CN115959643A - Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling - Google Patents
Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling Download PDFInfo
- Publication number
- CN115959643A CN115959643A CN202211549828.3A CN202211549828A CN115959643A CN 115959643 A CN115959643 A CN 115959643A CN 202211549828 A CN202211549828 A CN 202211549828A CN 115959643 A CN115959643 A CN 115959643A
- Authority
- CN
- China
- Prior art keywords
- iron
- byproduct
- salt
- solution
- steel pickling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006227 byproduct Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000005554 pickling Methods 0.000 title claims abstract description 49
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 44
- 239000010959 steel Substances 0.000 title claims abstract description 44
- 150000002505 iron Chemical class 0.000 title claims abstract description 42
- 150000003017 phosphorus Chemical class 0.000 title claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000243 solution Substances 0.000 claims abstract description 61
- 238000005406 washing Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000012535 impurity Substances 0.000 claims abstract description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 37
- 239000005562 Glyphosate Substances 0.000 claims abstract description 33
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940097068 glyphosate Drugs 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
- 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
- 238000001914 filtration Methods 0.000 claims abstract description 30
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 29
- 238000004064 recycling Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 15
- 239000003463 adsorbent Substances 0.000 claims abstract description 13
- 239000008394 flocculating agent Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 239000012528 membrane Substances 0.000 claims description 35
- 238000001556 precipitation Methods 0.000 claims description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000007254 oxidation reaction Methods 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001728 nano-filtration Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 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
- 239000003513 alkali Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 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
- 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
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 159000000014 iron salts Chemical class 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 16
- 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
- 239000010413 mother solution Substances 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 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 5
- 229940048086 sodium pyrophosphate Drugs 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 5
- 239000005955 Ferric phosphate Substances 0.000 description 4
- 229940032958 ferric phosphate Drugs 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
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000009270 solid waste treatment Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000004090 dissolution Methods 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 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
- 239000007787 solid 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000000694 effects Effects 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 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
- 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
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
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
Abstract
The invention relates to a resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling, which comprises the following steps: fully dissolving and hydrolyzing glyphosate byproduct phosphate, filtering, sequentially adding an oxidizing auxiliary agent and an adsorbent into the obtained filtrate, and filtering to obtain filtrate, namely phosphate purification solution; dissolving iron salt which is a byproduct of steel pickling in water, adding a simple substance of iron and a flocculating agent into the solution, and filtering to obtain a ferrous iron purified solution; and mixing the phosphorus salt purifying solution and the ferrous purifying solution with hydrogen peroxide for synthesis reaction to prepare an iron phosphate product, and chemically removing impurities and filtering the reaction mother solution and the washing waste solution to enter a sodium chloride recovery and water recycling unit. On one hand, the invention can reduce the raw material cost of iron phosphate production to the maximum 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, and particularly relates to a resource utilization method of glyphosate byproduct phosphorus salt and steel pickling byproduct iron salt.
Background
Iron phosphate is an important chemical raw material, and in recent years, it has been widely used as a precursor for synthesizing lithium iron phosphate, which is a positive electrode material of lithium batteries. Currently, iron phosphate is gradually replacing other precursors to become a core precursor of lithium iron phosphate. Ferric phosphate may be obtained from the reaction of ferrous salts and phosphoric acid/phosphates in the presence of an oxidizing agent.
Glyphosate is the herbicide product with the largest global use amount at present, a great amount of high-concentration organophosphorus wastewater is generated in the production process of the glyphosate, the organophosphorus wastewater is generally called glyphosate mother liquor, and if the organophosphorus wastewater is not subjected to proper treatment and is directly discharged, not only can serious environmental pollution be caused, but also larger waste of resources can be brought. At present, common treatment modes of 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 lower economic value. Related technology CN114933289A discloses a 'coproduction process for glyphosate and ferric phosphate', which comprises the steps of sequentially carrying out membrane separation, high-temperature oxidation and electrodialysis on glyphosate mother liquor to obtain mixed acid containing phosphoric acid and hydrochloric acid, and then reacting the mixed acid with iron powder to prepare the ferric phosphate. The process is only suitable for a glyphosate mother liquor wet catalytic oxidation technology, cannot be applied to a high-temperature incineration technology, and has the advantages of complex structure of an electrodialysis device, incomplete desalination and low water recovery rate.
China has a plurality of continuous pickling production lines for cold-rolled steel, 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 common pickling solution is hydrochloric acid, so a large amount of hydrochloric acid pickling waste liquid can be generated. The hydrochloric acid pickling waste liquid generally contains 1 to 5 percent of hydrochloric acid and 5 to 20 percent of ferrous chloride/ferric chloride, and is listed in national hazardous waste records due to serious corrosivity. The current treatment methods include high-temperature roasting method, extraction method, ion exchange method, membrane treatment method and crystallization method. Through a simple crystallization method, the obtained ferric salt product has high impurity content and low economic value. In the related technology CN114804215A, a method for producing battery-grade ferrous chloride from cold rolled steel pickling waste acid is disclosed, wherein a sulfur-containing compound is added to remove metal ion impurities, but more ferrous sulfide precipitates are generated at the same time, so that the utilization rate of an iron element in a solution is reduced.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a resource utilization method of glyphosate byproduct phosphorus salt and steel pickling byproduct iron salt, on one hand, the resource utilization method can reduce the raw material cost of iron phosphate production to the maximum 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.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the resource utilization method of the byproduct phosphorus salt and the byproduct iron salt in steel pickling comprises the following steps:
and (3) purifying the byproduct phosphorus salt: fully dissolving and hydrolyzing glyphosate byproduct phosphate 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 phosphate purification solution;
purifying iron and steel pickling byproduct iron salt: dissolving iron salt as a byproduct of steel pickling in water, and adding iron simple substance into the solution to perform reduction displacement reaction to realize Fe in the solution 3+ Reducing and precipitating part of heavy metal ion impurities, then adding a flocculating agent, and filtering to obtain a ferrous iron purifying solution;
the synthesis process of the iron phosphate comprises the following steps: and 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 finished, sequentially performing the procedures of filtering, washing, drying and removing crystal water to prepare an anhydrous iron phosphate product, wherein the mixed liquid of reaction mother liquid and washing waste liquid is subjected to chemical impurity removal and filtering and then enters a sodium chloride recovery and water recycling unit.
In some technical schemes, in the purification treatment step of the byproduct phosphorus salt,
the temperature for dissolving and hydrolyzing the glyphosate byproduct phosphate is 25-35 ℃, and the pH value is adjusted to 3-5 by using a pH regulator; and/or the presence of a gas in the gas,
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 presence of a gas in the gas,
the addition amount of the oxidizing auxiliary agent is 0.01-3% of the mass of the glyphosate byproduct phosphate; and/or the presence of a gas in the gas,
the adsorbent is an 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, the step of purifying the iron salt byproduct in the steel pickling process further comprises the following steps:
before adding a flocculating agent, a pH value of the solution is adjusted to be 4.0-5.5 by utilizing a pH regulator so as to realize hydrolytic precipitation of partial metal ion impurities in the solution, and the flocculating agent is used for reducing precipitation and removing hydrolytic precipitation.
In some technical schemes, in the purification treatment step of the iron and steel pickling byproduct iron salt,
the adding amount of the iron simple substance is 1 to 2 percent of the mass of the iron salt as the byproduct of the steel pickling; and/or the presence of a gas in the atmosphere,
the flocculant is added into ferrous salt solution of 0.1-0.2 g per liter.
In some technical schemes, the specific steps of mixing a proper amount of phosphate purification liquid and ferrous purification liquid with hydrogen peroxide for synthesis reaction are as follows:
taking a proper amount of phosphorus salt purified liquid and ferrous iron purified liquid according to a molar ratio P: fe = (1-1.2): 1, adjusting the pH value of the ferrous iron purified liquid to 1.5-3 by using a pH regulator, firstly introducing the ferrous iron purified liquid into a reaction kettle, heating to 40-45 ℃, and stopping supplying heat to the reaction kettle; then the
Mixing the phosphorus salt purified solution and hydrogen peroxide, then introducing the mixture into the reaction kettle containing the ferrous purified solution, carrying out oxidation and precipitation reactions, heating the reaction solution to 55-60 ℃ by means of reaction heat release, keeping the temperature for 1-1.5 h, heating to 95-98 ℃ again, and keeping the temperature for 1.5-4 h; wherein
The addition amount of the hydrogen peroxide is 0.6 to 0.8 time of the molar mass of the iron salt as the byproduct of the steel pickling.
In some technical schemes, in the step of synthesizing the iron phosphate,
the washing adopts a multi-stage membrane circulation washing mode, the later-stage washing waste liquid is applied to the previous-stage washing until the pH value of the washing waste liquid is 2.7-3.5.
In some technical schemes, in the synthesis process of the iron phosphate, the specific steps of chemical impurity removal are as follows:
firstly, adjusting the pH value of the mixed solution of reaction mother liquor and first-washing waste liquor to 3-6, then adding sulfide impurity-removing agent into the mixed solution to make 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 presence of a gas in the gas,
the addition amount of the sulfide impurity removing agent is 0.3-3% of the mass of the iron salt as a byproduct of the steel pickling.
In some technical solutions, the resource utilization step further includes:
and (3) sodium chloride recovery process: the mixed solution of the mother liquor and the washing waste liquor after chemical impurity removal and filtration treatment is sequentially treated by a nanofiltration membrane and a reverse osmosis membrane, the sodium chloride concentrated solution from the reverse osmosis membrane 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 alkali 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 can be reused in a system or sold outside the system.
In some technical solutions, the resource utilization step further includes:
the water recycling process: the concentrated solution from the nanofiltration membrane is reused for dissolving and hydrolyzing the glyphosate byproduct phosphorus salt; and the clear liquid discharged from the reverse osmosis membrane is reused in the washing procedure in the iron phosphate synthesis process.
In some embodiments, the pH adjusting agent is at least one of phosphoric acid, hydrochloric acid, sodium hydroxide, sodium carbonate, and sodium bicarbonate solution.
The invention adopts the technical scheme and at least has the following beneficial effects:
1. the method adopts the glyphosate byproduct phosphorus salt as a phosphorus source and the iron and steel pickling byproduct iron salt as an iron source, and applies the two wastes to the preparation of the iron phosphate material with high added value, thereby realizing the purpose of changing waste into valuable, reducing the raw material cost of iron phosphate production to the greatest extent, and opening a channel for comprehensively utilizing waste resources in different industries;
2. in the process flow, firstly, the glyphosate byproduct phosphorus salt and the steel pickling byproduct iron salt are respectively subjected to purification treatment, 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 a system is reduced, compared with the pre-chemical impurity removal, the utilization rate of iron elements can be obviously improved under the condition of not influencing the performance of iron phosphate products, and the process flow and equipment are relatively simple, the occupied area is small, and the investment is small;
4. according to the invention, sodium chloride and phosphate resources are contained in the reaction mother liquor and the first washing waste liquor after the synthesis of the iron phosphate, and after impurity removal and filtration, the sodium chloride is recycled and the water is recycled, so that the recycling of the phosphate and the recycling of sodium ions and chloride ions are realized, the effective recycling of the washing water is realized, the water consumption is greatly reduced, the evaporation and sewage treatment processes are not needed, the requirements of green recycling economy are met, and the national call for energy conservation and emission reduction is responded.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings and the reference numerals thereof used in the embodiments are briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a process flow diagram of a resource utilization method of glyphosate byproduct phosphonium salt and iron and steel pickling byproduct 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 be made with reference to the accompanying drawings. It is obvious that the drawings in the following description are only some examples of the invention, and that for a person skilled in the art, other drawings and embodiments can be derived from them without inventive effort.
For the sake of simplicity, only the parts relevant to the invention are schematically shown in the figures. It should be further understood that the term "and/or" as used in this 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 phosphate and iron and steel pickling byproduct iron salt is shown, which includes the steps of:
and (3) purifying the byproduct phosphorus salt: adding glyphosate byproduct phosphate into water, dissolving at 25-35 ℃, adjusting the pH value of the mixed solution to 3-5 by using a pH regulator, stirring for 30-60 min while maintaining the temperature, 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 active carbon adsorbent, and filtering to obtain the filtrate, namely the phosphate purification solution.
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, and the oxidizing auxiliary agent can react with organic matters in the mixed solution of the glyphosate byproduct phosphate to generate precipitates 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.
And (3) purifying a byproduct iron salt in steel pickling: dissolving iron and steel pickling by-product iron salt in water, adding an iron simple substance with the mass of 1-2% of the by-product iron salt into the solution, carrying out reduction reaction for 1-5 h at the temperature of 25-35 ℃, adding a flocculating agent, stirring, standing and filtering to obtain filtrate, namely the ferrous iron purification solution
Wherein the iron salt as a byproduct of the steel pickling is ferrous chloride as a byproduct of the hydrochloric acid pickling, namely crude ferrous chloride recovered from the waste liquid of the steel hydrochloric acid pickling by processes such as evaporation crystallization and the like.
In the embodiment, the iron simple substance is scrap iron, iron powder or iron sheets, and the iron simple substance on the one hand produces Fe in the iron salt solution as a byproduct of the steel pickling 3+ Reduction to Fe 2+ 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 value of the solution is adjusted to 4.0-5.5 by using a pH regulator before adding a flocculating agent, so as to realize hydrolytic precipitation of partial metal ion impurities in the solution, wherein the flocculating agent is used for reducing precipitation and removing the hydrolytic precipitation.
In a specific embodiment, the flocculating agent is polyacrylamide, the dosage of the flocculating agent added into each liter of ferrous salt solution is 0.1-0.2 g, the flocculating agent is added and the flocculation reaction is maintained for 10-60 min, and then the filtration is carried out to remove reduction precipitation and hydrolysis precipitation.
The synthesis process of the iron phosphate comprises the following steps: taking a proper amount of phosphorus salt purified liquid and ferrous iron purified liquid according to a molar ratio P: fe = (1-1.2): 1, wherein the ferrous iron purified liquid is adjusted to have a pH value of 1.5-3 by a pH regulator, firstly introducing the ferrous iron purified liquid into a reaction kettle, heating to 40-45 ℃, and stopping supplying heat to the reaction kettle; mixing phosphorus salt purification liquid with hydrogen peroxide with the molar mass of 0.6-0.8 times of that of iron salt as a byproduct of steel pickling, introducing the mixed liquid into the reaction kettle containing the ferrous iron purification liquid, carrying out oxidation and precipitation reactions, carrying out exothermic reaction to heat the reaction liquid to 55-60 ℃, preserving heat for 1-1.5 h, then heating to 95-98 ℃, preserving heat for 1.5-4 h, filtering, washing, drying and removing crystallization water after the reaction is finished to obtain an anhydrous iron phosphate product, and introducing the mixed liquid of reaction mother liquid and washing waste liquid into a sodium chloride recovery and water recycling unit after chemical impurity removal and filtration.
In a preferred embodiment, the washing of the solid product is performed by a multi-stage membrane circulation washing mode, and the subsequent stage of washing waste liquid is applied to the previous stage of washing of the iron phosphate solid product produced in the next batch, and the washing is performed until the pH value of the washing waste liquid is 2.7-3.5.
In a specific embodiment, chemical impurity removal is carried out, the pH value of a mixed solution of a reaction mother solution and a washing waste solution is firstly adjusted to be 3-6, then a sulfide impurity removing agent is added into the mixed solution, precipitation reaction is carried out for 1-2 hours, 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 a steel pickling iron salt byproduct.
The pH regulator used 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 recycling processes: the mixed solution of the mother liquor and the washing waste liquor after chemical impurity removal and filtration treatment is sequentially treated by a nanofiltration membrane and a reverse osmosis membrane, clear liquid generated by the nanofiltration membrane treatment is introduced into the reverse osmosis membrane, and generated concentrated solution is reused for dissolving and hydrolyzing glyphosate byproduct phosphorus salt; the clear liquid generated by reverse osmosis membrane treatment is reused in the washing process of a solid product in the iron 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 upper stream of glyphosate production, and directly enters the ionic membrane alkali preparation process to obtain sodium hydroxide, chlorine and hydrogen, the chlorine and the hydrogen can be synthesized into hydrochloric acid, and the sodium hydroxide and the hydrochloric acid can be reused in a system or sold outside.
The raw material required for preparing the alkali by the ionic membrane is a saturated sodium chloride solution, and when the concentration of the saturated sodium chloride solution is not reached, the saturated sodium chloride solution can be dissolved and mixed with external sodium chloride.
The aforesaid two solid waste residues that filter production in the purification treatment of relevant by-product phosphorus salt, the filter residue that filters production in the purification treatment of steel pickling by-product molysite to and the filter residue that filters gained after iron phosphate synthesis reaction mother liquor and the chemical edulcoration of washing waste liquid, because impurity content all is higher, directly carry to solid useless processing procedure.
The method integrates the recycling of two wastes, namely the glyphosate byproduct phosphorus salt and the iron and steel pickling byproduct iron salt, so as to prepare the iron phosphate material with high added value, and simultaneously obtain a pure sodium chloride byproduct, the byproduct sodium chloride can be directly introduced into the ionic membrane alkali preparation process without evaporation and other processes, so that sodium hydroxide, chlorine and hydrogen are obtained, and the chlorine and the hydrogen can be synthesized into hydrochloric acid, so that the recycling is realized.
In order to understand the resource utilization method and the technical effects thereof, the following specific examples are given.
Example 1
1) Mixing crude glyphosate byproduct sodium pyrophosphate and water in a dissolving hydrolysis kettle according to a mass ratio of 1. And then filtering the mixed solution, directly conveying filter residues to a solid waste treatment process, adding an oxidative auxiliary agent hydrogen peroxide with the mass of 0.15% of that of 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 that of the filtrate after reacting for 30min, adsorbing precipitates and floccules generated by oxidation of the organic matters in the filtrate, and conveying the filter residues generated by filtering and impurity removal to the solid waste treatment process, wherein the generated filtrate is the phosphorus salt purified solution.
After the process is continuously operated, the concentrated solution generated by the subsequent nanofiltration membrane treatment is reused for the dissolution and hydrolysis of the crude sodium pyrophosphate, the water usage amount is reduced, and the phosphorus resource can be effectively recovered.
2) Performing iron salt and water which are byproducts of steel pickling according to the mass ratio of 1Dissolving, adding reduced iron powder with the by-product iron salt mass of 1.5%, reacting at 25 deg.C for 5h, and adding Fe in the mixed solution 3+ Reduction to Fe 2+ And replacing partial heavy metal ion impurities, adjusting the pH value of the mixed solution to 5 by using a sodium hydroxide solution after the reaction is finished, performing hydrolysis precipitation on partial metal ion impurities, adding polyacrylamide for flocculation reaction for 20min, stirring, standing, and filtering to obtain filtrate, namely the ferrous purification solution.
3) Taking a proper amount of two purified liquids obtained in the step 1 and the step 2 according to a molar ratio P: fe = 1.05; and (2) mixing the phosphorus salt purified solution obtained in the step (1) with hydrogen peroxide with the molar weight of iron salt being 0.65 times, introducing the mixed solution into a reaction kettle containing the ferrous iron purified solution, carrying out oxidation and precipitation reactions, carrying out exothermic reaction to heat the reaction solution to about 55 ℃, keeping the temperature for 1 hour, heating to 95 ℃, keeping the temperature for 1.5 hours, and carrying out processes of filtering, washing, drying and removing crystallization water after the reaction is finished to obtain the anhydrous iron phosphate product. And washing the iron phosphate product by adopting a multi-stage membrane circulating washing mode, wherein the later-stage washing waste liquid can be applied to the previous-stage washing of the iron phosphate solid product produced in the next batch, and the iron phosphate solid product produced in the first batch is completely washed by clear water until the pH value of the washing waste liquid is 3.2. Mixing the primary washing waste liquid and the mother liquid generated in the primary washing, firstly adjusting the pH value of the mixed liquid to 5 by using sodium hydroxide, then adding sodium sulfide solid, uniformly stirring to carry out chemical impurity removal, carrying out filtration after reacting for 1.5h, enabling the 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) 3, treating a mixed solution of the mother liquor and the washing waste liquor subjected to chemical impurity removal and filtration treatment in the step 3 by using a nanofiltration membrane, recycling the generated concentrated solution for dissolving and hydrolyzing the crude sodium pyrophosphate in the step 1, and treating the generated clear solution by using 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 ionic membrane caustic soda device matched with the upper stream of glyphosate production, and directly enters an ionic membrane alkali preparation process to obtain sodium hydroxide, chlorine and hydrogen, the chlorine and the hydrogen synthesize hydrochloric acid, and the sodium hydroxide and the hydrochloric acid are reused in the process or sold for sale.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
It should be appreciated by those of skill in the art that while the present invention has been described in terms of several embodiments, not every embodiment includes only a single embodiment. The description is given for clearness of understanding only, and it is to be understood that all matters in the embodiments are to be interpreted as including technical equivalents which are related to the embodiments and which are combined with each other to illustrate the scope of the present invention.
Claims (10)
1. The resource utilization method of the byproduct phosphonium salt and the byproduct ferric salt in steel pickling is characterized by comprising the following steps:
and (3) purifying the byproduct phosphorus salt: fully dissolving and hydrolyzing glyphosate byproduct phosphate 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 phosphate purified liquor;
purifying iron and steel pickling byproduct iron salt: dissolving iron salt which is a byproduct of steel pickling in water, and adding iron simple substance into the solution to perform reduction displacement reaction to realize Fe in the solution 3+ Reducing and precipitating part of heavy metal ion impurities, then adding a flocculating agent, and filtering to obtain a ferrous iron purifying solution;
the synthesis process of the iron phosphate comprises the following steps: and 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 finished, sequentially performing the procedures of filtering, washing, drying and removing crystal water to prepare an anhydrous iron phosphate product, wherein the mixed liquid of reaction mother liquid and washing waste liquid is subjected to chemical impurity removal and filtering and then enters a sodium chloride recovery and water recycling unit.
2. The method for recycling by-product phosphorus salt and iron and steel pickling by-product iron salt according to claim 1, wherein in the step of purifying by-product phosphorus salt,
the temperature for dissolving and hydrolyzing the glyphosate byproduct phosphate is 25-35 ℃, and the pH value is adjusted to 3-5 by using a pH regulator; and/or the presence of a gas in the atmosphere,
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 presence of a gas in the atmosphere,
the addition amount of the oxidizing auxiliary agent is 0.01-3% of the mass of the glyphosate byproduct phosphate; and/or the presence of a gas in the gas,
the adsorbent is an activated carbon adsorbent, and the addition amount of the adsorbent is 0.05-0.3% of the mass of the filtrate.
3. The method of claim 1, wherein the step of purifying the iron salt as a by-product of iron and steel pickling further comprises:
before adding a flocculating agent, a pH value of the solution is adjusted to be 4.0-5.5 by utilizing a pH regulator so as to realize hydrolytic precipitation of partial metal ion impurities in the solution, and the flocculating agent is used for reducing precipitation and removing hydrolytic precipitation.
4. The method of recycling a phosphorus salt byproduct and an iron salt byproduct from steel pickling according to claim 1 or 3, wherein in the step of purifying the iron salt byproduct from steel pickling,
the adding amount of the iron simple substance is 1-2% of the mass of the iron salt as a byproduct of the steel pickling; and/or the presence of a gas in the atmosphere,
the flocculant is added into ferrous salt solution of 0.1-0.2 g per liter.
5. The resource utilization method of the byproduct phosphorus salt and the iron and steel pickling byproduct iron salt according to claim 1, wherein the specific steps of mixing a proper amount of phosphorus salt purified liquid and ferrous iron purified liquid with hydrogen peroxide for synthesis reaction are as follows:
taking a proper amount of phosphorus salt purifying solution and ferrous purifying solution according to a molar ratio of P: fe = (1-1.2): 1, adjusting the pH value of the ferrous purifying solution to 1.5-3 by using a pH regulator, firstly introducing the ferrous purifying solution into a reaction kettle, heating to 40-45 ℃, and stopping supplying heat to the reaction kettle; then the
Mixing the phosphorus salt purified solution with hydrogen peroxide, then introducing the mixture into the reaction kettle in which the ferrous purified solution exists, carrying out oxidation and precipitation reactions, heating the reaction solution to 55-60 ℃ by means of reaction heat release, preserving heat for 1-1.5 hours, heating to 95-98 ℃ again, and preserving heat for 1.5-4 hours; wherein
The addition of the hydrogen peroxide is 0.6 to 0.8 time of the molar mass of the iron salt as the byproduct of the steel pickling.
6. The method for recycling by-product phosphorus salt and iron and steel pickling by-product iron salt according to claim 1 or 5, wherein in the step of synthesizing iron phosphate,
the washing adopts a multi-stage membrane circulation washing mode, the later-stage washing waste liquid is applied to the previous-stage washing until the pH value of the washing waste liquid is 2.7-3.5.
7. The resource utilization method of the byproduct phosphorus salt and the iron and steel pickling byproduct iron salt according to claim 1 or 5, characterized in that in the synthesis process of the iron phosphate, the specific steps of chemical impurity removal are as follows:
firstly, adjusting the pH value of the mixed solution of reaction mother liquor and first-washing waste liquor to 3-6, then adding sulfide impurity-removing agent into the mixed solution to make 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 presence of a gas in the atmosphere,
the addition amount of the sulfide impurity removing agent is 0.3-3% of the mass of iron salt as a byproduct of steel pickling.
8. The method for recycling by-product phosphorus salts and iron and steel pickling by-product iron salts according to claim 1, wherein the recycling step further comprises:
and (3) sodium chloride recovery process: the mixed solution of the mother liquor and the washing waste liquor after chemical impurity removal and filtration treatment is sequentially treated by a nanofiltration membrane and a reverse osmosis membrane, the sodium chloride concentrated solution from the reverse osmosis membrane is directly used as a production raw material of an ionic membrane caustic soda device matched with the upper stream of glyphosate production, and directly enters an ionic membrane alkali 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 can be reused in a system or sold outside.
9. The method of claim 8, wherein the recycling step further comprises:
the water recycling process: the concentrated solution from the nanofiltration membrane is reused for dissolving and hydrolyzing the glyphosate byproduct phosphorus salt; and the clear liquid discharged from the reverse osmosis membrane is reused in the washing procedure in the iron phosphate synthesis process.
10. The method for recycling by-product phosphorus salt and iron and steel pickling by-product iron salt according to claim 2, 3 or 5,
the pH regulator is at least one of phosphoric acid, hydrochloric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211549828.3A CN115959643A (en) | 2022-12-05 | 2022-12-05 | Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211549828.3A CN115959643A (en) | 2022-12-05 | 2022-12-05 | Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115959643A true CN115959643A (en) | 2023-04-14 |
Family
ID=87354122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211549828.3A Pending CN115959643A (en) | 2022-12-05 | 2022-12-05 | Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115959643A (en) |
Citations (6)
| 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 |
| 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 |
-
2022
- 2022-12-05 CN CN202211549828.3A patent/CN115959643A/en active Pending
Patent Citations (6)
| 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 |
| 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 |
Non-Patent Citations (1)
| 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, 31 January 2012 (2012-01-31), pages 50 - 53 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110272144B (en) | Treatment method of iron phosphate production wastewater | |
| CN102795734B (en) | Process of treating glyphosate mother solution by catalytic air oxidation method | |
| JP2015529740A (en) | Method and apparatus for producing or recovering hydrochloric acid from a metal salt solution | |
| EP4335823A1 (en) | Manganese sulfate purification and crystallization method | |
| JP2001026418A (en) | Recovering method of industrially useful inorganic material and industrially useful inorganic material recovered by the same | |
| CN102745791B (en) | Method for treating industrial wastewater | |
| CN114524572B (en) | Comprehensive treatment method for wastewater generated in iron phosphate production | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN113955733B (en) | Method for preparing ferric phosphate by utilizing waste hydrochloric acid containing iron | |
| CN112645396B (en) | Method for treating fluorine-containing nickel slag generated in nitrogen trifluoride preparation process | |
| CN112479416A (en) | Inorganic wastewater treatment process | |
| CN115959643A (en) | Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling | |
| CN116443833A (en) | Recovery method for recovering multiple components from waste batteries | |
| CN114262089A (en) | Method for recycling and treating aluminum anodic oxidation wastewater containing phosphoric acid and sulfuric acid | |
| CN217323729U (en) | System for ferric phosphate contains full element resourceful treatment of ammonia nitrogen waste water | |
| CN114956126A (en) | Method for recycling mother solution in sodium method iron phosphate production process | |
| CN112687973B (en) | Method and equipment for treating material containing lithium iron phosphate | |
| JP2008200599A (en) | Method for cleaning waste water containing ammonia nitrogen | |
| CN219972063U (en) | Treatment system for waste water in iron phosphate production | |
| CN210559435U (en) | Device for separating and preparing manganese carbonate from manganese-containing wastewater | |
| JPS6055442B2 (en) | Method for purifying salt water for electrolysis | |
| JPH05320939A (en) | Treatment of phosphate sludge | |
| JP2960876B2 (en) | Copper electrolyte cleaning method | |
| JP2008229434A (en) | Method for purifying ammonia nitrogen-containing wastewater | |
| CN114455561A (en) | Comprehensive utilization process of hot galvanizing pickling wastewater and method for preparing battery-grade iron phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |