CN117069232A - Resource utilization method of chromium-containing gasification slag impurity removal acid liquor - Google Patents
Resource utilization method of chromium-containing gasification slag impurity removal acid liquor Download PDFInfo
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- CN117069232A CN117069232A CN202311337705.8A CN202311337705A CN117069232A CN 117069232 A CN117069232 A CN 117069232A CN 202311337705 A CN202311337705 A CN 202311337705A CN 117069232 A CN117069232 A CN 117069232A
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- aluminum
- impurity
- chromium
- treatment
- acid liquor
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- 239000002253 acid Substances 0.000 title claims abstract description 194
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002893 slag Substances 0.000 title claims abstract description 99
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 96
- 239000011651 chromium Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 80
- 238000002309 gasification Methods 0.000 title claims description 60
- 239000012535 impurity Substances 0.000 title claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 159
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 71
- 238000004064 recycling Methods 0.000 claims abstract description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000001502 supplementing effect Effects 0.000 claims abstract description 53
- 230000003647 oxidation Effects 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012629 purifying agent Substances 0.000 claims abstract description 37
- 238000000975 co-precipitation Methods 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 28
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 27
- 230000001590 oxidative effect Effects 0.000 claims description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 21
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000003472 neutralizing effect Effects 0.000 claims description 15
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 14
- 229910001447 ferric ion Inorganic materials 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 25
- 238000000926 separation method Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- -1 poly aluminum iron calcium Chemical compound 0.000 description 8
- 239000003245 coal Substances 0.000 description 6
- 238000001784 detoxification Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000009469 supplementation Effects 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a recycling utilization method of chromium-containing gasified slag impurity-removing acid liquor, which not only realizes the step separation of iron and chromium in the chromium-containing gasified slag impurity-removing acid liquor, but also prepares a qualified aluminum-series water purifying agent through neutralization aluminum supplementing treatment, selective oxidation treatment, iron and chromium co-precipitation treatment and polymerization regulation treatment. The recycling method disclosed by the invention is mild in reaction condition, simple to operate, good in economic and environmental benefits and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a recycling method of chromium-containing gasification slag impurity-removing acid liquor.
Background
The coal gasification technology is one of the core technologies of clean coal technology and is also the basis of the process industries of coal chemical industry, hydrogen production, fuel cells and the like. Due to the limitation of coal types, processes and equipment, a large amount of gasification slag mainly composed of unburned carbon and ash is generated in the coal gasification process, and the annual generation amount exceeds 5000 ten thousand t. The gasified slag has the dual attributes of resources and environment, on one hand, the gasified slag is rich in resources such as aluminum, silicon, calcium, iron, carbon and the like, and on the other hand, compared with raw coal, the gasified slag is highly rich in heavy metal elements, and the gasified slag can cause a certain degree of harm to the ecological environment in the utilization process.
At present, the acid leaching technology is mostly needed in the gasification slag treatment.
CN116140341a discloses a gasification slag high-value resource utilization method, which comprises the following steps: acid dissolving the gasified slag to separate out metal; carrying out suction filtration on the solution after acid dissolution for a plurality of times to extract useful metals; placing the residues after acid treatment into a microwave oven chamber for radiation heating activation treatment, so that the residues form active carbon with a porous structure; adjusting the PH value of the product, and carrying out hydrothermal crystallization treatment on the activated carbon with the expanded pores to obtain a molecular sieve; and carrying out plasma auxiliary deposition on the residual residues after the acid treatment, carrying out surface chemical modification and microwave heating regeneration on the activated carbon, and obtaining the high-adsorptivity activated carbon. The method can fully extract the metal in the gasified slag, and can fully extract the metal framework in the gasified slag, so that the supporting strength is high; the long carbon effect is improved by utilizing plasma to assist deposition; and the activated carbon is modified, so that the adsorption performance is improved.
CN115465869a discloses a method for preparing poly aluminum iron calcium silicate by using gas slag, which is implemented according to the following steps: step 1, placing the gas slag into an oven for drying, and then crushing and sieving for standby by a crusher; step 2, placing the gas slag and the fluxing agent into a muffle furnace for calcination to obtain solid slag, wherein the fluxing agent accounts for 2% -25% of the mass of the gas slag; step 3, mixing the solid slag obtained in the step 2 with 5% -10% hydrochloric acid in a reaction kettle, heating and stirring, and carrying out solid-liquid separation after full acid leaching to obtain pickle liquor, wherein the solid-liquid ratio of the solid slag to the hydrochloric acid is 1:5-1:10; step 4, regulating the pH value of the pickle liquor to 3-5 by using hydrochloric acid or alkali liquor, heating to the polymerization temperature, and obtaining a crude product of polysilicate aluminum ferric calcium after full reaction; and 5, carrying out solid-liquid separation, drying, crushing and sieving on the crude product of the calcium aluminum polysilicate to obtain a finished product of the calcium aluminum polysilicate.
CN115504555a discloses a coal gas slag base composite ferric aluminum silicate flocculant, a preparation method and application thereof. Taking coal gas slag, placing the coal gas slag into a container, adding hydrochloric acid solution, stirring under a closed condition to perform acid leaching reaction, carrying out suction filtration after reacting for a period of time, carrying out solid-liquid separation, and sealing acid leaching filtrate for later use; adding sodium hydroxide into the acid leaching filtrate, curing after the solution fully reacts, standing at normal temperature to thoroughly cure the solution, drying and grinding uniformly to obtain the gas slag-based composite ferric aluminum silicate flocculant. The preparation method utilizes the natural composition of the gas slag to the greatest extent, does not need additional energy input and chemical reagent addition except acid leaching treatment, and the acid wastewater generated in the acid leaching process can be recycled for the neutralization of industrial alkaline wastewater, so that no other secondary pollutants are generated in the production process, and the flocculant has excellent performance and can treat various complex wastewater.
Although the method can fully extract useful metals in the gasified slag, heavy metals enriched in the gasified slag can enter acid liquor along with other useful metals in the acid leaching process. The acid liquor has high acid concentration and complex components, realizes the cascade separation and detoxification and resource utilization of useful metal and heavy metal components in the gasified slag impurity removal acid liquor with high safety and low cost, improves the economic and environmental benefits, and becomes the problem which needs to be solved by the current technicians in the field.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a recycling utilization method of chromium-containing gasification slag impurity removal acid liquor, which is used for carrying out aluminum supplementation twice in a proper time in the process of removing iron and chromium, so that not only is the step separation of iron and chromium realized, but also a qualified aluminum water purifying agent is prepared, the recycling utilization of aluminum is realized, and the recycling utilization method has good economic and environmental benefits and wide application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a recycling method of chromium-containing gasification slag impurity removal acid liquor, which comprises the following steps:
(1) Mixing the chromium-containing gasification slag impurity-removing acid liquor with an aluminum neutralizing agent, and then carrying out neutralization and aluminum supplementing treatment to obtain a neutralization and aluminum supplementing impurity-removing acid liquor; adding an oxidant, and performing selective oxidation treatment to obtain a treated impurity-removing acid solution;
or mixing the chromium-containing gasified slag impurity-removing acid liquor with an oxidant, and performing selective oxidation treatment to obtain oxidized impurity-removing acid liquor; then adding an aluminum neutralizing agent, and carrying out neutralization and aluminum supplementing treatment to obtain the impurity-removing acid liquor after treatment;
(2) Mixing the impurity-removing acid liquor obtained in the step (1) with a pH regulator, and performing iron-chromium coprecipitation treatment to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with a basicity regulator, and performing polymerization regulation treatment to obtain the aluminum water purifying agent.
The recycling method of the chromium-containing gasification slag impurity removal acid liquor carries out twice aluminum supplementation through neutralization aluminum supplementation treatment and polymerization regulation treatment, and finally the content of alumina in the obtained aluminum water purifying agent is more than 8.0 percent, thereby meeting the product requirement of the aluminum water purifying agent. The neutralization and aluminum supplementing treatment must use an aluminum neutralizing agent, so that the dual functions of neutralization and aluminum supplementing can be achieved; when the neutralizing agent is a non-aluminum neutralizing agent, the neutralizing agent only has the effect of neutralization, or the step of neutralizing and supplementing aluminum is not performed, so that the alumina content of alumina in the finally obtained aluminum water purifying agent is less than 8.0 percent, and the product requirement of the aluminum water purifying agent is not met. The invention also carries out neutralization and aluminum supplementing treatment before the iron-chromium coprecipitation treatment, and the aluminum neutralizer can replace more than 90% of pH regulator in the iron-chromium coprecipitation treatment, thereby greatly reducing the addition amount of the pH regulator, reducing the alkali consumption and greatly reducing the treatment cost of the chromium-containing gasified slag impurity removal acid liquor.
The neutralization and aluminum supplementing treatment can be performed before or after the selective oxidation treatment, so that the concentration of aluminum ions in the solution can be increased, and the subsequent removal of iron and chromium is not influenced. The recycling method of the chromium-containing gasification slag impurity removal acid liquor is simple to operate, realizes the step separation and recycling of aluminum calcium and iron chromium in the chromium-containing gasification slag impurity removal acid liquor, and has good economic and environmental benefits.
Preferably, the chromium-containing gasification slag impurity removal acid solution in the step (1) comprises: h of 0.5-6 mol/L + For example, it may be 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, etc.;
the aluminum element of 5 to 100g/L may be, for example, 5g/L, 15g/L, 25g/L, 35g/L, 45g/L, 55g/L, 65g/L, 75g/L, 85g/L, 95g/L, 100g/L or the like;
the calcium element of 5 to 100g/L may be, for example, 5g/L, 15g/L, 25g/L, 35g/L, 45g/L, 55g/L, 65g/L, 75g/L, 85g/L, 95g/L, 100g/L or the like;
the iron element of 5 to 100g/L may be, for example, 5g/L, 15g/L, 25g/L, 35g/L, 45g/L, 55g/L, 65g/L, 75g/L, 85g/L, 95g/L, 100g/L or the like;
the chromium element of 200 to 1000ppm may be, for example, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm or 1000ppm, etc., but is not limited to the values listed, and other values not listed in the above-mentioned respective ranges are equally applicable.
The chromium element content in the chromium-containing gasified slag impurity-removing acid liquor is 200-1000 ppm, and the chromium-containing gasified slag impurity-removing acid liquor is discharged directly without treatment, so that the chromium-containing gasified slag impurity-removing acid liquor has serious influence on the environment and organisms. According to the recycling utilization method of the chromium-containing gasification slag impurity removal acid liquor, the condition of each metal element in the acid liquor is fully considered, the selective oxidation treatment is firstly carried out, divalent iron ions are fully oxidized into trivalent iron ions, and trivalent chromium ions are controlled not to be oxidized, so that the purpose of reducing the precipitation pH of the trivalent chromium ions is achieved; and then adding a pH regulator into the treated impurity-removed acid liquor by utilizing the difference of precipitation pH values, and accurately controlling the end-point pH value to induce the iron and chromium to perform coprecipitation and simultaneously controlling the aluminum and calcium not to perform precipitation so as to realize synchronous enrichment of the iron and the chromium.
The aluminum water purifying agent finally obtained by the recycling method of the chromium-containing gasification slag impurity removal acid liquor can meet the requirements of GB/T22627-2022 water treatment agent polyaluminium chloride, the content of aluminum oxide is more than or equal to 8%, and the basicity is 20% -98%.
Preferably, the aluminum-based neutralizing agent of step (1) comprises any one or a combination of at least two of calcium aluminate, aluminum oxide or aluminum hydroxide, of which typical but non-limiting examples are: a combination of calcium aluminate and aluminum oxide, a combination of calcium aluminate and aluminum hydroxide, or a combination of aluminum oxide and aluminum hydroxide, etc.
Preferably, the dosage of the aluminum neutralizer is 4-12 mL/g, which is the liquid-solid ratio of the chromium-containing gasification slag impurity-removing acid liquor and the aluminum neutralizer in the neutralization and aluminum supplementing treatment or the liquid-solid ratio of the impurity-removing acid liquor and the aluminum neutralizer after oxidation; for example, the concentration of the catalyst may be 4mL/g, 5mL/g, 6mL/g, 7mL/g, 8mL/g, 10mL/g, 12mL/g, etc., but the catalyst is not limited to the values listed, and other values not listed in the range of the values are equally applicable.
Preferably, the pH of the neutralization aluminum-supplementing impurity-removing acid solution in step (1) is less than 1, and may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The pH value of the neutralization aluminum-supplementing impurity-removing acid liquor is preferably less than 1, so that the effect of preventing ferric ions from hydrolyzing to generate ferric hydroxide colloid in the neutralization aluminum-supplementing process to cause difficult solid-liquid separation is achieved, and meanwhile, the phenomenon that ferric ions are lost in the neutralization aluminum-supplementing process to cause subsequent difficulty in inducing iron-chromium coprecipitation is avoided.
The temperature of the neutralization and aluminum-supplementing treatment is preferably 30 to 90 ℃, and may be, for example, 30 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, or 90 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the time for the neutralization and aluminum-supplementing treatment is 30 to 120min, for example, 30min, 50min, 60min, 70min, 80min, 90min, 100min or 120min, but the present invention is not limited to the listed values, and other values not listed in the range of the values are applicable.
Preferably, the oxidizing agent in step (1) is hydrogen peroxide.
The oxidant is preferably hydrogen peroxide, so that the complete selective oxidation of iron can be realized, and chromium is not oxidized; when other types of oxidants are selected, part or all of the chromium is oxidized simultaneously, and selective oxidation of iron cannot be achieved, which is disadvantageous for the subsequent iron-chromium co-precipitation treatment.
Preferably, the amount of the oxidizing agent is 1.0 to 2.0 times the theoretical amount required for oxidizing all ferrous ions in the neutralization aluminum-supplementing impurity-removing acid solution or the chromium-containing gasification slag impurity-removing acid solution to ferric ions, and may be, for example, 1.0 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, or 2.0 times, etc., but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The temperature of the selective oxidation treatment in the step (1) is preferably 30 to 90 ℃, and may be, for example, 30 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, or 90 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the time of the selective oxidation treatment is 10 to 60 minutes, for example, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, or the like, but the time is not limited to the listed values, and other values not listed in the range of the values are equally applicable.
Preferably, the pH adjuster in the step (2) includes sodium hydroxide, and the pH of the treated impurity-removed acid solution is adjusted to 1.5-3.0, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0, but not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
The pH value of the impurity-removing acid liquor after treatment is preferably adjusted to 1.5-3.0, and when the final pH value is less than 1.5, the coprecipitation rate of iron and chromium is too low, so that the detoxification effect of the impurity-removing acid liquor by selective oxidation is poor; when the pH value of the alkalization end point is more than 3.0, although the coprecipitation effect of iron and chromium is good, at the moment, aluminum can be precipitated, so that the aluminum content in the aluminum-rich impurity-removing acid liquor is lost, and the quality of the aluminum-based water purifying agent is affected.
The temperature of the iron-chromium coprecipitation treatment is preferably 50 to 90 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, or 90 ℃, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
Preferably, the time of the iron-chromium co-precipitation treatment is 30-180 min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min, etc., but the present invention is not limited to the listed values, and other non-listed values in the range of the values are applicable.
Preferably, the basicity modifier of step (3) comprises any one or a combination of at least two of calcium aluminate, alumina or aluminum hydroxide, of which typical but non-limiting examples are: a combination of calcium aluminate and aluminum oxide, a combination of calcium aluminate and aluminum hydroxide, or a combination of aluminum oxide and aluminum hydroxide, etc.
Preferably, the dosage of the basicity regulator is 6-14 mL/g, which is the liquid-solid ratio of the aluminum-rich impurity-removing acid liquid and the basicity regulator in the polymerization regulation treatment; for example, the concentration of the catalyst may be 6mL/g, 7mL/g, 8mL/g, 10mL/g, 11mL/g, 12mL/g, 14mL/g, etc., but the catalyst is not limited to the values listed, and other values not listed in the range are equally applicable.
The polymerization control treatment is preferably carried out at a temperature of 60 to 90 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, or 90 ℃, but the polymerization control treatment is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are applicable.
The polymerization regulation treatment temperature is preferably 60-90 ℃, so that the efficient dissolution of the pH regulator is enhanced, and the double advantages of improving the concentration of aluminum ions in the aluminum water purifying agent product and controlling the basicity are achieved. When the temperature is lower than 60 ℃, the dissolution rate of aluminum ions in the basicity regulator is too low, so that the content of aluminum oxide in the aluminum water purifying agent is less than 8 percent and is lower than the national standard requirement; when the temperature is higher than 90 ℃, the polymerization degree is too high, the basicity of the aluminum water purifying agent is higher than 98%, the solid-liquid separation is difficult, and the loss rate of aluminum ions is high.
Preferably, the polymerization control treatment time is 60 to 180min, for example, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min, but not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
As a preferable technical scheme of the invention, the resource utilization method comprises the following steps:
(1) Mixing the chromium-containing gasification slag impurity-removing acid liquor with an aluminum neutralizing agent, and then carrying out neutralization and aluminum supplementing treatment to obtain a neutralization and aluminum supplementing impurity-removing acid liquor with the pH value of less than 1; adding an oxidant, and performing selective oxidation treatment to obtain a treated impurity-removing acid solution;
or mixing the chromium-containing gasified slag impurity-removing acid liquor with an oxidant, and performing selective oxidation treatment to obtain oxidized impurity-removing acid liquor; then adding an aluminum neutralizing agent, and carrying out neutralization and aluminum supplementing treatment to obtain the impurity-removing acid liquor after treatment;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components:
h of 0.5-6 mol/L +
5-100 g/L of aluminum element
5-100 g/L of calcium element
Iron element of 5-100 g/L
200-1000 ppm of chromium element;
the aluminum neutralizer comprises any one or a combination of at least two of calcium aluminate, aluminum oxide or aluminum hydroxide; the dosage of the aluminum neutralizer is 4-12 mL/g;
the temperature of the neutralization and aluminum supplementing treatment is 30-90 ℃; the time for the neutralization and aluminum supplementing treatment is 30-120 min;
the oxidant is hydrogen peroxide; the dosage of the oxidant is 1.0-2.0 times of the theoretical dosage required by oxidizing all ferrous ions in the neutralization aluminum-supplementing impurity-removing acid liquor or the chromium-containing gasification slag impurity-removing acid liquor into ferric ions;
the temperature of the selective oxidation treatment is 30-90 ℃; the time of the selective oxidation treatment is 10-60 min;
(2) Mixing the impurity-removing acid liquor obtained in the step (1) with a pH regulator, and performing iron-chromium coprecipitation treatment at 50-90 ℃ for 30-180 min to obtain aluminum-enriched impurity-removing acid liquor;
the pH regulator comprises sodium hydroxide, and the pH of the treated impurity-removed acid liquor is regulated to 1.5-3.0;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with a basicity regulator, and performing polymerization regulation treatment at 60-90 ℃ for 60-180 min to obtain an aluminum water purifying agent;
the basicity regulator comprises any one or a combination of at least two of calcium aluminate, aluminum oxide or aluminum hydroxide; the dosage of the basicity regulator is 6-14 mL/g.
In a second aspect, the invention also provides an aluminum water purifying agent obtained by the recycling method of the chromium-containing gasification slag impurity removal acid liquor in the first aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
the recycling method of the chromium-containing gasification slag impurity removal acid liquor provided by the invention has the advantages of mild reaction conditions and simple operation, realizes the step separation and recycling of aluminum calcium and iron chromium in the chromium-containing gasification slag impurity removal acid liquor, has remarkable economic and environmental benefits, and can be popularized and applied to the fields of treatment and utilization of the heavy metal-containing acid liquor.
Drawings
Fig. 1 is a schematic flow chart of a recycling method of the chromium-containing gasification slag impurity removal acid liquor provided in embodiment 1 of the invention.
Fig. 2 is a schematic flow chart of a recycling method of the chromium-containing gasification slag impurity removal acid liquor provided in embodiment 2 of the invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides a recycling method of chromium-containing gasification slag impurity removal acid liquor, and a flow diagram of the recycling method is shown in figure 1;
the recycling method comprises the following steps:
(1) Mixing chromium-containing gasification slag impurity-removing acid liquor with calcium aluminate, and then carrying out neutralization and aluminum supplementing treatment to obtain neutralization and aluminum supplementing impurity-removing acid liquor with pH value of less than 1; adding hydrogen peroxide, and performing selective oxidation treatment to obtain the impurity-removed acid liquor after treatment; the dosage of the calcium aluminate is 6mL/g;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components: h of 2.5mol/L + 16.24g/L of aluminum element, 22.56g/L of calcium element, 13.18g/L of iron element and 334ppm of chromium element;
the temperature of the neutralization and aluminum supplementing treatment is 80 ℃; the time for the neutralization and aluminum supplementing treatment is 60min;
the dosage of the hydrogen peroxide is 1.5 times of the theoretical dosage required by oxidizing all ferrous ions in the neutralization aluminum supplementing and impurity removing acid liquor into ferric ions;
the temperature of the selective oxidation treatment is 60 ℃; the time of the selective oxidation treatment is 30min;
(2) Mixing the treated impurity-removing acid liquor obtained in the step (1) with sodium hydroxide, adjusting the pH value of the treated impurity-removing acid liquor to 2.0, and performing iron-chromium coprecipitation treatment at 60 ℃ for 60min to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with calcium aluminate, and performing polymerization regulation treatment at 80 ℃ for 120min to obtain an aluminum water purifying agent; the dosage of the calcium aluminate is 8mL/g.
Example 2
The embodiment provides a recycling method of chromium-containing gasification slag impurity removal acid liquor, and a flow diagram of the recycling method is shown in fig. 2;
the recycling method comprises the following steps:
(1) Mixing the chromium-containing gasified slag impurity-removing acid liquor with hydrogen peroxide, and performing selective oxidation treatment to obtain oxidized impurity-removing acid liquor; adding aluminum oxide, and performing neutralization and aluminum supplementing treatment to obtain the impurity-removed acid liquor after treatment;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components: h of 2.5mol/L + 16.24g/L of aluminum element, 22.56g/L of calcium element, 13.18g/L of iron element and 334ppm of chromium element;
the temperature of the neutralization and aluminum supplementing treatment is 60 ℃; the time for the neutralization and aluminum supplementing treatment is 120min; the dosage of the aluminum oxide is 10mL/g;
the dosage of the hydrogen peroxide is 1.2 times of the theoretical dosage required by oxidizing all ferrous ions in the impurity-removing acid liquor of the chromium-containing gasification slag into ferric ions;
the temperature of the selective oxidation treatment is 80 ℃; the time of the selective oxidation treatment is 60min;
(2) Mixing the treated impurity-removing acid liquor obtained in the step (1) with sodium hydroxide, adjusting the pH value of the treated impurity-removing acid liquor to 2.5, and performing iron-chromium coprecipitation treatment at 80 ℃ for 120min to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with calcium aluminate, and performing polymerization regulation treatment at 80 ℃ for 60min to obtain an aluminum water purifying agent; the dosage of the calcium aluminate is 8mL/g.
Example 3
The embodiment provides a recycling method of chromium-containing gasification slag impurity removal acid liquor, which comprises the following steps:
(1) Mixing the chromium-containing gasification slag impurity-removing acid liquor with aluminum hydroxide, and then carrying out neutralization and aluminum supplementing treatment to obtain the neutralization and aluminum supplementing impurity-removing acid liquor with the pH value of 0.4; adding hydrogen peroxide, and performing selective oxidation treatment to obtain the impurity-removed acid liquor after treatment;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components: h of 2.5mol/L + 16.24g/L of aluminum element, 22.56g/L of calcium element, 13.18g/L of iron element and 334ppm of chromium element;
the temperature of the neutralization and aluminum supplementing treatment is 30 ℃; the time for the neutralization and aluminum supplementing treatment is 30min; the dosage of the aluminum hydroxide is 8mL/g;
the dosage of the hydrogen peroxide is 1.8 times of the theoretical dosage required by oxidizing all ferrous ions in the neutralization aluminum supplementing and impurity removing acid liquor into ferric ions;
the temperature of the selective oxidation treatment is 30 ℃; the time of the selective oxidation treatment is 20min;
(2) Mixing the treated impurity-removing acid liquor obtained in the step (1) with sodium hydroxide, adjusting the pH value of the treated impurity-removing acid liquor to 1.6, and performing iron-chromium coprecipitation treatment at 80 ℃ for 120min to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with aluminum hydroxide, and performing polymerization regulation treatment at 80 ℃ for 60min to obtain an aluminum-based water purifying agent; the dosage of the aluminum hydroxide is 12mL/g.
Example 4
The embodiment provides a recycling method of chromium-containing gasification slag impurity removal acid liquor, which comprises the following steps:
(1) Mixing the chromium-containing gasification slag impurity-removing acid liquor with aluminum hydroxide, and then carrying out neutralization and aluminum supplementing treatment to obtain the neutralization and aluminum supplementing impurity-removing acid liquor with the pH value of 0.9; adding hydrogen peroxide, and performing selective oxidation treatment to obtain the impurity-removed acid liquor after treatment;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components: h of 2.5mol/L + 16.24g/L of aluminum element, 22.56g/L of calcium element, 13.18g/L of iron element and 334ppm of chromium element;
the temperature of the neutralization and aluminum supplementing treatment is 90 ℃; the time for the neutralization and aluminum supplementing treatment is 120min; the dosage of the aluminum hydroxide is 8mL/g;
the dosage of the hydrogen peroxide is 1.2 times of the theoretical dosage required by oxidizing all ferrous ions in the neutralization aluminum supplementing and impurity removing acid liquor into ferric ions;
the temperature of the selective oxidation treatment is 30 ℃; the time of the selective oxidation treatment is 60min;
(2) Mixing the treated impurity-removing acid liquor obtained in the step (1) with sodium hydroxide, adjusting the pH value of the treated impurity-removing acid liquor to 2.8, and performing iron-chromium coprecipitation treatment at 80 ℃ for 180min to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with calcium aluminate, and performing polymerization regulation treatment at 80 ℃ for 120min to obtain an aluminum water purifying agent; the dosage of the calcium aluminate is 8mL/g.
Example 5
The embodiment provides a recycling method of chromium-containing gasification slag impurity removal acid liquor, which comprises the following steps:
(1) Mixing the chromium-containing gasification slag impurity-removing acid liquor with alumina, and then carrying out neutralization and aluminum supplementing treatment to obtain neutralization and aluminum supplementing impurity-removing acid liquor with pH value of less than 1; adding hydrogen peroxide, and performing selective oxidation treatment to obtain the impurity-removed acid liquor after treatment;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components: h of 2.5mol/L + 16.24g/L of aluminum element, 22.56g/L of calcium element, 13.18g/L of iron element and 334ppm of chromium element;
the temperature of the neutralization and aluminum supplementing treatment is 90 ℃; the time for the neutralization and aluminum supplementing treatment is 120min; the dosage of the aluminum oxide is 12mL/g;
the dosage of the hydrogen peroxide is 2.0 times of the theoretical dosage required by oxidizing all ferrous ions in the neutralization aluminum supplementing and impurity removing acid liquor into ferric ions;
the temperature of the selective oxidation treatment is 90 ℃; the time of the selective oxidation treatment is 60min;
(2) Mixing the treated impurity-removing acid liquor obtained in the step (1) with sodium hydroxide, adjusting the pH value of the treated impurity-removing acid liquor to 2.4, and performing iron-chromium coprecipitation treatment at 50 ℃ for 120min to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with aluminum hydroxide, and performing polymerization regulation treatment at 60 ℃ for 180min to obtain an aluminum water purifying agent; the dosage of the aluminum hydroxide is 12mL/g.
Example 6
The embodiment provides a recycling method of chromium-containing gasification slag impurity removal acid liquor, which comprises the following steps:
(1) Mixing the chromium-containing gasified slag impurity-removing acid liquor with hydrogen peroxide, and performing selective oxidation treatment to obtain oxidized impurity-removing acid liquor; then adding calcium aluminate, and carrying out neutralization and aluminum supplementing treatment to obtain the impurity-removed acid liquor after treatment;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components: h of 2.5mol/L + 16.24g/L of aluminum element, 22.56g/L of calcium element, 13.18g/L of iron element and 334ppm of chromium element;
the temperature of the neutralization and aluminum supplementing treatment is 50 ℃; the time for the neutralization and aluminum supplementing treatment is 60min; the dosage of the calcium aluminate is 6mL/g;
the dosage of the hydrogen peroxide is 1.0 times of the theoretical dosage required by oxidizing all ferrous ions in the impurity-removing acid liquor of the chromium-containing gasification slag into ferric ions;
the temperature of the selective oxidation treatment is 80 ℃; the time of the selective oxidation treatment is 20min;
(2) Mixing the treated impurity-removing acid liquor obtained in the step (1) with sodium hydroxide, adjusting the pH value of the treated impurity-removing acid liquor to 1.5, and performing iron-chromium coprecipitation treatment at 90 ℃ for 180min to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with aluminum oxide, and performing polymerization regulation treatment at 80 ℃ for 120min to obtain an aluminum water purifying agent; the amount of alumina was 14mL/g.
Example 7
The present embodiment provides a recycling method for the impurity-removing acid solution of the chromium-containing gasified slag, and the recycling method is the same as that of embodiment 1 except that the oxidizing agent hydrogen peroxide in step (1) is replaced by calcium hypochlorite, so that no description is given here.
Example 8
The present embodiment provides a method for recycling the impurity-removing acid solution of the chromium-containing gasified slag, and the method for recycling the impurity-removing acid solution of the chromium-containing gasified slag is the same as that of embodiment 1 except that the pH of the neutralization and aluminum-supplementing impurity-removing acid solution in step (1) is 2, so that no description is given here.
Example 9
The present embodiment provides a method for recycling the impurity-removing acid solution of the chromium-containing gasification slag, and the method for recycling the impurity-removing acid solution is the same as that of embodiment 1 except that the amount of the calcium aluminate in step (3) is 4mL/g, so that no description is given here.
Example 10
The present embodiment provides a method for recycling the impurity-removing acid solution of the chromium-containing gasification slag, and the method for recycling the impurity-removing acid solution is the same as that of embodiment 1 except that the amount of the calcium aluminate in step (3) is 16mL/g, so that no description is given here.
Example 11
The present embodiment provides a method for recycling the impurity-removed acid solution of the chromium-containing gasified slag, and the method for recycling the impurity-removed acid solution is the same as that of embodiment 1 except that the temperature of the polymerization regulation treatment in step (3) is 50 ℃, so that the description thereof will not be repeated here.
Example 12
The present embodiment provides a method for recycling the impurity-removed acid solution of the chromium-containing gasified slag, and the method for recycling the impurity-removed acid solution is the same as that of embodiment 1 except that the temperature of the polymerization regulation treatment in step (3) is 100 ℃, so that no description is given here.
Comparative example 1
The comparative example provides a recycling method of the impurity-removing acid liquor of the chromium-containing gasification slag, and the recycling method is the same as that of example 1 except that the aluminum neutralizer calcium aluminate in step (1) is replaced by calcium oxide, so that the description thereof is omitted.
Comparative example 2
The comparative example provides a recycling method of the chromium-containing gasification slag impurity removal acid liquor, and the recycling method is the same as that of example 1 except that the neutralization and aluminum supplementing treatment in step (1) is not performed, so that the description thereof will not be repeated.
Comparative example 3
The comparative example provides a recycling method of the chromium-containing gasification slag impurity removal acid liquor, and the recycling method is the same as that of example 1 except that the selective oxidation treatment in step (1) is not performed, so that the description thereof will not be repeated here.
Comparative example 4
The comparative example provides a recycling method of the impurity-removed acid solution of the chromium-containing gasified slag, and the recycling method is the same as that of example 1 except that the pH of the impurity-removed acid solution treated in step (2) is adjusted to 1.2 to perform the iron-chromium co-precipitation treatment, so that no description is given here.
Comparative example 5
The comparative example provides a recycling method of the impurity-removed acid solution of the chromium-containing gasified slag, and the recycling method is the same as that of example 1 except that the pH of the impurity-removed acid solution treated in step (2) is adjusted to 3.5 to perform the iron-chromium co-precipitation treatment, so that no description is given here.
The iron precipitation rate, the chromium precipitation rate, the aluminum precipitation rate, and the alumina content of the aluminum-based water purifying agent in the above examples and comparative examples were measured by the ICP-OES test method, and the results are shown in Table 1.
TABLE 1
As can be seen from table 1:
(1) According to comprehensive examples 1-6, the recycling method of the chromium-containing gasification slag impurity removal acid liquor provided by the invention realizes the step separation and recycling of aluminum and calcium and iron and chromium, the iron precipitation rate can reach 88.28%, the chromium precipitation rate can reach 76.62% and the aluminum content of the aluminum-based water purifying agent can reach 15.49%, so that the method has good economic benefit and environmental benefit;
(2) As can be seen from the combination of example 1 and example 7, the replacement of the oxidizing agent hydrogen peroxide in step (1) in example 7 with calcium hypochlorite results in that part or all of chromium is oxidized simultaneously with iron, so that the complete selective oxidation of iron cannot be realized, the subsequent iron-chromium coprecipitation treatment is not convenient, the chromium precipitation rate is too low, and is only 35.68%, and the detoxification effect is poor;
(3) It can be seen from the combination of the examples 1 and 8 that the pH >1 of the neutralization and aluminum-supplementing impurity-removing acid solution described in the example 8 can cause the hydrolysis of ferric ions to generate ferric hydroxide colloid in the neutralization and aluminum-supplementing process, which results in difficult solid-liquid separation, and the loss of ferric ions in the neutralization and aluminum-supplementing process, which results in the subsequent difficulty in inducing iron-chromium co-precipitation, resulting in too low chromium precipitation rate of 42.38% and poor detoxification effect;
(4) It can be seen from the combination of examples 1 and 9-10 that the use of less calcium aluminate in example 9 results in less than 8.0% of alumina in the final aluminum water purifying agent, which does not meet the product requirements of the aluminum water purifying agent; in the embodiment 10, the use amount of the calcium aluminate is large, so that the basicity of the product is too high, the product requirement of the aluminum water purifying agent is not met, the preparation cost of the aluminum water purifying agent is increased, and the economical efficiency of the recycling method is poor;
(5) It can be seen from the combination of examples 1 and 11-12 that the lower temperature of the polymerization regulation treatment in example 11 can result in too low dissolution rate of aluminum ions in the basicity regulator, so that the aluminum oxide content in the aluminum water purifying agent is less than 8%, which is lower than the national standard requirement; the higher polymerization control treatment temperature described in example 12 can result in too high polymerization degree, resulting in basicity of aluminum water purifying agent greater than 98% and exceeding national standard requirements;
(6) As can be seen from the comprehensive examples 1 and 1, in the comparative example 1, the aluminum-based neutralizer calcium aluminate is replaced by calcium oxide, and has only a neutralization effect, so that aluminum supplementation cannot be realized, and the aluminum content in the impurity-removing acid liquor is too low, so that the aluminum oxide content of the water purifying agent is only 6.28% and less than 8.0%, and the product requirement of the aluminum-based water purifying agent is not met;
(7) As can be seen from the comprehensive examples 1 and 2, the comparative example 2 does not perform the neutralization and aluminum supplementing treatment, so that the aluminum content in the aluminum-rich impurity-removing acid liquor is too low, and is insufficient for preparing qualified aluminum-based water purifying agent through polymerization regulation, and the aluminum-based water purifying agent has the aluminum oxide content of only 5.38% and less than 8.0%;
(8) As can be seen from the comprehensive examples 1 and 3, in the comparative example 3, the selective oxidation treatment is not performed, and at this time, most of iron in the impurity-removed acid solution exists in the form of divalent ions and cannot be precipitated at a low pH value, so that in the subsequent iron-chromium coprecipitation treatment process, the efficient detoxification of the impurity-removed acid solution cannot be realized, the iron precipitation rate is only 6.32%, and the chromium precipitation rate is only 3.56%;
(9) As can be seen from the comprehensive examples 1 and comparative examples 4-5, the pH value of the impurity-removed acid solution after treatment in comparative example 4 is adjusted to be less than 1.5, and iron-chromium co-precipitation treatment is performed, at this time, the co-precipitation rate of trivalent iron and trivalent chromium is too low, so that the detoxification effect of the impurity-removed acid solution is poor, the iron precipitation rate is only 18.36%, and the chromium precipitation rate is only 14.33%; the pH of the treated impurity-removing acid solution in comparative example 5 was adjusted to be greater than 3.0, and iron-chromium co-precipitation was performed, and although the co-precipitation effect of iron and chromium was good at this time, aluminum in the impurity-removing acid solution was precipitated, resulting in excessive loss of aluminum content in the aluminum-rich impurity-removing acid solution, an aluminum precipitation rate of 67.15%, and an aluminum oxide content in the aluminum-based water purifying agent of only 7.44%, which did not meet the product requirements of the aluminum-based water purifying agent.
In conclusion, the recycling method of the chromium-containing gasification slag impurity removal acid liquor provided by the invention realizes the cascade separation and recycling of aluminum, calcium, iron and chromium, has mild reaction conditions, is simple to operate, has obvious economic and environmental benefits, and can be popularized and applied to the fields of treatment and utilization of the heavy metal-containing acid pickle.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The recycling method of the chromium-containing gasification slag impurity removal acid liquor is characterized by comprising the following steps of:
(1) Mixing the chromium-containing gasification slag impurity-removing acid liquor with an aluminum neutralizing agent, and then carrying out neutralization and aluminum supplementing treatment to obtain a neutralization and aluminum supplementing impurity-removing acid liquor; adding an oxidant, and performing selective oxidation treatment to obtain a treated impurity-removing acid solution;
or mixing the chromium-containing gasified slag impurity-removing acid liquor with an oxidant, and performing selective oxidation treatment to obtain oxidized impurity-removing acid liquor; then adding an aluminum neutralizing agent, and carrying out neutralization and aluminum supplementing treatment to obtain the impurity-removing acid liquor after treatment;
(2) Mixing the impurity-removing acid liquor obtained in the step (1) with a pH regulator, and performing iron-chromium coprecipitation treatment to obtain aluminum-enriched impurity-removing acid liquor;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with a basicity regulator, and performing polymerization regulation treatment to obtain the aluminum water purifying agent.
2. The recycling method according to claim 1, wherein the chromium-containing gasification slag impurity removal acid liquid in step (1) comprises:
h of 0.5-6 mol/L +
5-100 g/L of aluminum element
5-100 g/L of calcium element
Iron element of 5-100 g/L
200-1000 ppm of chromium element.
3. The recycling method according to claim 1, wherein the aluminum-based neutralizing agent in step (1) comprises any one or a combination of at least two of calcium aluminate, aluminum oxide, or aluminum hydroxide;
the dosage of the aluminum neutralizer is 4-12 mL/g.
4. The recycling method according to claim 1, wherein the pH of the neutralization aluminum-supplementing impurity-removing acid solution in step (1) is <1;
the temperature of the neutralization and aluminum supplementing treatment is 30-90 ℃;
the time for the neutralization and aluminum supplementing treatment is 30-120 min.
5. The recycling method according to claim 1, wherein the oxidizing agent in the step (1) is hydrogen peroxide;
the dosage of the oxidant is 1.0-2.0 times of the theoretical dosage required by oxidizing all ferrous ions in the neutralization aluminum-supplementing impurity-removing acid liquor or the chromium-containing gasification slag impurity-removing acid liquor into ferric ions.
6. The recycling method according to claim 1, wherein the temperature of the selective oxidation treatment in the step (1) is 30-90 ℃;
the time of the selective oxidation treatment is 10-60 min.
7. The recycling method according to claim 1, wherein the pH adjuster in step (2) comprises sodium hydroxide, and the pH of the treated impurity-removed acid solution is adjusted to 1.5-3.0;
the temperature of the iron-chromium coprecipitation treatment is 50-90 ℃;
the time of the iron-chromium coprecipitation treatment is 30-180 min.
8. The recycling method according to claim 1, wherein the basicity modifier of step (3) comprises any one or a combination of at least two of calcium aluminate, aluminum oxide or aluminum hydroxide;
the dosage of the basicity regulator is 6-14 mL/g;
the temperature of the polymerization regulation treatment is 60-90 ℃;
the polymerization regulation treatment time is 60-180 min.
9. The recycling method according to claim 1, characterized in that the recycling method comprises the steps of:
(1) Mixing the chromium-containing gasification slag impurity-removing acid liquor with an aluminum neutralizing agent, and then carrying out neutralization and aluminum supplementing treatment to obtain a neutralization and aluminum supplementing impurity-removing acid liquor with the pH value of less than 1; adding an oxidant, and performing selective oxidation treatment to obtain a treated impurity-removing acid solution;
or mixing the chromium-containing gasified slag impurity-removing acid liquor with an oxidant, and performing selective oxidation treatment to obtain oxidized impurity-removing acid liquor; then adding an aluminum neutralizing agent, and carrying out neutralization and aluminum supplementing treatment to obtain the impurity-removing acid liquor after treatment;
the chromium-containing gasification slag impurity removal acid liquor comprises the following components:
h of 0.5-6 mol/L +
5-100 g/L of aluminum element
5-100 g/L of calcium element
Iron element of 5-100 g/L
200-1000 ppm of chromium element;
the aluminum neutralizer comprises any one or a combination of at least two of calcium aluminate, aluminum oxide or aluminum hydroxide; the dosage of the aluminum neutralizer is 4-12 mL/g;
the temperature of the neutralization and aluminum supplementing treatment is 30-90 ℃; the time for the neutralization and aluminum supplementing treatment is 30-120 min;
the oxidant is hydrogen peroxide; the dosage of the oxidant is 1.0-2.0 times of the theoretical dosage required by oxidizing all ferrous ions in the neutralization aluminum-supplementing impurity-removing acid liquor or the chromium-containing gasification slag impurity-removing acid liquor into ferric ions;
the temperature of the selective oxidation treatment is 30-90 ℃; the time of the selective oxidation treatment is 10-60 min;
(2) Mixing the treated impurity-removing acid liquor in the step (1) with a pH regulator, regulating the pH of the treated impurity-removing acid liquor to 1.5-3.0, and performing iron-chromium coprecipitation treatment at 50-90 ℃ for 30-180 min to obtain aluminum-enriched impurity-removing acid liquor;
the pH regulator comprises sodium hydroxide;
(3) Mixing the aluminum-enriched impurity-removing acid liquor obtained in the step (2) with a basicity regulator, and performing polymerization regulation treatment at 60-90 ℃ for 60-180 min to obtain an aluminum water purifying agent;
the basicity regulator comprises any one or a combination of at least two of calcium aluminate, aluminum oxide or aluminum hydroxide; the dosage of the basicity regulator is 6-14 mL/g.
10. An aluminum water purifying agent obtained by a recycling method of the chromium-containing gasification slag impurity removal acid liquor according to any one of claims 1 to 9.
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