CN102556991B - Pre-treatment method applied to wet process phosphoric acid extraction and refining through composite extracting agents - Google Patents
Pre-treatment method applied to wet process phosphoric acid extraction and refining through composite extracting agents Download PDFInfo
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- CN102556991B CN102556991B CN2012100065933A CN201210006593A CN102556991B CN 102556991 B CN102556991 B CN 102556991B CN 2012100065933 A CN2012100065933 A CN 2012100065933A CN 201210006593 A CN201210006593 A CN 201210006593A CN 102556991 B CN102556991 B CN 102556991B
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000000605 extraction Methods 0.000 title claims abstract description 32
- 238000007670 refining Methods 0.000 title claims abstract description 26
- 238000002203 pretreatment Methods 0.000 title claims abstract description 9
- 238000004062 sedimentation Methods 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000003945 anionic surfactant Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- -1 olefin sulfonate Chemical class 0.000 claims description 6
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 5
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 238000009264 composting Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229940067741 sodium octyl sulfate Drugs 0.000 claims description 3
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 21
- 238000006477 desulfuration reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 19
- 238000006115 defluorination reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract 2
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 description 18
- 159000000009 barium salts Chemical class 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000011017 operating method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005202 decontamination Methods 0.000 description 5
- 230000003588 decontaminative effect Effects 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000000247 postprecipitation Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000016507 interphase Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IWPWMAJDSLSRIP-UHFFFAOYSA-N nezukone Chemical compound CC(C)C1=CC=CC(=O)C=C1 IWPWMAJDSLSRIP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical class CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
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- Extraction Or Liquid Replacement (AREA)
Abstract
The invention relates to a pre-treatment method applied to wet process phosphoric acid extraction and refining through composite extracting agents. The pre-treatment method sequentially comprises steps of defluorination, sedimentation and decoloration, wherein only the defluorination rate is pursued in the defluorination process, composite sedimentation agents are adopted for sedimentation in the sedimentation process, the composite sedimentation agents are water solution with the mass percentage concentration being 5 percent to 15 percent, solutes of the composite sedimentation agents are non-ionic surface active agents and anionic surface active agents prepared according to a mass ratio being 1:(10-50), powdery active carbon is adopted for decoloration in the decoloration process, and the solid content in extracted raw acid after the pre-treatment completion is lower than 0.05 weight percent. The design has the advantages that the purification effect is better, the subsequent process difficulty can be reduced, in addition, the operation process is simplified, and the desulfuration cost is reduced.
Description
Technical field
The present invention relates to a kind of pretreatment process that is applied to the extracting and refining phosphoric acid by wet process, especially a kind of pretreatment process that is applied to composite extractant extracting and refining phosphoric acid by wet process, specifically be applicable to strengthen pretreating effect, and reduce the subsequent production difficulty.
Background technology
At present, the pretreatment process in the extracting and refining phosphoric acid by wet process generally comprises defluorinate, desulfurization and filter operation.In practical application, first carry out defluorinate, desulfurization, filter that again phosphoric acid by wet process is carried out to purifying treatment, but because the most phosphorus ore of China is low-grade in being all, the phosphoric acid by wet process of producing with this phosphorus ore is after concentrating, in gelled acid, foreign matter content is high, solid particulate is many, viscosity is large, thereby during the filter operation after carrying out defluorinate, desulfurization, filtration will be very difficult, and not only operation easier is higher, and filter effect is bad, easily to subsequent technique, increases difficulty.
in addition, above-mentioned by mid low grade phosphate rock production, through the gelled acid after concentrated, not only has a foreign matter content high, solid particulate is many, the shortcoming that viscosity is large, and the various impurity in acid all are in hypersaturated state, namely enable to be filtered into reluctantly clear solution, but when placement one day or after the extraction agent extraction, those impurity that are in hypersaturated state in acid will form the solid precipitation solids precipitation out, thereby so-called " postprecipitation " phenomenon appears, this can bring serious problem to the extracting and refining of wet method phosphoric acid: 1, the solid particulate that " postprecipitation " phenomenon produces can cause mixed phase phase-splitting difficulty, even can't phase-splitting, 2, the solid particulate that produces of " postprecipitation " phenomenon can be attached on the pipeline and inwall of extraction equipment, causes the difficulty of transportation of liquid, even can blocking channel, and cause equipment to run well and even stop.
In traditional way, also there is the method for taking sedimentation after defluorinate, desulfurization to carry out purifying treatment to phosphoric acid by wet process, namely by sedimentation, allow solid particulate lean on gravity naturally to sink, but this technique is a kind of method of natural subsidence, not only the settling time is longer, general first quarter moon January at most at least, and effect of settling is poor, can only sedimentation go out larger solid particulate.
Summary of the invention
The objective of the invention is to overcome the purifying treatment effect that exists in prior art is poor, increase the subsequent technique difficulty defect and problem, the pretreatment process that is applied to composite extractant extracting and refining phosphoric acid by wet process that a kind of purifying treatment effect is better, reduce the subsequent technique difficulty is provided.
For realizing above purpose, technical solution of the present invention is:
A kind of pretreatment process that is applied to composite extractant extracting and refining phosphoric acid by wet process, this pretreatment process comprise defluorinate and decolouring step successively; Described pretreatment process also comprises precipitation step between defluorinate, decolouring step; Described pretreatment process comprises the following steps successively:
Defluorinate: the raw phosphoric acid that first wet method is made concentrates, until P in raw phosphoric acid
2O
5Mass percent concentration be 45%, then add Na in the raw phosphoric acid after concentrated
2CO
3Carry out defluorinate, described Na
2CO
3Add-on by stoichiometric 100% – 120% of free state fluorion in raw phosphoric acid after concentrated, calculate;
Sedimentation: first add compound sinking agent to carry out sedimentation in the raw phosphoric acid after above-mentioned defluorinate, the volume of described compound sinking agent is 1 ‰ – 10 ‰ of raw phosphoric acid volume after defluorinate, stir again, sedimentation can obtain the clear acid of sedimentation and underflow slag acid after 4 hours, the volume of the clear acid of described sedimentation is 85% – 90% of raw phosphoric acid after defluorinate, compound sinking agent volume sum, and composting between tumbril is sent in described underflow slag acid;
Described compound sinking agent is that mass percent concentration is the aqueous solution of 5% – 15%, and its solute is for pressing nonionogenic tenside and the anion surfactant of 1:10 – 50 mass ratio preparations;
Described nonionogenic tenside is: maleic acid-acrylic acid copolymer, acrylamide-acrylicacid methyl esters-2-acrylamide-2-methylpro panesulfonic acid multipolymer, AM-AA-DMA multipolymer a kind of or press any two kinds of 1:1 mass ratio preparation;
Described anion surfactant is a kind of of oil base polyoxyethylene (10) ether phosphate, sodium octyl sulfate, α-sodium olefin sulfonate, sodium lignosulfonate, stearyl sulfosuccinamic acid disodium, Texapon Special;
Decolouring: first in the clear acid of sedimentation obtained above, add the activated carbon of powdery to decolour, the mass volume ratio mg/ml of the clear acid of this activated carbon and sedimentation is 0.5% – 1.5%:1, then filters to be extracted ortho acid, and pre-treatment this moment finishes; Solid contents ﹤ 0.05wt% in described extraction ortho acid.
The volume of described compound sinking agent be after defluorinate the raw phosphoric acid volume 5 ‰, described compound sinking agent is that mass percent concentration is 10% the aqueous solution, its solute is for pressing nonionogenic tenside and the anion surfactant of the preparation of 1:30 mass ratio, and the mass volume ratio mg/ml of the clear acid of described activated carbon and sedimentation is 1.25%:1.
Compared with prior art, beneficial effect of the present invention is:
1, the present invention is a kind of to be applied in the pretreatment process of composite extractant extracting and refining phosphoric acid by wet process when the wet method phosphoric acid by wet process is carried out to purifying treatment, take compound sinking agent to carry out the method for sedimentation, the decontamination effect improving that not only can effectively avoid filter operation to bring is poor, there is the defect of " postprecipitation " phenomenon, and can reduce the operation easier of subsequent technique, its reason is that the compound sinking agent that the present invention takes has unique design, it not only defines the concentration of solution, also define the kind of solute, make and only have strength of solution, the compound sinking agent that solute species all meets could realize that the settling process that the present invention pursues is faster, effect of settling is purpose more thoroughly, thereby making the volume of the clear acid of sedimentation is raw phosphoric acid after defluorinate, 85% – 90% of compound sinking agent volume sum, and then guarantee the solid contents ﹤ 0.05wt% in the final extraction ortho acid that obtains.Therefore not only decontamination effect improving is better in the present invention, and can reduce the subsequent technique difficulty.
2, the present invention is a kind of to be applied to before purifying treatment, only need to carry out the defluorinate step in the pretreatment process of composite extractant extracting and refining phosphoric acid by wet process, and need to carry out defluorinate unlike prior art, desulfurization operations, simplified operating procedure, its reason is: at first, application of the present invention is composite extractant extracting and refining Wet Processes of Phosphoric Acid, in this technique, take composite extractant to carry out the extracting and refining phosphoric acid by wet process, because composite extractant has very high selectivity to phosphoric acid, selectivity is very little to sulfate radical, except the not only not obstruction of carrying out to extracting of sulfate radical, and little on sulfate radical content impact in extracted organic phase, thereby can after extraction, carry out again desulfurization fully, once desulfurization just can reach the requirement of GB to sulfate radical at that time, secondly, if the present invention after defluorinate with regard to desulfurization, due to general employing calcium salt or barium salt desulfurization in prior art, if employing calcium salt, the calcium sulfate that generates after desulfurization is larger in the solubleness of phosphoric acid the inside, not only can not thoroughly remove sulfate radical, and can bring calcium ion into, reduce phosphoric acid quality, hinder the extraction of follow-up composite extractant to phosphoric acid, if take barium salt, after defluorinate in phosphoric acid the content of sulfate radical much larger than the content of sulfate radical in phosphoric acid after extraction, thereby will certainly increase the consumption of barium salt, and the cost of barium salt is too high, thereby greatly increase desulphurization cost.Therefore the present invention has not only simplified operating procedure, and has reduced desulphurization cost.
3, a kind of pretreatment process of composite extractant extracting and refining phosphoric acid by wet process that is applied to of the present invention is in the defluorinate step, the object of defluorinate is the free state fluorion, do not pursue the defluorinate rate, only need suitably to reduce free fluorine in case it affects extraction process and equipment gets final product, its reason is: because a lot of phosphatic fertilizer companies adopt, contain the aluminium water conditioner, perhaps with containing the phosphorus ore that aluminium is higher, produce phosphoric acid by wet process, the existence of aluminium can make defluorination effect have a greatly reduced quality, if in the defluorinate process, too pursue the defluorinate rate, lose more than gain, thereby only need suitably to reduce the free state fluorion, guarantee that it does not affect extraction process and equipment gets final product, operating procedure has been simplified in this requirement greatly.Therefore the present invention has simplified operating procedure.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment and embodiment.
A kind of pretreatment process that is applied to composite extractant extracting and refining phosphoric acid by wet process, this pretreatment process comprises the following steps successively:
Defluorinate: the raw phosphoric acid that first wet method is made concentrates, until P in raw phosphoric acid
2O
5Mass percent concentration be 45%, then add Na in the raw phosphoric acid after concentrated
2CO
3Carry out defluorinate, described Na
2CO
3Add-on by stoichiometric 100% – 120% of free state fluorion in raw phosphoric acid after concentrated, calculate;
Sedimentation: first add compound sinking agent to carry out sedimentation in the raw phosphoric acid after above-mentioned defluorinate, the volume of described compound sinking agent is 1 ‰ – 10 ‰ of raw phosphoric acid volume after defluorinate, stir again, sedimentation can obtain the clear acid of sedimentation and underflow slag acid after 4 hours, the volume of the clear acid of described sedimentation is 85% – 90% of raw phosphoric acid after defluorinate, compound sinking agent volume sum, and composting between tumbril is sent in described underflow slag acid;
Described compound sinking agent is that mass percent concentration is the aqueous solution of 5% – 15%, and its solute is for pressing nonionogenic tenside and the anion surfactant of 1:10 – 50 mass ratio preparations;
Described nonionogenic tenside is: maleic acid-acrylic acid copolymer, acrylamide-acrylicacid methyl esters-2-acrylamide-2-methylpro panesulfonic acid multipolymer, AM-AA-DMA multipolymer a kind of or press any two kinds of 1:1 mass ratio preparation;
Described anion surfactant is a kind of of oil base polyoxyethylene (10) ether phosphate, sodium octyl sulfate, α-sodium olefin sulfonate, sodium lignosulfonate, stearyl sulfosuccinamic acid disodium, Texapon Special;
Decolouring: first in the clear acid of sedimentation obtained above, add the activated carbon of powdery to decolour, the mass volume ratio mg/ml of the clear acid of this activated carbon and sedimentation is 0.5% – 1.5%:1, then filters to be extracted ortho acid, and pre-treatment this moment finishes; Solid contents ﹤ 0.05wt% in described extraction ortho acid.
The volume of described compound sinking agent be after defluorinate the raw phosphoric acid volume 5 ‰, described compound sinking agent is that mass percent concentration is 10% the aqueous solution, its solute is for pressing nonionogenic tenside and the anion surfactant of the preparation of 1:30 mass ratio, and the mass volume ratio mg/ml of the clear acid of described activated carbon and sedimentation is 1.25%:1.
Principle of the present invention is described as follows:
1, about composite extractant extracting and refining phosphoric acid by wet process:
What the present invention is directed to is composite extractant extracting and refining phosphoric acid by wet process, this kind composite extractant not only has a highly selective (phosphoric acid extraction basically of pair phosphoric acid, and other impurity of considerably less extraction), high repellency to metal ion and impurity negatively charged ion, also have wider phosphoric acid extraction permissible concentration scope, can make percentage extraction further be promoted to 85-90%.These characteristics make composite extractant there is no what too many requirement to the extraction ortho acid, thereby this pretreatment process only otherwise allowing solid particulate, organism enter extraction tank just can meet the demands, namely extract solid contents ﹤ 0.05wt% in ortho acid, and need in pre-treatment, not carry out desulfurization, removing heavy-metal, even the defluorinate rate is not pursued in defluorinate yet, greatly simplified pretreatment process.
Composition and the weight part ratio thereof of the normal composite extractant that coordinates of the present invention are: ether ketone: alcohol: ester=60 – 80:15 – 20:5 – 15, and the composition of described ether ketone and weight part ratio thereof are: ketone: ether=95 – 60:5 – 40; Described ketone nail base nezukone, diisopropyl ketone, diisobutyl ketone, methyl iso-butyl ketone (MIBK) or pimelinketone, described ether refers to diisopropyl ether or diisobutyl ether, described alcohol make a comment or criticism butanols, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol or hexalin, described ester refers to three butoxyethyl group phosphoric acid ester or tributyl phosphates.
2, about desulfurization:
Application of the present invention is composite extractant extracting and refining Wet Processes of Phosphoric Acid, in this technique, take composite extractant to carry out the extracting and refining phosphoric acid by wet process, because composite extractant has very high selectivity to phosphoric acid, selectivity is very little to sulfate radical, except the not only not obstruction of carrying out to extracting of sulfate radical, and little on sulfate radical content impact in extracted organic phase, thereby can after extraction, carry out again desulfurization fully, once desulfurization just can reach the requirement of GB to sulfate radical at that time.If the present invention after defluorinate with regard to desulfurization, due to general employing calcium salt or barium salt desulfurization in prior art, if employing calcium salt, the calcium sulfate that generates after desulfurization is larger in the solubleness of phosphoric acid the inside, not only can not thoroughly remove sulfate radical, and can bring calcium ion into, and reduce phosphoric acid quality, hinder the extraction of follow-up composite extractant to phosphoric acid; If take barium salt, due to the content of sulfate radical in phosphoric acid after the defluorinate content much larger than sulfate radical in phosphoric acid after extraction, thereby will certainly increase the consumption of barium salt, and the cost of barium salt is too high, thereby greatly increases production cost.Therefore the present invention does not carry out desulfurization after defluorinate, has not only simplified operating procedure, sees on the whole, has also reduced desulphurization cost.
3, about sedimentation:
The sedimentation operation that the present invention takes is follow-up composite extractant extracting and refining phosphoric acid by wet process service, by above-mentioned as can be known to introducing of composite extractant extracting and refining phosphoric acid by wet process, the characteristics of this kind composite extractant are: phosphoric acid is had to highly selective, metal ion, impurity negatively charged ion are had to high repellency, also have wider phosphoric acid extraction permissible concentration scope, make percentage extraction further be promoted to 85-90%.Thereby the purpose of sedimentation of the present invention is exactly to remove more thoroughly, faster the solid particulate in phosphoric acid, (decontamination effect improving can be 85% – 90% of raw phosphoric acid after defluorinate, compound sinking agent volume sum from the volume of the clear acid of sedimentation to improve decontamination effect improving, and proof on solid contents ﹤ 0.05wt% in the extraction ortho acid), thus guarantee the effect of follow-up extraction agent extracting and refining phosphoric acid by wet process.For achieving this end, the present invention has carried out unique design to strength of solution, the solute species of compound sinking agent, and this unique design produces in settling process effect is as follows:
The anion surfactant that the present invention takes is in the deposit seeds surface adsorption, the surface that has reduced the deposit seeds surface can, impel more sedimentary molecule to separate out at this surface crystallization, and the nonionogenic tenside that the present invention takes is to the absorption of fine particle, make these fine particles be gathered into larger particles, thus can very fast sedimentation; Add the viscosity reduction effect of anion surfactant to phosphoric acid solution, make settling process sooner, more thorough; If change the kind of solute in compound sinking agent, its effect of settling is obviously not as the present invention: otherwise due to bridging action, the shared ratio of the clear acid of the sedimentation that sedimentation obtains is less than 20% of reaction soln total height in subsider, otherwise is exactly there is no effect of settling; If change proportioning or cooperation in compound sinking agent, will cause extracting ortho acid thickness more, not only reduce decontamination effect improving, also be unfavorable for the carrying out of subsequent technique.
4, about defluorinate:
In the present invention, the object of defluorinate is the free state fluorion, do not pursue the defluorinate rate, its reason is: because a lot of phosphatic fertilizer companies adopt, contain the aluminium water conditioner, perhaps with containing the phosphorus ore that aluminium is higher, produce phosphoric acid by wet process, the existence of aluminium can make defluorination effect have a greatly reduced quality, therefore the defluorinate process in the present invention is not pursued the defluorinate rate, if too pursue the defluorinate rate, lose more than gain, thereby only need suitably to reduce the free state fluorion, guarantee that it does not affect extraction process and equipment gets final product, thereby simplified operating procedure.
5, about decolouring:
Decolouring is that (accumulation of interphase impurity can make the thickness of interphase impurity increase because the organism in the extraction ortho acid produces a large amount of interphase impurities in the extracting and refining process at phosphoric acid by wet process, phase-splitting can't be completed, cause extraction process to carry out), thus the carrying out of extraction process directly affected.
Embodiment 1:
A kind of pretreatment process that is applied to composite extractant extracting and refining phosphoric acid by wet process, this pretreatment process comprises the following steps successively:
Defluorinate: the raw phosphoric acid that first wet method is made concentrates, until P in raw phosphoric acid
2O
5Mass percent concentration be 45%, then add Na in the raw phosphoric acid after concentrated
2CO
3Carry out defluorinate, described Na
2CO
3Add-on by stoichiometric 100% – 120% of free state fluorion in raw phosphoric acid after concentrated, calculate;
Sedimentation: first add compound sinking agent to carry out sedimentation in the raw phosphoric acid after above-mentioned defluorinate, the volume of described compound sinking agent be after defluorinate the raw phosphoric acid volume 1 ‰, stir again, sedimentation can obtain the clear acid of sedimentation and underflow slag acid after 4 hours, the volume of the clear acid of described sedimentation is 85% – 90% of raw phosphoric acid after defluorinate, compound sinking agent volume sum, and composting between tumbril is sent in described underflow slag acid;
Described compound sinking agent is that mass percent concentration is 5% the aqueous solution, and its solute is for pressing nonionogenic tenside and the anion surfactant of the preparation of 1:10 mass ratio;
Described nonionogenic tenside is: acrylamide-acrylicacid methyl esters-2-acrylamide-2-methylpro panesulfonic acid multipolymer, and described anion surfactant is sodium lignosulfonate;
Decolouring: first in the clear acid of sedimentation obtained above, add the activated carbon of powdery to decolour, the mass volume ratio mg/ml of the clear acid of this activated carbon and sedimentation is 0.5%:1, then filters to be extracted ortho acid, and pre-treatment this moment finishes; Solid contents ﹤ 0.05wt% in described extraction ortho acid.
Embodiment 2:
Step is with embodiment 1, and difference is:
Sedimentation: the volume of described compound sinking agent be after defluorinate the raw phosphoric acid volume 5 ‰, described compound sinking agent is that mass percent concentration is 10% the aqueous solution, its solute is for pressing nonionogenic tenside and the anion surfactant of the preparation of 1:30 mass ratio, described nonionogenic tenside is AM-AA-DMA multipolymer and the maleic acid-acrylic acid copolymer of 1:1 mixing in mass ratio, and described anion surfactant is oil base polyoxyethylene (10) ether phosphate;
Decolouring: the mass volume ratio mg/ml of the clear acid of described activated carbon and sedimentation is 1.25%:1.
Embodiment 3:
Step is with embodiment 1, and difference is:
Sedimentation: the volume of described compound sinking agent be after defluorinate the raw phosphoric acid volume 10 ‰, described compound sinking agent is that mass percent concentration is 15% the aqueous solution, its solute is for pressing nonionogenic tenside and the anion surfactant of the preparation of 1:50 mass ratio, described nonionogenic tenside is maleic acid-acrylic acid copolymer, and described anion surfactant is stearyl sulfosuccinamic acid disodium;
Decolouring: the mass volume ratio mg/ml of the clear acid of described activated carbon and sedimentation is 1.5%:1.
The foregoing is only better embodiment of the present invention; protection scope of the present invention is not limited with above-mentioned embodiment; as long as the equivalence that those of ordinary skills do according to disclosed content is modified or changed, all should include in the protection domain of putting down in writing in claims.
Claims (2)
1. pretreatment process that is applied to composite extractant extracting and refining phosphoric acid by wet process, this pretreatment process comprise defluorinate and decolouring step successively, it is characterized in that: described pretreatment process also comprises precipitation step between defluorinate, decolouring step; Described pretreatment process comprises the following steps successively:
Defluorinate: the raw phosphoric acid that first wet method is made concentrates, until P in raw phosphoric acid
2O
5Mass percent concentration be 45%, then add Na in the raw phosphoric acid after concentrated
2CO
3Carry out defluorinate, described Na
2CO
3Add-on by stoichiometric 100% – 120% of free state fluorion in raw phosphoric acid after concentrated, calculate;
Sedimentation: first add compound sinking agent to carry out sedimentation in the raw phosphoric acid after above-mentioned defluorinate, the volume of described compound sinking agent is 1 ‰ – 10 ‰ of raw phosphoric acid volume after defluorinate, stir again, sedimentation can obtain the clear acid of sedimentation and underflow slag acid after 4 hours, the volume of the clear acid of described sedimentation is 85% – 90% of raw phosphoric acid after defluorinate, compound sinking agent volume sum, and composting between tumbril is sent in described underflow slag acid;
Described compound sinking agent is that mass percent concentration is the aqueous solution of 5% – 15%, and its solute is for pressing nonionogenic tenside and the anion surfactant of 1:10 – 50 mass ratio preparations;
Described nonionogenic tenside is: maleic acid-acrylic acid copolymer, acrylamide-acrylicacid methyl esters-2-acrylamide-2-methylpro panesulfonic acid multipolymer, AM-AA-DMA multipolymer a kind of or press any two kinds of 1:1 mass ratio preparation;
Described anion surfactant is a kind of of oil base polyoxyethylene (10) ether phosphate, sodium octyl sulfate, α-sodium olefin sulfonate, sodium lignosulfonate, stearyl sulfosuccinamic acid disodium, Texapon Special;
Decolouring: first in the clear acid of sedimentation obtained above, add the gac of powdery to decolour, the mass volume ratio mg/ml of the clear acid of this gac and sedimentation is 0.5% – 1.5%:1, then filters to be extracted ortho acid, and pre-treatment this moment finishes; Solid contents ﹤ 0.05wt% in described extraction ortho acid.
2. a kind of pretreatment process that is applied to composite extractant extracting and refining phosphoric acid by wet process according to claim 1, it is characterized in that: the volume of described compound sinking agent be after defluorinate the raw phosphoric acid volume 5 ‰, described compound sinking agent is that mass percent concentration is 10% the aqueous solution, its solute is for pressing nonionogenic tenside and the anion surfactant of the preparation of 1:30 mass ratio, and the mass volume ratio mg/ml of the clear acid of described gac and sedimentation is 1.25%:1.
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| CN108928808A (en) * | 2018-07-03 | 2018-12-04 | 昆明川金诺化工股份有限公司 | A kind of solvent extraction new method of purifying low-concentration phosphoric acid by wet process |
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| CN115092898B (en) * | 2022-06-21 | 2023-09-19 | 云南磷化集团有限公司 | Method for removing sulfate radical in wet-process phosphoric acid by utilizing yellow phosphorus slag |
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| CN1751988A (en) * | 2005-11-04 | 2006-03-29 | 华中师范大学 | Method of fast eliminating solid matter and fluorine in wet method crude phoshporic acid |
| CN1762797A (en) * | 2005-08-19 | 2006-04-26 | 武汉化工学院 | Wet method purification method for phosphate or soluble phosphate |
| CN102267691A (en) * | 2011-07-05 | 2011-12-07 | 侯炎学 | Settling agent for wet phosphoric acid refining desulfuration and using method thereof |
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| CN1762797A (en) * | 2005-08-19 | 2006-04-26 | 武汉化工学院 | Wet method purification method for phosphate or soluble phosphate |
| CN1751988A (en) * | 2005-11-04 | 2006-03-29 | 华中师范大学 | Method of fast eliminating solid matter and fluorine in wet method crude phoshporic acid |
| CN102267691A (en) * | 2011-07-05 | 2011-12-07 | 侯炎学 | Settling agent for wet phosphoric acid refining desulfuration and using method thereof |
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