CN116216672A - Method for removing sulfate radical in phosphoric acid preparation process - Google Patents
Method for removing sulfate radical in phosphoric acid preparation process Download PDFInfo
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- CN116216672A CN116216672A CN202211627908.6A CN202211627908A CN116216672A CN 116216672 A CN116216672 A CN 116216672A CN 202211627908 A CN202211627908 A CN 202211627908A CN 116216672 A CN116216672 A CN 116216672A
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- phosphoric acid
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 320
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940063953 ammonium lauryl sulfate Drugs 0.000 claims abstract description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 6
- YXLIYGUJLJFLJH-UHFFFAOYSA-L disodium;4-(octadecylamino)-4-oxo-2-sulfonatobutanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCCCCCCCNC(=O)CC(C([O-])=O)S([O-])(=O)=O YXLIYGUJLJFLJH-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229940067741 sodium octyl sulfate Drugs 0.000 claims abstract description 3
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000000605 extraction Methods 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 11
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000010413 mother solution Substances 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000005955 Ferric phosphate Substances 0.000 abstract description 5
- 229940032958 ferric phosphate Drugs 0.000 abstract description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 5
- 239000002367 phosphate rock Substances 0.000 abstract description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001422 barium ion Inorganic materials 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- YLIMHFXLIKETBC-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCC[Na] YLIMHFXLIKETBC-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- KIFVCRFNBOANAW-UHFFFAOYSA-N [Na].[Na].C(CCCCCCCCCCCCCCCCC)C(C(=O)O)(CC(=O)N)S(=O)(=O)O Chemical compound [Na].[Na].C(CCCCCCCCCCCCCCCCC)C(C(=O)O)(CC(=O)N)S(=O)(=O)O KIFVCRFNBOANAW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LAZOHFXCELVBBV-UHFFFAOYSA-N [Mg].[Ca].[Si] Chemical compound [Mg].[Ca].[Si] LAZOHFXCELVBBV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/2372—Anionic impurities, e.g. silica or boron compounds
- C01B25/2377—Sulfate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/2372—Anionic impurities, e.g. silica or boron compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention relates to the technical field of phosphorite processing, in particular to a method for removing sulfate radical in the process of preparing phosphoric acid; the application discloses a method for removing sulfate radical in the process of preparing phosphoric acid, which comprises the following steps: washing the extract containing crude phosphoric acid with a dilute phosphoric acid solution of barium carbonate; the extract containing crude phosphoric acid is obtained by extracting the crude phosphoric acid liquid with an extracting agent; the extractant comprises the following raw materials in percentage by weight: 30-40% of tributyl phosphate, 5-10% of ether solvent, 5-8% of oil-based polyoxyethylene ether phosphate, 2-5% of sodium octyl sulfate, 5-8% of disodium stearyl sulfosuccinamate, 10-13% of ammonium lauryl sulfate and the balance of alcohol solvent. According to the method for removing sulfate radicals, the sulfur content in the obtained concentrated phosphoric acid is reduced to below 10ppm, and the requirements for preparing ferric phosphate and lithium iron phosphate are met.
Description
Technical Field
The invention relates to the technical field of phosphorite processing, in particular to a method for removing sulfate radical in the process of preparing phosphoric acid.
Background
In the current phosphoric acid preparation process of phosphorite, the sulfate radical content is too high, and a further removal method is needed, so that the sulfur element content in phosphoric acid reaches the requirement of preparing lithium iron phosphate; because the sulfate radical content in the phosphoric acid solution is too high, the quality of the phosphoric acid solution after the ferric phosphate is prepared and the lithium iron phosphate is prepared by using the ferric phosphate can not meet the requirements of lithium battery preparation.
In the current process of preparing phosphoric acid, the prior stage treatment process needs to use sulfuric acid solution to remove calcium from phosphorite, or needs to use sulfuric acid solution to further remove calcium in the purification process, and sulfate radical is introduced in the operation process; the acid solution of sulfate radical and calcium ion can form dynamic balance, namely, the sulfate radical is difficult to remove due to calcium removal, and the calcium ion is difficult to remove due to sulfate radical removal, so that the calcium ion and the sulfate radical ion can not be completely removed; even though sulfate radical is removed by extraction at present, excessive salt is generated, so that the extraction process is easy to emulsify, and the purification yield of phosphoric acid and the ion separation effect are reduced.
Therefore, the invention provides a method for removing sulfate radical in the process of preparing phosphoric acid, which can effectively ensure that the sulfur content in concentrated phosphoric acid is reduced to below 10ppm.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for removing sulfate radical in the process of preparing phosphoric acid, which comprises the steps of washing an extracting solution containing phosphoric acid by using a dilute phosphoric acid solution of barium carbonate, carrying out extraction treatment on a crude phosphoric acid solution by using an extracting agent, so that most of non-metal ions and metal ions dissolved in water are brought into a water phase, washing the extracting solution containing phosphoric acid by using a dilute phosphoric acid solution of barium carbonate, further reducing the concentration of sulfate radical in the extracting solution containing phosphoric acid, and obtaining concentrated phosphoric acid by back extraction and concentration treatment, wherein the sulfur content in the concentrated phosphoric acid can be reduced to below 10ppm, thereby meeting the requirements of preparing ferric phosphate and lithium iron phosphate.
The technical scheme adopted for solving the technical problems is as follows:
a method for removing sulfate radical in the process of preparing phosphoric acid, comprising the following steps: washing the extract containing crude phosphoric acid with a dilute phosphoric acid solution of barium carbonate;
the extract containing crude phosphoric acid is obtained by extracting the crude phosphoric acid liquid with an extracting agent;
the extractant comprises the following raw materials in percentage by weight:
30-40% of tributyl phosphate, 5-10% of ether solvent, 5-8% of oil-based polyoxyethylene ether phosphate, 2-5% of sodium octyl sulfate, 5-8% of disodium stearyl sulfosuccinamate, 10-13% of ammonium lauryl sulfate and the balance of alcohol solvent.
Preferably, the ether solvent is one or two of n-butyl ether and isopropyl ether.
Preferably, the alcohol solvent is one or two of ethanol and n-butanol.
Preferably, the diluted phosphoric acid solution of barium carbonate is obtained by adding solid barium carbonate into a diluted phosphoric acid solution with the weight concentration of 1-10% of phosphoric acid to reach dissolution saturation. Wherein the dilute phosphoric acid solution of barium carbonate is obtained by adding barium carbonate into the dilute phosphoric acid solution to reach dissolution saturation; the specific dilute phosphoric acid solution of barium carbonate is a solution obtained by adding barium carbonate solid into dilute phosphoric acid solution, then filtering out insoluble barium carbonate after reaching dissolution saturation; alternatively, a dilute phosphoric acid solution to which barium carbonate is added is prepared so that the molar concentration of barium ions is 1X 10 -4 mol/kg to 5X 10 -4 A barium ion solution of mol/kg; for example, the molar concentration of barium ions may be 1X 10 -4 mol/kg、1.5×10 -4 mol/kg、2×10 -4 mol/kg、2.5×10 -4 mol/kg、3×10 -4 mol/kg、3.5×10 -4 mol/kg、4.5×10 -4 mol/kg or 5X 10 -4 mol/kg, but not limited to the values recited, other values not recited in the numerical range are equally applicable.
More preferably, the molar amount of phosphoric acid in the dilute phosphoric acid solution in the process of preparing the barium ion solution is 2-100 times of the molar amount of the barium ion; for example, the ratio of the molar amount of phosphoric acid to the molar amount of barium ion in the dilute phosphoric acid solution may be 2-fold, 3-fold, 4-fold, 5-fold, 6-fold, 7-fold, 8-fold, 9-fold, 10-fold, 15-fold, 20-fold, 21-fold, 22-fold, 23-fold, 24-fold, 25-fold, 30-fold, 35-fold, 40-fold, 41-fold, 42-fold, 43-fold, 44-fold, 45-fold, 46-fold, 47-fold, 48-fold, 49-fold, 50-fold, 55-fold, 60-fold, 65-fold, 70-fold, 75-fold, 80-fold, 85-fold, 90-fold, 95-fold, or 100-fold, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable; wherein, the mass concentration of phosphoric acid in the dilute phosphoric acid solution for preparing the barium ion solution is 1-10%; for example, the specific phosphoric acid mass concentration may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, a method for removing sulfate radical in the process of preparing phosphoric acid comprises the following steps:
extracting the crude phosphoric acid liquid by using an extracting agent to obtain an extract liquid containing crude phosphoric acid;
washing an extract containing crude phosphoric acid by using a dilute phosphoric acid solution of barium carbonate, standing for phase separation after washing, and separating out a water phase to obtain an organic solution containing the crude phosphoric acid;
the organic solution containing crude phosphoric acid is back extracted with water, and the aqueous phase containing phosphoric acid and the raffinate organic phase are obtained after phase separation.
As used herein, liquid-liquid extraction, also referred to as solvent extraction, refers primarily to the process of transferring a solute in one liquid phase to another liquid phase or redistributing it in two phases, through physical or chemical action, after contact of two completely or partially immiscible liquid phases or solutions, and is one of the important unit operations for separating and purifying materials. That is, the extraction process utilizes the different distribution relations of each component in the solution between two liquid phases to achieve the purposes of separation, enrichment and purification through inter-phase transfer;
mixing the crude phosphoric acid solution by using an extractant, then standing the phosphoric acid-containing extract by using a dilute phosphoric acid solution of barium carbonate, wherein the upper layer (organic layer) is an organic solution containing phosphoric acid, and the lower layer is a water phase, and separating the water phase to obtain an organic solution containing phosphoric acid; at this time, insoluble barium sulfate is contained in the water phase, and the barium sulfate filter residue is obtained after filtration;
back-extracting organic solution containing phosphoric acid with water, standing, and collecting the lower layer as water phase containing phosphoric acid; during back extraction, the mass ratio of the organic solution containing phosphoric acid to water is 1-5:1. For example, the mass of the organic solution containing phosphoric acid and water may be 1:1, 2:1, 3:1, 4:1, or 5:1, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the volume ratio of the extractant to the crude phosphoric acid liquid is 1-6:1, and the extraction temperature is 10-40 ℃. For example, the volume of extractant and crude phosphoric acid solution may be 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable. For example, the extraction temperature may be 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, or 40 ℃, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the raffinate organic phase is recycled for extraction of crude phosphoric acid liquid after water washing.
Preferably, the aqueous phase containing phosphoric acid is concentrated and filtered to obtain concentrated phosphoric acid.
Preferably, the crude phosphoric acid solution: and (3) performing acidolysis on the phosphate concentrate to obtain acidolysis solution, performing freezing crystallization on the acidolysis solution to obtain frozen mother liquor, performing deep calcium removal on the frozen mother liquor, performing denitration on filtrate after calcium removal, and obtaining a crude phosphoric acid solution as a solution after denitration.
The beneficial effects of the invention are that
According to the method provided by the application, after the crude phosphoric acid liquid is subjected to extraction treatment by the extractant, most of non-metal ions and metal ions dissolved in water are brought into the water phase, then the dilute phosphoric acid solution of barium carbonate is used for washing the phosphoric acid-containing extract, the concentration of sulfate radical in the phosphoric acid-containing extract is further reduced, and then the concentrated phosphoric acid is obtained through back extraction and concentration treatment, wherein the sulfur content in the concentrated phosphoric acid is reduced to below 10ppm, so that the requirements of preparing ferric phosphate and lithium iron phosphate are met.
Detailed Description
The achievement of the object, functional features and advantages of the present invention will be further described with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
As used herein, "and/or" includes any and all combinations of one or more of the associated listed items. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The exemplary invention described herein may suitably lack any one or more of the element limitations not specifically disclosed herein. Thus, the terms "comprising," "including," "containing," and the like are to be construed broadly and without limitation. In addition, the term expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms of description not including any equivalents of the features shown and described, but rather, in accordance with the claims, various modifications are possible within the scope of the invention. Thus, while the invention has been specifically disclosed by preferred embodiments and optional features, modification of the invention disclosed herein may be resorted to by those skilled in the art, and such modifications and variations are considered to be within the scope of this invention.
A method for removing sulfate radical in the process of preparing phosphoric acid, comprising the following steps: the phosphoric acid-containing extract was washed with a dilute phosphoric acid solution of barium carbonate.
Wherein the extract liquid containing phosphoric acid is obtained by extracting crude phosphoric acid liquid with an extracting agent. Specifically, the crude phosphoric acid liquid is: and (3) performing deep calcium removal on the frozen mother liquor, performing denitration on filtrate after calcium removal, wherein the solution obtained after denitration is crude phosphoric acid solution, and measuring the (weight) content of various ions in the crude phosphoric acid solution: NO (NO) 3 2- 0.0881, P 2 O 5 (P which can be formed with phosphorus element) 2 O 5 Calculated) is 53.62%, SO 4 2- 7.651%, F - 0.0785% of Fe 2 O 3 (Fe which can be formed as elemental iron) 2 O 3 Calculated) is 0.429%, al 2 O 3 (Al which can be formed as aluminum element) 2 O 3 Calculated)) of 0.7121%, ca 2+ 0.005% of Mg 2+ 0.737% and a deviation of not more than 2%.
Wherein the dilute phosphoric acid solution of barium carbonate is obtained by adding barium carbonate into the dilute phosphoric acid solution to reach dissolution saturation; the specific dilute phosphoric acid solution of barium carbonate is a solution obtained by adding barium carbonate solid into dilute phosphoric acid solution, then filtering out insoluble barium carbonate after reaching dissolution saturation; alternatively, a dilute phosphoric acid solution to which barium carbonate is added is prepared so that the molar concentration of barium ions is 1X 10 -4 mol/kg to 5X 10 -4 A barium ion solution of mol/kg; specifically, the molar amount of phosphoric acid in the dilute phosphoric acid solution in the process of preparing the barium ion solution is barium ion2-100 times of the molar quantity; alternatively, the molar amount of phosphoric acid in the dilute phosphoric acid solution is 2-50 times the molar amount of barium ions. Wherein the mass concentration of phosphoric acid in the dilute phosphoric acid solution for preparing the barium ion solution is 1-10%.
The raw materials or reagents used in the examples and comparative examples of the present invention were purchased from mainstream commercial manufacturers, and were of analytically pure grade that could be conventionally obtained without any particular limitation, as long as they were capable of achieving the intended effects. The apparatus and equipment such as the reaction vessel and the rotary evaporator used in this example are purchased from major commercial manufacturers, and are not particularly limited as long as they can function as intended. No particular technique or condition is identified in this example, which is performed according to techniques or conditions described in the literature in this field or according to product specifications.
Example 1
A method for removing sulfate radical in the process of preparing phosphoric acid, comprising the following steps:
step 1: preparation of a dilute phosphoric acid solution containing barium carbonate:
taking 10g of analysis grade phosphoric acid solution, adding 1000g of distilled water, slowly adding barium carbonate powder at normal temperature, dissolving under stirring for 1 hour, filtering out solid barium carbonate to obtain dilute phosphoric acid solution containing barium carbonate, and measuring the content of barium ions to be 325 multiplied by 10 -6 mol/kg。
Step 2: extraction of crude phosphoric acid solution
1000g of crude phosphoric acid solution (the mass concentration of phosphoric acid is 40%) is taken, 1500g of extractant is added and stirred, and each 100g of extractant comprises the following raw materials in parts by weight:
40g of tributyl phosphate, 7g of n-butyl ether, 3g of isopropyl ether, 8g of oleyl polyoxyethylene ether phosphate, 5g of octyl sodium sulfate, 8g of disodium stearyl sulfosuccinamate, 13g of ammonium lauryl sulfate and the balance of ethanol.
Step 3: removal of sulfate
And (3) standing after extraction, separating liquid after standing to obtain an organic phase containing phosphoric acid, measuring the sulfate radical concentration in the organic phase, wherein the sulfate radical concentration is 2064mg/kg based on the mass of sulfur, adding 365g of the dilute phosphoric acid solution added with barium carbonate in the step (1) into the organic phase, fully stirring, filtering to obtain filtrate, adding 1300g of distilled water for back extraction, standing the solution after back extraction, separating out a water phase, concentrating to obtain 80% concentrated phosphoric acid, and measuring the sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into 93mg/kg based on the mass of sulfur and 5ppm based on the mass of magnesium. And adding a little water into the filtered barium sulfate precipitate for washing, and then transferring the washed barium sulfate filter residues to a silicon-calcium-magnesium workshop for new product planning. During the back extraction, no emulsification phenomenon exists.
Extracting with the extractant for 2 times, back extracting with water for 2 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the mass content of sulfur is 33mg/kg, and the mass content of magnesium is 4ppm; extracting with the extractant for 3 times, back extracting with water for 3 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into sulfur with a mass content of 13mg/kg and magnesium with a mass content of 4ppm; extracting with the extractant for 5 times, back extracting with water for 5 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into sulfur with a mass content of 5mg/kg and magnesium with a mass content of 3ppm;
example 2
Every 100g of extractant comprises the following raw materials in parts by weight: 30g of tributyl phosphate, 5g of n-butyl ether, 5g of oleyl polyoxyethylene ether phosphate, 2g of octyl sodium sulfate, 5g of stearyl sulfosuccinamic acid disodium, 10g of ammonium lauryl sulfate and the balance of ethanol; the remaining conditions were the same as in example 1; obtaining 80% of concentrated phosphoric acid, and measuring the sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into 104mg/kg of sulfur and 10ppm of magnesium by mass;
extracting with the extractant for 2 times, back extracting with water for 2 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into 53mg/kg of sulfur and the magnesium content is 8ppm; extracting with the extractant for 3 times, back extracting with water for 3 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into 35mg/kg of sulfur and 8ppm of magnesium; extracting with the extractant for 5 times, back extracting with water for 5 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into 10mg/kg of sulfur and the magnesium content is 7ppm.
Example 3
Every 100g of extractant comprises the following raw materials in parts by weight: 35g of tributyl phosphate, 8g of isopropyl ether, 6g of oleyl polyoxyethylene ether phosphate, 4g of octyl sodium sulfate, 6g of stearyl sulfosuccinamic acid disodium, 11g of ammonium lauryl sulfate, 5g of n-butyl alcohol and the balance of ethanol; the remaining conditions were the same as in example 1;
obtaining 80% of concentrated phosphoric acid, and measuring the sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into 52mg/kg of sulfur and 11ppm of magnesium;
extracting with the extractant for 2 times, back extracting with water for 2 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into 11mg/kg of sulfur and the magnesium content is 10ppm; extracting with the extractant for 3 times, back extracting with water for 3 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into sulfur with a mass content of 4mg/kg and magnesium with a mass content of 10ppm; extracting with the extractant for 5 times, back extracting with water for 5 times to obtain 80% concentrated phosphoric acid, and measuring sulfate radical content in the concentrated phosphoric acid, wherein the sulfate radical content is converted into sulfur content of 1mg/kg and magnesium content of 10ppm.
Comparative example 1
The extractant is tributyl phosphate, and the other conditions are the same as those of the example 1;
the extractant is extracted for 2 times, water is used for back extraction for 2 times, emulsification (halogenation) occurs in the back washing process, layering is not good, and back extraction fails.
The foregoing embodiments and the specific schemes are not limited to the scope of the invention, and all equivalent structures or equivalent flow changes made by the content of the present disclosure, or direct or indirect application in other related technical fields are included in the scope of the invention.
Claims (10)
1. A method for removing sulfate radical in the process of preparing phosphoric acid, which is characterized by comprising the following steps: washing the extract containing crude phosphoric acid with a dilute phosphoric acid solution of barium carbonate;
the extract containing crude phosphoric acid is obtained by extracting the crude phosphoric acid liquid with an extracting agent;
the extractant comprises the following raw materials in percentage by weight:
30-40% of tributyl phosphate, 5-10% of ether solvent, 5-8% of oil-based polyoxyethylene ether phosphate, 2-5% of sodium octyl sulfate, 5-8% of disodium stearyl sulfosuccinamate, 10-13% of ammonium lauryl sulfate and the balance of alcohol solvent.
2. The method for removing sulfate radical in the process of preparing phosphoric acid according to claim 1, wherein the ether solvent is one or two of n-butyl ether and isopropyl ether.
3. The method for removing sulfate radical in the process of preparing phosphoric acid according to claim 1, wherein the alcohol solvent is one or two of ethanol and n-butanol.
4. The method for removing sulfate radical in the process of preparing phosphoric acid according to claim 1, wherein the dilute phosphoric acid solution of barium carbonate is obtained by adding solid barium carbonate to a dilute phosphoric acid solution with a phosphoric acid weight concentration of 1-10% until the solution is saturated.
5. A method for removing sulphate groups in a process for preparing phosphoric acid according to claim 1 comprising the steps of:
extracting the crude phosphoric acid liquid by using an extracting agent to obtain an extract liquid containing crude phosphoric acid;
washing an extract containing crude phosphoric acid by using a dilute phosphoric acid solution of barium carbonate, standing for phase separation after washing, and separating out a water phase to obtain an organic solution containing the crude phosphoric acid;
the organic solution containing crude phosphoric acid is back extracted with water, and the aqueous phase containing phosphoric acid and the raffinate organic phase are obtained after phase separation.
6. The method for removing sulfate radical in the process of preparing phosphoric acid according to claim 5, wherein the extraction temperature is 10-40 ℃ in the volume ratio of the extractant to the crude phosphoric acid solution of 1-6:1.
7. A method for removing sulfate radical in a process for preparing phosphoric acid according to claim 5, wherein the raffinate organic phase is recycled for extraction of crude phosphoric acid liquid after washing with water.
8. A method for removing sulfate radical in a process for preparing phosphoric acid according to claim 5, wherein the aqueous phase containing phosphoric acid is concentrated and filtered to obtain concentrated phosphoric acid.
9. A method for removing sulfate radical in a process for preparing phosphoric acid according to claim 5, wherein the aqueous phase containing phosphoric acid is concentrated and filtered to obtain concentrated phosphoric acid.
10. The method for removing sulfate radical in the process of preparing phosphoric acid according to claim 1 or 5, wherein the acidolysis solution obtained after acidolysis of phosphate concentrate is frozen and crystallized to obtain frozen mother solution, the frozen mother solution is subjected to deep decalcification, the filtrate after decalcification is subjected to denitration, and the solution obtained after denitration is crude phosphoric acid solution.
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| US4041134A (en) * | 1976-02-13 | 1977-08-09 | Toyo Soda Manufacturing Co., Ltd | Process for removing sulfate ions from extracted phosphoric acid employing barium compounds and activated carbon |
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| CN106348273A (en) * | 2016-08-17 | 2017-01-25 | 湖北三宁化工股份有限公司 | Extraction agent for preparing industrial phosphoric acid through hydrochloric acid method and extraction method thereof |
| CN111777052A (en) * | 2020-07-24 | 2020-10-16 | 瓮福（集团）有限责任公司 | Fine desulfurization method for phosphoric acid |
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| US4041134A (en) * | 1976-02-13 | 1977-08-09 | Toyo Soda Manufacturing Co., Ltd | Process for removing sulfate ions from extracted phosphoric acid employing barium compounds and activated carbon |
| US4321245A (en) * | 1979-11-14 | 1982-03-23 | Hoechst Aktiengesellschaft | Process for the purification of wet-processed phosphoric acid |
| CN102718200A (en) * | 2012-07-10 | 2012-10-10 | 中海石油化学股份有限公司 | Method for preparing industrial-grade phosphoric acid by decomposing mid-low-grade phosphorite with nitric acid |
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