CN115959643B - Method for recycling byproduct phosphate and iron and steel pickling byproduct ferric salt - Google Patents
Method for recycling byproduct phosphate and iron and steel pickling byproduct ferric salt Download PDFInfo
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- CN115959643B CN115959643B CN202211549828.3A CN202211549828A CN115959643B CN 115959643 B CN115959643 B CN 115959643B CN 202211549828 A CN202211549828 A CN 202211549828A CN 115959643 B CN115959643 B CN 115959643B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000006227 byproduct Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000005554 pickling Methods 0.000 title claims abstract description 50
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 45
- 239000010959 steel Substances 0.000 title claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 40
- 238000004064 recycling Methods 0.000 title claims abstract description 34
- 150000003839 salts Chemical class 0.000 title claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 25
- 239000010452 phosphate Substances 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 71
- 238000005406 washing Methods 0.000 claims abstract description 44
- 239000012535 impurity Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 33
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 33
- 239000005562 Glyphosate Substances 0.000 claims abstract description 32
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229940097068 glyphosate Drugs 0.000 claims abstract description 32
- 239000002699 waste material Substances 0.000 claims abstract description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003017 phosphorus Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- 150000002505 iron Chemical class 0.000 claims abstract description 18
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 14
- 239000003463 adsorbent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 239000012528 membrane Substances 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 31
- 239000005955 Ferric phosphate Substances 0.000 claims description 24
- 229940032958 ferric phosphate Drugs 0.000 claims description 24
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 24
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 238000001223 reverse osmosis Methods 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000010413 mother solution Substances 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000001728 nano-filtration Methods 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 150000004714 phosphonium salts Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 3
- 229960002218 sodium chlorite Drugs 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 9
- 239000012452 mother liquor Substances 0.000 abstract description 9
- 230000002829 reductive effect Effects 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 3
- 239000008394 flocculating agent Substances 0.000 abstract 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 7
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 238000009270 solid waste treatment Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a resource utilization method of byproduct phosphate and iron and steel pickling byproduct ferric salt, which comprises the following steps: fully dissolving and hydrolyzing the glyphosate byproduct phosphate, filtering, sequentially adding an oxidizing aid and an adsorbent into the obtained filtrate, and filtering again to obtain a filtrate, namely a phosphate purifying liquid; adding water into iron salt which is a byproduct of steel pickling to dissolve, adding an iron simple substance and a flocculating agent into the solution, and filtering to obtain a ferrous purification liquid; mixing the phosphorus salt purifying liquid and the ferrous purifying liquid with hydrogen peroxide to perform a synthetic reaction to prepare an iron phosphate product, and enabling the reaction mother liquor and the primary washing waste liquid to enter a sodium chloride recovery and water recycling unit after chemical impurity removal and filtration. On one hand, the invention can reduce the raw material cost of iron phosphate production to the greatest extent and improve the utilization rate of iron element; on the other hand, the recycling of phosphate and the recycling of sodium ions and chloride ions can be realized; meanwhile, the water recycling is realized, and the water consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of chemical production, in particular to a resource utilization method of glyphosate byproduct phosphate and iron and steel pickling byproduct ferric salt.
Background
Iron phosphate is an important chemical raw material, and in recent years, is widely used as a precursor for synthesizing lithium iron phosphate as a positive electrode material of a lithium battery. Currently, iron phosphate is gradually replacing other precursors and becomes a core precursor of lithium iron phosphate. Iron phosphate is obtained by reacting ferrous salts with phosphoric acid/phosphate under the action of an oxidizing agent.
Glyphosate is the herbicide product with the greatest global usage amount at present, and a large amount of high-concentration organophosphorus wastewater is generated in the production process, and is commonly called as 'glyphosate mother liquor', and the phosphorus wastewater is directly discharged without proper treatment, so that serious environmental pollution is caused, and larger resource waste is brought. At present, common treatment modes of the glyphosate mother liquor comprise a high-temperature incineration technology, a wet catalytic oxidation technology and the like. However, the phosphorus salt product obtained by the treatment method has high impurity content, poor product quality and low economic value. The related art CN114933289A discloses a co-production process for glyphosate and ferric phosphate, which sequentially carries out membrane separation, high-temperature oxidation and electrodialysis on glyphosate mother liquor to obtain mixed acid comprising phosphoric acid and hydrochloric acid, and then reacts with iron powder to prepare the ferric phosphate. The process is only suitable for the wet catalytic oxidation technology of the glyphosate mother liquor, cannot be suitable for the high-temperature incineration technology, and has the advantages of complex electrodialysis device structure, incomplete desalination and low water recovery rate.
In China, a plurality of cold rolled steel continuous pickling production lines are provided, and the surfaces of the steel products need to be pickled in the deep processing process to remove iron scales on the surfaces, wherein the most commonly used pickling solution is hydrochloric acid, so that a large amount of hydrochloric acid pickling waste liquid is generated. The hydrochloric acid pickling waste liquid generally contains 1% -5% of hydrochloric acid and 5% -20% of ferrous chloride/ferric chloride, and is listed in the national hazardous waste directory because of serious corrosiveness. The current treatment methods comprise a high-temperature roasting method, an extraction method, an ion exchange method, a membrane treatment method and a crystallization method. The obtained ferric salt product has higher impurity content and lower economic value through a simple crystallization method. In the related art CN114804215A, a method for producing battery grade ferrous chloride from cold rolled steel pickling waste acid is disclosed, and the method removes metal ion impurities by adding sulfur-containing compounds, but more ferrous sulfide precipitates are generated at the same time, so that the utilization rate of iron element in the solution is reduced.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a resource utilization method of glyphosate byproduct phosphate and iron and steel pickling byproduct ferric salt, which can reduce the raw material cost of iron phosphate production to the greatest extent and improve the utilization rate of iron element on one hand; on the other hand, the recycling of phosphate and the recycling of sodium ions and chloride ions can be realized; meanwhile, the water recycling is realized, and the water consumption is reduced.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The resource utilization method of byproduct phosphate and iron and steel pickling byproduct ferric salt comprises the following steps:
Purifying treatment of byproduct phosphate: fully dissolving and hydrolyzing the glyphosate byproduct phosphonium salt under the conditions of proper temperature and pH value, filtering, sequentially adding an oxidizing auxiliary agent into the obtained filtrate for oxidation reaction, adsorbing by an adsorbent, and filtering to obtain filtrate, namely a phosphonium salt purifying solution;
Purifying treatment of iron and steel pickling byproduct ferric salt: adding water into iron salt which is a byproduct of steel pickling to dissolve, adding iron simple substance into the solution to perform reduction and displacement reaction to reduce Fe 3+ in the solution and reduce and precipitate part of heavy metal ion impurities, adding flocculant, and filtering to obtain ferrous purification liquid;
The synthesis process of the ferric phosphate comprises the following steps: mixing a proper amount of phosphorus salt purifying liquid and ferrous iron purifying liquid with hydrogen peroxide for synthesis reaction, and after the reaction is completed, sequentially performing the procedures of filtering, washing, drying and de-crystallization to obtain an anhydrous ferric phosphate product, wherein the mixed liquid of the reaction mother solution and the primary washing waste liquid enters a sodium chloride recovery and water recycling unit after chemical impurity removal and filtration.
In some technical schemes, in the purification treatment step of the byproduct phosphorus salt,
The temperature of the dissolution and the hydrolysis of the glyphosate byproduct phosphate is 25-35 ℃, and the pH value is adjusted to 3-5 by utilizing a pH regulator; and/or the number of the groups of groups,
The oxidizing auxiliary agent is one or a combination of more of hydrogen peroxide, sodium perchlorate, sodium chlorate, sodium chlorite and sodium hypochlorite; and/or the number of the groups of groups,
The addition amount of the oxidizing auxiliary agent is 0.01-3% of the mass of the byproduct phosphate salt of the glyphosate; and/or the number of the groups of groups,
The adsorbent is activated carbon adsorbent, and the addition amount of the adsorbent is 0.05-0.3% of the mass of the filtrate.
In some technical schemes, in the purification treatment step of the byproduct ferric salt of steel pickling, the method further comprises the following steps:
Before adding the flocculant, the pH value of the solution is regulated to be 4.0-5.5 by utilizing a pH regulator so as to realize the hydrolytic precipitation of partial metal ion impurities in the solution, and the flocculant is used for reduction precipitation and removal of hydrolytic precipitation.
In some technical schemes, in the purification treatment step of the byproduct ferric salt of the steel pickling,
The addition amount of the iron simple substance is 1% -2% of the mass of iron salt which is a byproduct of steel pickling; and/or the number of the groups of groups,
The flocculant is added with 0.1-0.2 g per liter of ferrous salt solution.
In some technical schemes, the specific steps of mixing a proper amount of phosphorus salt purifying liquid and ferrous iron purifying liquid with hydrogen peroxide for synthesis reaction are as follows:
Taking a proper amount of phosphorus salt purifying liquid and ferrous purifying liquid according to the molar ratio P of Fe= (1-1.2), regulating the pH value of the ferrous purifying liquid to 1.5-3 by utilizing a pH regulator, firstly introducing the ferrous purifying liquid into a reaction kettle, heating to 40-45 ℃, and stopping heating the reaction kettle; then
Mixing the phosphorus salt purifying liquid and hydrogen peroxide, introducing the mixture into the reaction kettle containing the ferrous purifying liquid, carrying out oxidation and precipitation reaction, heating the reaction liquid to 55-60 ℃ by exothermic heat, preserving heat for 1-1.5 h, and then heating to 95-98 ℃ and preserving heat for 1.5-4 h; wherein the method comprises the steps of
The addition amount of the hydrogen peroxide is 0.6 to 0.8 times of the molar mass of the iron salt byproduct in the steel pickling.
In some embodiments, during the step of synthesizing the iron phosphate,
The washing adopts a multistage membrane circulation washing mode, and the washing waste liquid of the later stage is applied to the washing of the upper stage until the pH value of the washing waste liquid is 2.7-3.5.
In some technical schemes, in the synthesis process of ferric phosphate, the specific steps of chemical impurity removal are as follows:
firstly, regulating the pH value of the mixed solution of the reaction mother solution and the washing waste liquid to 3-6, then adding sulfide impurity removing agent into the mixed solution to carry out precipitation reaction,
The sulfide impurity removing agent is at least one of sodium sulfide, potassium sulfide, barium sulfide, ferrous sulfide and ammonium sulfide; and/or the number of the groups of groups,
The addition amount of the sulfide impurity removing agent is 0.3-3% of the mass of iron salt which is a byproduct of steel pickling.
In some technical solutions, the step of recycling further includes:
Sodium chloride recovery process: the mixed solution of the mother solution subjected to chemical impurity removal and filtration treatment and the washing waste liquid is sequentially treated by a nanofiltration membrane and a reverse osmosis membrane, the sodium chloride concentrated solution discharged from the reverse osmosis membrane is directly used as the production raw material of an ionic membrane caustic soda device matched with the upstream of glyphosate production, and directly enters an ionic membrane caustic soda process to obtain sodium hydroxide, chlorine and hydrogen, the chlorine and the hydrogen synthesize hydrochloric acid, and the sodium hydroxide and the hydrochloric acid can be recycled in a system or sold.
In some technical solutions, the step of recycling further includes:
the water recycling process comprises the following steps: the concentrated solution obtained from the nanofiltration membrane is reused for dissolving and hydrolyzing the byproduct phosphate salt of glyphosate; the clear liquid from the reverse osmosis membrane is reused in the washing procedure in the ferric phosphate synthesis process.
In some embodiments, the pH adjuster is at least one of phosphoric acid, hydrochloric acid, sodium hydroxide, sodium carbonate, and sodium bicarbonate solution.
The technical scheme adopted by the invention has at least the following beneficial effects:
1. According to the invention, the glyphosate byproduct phosphate is used as a phosphorus source, the iron and steel pickling byproduct ferric salt is used as an iron source, and two wastes are applied to the preparation of the high-added-value ferric phosphate material, so that the aim of changing waste into valuables is fulfilled, the raw material cost of ferric phosphate production is reduced to the greatest extent, and channels for comprehensively utilizing waste resources among different industries are opened;
2. In the process flow, the glyphosate byproduct phosphate and the iron and steel pickling byproduct ferric salt are purified respectively, and filter residues with high impurity content are discharged out of the system in the purification treatment process, so that the accumulation of impurities in the system is reduced, and the purity of a final product is improved;
3. According to the invention, through a post chemical impurity removal process, metal impurity ions in the mother liquor and the washing waste liquor are removed, the accumulation of the metal impurity ions in the system is reduced, compared with the pre chemical impurity removal process, the utilization rate of iron element can be remarkably improved under the condition that the performance of an iron phosphate product is not affected, and the process flow and the equipment are relatively simple, the occupied area is small, and the investment is small;
4. The reaction mother liquor and the first washing waste liquor after iron phosphate synthesis contain sodium chloride and phosphate resources, and after impurity removal and filtration, the sodium chloride is recycled and water is recycled, so that the recycling of phosphate and the recycling of sodium ions and chloride ions are realized, meanwhile, the effective recycling of washing water is realized, the water consumption is greatly reduced, the evaporation and sewage treatment procedures are not needed, the requirements of green recycling economy are met, and the national call of energy conservation and emission reduction is responded.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, reference will be made to the drawings and the signs used in the embodiments, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for recycling a glyphosate byproduct, a phosphorus salt, and a steel pickling byproduct, an iron salt, according to an embodiment of the invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will explain the specific embodiments of the present invention with reference to the accompanying drawings. It is evident that the drawings in the following description are only examples of the invention, from which other drawings and other embodiments can be obtained by a person skilled in the art without inventive effort.
For simplicity of the drawing, only the parts relevant to the application are schematically shown in the drawings. It should be further understood that the term "and/or" as used in the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
Referring to fig. 1, a method for recycling glyphosate byproduct phosphorus salt and iron and steel pickling byproduct ferric salt is shown, comprising the following steps:
Purifying treatment of byproduct phosphate: adding glyphosate byproduct phosphate into water, dissolving at 25-35 ℃, regulating the pH value of the mixed solution to 3-5 by using a pH regulator, maintaining the temperature and stirring for 30-60 min, filtering after full dissolution and hydrolysis, adding an oxidizing auxiliary agent into the obtained filtrate, stirring for 10-60 min for oxidation reaction, then adding an activated carbon adsorbent, and filtering to obtain the filtrate, namely the phosphate purifying solution.
Wherein the glyphosate byproduct phosphate comprises at least one of crude sodium pyrophosphate, sodium phosphate, sodium tripolyphosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate and sodium hexametaphosphate.
In a specific embodiment, the oxidizing auxiliary agent is one or a combination of more of hydrogen peroxide, sodium perchlorate, sodium chlorate, sodium chlorite and sodium hypochlorite, the adding amount of the oxidizing auxiliary agent is 0.01-3% of the mass of the glyphosate byproduct phosphate salt, and the oxidizing auxiliary agent can react with organic matters in the glyphosate byproduct phosphate salt mixed solution to generate precipitate or floccules so as to degrade the organic matters.
In another specific embodiment, the activated carbon adsorbent can adsorb oily organic matters and colloidal precipitates, and the addition amount of the activated carbon adsorbent is 0.05-0.3% of the mass of the filtrate.
Purifying treatment of iron and steel pickling byproduct ferric salt: adding water to dissolve iron and iron salt as byproduct, adding iron simple substance with the mass of 1-2% of iron salt as byproduct into the solution, carrying out reduction reaction for 1-5 h at 25-35 ℃, adding flocculant, stirring, standing and filtering to obtain filtrate, namely ferrous purification liquid
Wherein, the iron and steel pickling byproduct ferric salt is hydrochloric acid pickling byproduct ferrous chloride, namely crude ferrous chloride recovered from the iron and steel hydrochloric acid pickling waste liquid through processes such as evaporation crystallization and the like.
In the embodiment, the iron simple substance is scrap iron, iron powder or iron sheet, and on one hand, the iron simple substance reduces Fe 3+ in the iron and steel pickling byproduct ferric salt solution to Fe 2+, and on the other hand, part of heavy metal ion impurities in the solution are replaced to generate reduction precipitation.
In a preferred embodiment, the pH of the solution is adjusted to 4.0 to 5.5 with a pH adjustor to effect hydrolytic precipitation of a portion of the metal ion impurities in the solution prior to addition of the flocculant, which is used for both reductive precipitation and removal of the hydrolytic precipitate.
In one embodiment, the flocculant is polyacrylamide and the amount of flocculant added per liter of the ferrous salt solution is 0.1-0.2 g, the flocculant is added and the flocculation reaction is maintained for 10-60 minutes, and then the filtration is performed to remove the reduction precipitate and the hydrolysis precipitate.
The synthesis process of the ferric phosphate comprises the following steps: taking a proper amount of phosphorus salt purifying liquid and ferrous purifying liquid according to a molar ratio P of Fe= (1-1.2), wherein the ferrous purifying liquid is adjusted to have a pH value of 1.5-3 by using a pH regulator, and then the ferrous purifying liquid is firstly introduced into a reaction kettle, and is heated to 40-45 ℃ to stop heating the reaction kettle; mixing the phosphorus salt purifying liquid with hydrogen peroxide with the molar mass of 0.6-0.8 times of that of iron salt byproduct in steel pickling, then introducing the mixed liquid into the reaction kettle storing the ferrous purifying liquid for oxidation and precipitation reaction, heating the reaction liquid to about 55-60 ℃ by exothermic heat, preserving heat for 1-1.5 h, heating to 95-98 ℃, preserving heat for 1.5-4 h, filtering, washing, drying and removing crystal water after the reaction is completed, thus obtaining anhydrous ferric phosphate product, and introducing the mixed liquid of the reaction mother liquid and the washing waste liquid into a sodium chloride recycling and water reusing unit after chemical impurity removal and filtration.
In a preferred embodiment, the washing of the solid product is performed by adopting a multi-stage membrane circulation washing mode, and the washing waste liquid of the later stage is applied to the washing of the last stage of the solid product of ferric phosphate produced in the next batch until the pH value of the washing waste liquid is 2.7-3.5.
In a specific embodiment, the pH value of the mixed solution of the reaction mother solution and the washing waste solution is firstly adjusted to 3-6, then sulfide impurity removing agent is added into the mixed solution, the precipitation reaction is carried out for 1-2 h, the sulfide impurity removing agent is at least one of sodium sulfide, potassium sulfide, barium sulfide, ferrous sulfide and ammonium sulfide, and the adding amount of the sulfide impurity removing agent is 0.3-3% of the mass of iron and steel pickling byproduct ferric salt.
The pH regulator in the purification and synthesis process is one of phosphoric acid, hydrochloric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate solution.
Sodium chloride recovery and water reuse process: the mixed solution of the mother solution subjected to chemical impurity removal and filtration treatment and the primary washing waste solution is sequentially treated by a nanofiltration membrane and a reverse osmosis membrane, clear solution generated by the nanofiltration membrane treatment is introduced into the reverse osmosis membrane, and the generated concentrated solution is reused for dissolving and hydrolyzing the glyphosate byproduct phosphate; clear liquid generated by reverse osmosis membrane treatment is recycled to a washing procedure of a solid product in the ferric phosphate synthesis process, the generated concentrated liquid is directly used as a production raw material of an ionic membrane caustic soda device matched with the upstream of glyphosate production, and directly enters an ionic membrane caustic soda preparation procedure to obtain sodium hydroxide, chlorine and hydrogen, wherein the chlorine and the hydrogen can be synthesized into hydrochloric acid, and the sodium hydroxide and the hydrochloric acid can be recycled for a system or sold.
The raw material required by the ionic membrane alkali preparation is saturated sodium chloride solution, and when the concentration is not reached, the raw material can be dissolved and mixed with outsourcing sodium chloride.
The solid waste residue generated by filtering in two places in the purification treatment of the byproduct phosphate, the filter residue generated by filtering in the purification treatment of the byproduct ferric salt of steel pickling, and the filter residue obtained by filtering after chemical impurity removal of the mother liquor of the ferric phosphate synthesis reaction and the one-wash waste liquid are directly conveyed to a solid waste treatment process due to higher impurity content.
According to the application, two wastes of glyphosate byproduct phosphate and iron and steel pickling byproduct ferric salt are recycled and integrated to prepare the high-added-value ferric phosphate material, meanwhile, pure sodium chloride byproduct is obtained, the byproduct sodium chloride can be directly introduced into an ion membrane alkali preparation process without evaporation and other processes, so that sodium hydroxide, chlorine and hydrogen are obtained, and the chlorine and hydrogen can be synthesized into hydrochloric acid, thereby realizing recycling.
In order to understand the resource utilization method and the technical effects thereof, the following specific examples are given.
Example 1
1) Mixing the glyphosate byproduct crude sodium pyrophosphate and water in a dissolution hydrolysis kettle according to a mass ratio of 1:1, controlling the temperature of the mixed solution to be 25 ℃, adjusting the pH value of the mixed solution to be about 4.5 by utilizing phosphoric acid, maintaining the temperature and stirring for 1h, so that the crude sodium pyrophosphate is fully dissolved and hydrolyzed, and hydrolyzing part of metal ion impurities to generate precipitate. And then filtering the mixed solution, directly conveying filter residues to a solid waste treatment process, adding an oxidizing auxiliary agent hydrogen peroxide with the mass of 0.15% of the crude sodium pyrophosphate into the filtrate, reacting with organic matters in the filtrate, adding an activated carbon adsorbent with the mass of 0.1% of the filtrate after reacting for 30min, adsorbing precipitate and floccules generated by oxidizing the organic matters in the filtrate, and conveying filter residues generated by filtering and removing impurities to the solid waste treatment process, wherein the generated filtrate is the phosphorus salt purifying liquid.
After the process is continuously operated, the concentrated solution generated by subsequent nanofiltration membrane treatment is reused for dissolving and hydrolyzing crude sodium pyrophosphate, the use amount of water is reduced, and the phosphorus resource can be effectively recovered.
2) Dissolving iron and water as byproduct of iron and steel pickling according to the mass ratio of 1:1, adding reduced iron powder with the mass of 1.5% of that of the byproduct iron, reacting for 5 hours at the temperature of 25 ℃, reducing Fe 3+ in the mixed solution into Fe 2+, displacing part of heavy metal ion impurities, regulating the pH value of the mixed solution to 5 by using sodium hydroxide solution after the reaction is finished, carrying out hydrolysis precipitation on part of the metal ion impurities, adding polyacrylamide for flocculation reaction for 20 minutes, stirring, standing and filtering to obtain filtrate, namely the ferrous purification liquid.
3) Taking a proper amount of the two purifying solutions obtained in the step 1 and the step 2 according to the molar ratio P of Fe=1.05:1, wherein the pH value of the ferrous purifying solution obtained in the step 2 is regulated to 1.7 by phosphoric acid, firstly, introducing the ferrous purifying solution into a reaction kettle, heating to 40 ℃, and stopping heating the reaction kettle; mixing the phosphorus salt purifying liquid obtained in the step 1 with hydrogen peroxide with the molar quantity of 0.65 times of that of the ferric salt, then introducing the mixed liquid into a reaction kettle with ferrous purifying liquid for oxidation and precipitation reaction, heating the reaction liquid to about 55 ℃ by exothermic heat of reaction, preserving heat for 1h, heating to 95 ℃ and preserving heat for 1.5h, and carrying out filtration, washing, drying and de-crystallization water processes after the reaction is completed to obtain the anhydrous ferric phosphate product. The washing of the ferric phosphate products is carried out in a multi-stage membrane circulation washing mode, the washing waste liquid of the later stage can be used for the washing of the ferric phosphate solid products produced in the next batch, and the ferric phosphate solid products produced in the first batch are all washed by clean water until the pH value of the washing waste liquid is 3.2. Mixing the primary washing waste liquid and the mother liquor generated in the primary washing, firstly utilizing sodium hydroxide to adjust the pH value of the mixed liquor to be 5, then adding sodium sulfide solid, uniformly stirring to perform chemical impurity removal, reacting for 1.5h, filtering, enabling filtrate to enter a sodium chloride recovery and water recycling unit, enabling the impurity content of filter residues to be high, and directly conveying the filter residues to a solid waste treatment process.
4) In the step 3, the mixed solution of the mother solution subjected to chemical impurity removal and filtration treatment and the primary washing waste solution is firstly treated by a nanofiltration membrane, the generated concentrated solution is recycled to the dissolution and hydrolysis of the crude sodium pyrophosphate in the step 1, and the generated clear solution is treated by a reverse osmosis membrane; the clear liquid generated by the reverse osmosis membrane can be reused for washing the ferric phosphate solid product, and the generated concentrated liquid is purified sodium chloride concentrated liquid. The sodium chloride concentrated solution is directly used as a production raw material of an ion membrane caustic soda device matched with the upstream of glyphosate production, and directly enters an ion membrane caustic soda preparation process to obtain sodium hydroxide, chlorine and hydrogen, the chlorine and the hydrogen are synthesized into hydrochloric acid, and the sodium hydroxide and the hydrochloric acid are recycled in the process or are sold.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
It should be understood by those skilled in the art that while the present invention has been described in terms of several embodiments, not every embodiment contains only one independent technical solution. The description is given for clearness of understanding only, and those skilled in the art will understand the description as a whole and will recognize that the technical solutions described in the various embodiments may be combined with one another to understand the scope of the present invention.
Claims (10)
1. The resource utilization method of byproduct phosphorus salt and iron and steel pickling byproduct ferric salt is characterized by comprising the following steps:
Purifying treatment of byproduct phosphate: fully dissolving and hydrolyzing the glyphosate byproduct phosphonium salt under the conditions of proper temperature and pH value, filtering, sequentially adding an oxidizing auxiliary agent into the obtained filtrate for oxidation reaction, adsorbing by an adsorbent, and filtering to obtain filtrate, namely a phosphonium salt purifying solution;
Purifying treatment of iron and steel pickling byproduct ferric salt: adding water into iron salt which is a byproduct of steel pickling to dissolve, adding iron simple substance into the solution to perform reduction and displacement reaction to reduce Fe 3+ in the solution and reduce and precipitate part of heavy metal ion impurities, adding flocculant, and filtering to obtain ferrous purification liquid;
The synthesis process of the ferric phosphate comprises the following steps: mixing a proper amount of phosphorus salt purifying liquid and ferrous iron purifying liquid with hydrogen peroxide for synthesis reaction, and after the reaction is completed, sequentially performing the procedures of filtering, washing, drying and de-crystallization to obtain an anhydrous ferric phosphate product, wherein the mixed liquid of the reaction mother solution and the primary washing waste liquid enters a sodium chloride recovery and water recycling unit after chemical impurity removal and filtration.
2. The method for recycling byproduct phosphorus salt and iron and steel pickling byproduct ferric salt according to claim 1, wherein in the step of purifying byproduct phosphorus salt,
The temperature of the dissolution and the hydrolysis of the glyphosate byproduct phosphate is 25-35 ℃, and the pH value is adjusted to 3-5 by utilizing a pH regulator; and/or the number of the groups of groups,
The oxidizing auxiliary agent is one or a combination of more of hydrogen peroxide, sodium perchlorate, sodium chlorate, sodium chlorite and sodium hypochlorite; and/or the number of the groups of groups,
The addition amount of the oxidizing auxiliary agent is 0.01-3% of the mass of the byproduct phosphate salt of the glyphosate; and/or the number of the groups of groups,
The adsorbent is activated carbon adsorbent, and the addition amount of the adsorbent is 0.05-0.3% of the mass of the filtrate.
3. The method for recycling a byproduct phosphorus salt and a byproduct iron salt for steel pickling according to claim 1, wherein the step of purifying the byproduct iron salt for steel pickling further comprises:
Before adding the flocculant, the pH value of the solution is regulated to be 4.0-5.5 by utilizing a pH regulator so as to realize the hydrolytic precipitation of partial metal ion impurities in the solution, and the flocculant is used for reduction precipitation and removal of hydrolytic precipitation.
4. The method for recycling a byproduct phosphorus salt and a byproduct iron salt for steel pickling according to claim 1 or 3, wherein in the step of purifying the byproduct iron salt for steel pickling,
The addition amount of the iron simple substance is 1% -2% of the mass of iron salt which is a byproduct of steel pickling; and/or the number of the groups of groups,
The flocculant is added with 0.1-0.2 g per liter of ferrous salt solution.
5. The resource utilization method of byproduct phosphorus salt and iron and steel pickling byproduct ferric salt according to claim 1, wherein the specific steps of mixing a proper amount of phosphorus salt purifying liquid and ferrous iron purifying liquid with hydrogen peroxide for synthesis reaction are as follows:
Taking a proper amount of phosphorus salt purifying liquid and ferrous purifying liquid according to the molar ratio P of Fe= (1-1.2), regulating the pH value of the ferrous purifying liquid to 1.5-3 by utilizing a pH regulator, firstly introducing the ferrous purifying liquid into a reaction kettle, heating to 40-45 ℃, and stopping heating the reaction kettle; then
Mixing the phosphorus salt purifying liquid and hydrogen peroxide, introducing the mixture into the reaction kettle containing the ferrous purifying liquid, carrying out oxidation and precipitation reaction, heating the reaction liquid to 55-60 ℃ by exothermic heat, preserving heat for 1-1.5 h, and then heating to 95-98 ℃ and preserving heat for 1.5-4 h; wherein the method comprises the steps of
The addition amount of the hydrogen peroxide is 0.6 to 0.8 times of the molar mass of the iron salt byproduct in the steel pickling.
6. The method for recycling byproduct phosphorus salt and iron and steel pickling byproduct ferric salt according to claim 1 or 5, wherein in the step of synthesizing ferric phosphate,
The washing adopts a multistage membrane circulation washing mode, and the washing waste liquid of the later stage is applied to the washing of the upper stage until the pH value of the washing waste liquid is 2.7-3.5.
7. The recycling method for byproduct phosphorus salt and iron and steel pickling byproduct ferric salt according to claim 1 or 5, wherein the specific steps of chemical impurity removal in the process of synthesizing ferric phosphate are as follows:
firstly, regulating the pH value of the mixed solution of the reaction mother solution and the washing waste liquid to 3-6, then adding sulfide impurity removing agent into the mixed solution to carry out precipitation reaction,
The sulfide impurity removing agent is at least one of sodium sulfide, potassium sulfide, barium sulfide, ferrous sulfide and ammonium sulfide; and/or the number of the groups of groups,
The addition amount of the sulfide impurity removing agent is 0.3-3% of the mass of iron salt which is a byproduct of steel pickling.
8. The method for recycling byproduct phosphorus salt and iron and steel pickling byproduct ferric salt according to claim 1, wherein the recycling step further comprises:
Sodium chloride recovery process: the mixed solution of the mother solution subjected to chemical impurity removal and filtration treatment and the washing waste liquid is sequentially treated by a nanofiltration membrane and a reverse osmosis membrane, the sodium chloride concentrated solution discharged from the reverse osmosis membrane is directly used as the production raw material of an ionic membrane caustic soda device matched with the upstream of glyphosate production, and directly enters an ionic membrane caustic soda process to obtain sodium hydroxide, chlorine and hydrogen, the chlorine and the hydrogen synthesize hydrochloric acid, and the sodium hydroxide and the hydrochloric acid can be recycled in a system or sold.
9. The method for recycling byproduct phosphorus salt and iron and steel pickling byproduct ferric salt according to claim 8, wherein the recycling step further comprises:
the water recycling process comprises the following steps: the concentrated solution obtained from the nanofiltration membrane is reused for dissolving and hydrolyzing the byproduct phosphate salt of glyphosate; the clear liquid from the reverse osmosis membrane is reused in the washing procedure in the ferric phosphate synthesis process.
10. The method for recycling byproduct phosphorus salt and byproduct iron salt for steel pickling according to claim 2, 3 or 5, which is characterized in that,
The pH regulator is at least one of phosphoric acid, hydrochloric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate solution.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE774963A (en) * | 1970-11-24 | 1972-05-05 | Wire Sales Co | PROCESS AIMING TO ELIMINATE THE SPILL OF PICKLING SLUDGE BY TRANSFORMING THEM INTO USEFUL PRODUCTS |
| CN102459091A (en) * | 2009-05-18 | 2012-05-16 | 孟山都技术公司 | Recovery of phosphorus values and salt impurities from aqueous waste streams |
| CN102874786A (en) * | 2012-10-12 | 2013-01-16 | 山东潍坊润丰化工有限公司 | Processing method of glyphosate mother liquor |
| CN105692576A (en) * | 2016-03-10 | 2016-06-22 | 三峡大学 | Method for preparing battery-grade FePO4 from industrial iron-containing waste |
| WO2019005718A1 (en) * | 2017-06-26 | 2019-01-03 | Monsanto Technology Llc | Phosphorus control for waste streams from glyphosate manufacturing processes |
| CN113896349A (en) * | 2021-10-11 | 2022-01-07 | 盐城工学院 | Glyphosate byproduct high-salt waste salt phosphorus removal and impurity removal system and process |
| CN113955733A (en) * | 2021-11-12 | 2022-01-21 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron phosphate by using iron-containing waste hydrochloric acid |
| WO2022116702A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate and use thereof |
| CN114933289A (en) * | 2022-06-22 | 2022-08-23 | 四川福思达生物技术开发有限责任公司 | Co-production process for glyphosate and ferric phosphate |
| CN115321736A (en) * | 2022-08-24 | 2022-11-11 | 中国科学院过程工程研究所 | Treatment method of glyphosate production wastewater and high-value recycling of phosphorus-containing waste |
-
2022
- 2022-12-05 CN CN202211549828.3A patent/CN115959643B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE774963A (en) * | 1970-11-24 | 1972-05-05 | Wire Sales Co | PROCESS AIMING TO ELIMINATE THE SPILL OF PICKLING SLUDGE BY TRANSFORMING THEM INTO USEFUL PRODUCTS |
| CN102459091A (en) * | 2009-05-18 | 2012-05-16 | 孟山都技术公司 | Recovery of phosphorus values and salt impurities from aqueous waste streams |
| CN102874786A (en) * | 2012-10-12 | 2013-01-16 | 山东潍坊润丰化工有限公司 | Processing method of glyphosate mother liquor |
| CN105692576A (en) * | 2016-03-10 | 2016-06-22 | 三峡大学 | Method for preparing battery-grade FePO4 from industrial iron-containing waste |
| WO2019005718A1 (en) * | 2017-06-26 | 2019-01-03 | Monsanto Technology Llc | Phosphorus control for waste streams from glyphosate manufacturing processes |
| WO2022116702A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate and use thereof |
| CN113896349A (en) * | 2021-10-11 | 2022-01-07 | 盐城工学院 | Glyphosate byproduct high-salt waste salt phosphorus removal and impurity removal system and process |
| CN113955733A (en) * | 2021-11-12 | 2022-01-21 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron phosphate by using iron-containing waste hydrochloric acid |
| CN114933289A (en) * | 2022-06-22 | 2022-08-23 | 四川福思达生物技术开发有限责任公司 | Co-production process for glyphosate and ferric phosphate |
| CN115321736A (en) * | 2022-08-24 | 2022-11-11 | 中国科学院过程工程研究所 | Treatment method of glyphosate production wastewater and high-value recycling of phosphorus-containing waste |
Non-Patent Citations (2)
| Title |
|---|
| 梅荣武 ; 韦彦斐 ; 沈浙萍 ; 陈雳华 ; .草甘膦废水预处理研究与工程应用.给水排水. * |
| 梅荣武 ; 韦彦斐 ; 沈浙萍 ; 陈雳华 ; .草甘膦废水预处理研究与工程应用.给水排水.2012,50-53. * |
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