CN111203427A - System and method for co-processing waste glass powder and pickling waste liquid - Google Patents
System and method for co-processing waste glass powder and pickling waste liquid Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 98
- 239000007788 liquid Substances 0.000 title claims abstract description 86
- 238000005554 pickling Methods 0.000 title claims abstract description 62
- 239000011521 glass Substances 0.000 title claims abstract description 61
- 239000000843 powder Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000002253 acid Substances 0.000 claims abstract description 74
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 239000006096 absorbing agent Substances 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 238000009833 condensation Methods 0.000 claims abstract description 11
- 230000005494 condensation Effects 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 58
- 239000006228 supernatant Substances 0.000 claims description 32
- 238000001704 evaporation Methods 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims description 17
- 239000003814 drug Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 11
- 159000000009 barium salts Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 235000021110 pickles Nutrition 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 50
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 7
- 229940104869 fluorosilicate Drugs 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 229910003638 H2SiF6 Inorganic materials 0.000 description 15
- 229910004014 SiF4 Inorganic materials 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910020440 K2SiF6 Inorganic materials 0.000 description 3
- 229910004883 Na2SiF6 Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910004074 SiF6 Inorganic materials 0.000 description 2
- 239000010922 glass waste Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
Images
Classifications
-
- 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
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a cooperative treatment system and a treatment method for waste glass powder and pickling waste liquid, wherein the treatment system comprises a waste acid tank, a glass powder tank, a first reaction device, a separation device, an evaporator, a condensation absorber, a dosing tank, a second reaction device, a precipitation device, a centrifugal machine, a regenerated acid tank and a crystallization device; the treatment method of the invention treats waste with waste, and can recover fluorosilicate and nitric acid, the waste water is reused in the production line, the zero discharge of waste liquid is realized, and meanwhile, the hydrofluoric acid and the nitric acid realize the product conversion and the recycling, so a large amount of dangerous waste residues generated by neutralization are greatly reduced, the treatment cost is saved, and good economic benefit and environmental benefit are generated.
Description
Technical Field
The invention relates to the technical field of waste treatment, in particular to a system and a method for cooperatively treating waste glass powder and pickling waste liquid.
Background
A large amount of waste glass exists in glass production and processing enterprises, the waste glass in urban garbage is the most common garbage, and the statistics data of the united nations show that 7 percent of global solid waste residues are glass.
Because of incomplete garbage classification in China, low glass recovery value and the like, the recovery rate of glass waste is low, and the glass waste is generally treated in a landfill mode, so that resources are wasted and land is occupied.
In stainless steel product processing enterprises, two-stage pickling process is often adopted, the first stage pickling adopts sulfuric acid pickling, the second stage adopts mixed acid of nitric acid and hydrofluoric acid to prepare pickling solution to clean the surface oxide film of stainless steel, after repeated cleaning, the concentration of metal ions in the pickling solution is increased, the cleaning effect is reduced, and finally the stainless steel has to be discarded. Waste liquid generated by the two-stage pickling process is mixed, and is also referred to as waste acid hereinafter. The waste acid contains sulfuric acid, nitric acid, hydrofluoric acid, a large amount of heavy metal ions, iron ions and the like, and the traditional method adopts lime for neutralization to generate a large amount of waste residues.
How to recycle waste glass becomes a hot point of research in recent years, and a large amount of nitric acid and hydrofluoric acid in pickling waste liquid causes serious pollution to the environment. If the two can be fully utilized for recycling, changing waste into valuable and turning harmful into beneficial, the method has positive benefits on the environment.
Disclosure of Invention
Accordingly, there is a need for a treatment system and a treatment method for co-treating waste glass powder and pickling waste liquid to realize recycling.
A system for the co-processing of waste glass powder and pickling waste liquid comprises:
the waste acid tank is used for storing pickling waste liquid;
the glass powder groove is used for storing glass powder;
the first reaction device is used for reacting the pickling waste liquid of the waste acid tank with the glass powder in the glass powder storage tank to obtain a reaction liquid;
the separation device is used for carrying out solid-liquid separation on the reaction liquid after the reaction to obtain supernatant;
the evaporator is used for heating and evaporating the supernatant to obtain an evaporated liquid;
the condensation absorber is used for condensing and absorbing the evaporated liquid to obtain condensate;
the medicine feeding groove is used for storing soluble salt medicines which react with the condensate;
and the second reaction device is used for reacting the condensate with the medicament.
This processing system can coprocessing waste glass powder and stainless steel pickling waste liquid, and the reaction principle is as follows:
4HF+SiO2→SiF4↑+2H2O (1)；
SiF4+2HF→H2SiF6(2)；
2NaNO3+H2SiF6→Na2SiF6↓+2HNO3(3)；
2KNO3+H2SiF6→K2SiF6↓+2HNO3(4)；
Ba(NO3)2+H2SiF6→Ba F6Si↓+2HNO3(5)；
hydrofluoric acid in the waste acid reacts with silicon dioxide in the glass powder to generate SiF4By thermal evaporation, SiF4And HF, HNO3Is evaporated and condensed to obtain mixed acid, SiF4Condensing and absorbing the hydrogen fluoride, and further reacting the hydrogen fluoride with hydrofluoric acid to generate H2SiF6The fluosilicic acid reacts with soluble sodium, potassium and barium salts to generate sodium fluosilicate, potassium fluosilicate and barium fluosilicate precipitates for separation.
In one embodiment, the treatment system further comprises a precipitation device for performing solid-liquid separation on the reaction liquid after the reaction in the second reaction device.
In one embodiment, the processing system further comprises a centrifuge for centrifuging the sediment after the sediment is settled by the settling device.
In one embodiment, the treatment system further comprises a crystallization device for cooling the residual mother liquor of the evaporator.
In one embodiment, a heater and a stirrer are arranged in the first reaction device.
In one embodiment, a feeder is arranged between the glass powder groove and the first reaction device, and the feeder feeds the glass powder into the first reaction device.
In one embodiment, the treatment system further comprises a sulfuric acid tank for adding sulfuric acid to the evaporator.
In one embodiment, the treatment device further comprises a regenerated acid tank, and the regenerated acid tank is used for storing and storing supernatant of the precipitation device to be reused as the pickling supplementary liquid.
In one embodiment, the agent is a soluble sodium, potassium or barium salt.
In one embodiment, the agent in the treatment device is sodium nitrate, potassium nitrate or barium nitrate.
A method for the cooperative treatment of waste glass powder and pickling waste liquid comprises the following steps:
reacting the waste pickle liquor to be treated with glass powder to obtain reaction liquid;
standing the reaction solution after the reaction to precipitate and separate reaction residues to obtain a supernatant;
heating and evaporating the supernatant to obtain an evaporated liquid;
condensing and absorbing the evaporated liquid to obtain condensate;
the condensate reacts with the soluble salt medicament.
In one embodiment, the processing device further comprises a step of precipitating and separating the reaction liquid obtained after the condensate liquid reacts with the medicament to obtain a precipitate.
In one embodiment, the processing device further comprises a step of cooling and crystallizing the evaporation residual liquid for heating and evaporating the supernatant, and the liquid after cooling and crystallizing is recycled as the pickling supplementary liquid.
In one embodiment, the processing device further comprises a step of supplementing sulfuric acid during heating and evaporating the supernatant.
In one embodiment, the method further comprises the steps of centrifuging and washing the precipitate to obtain filtrate and a solid product.
In one embodiment, the method further comprises the step of recycling supernatant and filtrate obtained after the reaction liquid obtained after the condensate and the medicament are reacted is precipitated as acid washing supplementary liquid.
In one embodiment, the agent is a soluble sodium, potassium or barium salt, preferably sodium, potassium or barium nitrate.
Drawings
FIG. 1 is a schematic structural diagram of a system for co-processing waste glass powder and pickle liquor according to an embodiment;
FIG. 2 is a schematic flow chart of a co-processing method of waste glass powder and pickle liquor according to an embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Referring to fig. 1, a system for co-processing waste glass powder and waste pickling solution according to an embodiment includes a waste acid tank 10, a glass powder tank 20, a feeder 21, a first reaction device 30, a separation device 40, an evaporator 50, a sulfuric acid tank 51, a condensation absorber 60, a dosing tank 70, a second reaction device 80, a precipitation device 90, a centrifuge 91, a regenerated acid tank 100, and a crystallization device 101;
the waste acid tank 10 is used for storing pickling waste liquid; in the pickling process of stainless steel products, a two-stage pickling process is generally adopted, wherein the first stage pickling process adopts sulfuric acid pickling, the second stage adopts mixed acid of nitric acid and hydrofluoric acid to prepare pickling solution to clean the surface oxide film of the stainless steel, after repeated cleaning, the concentration of metal ions in the pickling solution is increased, and waste liquid generated by the two-stage pickling process is mixed to obtain the stainless steel pickling waste liquid of the embodiment. The waste acid of the stainless steel pickling waste liquid contains sulfuric acid, nitric acid, hydrofluoric acid, a large amount of heavy metal ions, iron ions and the like.
The glass powder groove 20 is used for storing waste glass powder; the glass powder tank 20 is connected with a feeder 21, and the feeder 21 can feed the glass powder in the glass powder tank 20 to the first reaction device 30 according to the residual amount in the stainless steel pickling waste liquid in a proper proportion;
the first reaction device 30 is used for reacting the waste pickle liquor of the waste acid tank with the waste glass powder of the glass powder tank; a stirrer and a heater (not shown in the figure) are arranged in the first reaction device 30, and the appropriate reaction temperature can be controlled to fully perform the reaction, specifically, the appropriate temperature is 30-40 ℃, in this range, the reaction can be facilitated, the temperature is too low, the reaction is not thorough, and the acid can escape due to too high temperature.
The waste acid tank 10 is communicated with a first reaction device 30 through a delivery pump 11, the delivery pump 11 delivers the pickling waste liquid into the first reaction device 30, a feeder feeds glass powder into the first reaction device 30, a stirrer and a heater in the first reaction device 30 are started, and simultaneously, the glass powder is added according to a certain proportion according to the content of hydrofluoric acid in the waste acid, and the heating reaction and the continuous stirring are carried out, so that the reaction of the hydrofluoric acid and the glass powder is more thorough, and a reaction solution is obtained; the chemical principle of the reaction is as follows:
4HF+SiO2→SiF4↑+2H2O (1)；
hydrofluoric acid in the waste acid reacts with silicon dioxide in the glass powder to generate SiF4；
The separation device 40 is used for carrying out solid-liquid separation on the reaction liquid after the reaction, settling and separating reaction residues through standing, and discarding glass powder residues to obtain supernatant; specifically, the separation device 40 communicates with the first reaction device 30 through a pipe;
the evaporator 50 is used for heating and evaporating the supernatant separated by the separation device to obtain an evaporated liquid; evaporator 50 andthe separation device 40 is communicated through a pipeline; by evaporation under heating, SiF4And HF, HNO3Is evaporated out; further, the evaporator 50 employs a decompression evaporator;
the sulfuric acid tank 51 is used for replenishing sulfuric acid in the evaporator, specifically, the sulfuric acid tank 51 is communicated with the evaporator 50 through a sulfuric acid dosing pump 52, and when the concentration of the sulfuric acid in the evaporator 50 is insufficient, the sulfuric acid tank 51 is conveyed to the evaporator 50 through the sulfuric acid dosing pump 52 for replenishment;
the condensation absorber 60 is configured to condense and absorb the evaporated liquid evaporated by the evaporator 50 to obtain a condensate; specifically, the condensation absorber 60 communicates with the evaporator 50. Condensing to obtain mixed acid, SiF4Condensing and absorbing the hydrogen fluoride, and further reacting the hydrogen fluoride with hydrofluoric acid to generate H2SiF6Specifically, the chemical principle of the reaction is:
SiF4+2HF→H2SiF6(2)；
the medicine adding tank 70 is used for storing soluble salt medicines which react with the condensate; specifically, the soluble metal salt agent is soluble sodium salt, potassium salt or barium salt, and the soluble metal salt agent can not bring pollution of new ions, and in one embodiment, the soluble salt can be one of sodium nitrate, potassium nitrate and barium nitrate.
The second reaction means 80 is used to react the condensate with the soluble pharmaceutical agent. The second reaction apparatus 80 is provided with a stirrer and a heater (not shown) for controlling a suitable reaction temperature to allow the reaction to proceed sufficiently. Wherein the dosing tank 70 is communicated with the second reaction device 80 through the dosing pump 71, the condensation absorber 60 is communicated with the second reaction device 80, the condensate and the soluble salt medicament are conveyed to the second reaction device 80, the stirrer and the associated heater in the second reaction device 80 are started, and the heating reaction and the continuous stirring are carried out to ensure that H is reacted and stirred continuously2SiF6Reacting with soluble sodium, potassium and barium salts to generate sodium fluosilicate, potassium fluosilicate and barium fluosilicate precipitates;
specifically, the chemical principle of the reaction is:
2NaNO3+H2SiF6→Na2SiF6↓+2HNO3(3)；
2KNO3+H2SiF6→K2SiF6↓+2HNO3(4)；
Ba(NO3)2+H2SiF6→Ba F6Si↓+2HNO3(5)；
the precipitation device 90 is used for performing solid-liquid separation on the reaction liquid after the reaction in the second reaction device. The precipitation device 90 is communicated with the second reaction device 80;
the centrifuge 91 is used for centrifugally separating precipitates precipitated by the precipitation device 90, specifically, the precipitation device 90 is communicated with the centrifuge 91 through a slurry pump 92, and the centrifuge 91 centrifuges to obtain filtrate and a solid fluorosilicate product;
the regenerated acid tank 100 is used for storing the supernatant of the precipitation device 90 or the filtrate obtained after centrifugal separation by the centrifuge 91, and is used as the supplementary solution of the acid tank of the second-stage acid washing process for recycling. The second-stage pickling process is a pickling process in the cleaning process of the stainless steel product, and mixed acid of nitric acid and hydrofluoric acid is adopted to prepare pickling solution to clean the surface oxide film of the stainless steel; wherein, the precipitation device 90 is communicated with the evaporator 50, the condensation absorber 60 and the regenerated acid tank 100 in sequence; the centrifuge 91 is communicated with the evaporator 50, the condensation absorber 60 and the regenerated acid tank 100 in sequence; namely, the supernatant of the precipitation device 90 and the filtrate after centrifugal separation by the centrifuge 91 are evaporated by the evaporator, the recovered acid liquid (nitric acid) is evaporated, the condensed absorber 60 is cooled and then enters the regenerated acid tank 100 to be reused for acid liquid supplement of the second-stage acid washing process of the production line and then returned to the acid washing tank.
The crystallizing device 101 is used to cool the residual evaporation raffinate from the evaporator 50. The remaining liquid from the evaporator 50 is cooled by the crystallizer 101 to crystallize and separate out the metal salt. The residual liquid can be used as cleaning waste water of a first-stage acid cleaning process (sulfuric acid cleaning is adopted in the first-stage acid cleaning), and when the concentration of acid in the liquid is high enough, the residual liquid is used as waste acid for repeated treatment, so that zero emission of the waste acid is realized.
The working process of the processing system of the embodiment is as follows:
the method comprises the steps of introducing the pickling waste liquid in a waste acid tank 10 into a first reaction device 30 through a conveying pump 11, starting a stirrer 31 and a heater 32 in the first reaction device 30, adding glass powder according to the content of hydrofluoric acid in waste acid, heating, reacting and continuously stirring to enable the hydrofluoric acid to react with the glass powder more thoroughly, carrying out solid-liquid separation after the reaction is finished, discarding glass powder residues, pumping the obtained supernatant into an evaporator 50 for evaporation, condensing and absorbing the evaporated liquid through a condensing absorber 60, collecting the evaporated liquid in a second reaction device 80, adding soluble sodium salt, potassium salt or barium salt into the second reaction device 80, and precipitating and separating the generated fluosilicate in the second reaction device 80 in a precipitation device 90. And (3) centrifugally separating sediments at the bottom of the precipitation device 90 to obtain a fluorosilicate product, and returning nitric acid contained in the supernatant and the centrifugally separated filtrate of the precipitation device 90 to the pickling workshop of the first pickling process stage for recycling. The residual liquid after evaporation in the evaporator 50 is cooled to crystallize and separate out the metal salt, and the residual liquid can be used as cleaning wastewater in the first pickling process section, and when the acid concentration in the residual liquid is high enough, the residual liquid is used as waste acid to be repeatedly treated by the process, so that zero discharge of the waste acid is realized.
Referring to fig. 2, a method for co-processing waste glass powder and waste pickle liquor includes the following steps:
step S100: reacting the waste pickle liquor to be treated with glass powder to obtain reaction liquid;
the pickling waste liquid is a waste liquid mixed liquid of two-stage pickling processes of a stainless steel product pickling process, specifically, a first-stage pickling process adopts sulfuric acid pickling, a second-stage pickling process adopts mixed acid of nitric acid and hydrofluoric acid to prepare a pickling liquid for cleaning an oxide film on the surface of stainless steel, after repeated cleaning, the concentration of metal ions in the pickling liquid is increased, and waste liquids generated by the two-stage pickling processes are mixed to obtain the stainless steel pickling waste liquid of the embodiment.
Furthermore, the waste acid of the stainless steel pickling waste liquid contains sulfuric acid, nitric acid, hydrofluoric acid, a large amount of heavy metal ions, iron ions and the like.
In the embodiment, the waste pickling solution is fed into the first reaction device 30 through the waste acid tank 10 and the delivery pump 11; the glass powder passes through a feeder 21 from a glass powder tank 20, and the feeder 21 can feed the glass powder in the glass powder tank 20 to a first reaction device 30 according to the residual amount in the stainless steel pickling waste liquid in a proper proportion;
starting a stirrer 31 and a heater 32 in the first reaction device 30, heating for reaction and continuously stirring to ensure that the reaction of hydrofluoric acid and glass powder is more thorough to obtain a reaction solution; the chemical principle of the reaction is as follows:
4HF+SiO2→SiF4↑+2H2O (1)；
hydrofluoric acid in the waste acid reacts with silicon dioxide in the glass powder to generate SiF4；
Step S110: carrying out solid-liquid separation on the reaction liquid after the reaction to obtain supernatant;
further, solid-liquid separation is carried out on the reaction liquid after the reaction by adopting a separation device 40, the reaction residue is precipitated and separated by standing, and the glass powder residue is discarded to obtain supernatant;
step S120: heating and evaporating the supernatant to obtain an evaporated liquid;
further, the separated supernatant is heated and evaporated by an evaporator 50 to obtain an evaporated liquid; by evaporation under heating, SiF4And HF, HNO3Is evaporated out; further, a reduced pressure evaporation mode is adopted;
when the concentration of sulfuric acid is insufficient during the evaporation process, the method may further include step S121: acid liquor is supplemented in the evaporation process, and when the concentration of sulfuric acid is appropriate in the evaporation process, the step S121 can be omitted.
Specifically, a sulfuric acid tank 51 is adopted for replenishing sulfuric acid in the evaporator, and the sulfuric acid is conveyed from the sulfuric acid tank 51 to the evaporator 50 through a sulfuric acid dosing pump 52 for replenishing;
step S120 is followed by step S121: and (3) cooling and crystallizing residual mother liquor obtained after heating and evaporating the supernatant, and recycling the supernatant obtained after cooling and crystallizing as an acid washing supplementary solution.
Specifically, the residual mother liquid of the evaporator 50 is cooled by the crystallizing device 101. The evaporation residual liquid of the evaporator 50 is cooled by the crystallizing device 101, the metal salt is crystallized and separated out and can be used as cleaning waste water of a first-stage pickling process (sulfuric acid pickling is adopted in the first-stage pickling process), and when the concentration of acid in the liquid is high enough, the liquid is repeatedly treated as waste acid, so that zero emission of waste acid is realized.
Step S130: condensing and absorbing the evaporated liquid to obtain condensate;
condensing and absorbing the evaporated liquid evaporated by the evaporator 50 by using a condensation absorber 60 to obtain a condensate; condensing to obtain mixed acid, SiF4Condensing and absorbing the hydrogen fluoride, and further reacting the hydrogen fluoride with hydrofluoric acid to generate H2SiF6Specifically, the chemical principle of the reaction is:
SiF4+2HF→H2SiF6(2)；
step S140: and (3) reacting the condensate with a soluble salt medicament.
Reacting the soluble salt medicament in the medicament feeding groove 70 with the condensate in the second reaction device 80; specifically, the soluble metal salt agent is soluble sodium salt, potassium salt or barium salt, and the soluble metal salt agent can not bring pollution of new ions, and in one embodiment, the soluble salt can be one of sodium nitrate, potassium nitrate and barium nitrate.
The stirrer 81 and the associated heater 82 in the second reaction apparatus 80 were started to heat the reaction and continue stirring, thereby causing H to be generated2SiF6Reacting with soluble sodium, potassium and barium salts to generate sodium fluosilicate, potassium fluosilicate and barium fluosilicate precipitates;
specifically, the chemical principle of the reaction is:
2NaNO3+H2SiF6→Na2SiF6↓+2HNO3(3)；
2KNO3+H2SiF6→K2SiF6↓+2HNO3(4)；
Ba(NO3)2+H2SiF6→Ba F6Si↓+2HNO3(5)；
step S150: and carrying out solid-liquid separation on the reaction liquid obtained after the condensate liquid reacts with the medicament to obtain a supernatant and a precipitate.
Step S160: carrying out centrifugal separation and washing on the precipitate to obtain filtrate and a solid product;
specifically, the centrifugal machine 91 is adopted to centrifugally separate the precipitate precipitated by the precipitation device 90, and specifically, the centrifugal machine 91 is used to centrifugally obtain filtrate and a solid fluorosilicate product.
Step S170: and (4) recycling the filtrate obtained after centrifugation and the supernatant obtained after precipitation in the step (S150) as an acid washing supplementary solution.
Specifically, step S170 includes:
step S171: evaporating the filtrate obtained after centrifugation and the supernatant precipitated in the step S150 to obtain acid liquor;
specifically, the acid solution (nitric acid) is evaporated by evaporation in the evaporator 50;
step S172: cooling the acid liquor, and then recycling the acid liquor as an acid washing supplementary solution;
specifically, the acid solution enters the regenerated acid tank 100 after being cooled by the condensation absorber 60, and is recycled for the second-stage acid washing process of the production line (the acid washing process in the second-stage stainless steel product cleaning process is to use mixed acid of nitric acid and hydrofluoric acid to prepare acid washing solution for cleaning the surface oxide film of the stainless steel) and then is supplemented by the acid solution in the acid washing tank.
The system and the method for the cooperative treatment of the waste glass powder and the pickling waste liquid have the following advantages that:
1) the treatment method of the embodiment treats waste by waste, can recover fluorosilicate and nitric acid, recycles waste water to a production line, realizes zero discharge of waste liquid, and simultaneously realizes product conversion and recycling of hydrofluoric acid and nitric acid, so that a large amount of dangerous waste residues generated by neutralization are greatly reduced, the treatment cost is saved, and good economic benefit and environmental benefit are generated.
2) The method has the advantages of recycling waste, realizing zero discharge of the stainless steel pickling waste liquid, obtaining silicate products and nitric acid and greatly reducing the sewage treatment cost of stainless steel pickling enterprises. The process method is reliable, low in cost, small in equipment occupation area and large in treatment capacity, can realize recycling, reduction and harmlessness of wastes, and is suitable for popularization.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (16)
1. The utility model provides a coprocessing system of abandonment glass powder and pickling waste liquid which characterized in that includes:
the waste acid tank is used for storing pickling waste liquid;
the glass powder groove is used for storing waste glass powder;
the first reaction device is used for reacting the waste pickling liquid in the waste acid tank with the waste glass powder in the glass powder tank to obtain a reaction liquid;
the separation device is used for carrying out solid-liquid separation on the reaction liquid after the reaction to obtain supernatant;
the evaporator is used for heating and evaporating the supernatant to obtain an evaporated liquid;
the condensation absorber is used for condensing and absorbing the evaporated liquid to obtain condensate;
the medicine feeding groove is used for storing soluble salt medicines which react with the condensate;
and the second reaction device is used for reacting the condensate with the soluble salt medicament.
2. The treatment system according to claim 1, further comprising a precipitation device for performing solid-liquid separation on the reaction liquid reacted in the second reaction device.
3. The processing system of claim 2, further comprising a centrifuge that centrifuges the sediment after sedimentation by the sedimentation device.
4. The processing system according to claim 1, further comprising a crystallization device for cooling residual mother liquor of the evaporator.
5. The treatment system of claim 1, wherein a heater and a stirrer are provided in the first reaction apparatus and the second reaction apparatus.
6. The processing system according to claim 1, wherein a feeder is provided between the glass powder tank and the first reaction device, and the feeder feeds the glass powder into the first reaction device.
7. The treatment system of claim 1, further comprising a sulfuric acid tank for adding sulfuric acid to the evaporator.
8. The treatment system of claim 3, further comprising a regenerated acid tank for storing supernatant from the settling device or filtrate from centrifuge centrifugation for reuse as a makeup acid wash.
9. The treatment system according to claim 1, wherein the agent is a soluble sodium, potassium or barium salt, preferably the agent is sodium, potassium or barium nitrate.
10. A method for the cooperative treatment of waste glass powder and pickling waste liquid is characterized by comprising the following steps:
reacting the waste pickle liquor to be treated with glass powder to obtain reaction liquid;
carrying out solid-liquid separation on the reaction liquid after the reaction to obtain supernatant;
heating and evaporating the supernatant to obtain an evaporated liquid;
condensing and absorbing the evaporated liquid to obtain condensate;
and (3) reacting the condensate with a soluble salt medicament.
11. The treatment method according to claim 10, further comprising a step of subjecting the reaction solution obtained by reacting the condensate with the chemical to solid-liquid separation to obtain a supernatant and a precipitate.
12. The process of claim 10, further comprising the step of cooling and crystallizing the evaporated raffinate from the heated and evaporated supernatant, wherein the cooled and crystallized liquid is recycled as a makeup acid wash.
13. The process of claim 10, further comprising the step of adding sulfuric acid during the heating and evaporating of the supernatant.
14. The process of claim 11, further comprising the step of centrifuging and washing the precipitate to obtain a filtrate and a solid product.
15. The method according to claim 14, further comprising the step of recycling a supernatant and a filtrate obtained by precipitating the reaction solution obtained by reacting the condensate with the chemical as the acid-washing replenishment solution.
16. The treatment process according to claim 10, characterized in that said agent is a soluble sodium, potassium or barium salt, preferably sodium, potassium or barium nitrate.
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