for organic silicon waste residue slurry - Google Patents
Treatment method and treatment system for organic silicon waste residue slurry Download PDFInfo
- Publication number
- CN113582183A CN113582183A CN202110986138.3A CN202110986138A CN113582183A CN 113582183 A CN113582183 A CN 113582183A CN 202110986138 A CN202110986138 A CN 202110986138A CN 113582183 A CN113582183 A CN 113582183A
- Authority
- CN
- China
- Prior art keywords
- waste residue
- organic silicon
- solid
- solution
- acidic solution
- 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
- 239000002699 waste material Substances 0.000 title claims abstract description 128
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000010703 silicon Substances 0.000 title claims abstract description 82
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 78
- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 72
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003929 acidic solution Substances 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 47
- 238000004062 sedimentation Methods 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 26
- 230000005484 gravity Effects 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 10
- 229940045803 cuprous chloride Drugs 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 239000002918 waste heat Substances 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims 1
- 239000011863 silicon-based powder Substances 0.000 abstract description 27
- 238000011084 recovery Methods 0.000 abstract description 15
- 238000003672 processing method Methods 0.000 abstract 2
- 238000002386 leaching Methods 0.000 description 31
- 238000003756 stirring Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011344 liquid material Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- GTPDFCLBTFKHNH-UHFFFAOYSA-N chloro(phenyl)silicon Chemical compound Cl[Si]C1=CC=CC=C1 GTPDFCLBTFKHNH-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a processing method and a processing system of organic silicon waste residue slurry, wherein the processing method of the organic silicon waste residue slurry comprises the following steps: carrying out gravity centrifugal sedimentation treatment on the organic silicon waste residue slurry to obtain waste liquid and waste residue; adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution; adding a sulfuric acid solution into the first acidic solution, mixing and reacting to obtain a second acidic solution, and then carrying out solid-liquid separation on the second acidic solution; calcining the solid substance obtained after the solid-liquid separation at high temperature to obtain simple substance silicon; and adding an alkaline substance into the liquid substance obtained after the solid-liquid separation to adjust the pH value of the solution to 9.0-10.0. The method provided by the invention can effectively recover the silicon powder in the organic silicon waste residue slurry, and is simple in process, wherein the recovery rate of the silicon powder reaches 93-96%, and the purity of the silicon powder reaches more than 95%.
Description
Technical Field
The invention relates to the technical field of organic silicon waste residue treatment, in particular to a treatment method and a treatment system of organic silicon waste residue slurry.
Background
In the production process of organic silicon chemical products such as methyl chlorosilane, phenyl chlorosilane and the like, an organic silicon monomer is a main raw material, copper powder or copper salt is used as a catalyst, a mixture of unreacted silicon powder and the catalyst in the production process is called organic silicon waste residue, the organic silicon waste residue contains a considerable amount of silicon powder, copper powder and carbon powder, and a certain amount of high-boiling-point substances such as siloxane and the like are contained, so that the organic silicon waste residue has high recovery value, if the organic silicon waste residue is directly buried, not only is serious environmental pollution caused, but also a large amount of silicon and copper can be lost, and the great waste of resources is caused. With the continuous expansion of the production scale of organic silicon, the number of the organic silicon waste residues is continuously increased, how to effectively recycle the silicon powder in the organic silicon waste residues and realize the resource recycling of the organic silicon waste residues is realized, and the method has important significance for promoting the green sustainable development of an organic silicon industrial chain.
Disclosure of Invention
The invention mainly aims to provide a treatment method and a treatment system for organic silicon waste residue slurry, and aims to provide a method for effectively recovering silicon powder from organic silicon waste residue.
In order to realize the purpose, the invention provides a method for treating organic silicon waste residue slurry, which comprises the following steps:
carrying out gravity centrifugal sedimentation treatment on the organic silicon waste residue slurry to obtain waste liquid and waste residue;
adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution;
adding a sulfuric acid solution into the first acidic solution, mixing and reacting to obtain a second acidic solution, and then carrying out solid-liquid separation on the second acidic solution;
calcining the solid substance obtained after the solid-liquid separation at high temperature to obtain simple substance silicon;
and adding an alkaline substance into the liquid substance obtained after the solid-liquid separation to adjust the pH value of the solution to 9.0-10.0.
Optionally, the step of adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution comprises:
the mass fraction of the hydrochloric acid solution is 10-15%, and the addition mass of the hydrochloric acid solution is 1.6-2 times of the mass of the organic silicon waste residue slurry.
Optionally, the step of adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution comprises:
the temperature of the mixing reaction is 30-40 ℃, and the time is 24-36 h.
Optionally, a sulfuric acid solution is added into the first acidic solution, a second acidic solution is obtained after mixing and reacting, and then the second acidic solution is subjected to solid-liquid separation, wherein:
the mass fraction of the sulfuric acid solution is 30-35%, and the adding mass of the sulfuric acid solution is 2-2.5 times of the mass of the organic silicon waste residue slurry.
Optionally, a sulfuric acid solution is added into the first acidic solution, a second acidic solution is obtained after mixing and reacting, and then the second acidic solution is subjected to solid-liquid separation, wherein:
the temperature of the mixing reaction is 40-45 ℃ and the time is 2.5-3 h.
Optionally, calcining the solid substance obtained after the solid-liquid separation at a high temperature to obtain elemental silicon, wherein the solid substance is obtained by:
the calcining temperature is 1900-2200 ℃ and the calcining time is 3-5 h.
Optionally, after the step of calcining the solid substance obtained after the solid-liquid separation at a high temperature to obtain elemental silicon, the method includes:
and recovering the waste heat after the calcination, and introducing the gas generated in the calcination process into a mixed solution of hydrochloric acid and cuprous chloride for tail gas treatment.
Optionally, adding an alkaline substance into the liquid substance obtained after the solid-liquid separation to adjust the pH value of the solution to 9.0-10.0, wherein:
the alkaline substance is a mixture of sodium hydroxide and ammonium chloride.
Further, the invention also provides a treatment system of the organic silicon waste residue slurry, which comprises:
the acid pickling device comprises a sedimentation tank, a first acid pickling tank, a second acid pickling tank and a neutralization treatment tank which are sequentially arranged, wherein the sedimentation tank is provided with a feed inlet, a solid discharge outlet and a liquid discharge outlet; and the number of the first and second groups,
and a feed inlet of the high-temperature reactor is connected with a solid discharge outlet of the sedimentation tank.
Optionally, the high-temperature reactor is provided with an exhaust port, and the exhaust port is connected with an exhaust pipeline;
the processing system of organosilicon waste residue thick liquid still includes the tail gas treatment jar, the mixed solution of hydrochloric acid and cuprous chloride is equipped with in the tail gas treatment jar, exhaust end of exhaust duct stretches into to being located in the mixed solution in the tail gas treatment jar.
According to the technical scheme provided by the invention, firstly, the organic silicon waste residue slurry is subjected to gravity centrifugal sedimentation treatment to separate most of high-boiling-point substances (namely waste liquid) and waste residues, then a hydrochloric acid solution and a sulfuric acid solution are sequentially used for reacting with the waste residues, the hydrochloric acid solution and the waste residues are reacted to generate silicon and silicon dioxide, copper powder in the waste residues is changed into copper ions through the sulfuric acid solution, solid substances and liquid substances are respectively collected after the reaction is finished, then the solid substances are calcined, silicon powder is recovered, and alkaline substances are added into the liquid substances to neutralize acidity, so that the waste liquid meets the discharge standard. The method provided by the invention can effectively recover the silicon powder in the organic silicon waste residue slurry, and is simple in process, wherein the recovery rate of the silicon powder reaches 93-96%, and the purity of the silicon powder reaches more than 95%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart of an embodiment of a method for treating waste organosilicon slurry;
fig. 2 is a schematic view of an embodiment of a system for treating waste silicone residue slurry provided by the present invention.
The reference numbers illustrate:
| reference numerals | Name (R) | Reference numerals | Name (R) |
| 1 | |
5 | |
| 2 | First |
6 | Waste |
| 3 | Second |
7 | |
| 4 | |
8 | Tail gas treatment tank |
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to effectively recover the silicon powder in the organic silicon waste residue slurry and realize the resource recycling of the organic silicon waste residue slurry, the invention provides a method for treating the organic silicon waste residue slurry, and fig. 1 shows an embodiment of the method for treating the organic silicon waste residue slurry provided by the invention. Referring to fig. 1, in this embodiment, the method for processing the waste organosilicon slurry includes the following steps:
step S10, carrying out gravity centrifugal sedimentation treatment on the organic silicon waste residue slurry to obtain waste liquid and waste residue;
firstly, placing the organic silicon waste residue slurry in a gravity settling centrifuge for gravity centrifugal settling treatment to form waste liquid and waste residue, and respectively collecting the waste liquid and the waste residue, wherein the waste liquid mainly contains disilane, disiloxane, siloxane and the like with boiling points higher than 75 ℃, the waste liquid can be used for extracting organic matters in the waste liquid by cracking, fractionating, extracting and the like, and the waste residue mainly contains silicon, carbon, copper and the like.
Step S20, adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution;
adding a hydrochloric acid solution into the waste residue to react to generate silicon and silicon dioxide, wherein the concentration of the hydrochloric acid solution is not limited and can be realized by dilute hydrochloric acid, in a specific embodiment of the invention, the mass fraction of the hydrochloric acid solution is preferably 10-15%, and the adding mass of the hydrochloric acid solution is 1.6-2 times of the mass of the organic silicon waste residue slurry. Therefore, the hydrochloric acid solution can fully convert the residual silicon element in the waste residue into silicon and silicon dioxide, so that the recovery amount of silicon is improved, and the acidity of the hydrochloric acid solution is not too strong to cause unnecessary corrosion or damage to a reaction vessel and the like.
Further, the mixing reaction in step S20 can be performed at normal temperature, and more preferably, it is properly heated and performed under the stirring action, which is beneficial to increase the reaction rate and efficiency and shorten the reaction time. Specifically, in the embodiment of the invention, the temperature of the mixing reaction is 30-40 ℃ and the time is 24-36. In addition, the stirring speed can be set to be 200-300 rpm.
Step S30, adding a sulfuric acid solution into the first acidic solution, mixing and reacting to obtain a second acidic solution, and then carrying out solid-liquid separation on the second acidic solution;
firstly, adding a sulfuric acid solution into the second acidic solution to react copper therein to generate copper ions, wherein the concentration of the sulfuric acid solution is not limited and can be realized by only using dilute sulfuric acid, in a specific embodiment of the invention, the mass fraction of the sulfuric acid solution is 30-35%, and the adding mass of the sulfuric acid solution is 2-2.5 times of the mass of the organic silicon waste residue slurry. Therefore, the sulfuric acid solution can fully convert copper powder in the waste residue into copper ions, so that copper can be recovered in a mode of oxidation reduction and the like in the follow-up process, and on the other hand, unnecessary corrosion or damage to a reaction container and the like due to over-strong acidity of the sulfuric acid solution can be avoided.
Further, the mixing reaction of step S30 can be performed at normal temperature, and more preferably, it is properly heated and performed under the stirring action, which is beneficial to increase the reaction rate and efficiency and shorten the reaction time. Specifically, in the embodiment of the invention, the temperature of the mixing reaction is 40-45 ℃ and the time is 2.5-3 h. In addition, the stirring speed can be set to be 300-400 rpm.
After the second acidic solution is obtained, solid-liquid separation can be performed by adopting filtration, centrifugation and other modes, preferably by adopting a gravity settling centrifuge, so that the separation efficiency is higher, and the separation can be realized by utilizing the gravity settling centrifuge used in the step S10, thereby being beneficial to reducing the equipment cost.
Step S40, calcining the solid matter obtained after the solid-liquid separation at high temperature to obtain simple substance silicon;
after solid-liquid separation is carried out to obtain solid substances and liquid substances respectively, the solid substances contain silicon powder and carbon powder which are not reacted in the organic silicon synthesis reaction, and silicon dioxide generated in the step S20, the solid substances are calcined, so that the silicon dioxide and the carbon react at a high temperature to generate simple substance silicon, and specifically, the calcining temperature is 1900-2200 ℃ and the calcining time is 3-5 hours. Through the calcination treatment, on one hand, the recovery amount of silicon can be improved, on the other hand, carbon powder in the organic silicon waste residue is fully utilized, and the pollution to the environment caused by the discharge of the organic silicon waste residue is reduced.
Further, the calcination process generates a large amount of waste heat, and both the step S20 and the step S30 are preferably performed under appropriate heating conditions, so that the waste heat generated by the calcination process can be recycled for heating in the step S20 and the step S30, which is beneficial to reducing the process cost. In addition, the calcination process may also react to generate carbon monoxide, and the generated carbon monoxide may be directly disposed of by combustion, but in order to reduce carbon dioxide emission, in the embodiment of the present invention, it is preferable to perform an absorption treatment on the carbon monoxide generated in the calcination process by using an off-gas absorption liquid, specifically, to perform an off-gas treatment by introducing the gas generated in the calcination process into a mixed solution of hydrochloric acid and cuprous chloride. In other embodiments of the present invention, a gas collection device may also be provided to collect carbon monoxide for other uses.
And step S50, adding an alkaline substance into the liquid material obtained after the solid-liquid separation to adjust the pH value of the solution to 9.0-10.0.
The liquid material obtained after the solid-liquid separation in step S30 is acidic and hardly meets the discharge requirement of wastewater, and in the present invention, an alkaline substance is added to adjust the pH value to be weakly alkaline to meet the discharge requirement, and the specific type of the alkaline substance is not limited, and includes, but is not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. Specifically, in the embodiment of the present invention, in order to add a mixture of sodium hydroxide and ammonium chloride to the liquid material, the addition amount of the mixture of sodium hydroxide and ammonium chloride is not limited, and the pH of the liquid material is adjusted to 9.0 to 10.0. Meanwhile, the addition of the mixture of sodium hydroxide and ammonium chloride can also enable copper ions in the liquid substance to react to generate copper hydroxide precipitate to be separated out, so that the copper hydroxide can be further treated by other modes, the effective recovery of copper is realized, and the resource utilization rate of the organic silicon waste residue is further improved.
According to the technical scheme provided by the invention, firstly, the organic silicon waste residue slurry is subjected to gravity centrifugal sedimentation treatment to separate most of high-boiling-point substances (namely waste liquid) and waste residues, then a hydrochloric acid solution and a sulfuric acid solution are sequentially used for reacting with the waste residues, the hydrochloric acid solution and the waste residues are reacted to generate silicon and silicon dioxide, copper powder in the waste residues is changed into copper ions through the sulfuric acid solution, solid substances and liquid substances are respectively collected after the reaction is finished, then the solid substances are calcined, silicon powder is recovered, and alkaline substances are added into the liquid substances to neutralize acidity, so that the waste liquid meets the discharge standard. The method provided by the invention can effectively recover the silicon powder in the organic silicon waste residue slurry, and is simple in process, wherein the recovery rate of the silicon powder reaches 93-96%, and the purity of the silicon powder reaches more than 95%.
Based on the method for processing the organic silicon waste residue slurry provided by the invention, the invention further provides a processing system for the organic silicon waste residue slurry, and fig. 2 is a schematic diagram of an embodiment of the processing system for the organic silicon waste residue slurry provided by the invention. Referring to fig. 2, in this embodiment, the processing system of the organic silicon waste residue slurry includes a sedimentation tank 1, a first acid leaching tank 2, a second acid leaching tank 3, and a neutralization treatment tank 4, which are sequentially distributed, where the sedimentation tank 1 is provided with a feed port, a solid discharge port, and a liquid discharge port, the liquid discharge port of the sedimentation tank 1 is connected to the neutralization treatment tank 4, and the liquid outlet of the second acid leaching tank 2 is connected to the feed port of the sedimentation tank 1; in addition, the processing system of the organic silicon waste residue slurry also comprises a high-temperature reactor 5, wherein a feed inlet of the high-temperature reactor 5 is connected with a solid discharge hole of the sedimentation tank 1.
The sedimentation tank 1 is used for performing gravity sedimentation centrifugation treatment on the organic silicon waste residue slurry, and specifically, a gravity sedimentation centrifuge can be arranged in the sedimentation tank 1, or a material cavity of the gravity sedimentation centrifuge forms the sedimentation tank 1; the first acid leaching tank 2 is used for carrying out hydrochloric acid mixing treatment on waste residues collected after the gravity settling and centrifugal treatment, the solution treated by the first acid leaching tank 2 is a first acidic solution, and a stirring device and a heating device are arranged in the first acid leaching tank 2; the second acid leaching tank 3 is used for carrying out sulfuric acid mixing treatment on the first acid solution, the solution treated by the second acid leaching tank 3 is a second acid solution, and a stirring device and a heating device are arranged in the second acid leaching tank 3; and the second acidic solution treated by the second acid leaching tank 3 enters the sedimentation tank 1 again for solid-liquid separation, then enters the high-temperature reactor 5 for calcination and subsequent treatment after the solid-liquid separation in the sedimentation tank 1, so as to realize the recovery of silicon powder, and enters the neutralization treatment tank 4 for alkali neutralization treatment.
In addition, the high-temperature reactor 5 is further provided with a waste heat recovery device 6, and the waste heat recovery device 6 is connected with the first acid leaching tank 2 and the second acid leaching tank 3 and used for heating the first acid leaching tank 2 and the second acid leaching tank 3, so that resources are fully utilized. The organic silicon waste residue slurry treatment device provided by the embodiment of the invention can effectively recover silicon powder, fully utilizes partial equipment and heat generated in the treatment process, and reduces equipment cost and process cost.
Further, the high-temperature reactor 5 is also provided with an exhaust port, and the exhaust port is connected with an exhaust pipeline 7; the processing system of organosilicon waste residue thick liquid still includes tail gas treatment tank 8, the mixed solution of hydrochloric acid and cuprous chloride is equipped with in the tail gas treatment tank 8, exhaust end of exhaust duct 7 stretches into to being located in the mixed solution in the tail gas treatment tank 8, be located below the liquid level promptly, thereby it is right carbon monoxide that the reaction produced in the high temperature reactor 5 absorbs, reduces the pollution to the environment.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Carrying out gravity settling centrifugal treatment on the organic silicon waste residue slurry in a settling tank 1 to obtain waste liquid and waste residue;
(2) inputting the obtained waste residue into a first acid leaching tank 2, adding a hydrochloric acid solution with the mass 1.6 times that of the waste residue and the mass concentration of 10% into a second acid leaching tank 2, and reacting for 36 hours at the temperature of 30 ℃ and the stirring speed of 200rpm to obtain a first acid solution;
(3) inputting the obtained first acidic solution into a second acid leaching tank 3, adding a sulfuric acid solution with the mass concentration of 30% which is 2 times of the mass of the waste residue into the second acid leaching tank, reacting for 3 hours at the temperature of 40 ℃ and the stirring speed of 300rpm to obtain a second acidic solution, and inputting the obtained second acidic solution into a settling tank 1 for solid-liquid separation;
(4) inputting the material discharged from the solid discharge port of the sedimentation tank 1 in the step (3) into a high-temperature reactor 5, calcining for 3h at 1900 ℃, naturally cooling to obtain silicon powder, and simultaneously discharging gas generated in the high-temperature reactor 5 into a tail gas treatment tank 8 filled with a mixed solution of hydrochloric acid and cuprous chloride through an exhaust pipeline 7 for tail gas treatment;
(6) and (4) inputting the material discharged from the liquid discharge port of the sedimentation tank 1 in the step (3) into a neutralization treatment tank 4, adding a mixture of sodium hydroxide and ammonium chloride into the neutralization treatment tank 4, and adjusting the pH value to 9.0-10.0.
The recovery rate of the recovered silicon powder was 95%, and the purity was 95.8%.
Example 2
(1) Carrying out gravity settling centrifugal treatment on the organic silicon waste residue slurry in a settling tank 1 to obtain waste liquid and waste residue;
(2) inputting the obtained waste residue into a first acid leaching tank 2, adding a hydrochloric acid solution with the mass 1.7 times that of the waste residue and the mass concentration of 12% into a second acid leaching tank 2, and reacting for 28 hours at the temperature of 34 ℃ and the stirring speed of 220rpm to obtain a first acid solution;
(3) inputting the obtained first acidic solution into a second acid leaching tank 3, adding a sulfuric acid solution with the mass being 2.1 times of that of the waste residue and the mass concentration being 32% into the second acid leaching tank, reacting for 2.6h at the temperature of 42 ℃ and the stirring speed of 340rpm to obtain a second acidic solution, and inputting the obtained second acidic solution into a settling pond 1 for solid-liquid separation;
(4) inputting the material discharged from the solid discharge port of the sedimentation tank 1 in the step (3) into a high-temperature reactor 5, calcining the material at the temperature of 2000 ℃ for 3.5 hours, naturally cooling the calcined material to obtain silicon powder, and simultaneously discharging gas generated in the high-temperature reactor 5 into a tail gas treatment tank 8 filled with a mixed solution of hydrochloric acid and cuprous chloride through an exhaust pipeline 7 to perform tail gas treatment;
(6) and (4) inputting the material discharged from the liquid discharge port of the sedimentation tank 1 in the step (3) into a neutralization treatment tank 4, adding a mixture of sodium hydroxide and ammonium chloride into the neutralization treatment tank 4, and adjusting the pH value to 9.0-10.0.
The recovery rate of the recovered silicon powder was 96.3%, and the purity was 96.1%.
Example 3
(1) Carrying out gravity settling centrifugal treatment on the organic silicon waste residue slurry in a settling tank 1 to obtain waste liquid and waste residue;
(2) inputting the obtained waste residue into a first acid leaching tank 2, adding a hydrochloric acid solution with the mass 1.8 times that of the waste residue and the mass concentration of 14% into a second acid leaching tank 2, and reacting for 32 hours at the temperature of 38 ℃ and the stirring speed of 260rpm to obtain a first acid solution;
(3) inputting the obtained first acidic solution into a second acid leaching tank 3, adding a sulfuric acid solution with the mass being 2.4 times of that of the waste residue and the mass concentration being 33% into the second acid leaching tank, reacting for 2.8h at the temperature of 44 ℃ and the stirring speed of 370rpm to obtain a second acidic solution, and inputting the obtained second acidic solution into a settling pond 1 for solid-liquid separation;
(4) inputting the material discharged from the solid discharge port of the sedimentation tank 1 in the step (3) into a high-temperature reactor 5, calcining for 4 hours at the temperature of 2100 ℃, naturally cooling to obtain silicon powder, and simultaneously discharging gas generated in the high-temperature reactor 5 into a tail gas treatment tank 8 filled with a mixed solution of hydrochloric acid and cuprous chloride through an exhaust pipeline 7 for tail gas treatment;
(6) and (4) inputting the material discharged from the liquid discharge port of the sedimentation tank 1 in the step (3) into a neutralization treatment tank 4, adding a mixture of sodium hydroxide and ammonium chloride into the neutralization treatment tank 4, and adjusting the pH value to 9.0-10.0.
The recovery rate of the recovered silicon powder was 97.2%, and the purity was 95.5%.
Example 4
(1) Carrying out gravity settling centrifugal treatment on the organic silicon waste residue slurry in a settling tank 1 to obtain waste liquid and waste residue;
(2) inputting the obtained waste residue into a first acid leaching tank 2, adding a hydrochloric acid solution with the mass being 2 times that of the waste residue and the mass concentration being 15% into a second acid leaching tank 2, and reacting for 24 hours at the temperature of 40 ℃ and the stirring speed of 300rpm to obtain a first acid solution;
(3) inputting the obtained first acidic solution into a second acid leaching tank 3, adding a sulfuric acid solution with the mass being 2.5 times of that of the waste residue and the mass concentration being 35% into the second acid leaching tank, reacting for 3 hours at the temperature of 45 ℃ and the stirring speed of 400rpm to obtain a second acidic solution, and inputting the obtained second acidic solution into a settling tank 1 for solid-liquid separation;
(4) inputting the material discharged from the solid discharge port of the sedimentation tank 1 in the step (3) into a high-temperature reactor 5, calcining for 5 hours at the temperature of 2200 ℃, naturally cooling to obtain silicon powder, and simultaneously discharging gas generated in the high-temperature reactor 5 into a tail gas treatment tank 8 filled with a mixed solution of hydrochloric acid and cuprous chloride through an exhaust pipeline 7 for tail gas treatment;
(6) and (4) inputting the material discharged from the liquid discharge port of the sedimentation tank 1 in the step (3) into a neutralization treatment tank 4, adding a mixture of sodium hydroxide and ammonium chloride into the neutralization treatment tank 4, and adjusting the pH value to 9.0-10.0.
The recovery rate of the recovered silicon powder was 97.8%, and the purity was 96.6%.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. The method for treating the organic silicon waste residue slurry is characterized by comprising the following steps of:
carrying out gravity centrifugal sedimentation treatment on the organic silicon waste residue slurry to obtain waste liquid and waste residue;
adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution;
adding a sulfuric acid solution into the first acidic solution, mixing and reacting to obtain a second acidic solution, and then carrying out solid-liquid separation on the second acidic solution;
calcining the solid substance obtained after the solid-liquid separation at high temperature to obtain simple substance silicon;
and adding an alkaline substance into the liquid substance obtained after the solid-liquid separation to adjust the pH value of the solution to 9.0-10.0.
2. The method for treating the organic silicon waste residue slurry as claimed in claim 1, wherein the step of adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution comprises the following steps:
the mass fraction of the hydrochloric acid solution is 10-15%, and the addition mass of the hydrochloric acid solution is 1.6-2 times of the mass of the organic silicon waste residue slurry.
3. The method for treating the organic silicon waste residue slurry as claimed in claim 1, wherein the step of adding a hydrochloric acid solution into the waste residue, and mixing and reacting to obtain a first acidic solution comprises the following steps:
the temperature of the mixing reaction is 30-40 ℃, and the time is 24-36 h.
4. The method for treating the organic silicon waste residue slurry according to claim 1, wherein a sulfuric acid solution is added into the first acidic solution, a second acidic solution is obtained after mixing and reaction, and then the step of performing solid-liquid separation on the second acidic solution comprises:
the mass fraction of the sulfuric acid solution is 30-35%, and the adding mass of the sulfuric acid solution is 2-2.5 times of the mass of the organic silicon waste residue slurry.
5. The method for treating the organic silicon waste residue slurry according to claim 1, wherein a sulfuric acid solution is added into the first acidic solution, a second acidic solution is obtained after mixing and reaction, and then the step of performing solid-liquid separation on the second acidic solution comprises:
the temperature of the mixing reaction is 40-45 ℃ and the time is 2.5-3 h.
6. The method for treating the organic silicon waste residue slurry as claimed in claim 1, wherein the step of calcining the solid substance obtained after the solid-liquid separation at a high temperature to obtain elemental silicon comprises:
the calcining temperature is 1900-2200 ℃ and the calcining time is 3-5 h.
7. The method for treating the organic silicon waste residue slurry as claimed in claim 1, wherein the step of calcining the solid substance obtained after the solid-liquid separation at a high temperature to obtain elemental silicon comprises the following steps:
and recovering the waste heat after the calcination, and introducing the gas generated in the calcination process into a mixed solution of hydrochloric acid and cuprous chloride for tail gas treatment.
8. The method for treating the organic silicon waste residue slurry according to claim 1, wherein an alkaline substance is added to the liquid substance obtained after the solid-liquid separation to adjust the pH value of the solution to 9.0-10.0, and the method comprises the following steps:
the alkaline substance is a mixture of sodium hydroxide and ammonium chloride.
9. A processing system of organosilicon waste residue thick liquid, characterized by includes:
the acid pickling device comprises a sedimentation tank, a first acid pickling tank, a second acid pickling tank and a neutralization treatment tank which are sequentially arranged, wherein the sedimentation tank is provided with a feed inlet, a solid discharge outlet and a liquid discharge outlet; and the number of the first and second groups,
and a feed inlet of the high-temperature reactor is connected with a solid discharge outlet of the sedimentation tank.
10. The system for treating waste organosilicon slag slurry according to claim 9, wherein the high-temperature reactor is provided with an exhaust port, and an exhaust pipeline is connected to the exhaust port;
the processing system of organosilicon waste residue thick liquid still includes the tail gas treatment jar, the mixed solution of hydrochloric acid and cuprous chloride is equipped with in the tail gas treatment jar, exhaust end of exhaust duct stretches into to being located in the mixed solution in the tail gas treatment jar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110986138.3A CN113582183A (en) | 2021-08-26 | 2021-08-26 | Treatment method and treatment system for organic silicon waste residue slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110986138.3A CN113582183A (en) | 2021-08-26 | 2021-08-26 | Treatment method and treatment system for organic silicon waste residue slurry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113582183A true CN113582183A (en) | 2021-11-02 |
Family
ID=78239505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110986138.3A Pending CN113582183A (en) | 2021-08-26 | 2021-08-26 | Treatment method and treatment system for organic silicon waste residue slurry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113582183A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524408A (en) * | 2022-02-14 | 2022-05-24 | 浙江大学 | Environment-friendly comprehensive recycling method of organic silicon pulp residues |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110262339A1 (en) * | 2008-09-30 | 2011-10-27 | Hartwig Rauleder | Production of solar-grade silicon from silicon dioxide |
| CN102943177A (en) * | 2012-10-29 | 2013-02-27 | 浙江特力再生资源有限公司 | Method for recovering cooper and silicon powder from organosilicon waste residue |
| CN106623370A (en) * | 2017-01-18 | 2017-05-10 | 山东省环境保护科学研究设计院 | Treatment process and system for organic silica mud |
| 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 |
| CN108570558A (en) * | 2018-05-15 | 2018-09-25 | 成都斯力康科技股份有限公司 | The method that copper is recycled from organosilicon slag slurry |
| US20180363098A1 (en) * | 2015-06-16 | 2018-12-20 | Grirem Advanced Materials Co., Ltd. | Method of recovering rare earth aluminum and silicon from rare earth-containing aluminum-silicon scraps |
| CN112321626A (en) * | 2020-11-10 | 2021-02-05 | 云南能投硅材科技发展有限公司 | Method for treating organic silicon slag slurry |
-
2021
- 2021-08-26 CN CN202110986138.3A patent/CN113582183A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110262339A1 (en) * | 2008-09-30 | 2011-10-27 | Hartwig Rauleder | Production of solar-grade silicon from silicon dioxide |
| CN102943177A (en) * | 2012-10-29 | 2013-02-27 | 浙江特力再生资源有限公司 | Method for recovering cooper and silicon powder from organosilicon waste residue |
| US20180363098A1 (en) * | 2015-06-16 | 2018-12-20 | Grirem Advanced Materials Co., Ltd. | Method of recovering rare earth aluminum and silicon from rare earth-containing aluminum-silicon scraps |
| CN106623370A (en) * | 2017-01-18 | 2017-05-10 | 山东省环境保护科学研究设计院 | Treatment process and system for organic silica mud |
| 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 |
| CN108570558A (en) * | 2018-05-15 | 2018-09-25 | 成都斯力康科技股份有限公司 | The method that copper is recycled from organosilicon slag slurry |
| CN112321626A (en) * | 2020-11-10 | 2021-02-05 | 云南能投硅材科技发展有限公司 | Method for treating organic silicon slag slurry |
Non-Patent Citations (2)
| Title |
|---|
| 刘春玲等: "有机硅渣浆无害化处理的研究", 《化工科技》 * |
| 王宇光等: "甲基氯硅烷生产中废弃物及副产物的综合利用", 《有机硅材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524408A (en) * | 2022-02-14 | 2022-05-24 | 浙江大学 | Environment-friendly comprehensive recycling method of organic silicon pulp residues |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11923518B2 (en) | Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries | |
| CN102267769B (en) | Vacuum potassium carbonate method for utilizing coke oven coal gas desulphurization and decyanation waste liquid as resource | |
| CN106623370B (en) | Organic silicon slurry slag treatment process and system | |
| CN101985359A (en) | Method for preparing thiocyanate and sulfate by utilizing desulfuration waste liquor in coking plant | |
| CN102020307B (en) | Disposal method of organic silicon copper-containing waste catalyst | |
| CN105483395B (en) | A kind of selectivity efficient from dust with zinc of electric furnace carries zinc and except the method for iron | |
| CN104628035A (en) | Resourceful utilization method of waste catalyst | |
| CN102267778B (en) | Resource method of waste liquid from coke oven gas desulphurization and decyanation | |
| CN106277006A (en) | A kind of method for refined crystalline aluminium chloride deliming | |
| CN113582183A (en) | Treatment method and treatment system for organic silicon waste residue slurry | |
| CN114031500A (en) | Preparation process of dimethyl carbonate and catalyst thereof | |
| CN102390832A (en) | Method for treating waste silicon powder produced in trichlorosilane synthesis process | |
| CN103303974B (en) | Method for recycling waste silicon slag discharged in production of zirconyl chloride | |
| CN217251531U (en) | Aluminum ash recovery processing device | |
| JP7115115B2 (en) | Method for recovering phosphate from steel slag | |
| CN102531027A (en) | Method for preparing heavy basic copper carbonate | |
| CN109095575A (en) | A method of utilizing heavy metal in carbon bisulfide hydrolytic hydrogen sulfide treatment waste acid | |
| JP2010265455A (en) | Method for producing treated coal and silica from fly ash-including coal | |
| CN109942000B (en) | Treatment device and process for slag slurry generated in cold hydrogenation synthesis process | |
| CN1232662C (en) | Method for extracting cobalt from industrial waste residue | |
| CN113699378B (en) | Method and system for treating organic silicon waste residues | |
| CN101538647A (en) | Circulating type method for reclaiming copper and coagulant from heavy metal sludge | |
| CN203333317U (en) | Equipment system for recycling sulfates from desulfurized waste liquid | |
| CN214763075U (en) | Processing device of organosilicon sediment thick liquid | |
| CN114774142B (en) | Processing system of living beings pyrolysis gas |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211102 |
|
| RJ01 | Rejection of invention patent application after publication |