CN114538396A - Process system and method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof - Google Patents
Process system and method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof Download PDFInfo
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- CN114538396A CN114538396A CN202210343961.7A CN202210343961A CN114538396A CN 114538396 A CN114538396 A CN 114538396A CN 202210343961 A CN202210343961 A CN 202210343961A CN 114538396 A CN114538396 A CN 114538396A
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- yellow phosphorus
- fluorine
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- furnace gas
- potassium
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- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 266
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 105
- 239000011737 fluorine Substances 0.000 title claims abstract description 103
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000001816 cooling Methods 0.000 claims abstract description 87
- 239000000428 dust Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000012267 brine Substances 0.000 claims abstract description 30
- 238000007670 refining Methods 0.000 claims abstract description 30
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 238000009833 condensation Methods 0.000 claims abstract description 13
- 230000005494 condensation Effects 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 238000005192 partition Methods 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 160
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 101
- 239000011698 potassium fluoride Substances 0.000 claims description 89
- 235000003270 potassium fluoride Nutrition 0.000 claims description 77
- 239000007788 liquid Substances 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
- 239000011775 sodium fluoride Substances 0.000 claims description 50
- 235000013024 sodium fluoride Nutrition 0.000 claims description 50
- 239000007921 spray Substances 0.000 claims description 50
- 239000000047 product Substances 0.000 claims description 45
- 229910052785 arsenic Inorganic materials 0.000 claims description 40
- 239000013078 crystal Substances 0.000 claims description 38
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 35
- 239000011591 potassium Substances 0.000 claims description 35
- 229910052700 potassium Inorganic materials 0.000 claims description 35
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 34
- 239000002826 coolant Substances 0.000 claims description 33
- 239000012535 impurity Substances 0.000 claims description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 25
- 239000012452 mother liquor Substances 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 238000005507 spraying Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- 230000005484 gravity Effects 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000006227 byproduct Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 150000002221 fluorine Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000011555 saturated liquid Substances 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000010413 mother solution Substances 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 47
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 47
- 239000011574 phosphorus Substances 0.000 abstract description 47
- 229960004029 silicic acid Drugs 0.000 abstract description 6
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000000741 silica gel Substances 0.000 abstract description 3
- 229910002027 silica gel Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 120
- 239000002956 ash Substances 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- 229960001866 silicon dioxide Drugs 0.000 description 15
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 12
- 235000011181 potassium carbonates Nutrition 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000004064 recycling Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000012047 saturated solution Substances 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- 229910004014 SiF4 Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229940104869 fluorosilicate Drugs 0.000 description 5
- 239000011736 potassium bicarbonate Substances 0.000 description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 4
- 239000007962 solid dispersion Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229910020440 K2SiF6 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002367 phosphate rock Substances 0.000 description 3
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000010977 unit operation Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910003641 H2SiO3 Inorganic materials 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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-
- 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
- C01B25/02—Preparation of phosphorus
- C01B25/027—Preparation of phosphorus of yellow phosphorus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/02—Fluorides
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Compounds (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to the technical field of clean production of phosphorus chemical industry, and particularly relates to a process system and a method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof. The invention carries out dust removal treatment on high-temperature furnace gas leaving a yellow phosphorus electric furnace in the yellow phosphorus production process, then carries out the steps of primary or secondary partition wall air cooling or water cooling, primary fluorine-containing saline water direct contact cooling, primary cold water washing and the like, collects yellow phosphorus crude products obtained by condensation in different temperature stages respectively, and then obtains yellow phosphorus with different qualities by conventional refining respectively. The fluorine-containing brine contacts furnace gas and SiF in the circulating process4The fluosilicate precipitate is produced by reaction, and the fluosilicate resource is recycled, thereby eliminating the generation of phosphorus mud containing hydrated silica gel and process wastewater.
Description
Technical Field
The invention belongs to the technical field of clean production of phosphorus chemical industry, and particularly relates to a process system and a method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof.
Background
At present, industrial yellow phosphorus is produced at home and abroad by a method of reducing phosphate in phosphate ore in a high-temperature yellow phosphorus electric furnace by utilizing phosphate ore, silica, coke and the like. The production process is that the apatite in the phosphate rock under the high temperature condition is reduced by coke to form phosphorus vapor (P)2) Mixed gas (commonly called yellow phosphorus furnace gas) such as CO enters into a series connection three-stage direct water washing for cooling through a gas guide pipe, so that simple substance phosphorus steam in the furnace gas is condensed to become liquid yellow phosphorus(P4) And mixing the raw materials into coarse industrial yellow phosphorus, and obtaining the industrial yellow phosphorus through conventional refining. Meanwhile, arsenate in phosphate ore is reduced into simple substance arsenic under high-temperature reducing atmosphere in the electric furnace, and fluoride such as fluorapatite in the phosphate ore reacts with silicon dioxide to produce SiF4A gas. Under the normal condition, the fluorine content in the phosphate ore is within the range of 1-4%, the gas phase escape rate of fluorine element in the process of producing yellow phosphorus by an electric furnace method is influenced by the acidity of furnace burden, the acidity index is high, and then SiO in the furnace burden is2When the content is increased, the gas phase escape rate of fluorine is higher, the escape rate of fluorine is about 10-90% under the conventional acidity index, and the residual fluorine is remained in the phosphorous slag. Obviously, the yellow phosphorus furnace gas entering the electric furnace eduction tube contains not only phosphorus vapor and carbon monoxide, but also silicon tetrafluoride gas, simple substance arsenic, dust and other impurities, and the impurities washed in the traditional three-stage water washing process can have adverse effects on the refining process of crude yellow phosphorus and the quality of yellow phosphorus, because SiF in the furnace gas in the water washing process4The silica colloid generated by hydrolysis is mixed with ash and yellow phosphorus, and the existence of hydrated silica colloid causes difficulty in the separation of yellow phosphorus and ash, so that the existing traditional yellow phosphorus process can not avoid the generation of a large amount of phosphorus mud with high phosphorus content, directly influences the yield of yellow phosphorus products, not only causes resource waste, but also causes serious problems of water pollution, arsenic pollution of soil and the like.
The invention patent (CN 104276549B) fully utilizes the large difference between the condensation temperature and the desublimation temperature of yellow phosphorus and arsenic steam, and realizes the separation of arsenic and phosphorus, and proposes that yellow phosphorus furnace gas is firstly subjected to dust removal treatment to remove most of dust in the furnace gas and solid simple substance arsenic precipitated by desublimation (or adsorbed on the dust), then the furnace gas is directly washed by water in a grading (section) way, and yellow phosphorus precipitated by condensation is collected in a grading (section) way and is respectively refined, so that yellow phosphorus products with different (arsenic-containing) qualities are obtained. In addition, the invention also proposes to utilize SiF4The hydrolysis reaction temperature is below 120 ℃, and dust and SiF are partially avoided by the step-by-step dust removal and temperature reduction of furnace gas4The mixture of colloidal silica particles produced by hydrolysis and yellow phosphorus is apparently in direct contact with the water in the furnace gasDifficult to completely eliminate SiF in furnace gas under the condition of contact4The influence of the hydrated colloidal silica generated by hydrolysis on the separation of yellow phosphorus from dust has certain difficulty in industrial process control, and a small amount of phosphorus mud can be generated and the quality of the yellow phosphorus can be influenced. In addition, the process method disclosed in the patent cannot solve the problem of recovery of fluorine and silicon resources in the production process.
At present, the capacity of the existing yellow phosphorus enterprises in China is large in scale, although the production process of the yellow phosphorus is simple, the content of impurities in the produced yellow phosphorus is high, particularly the yellow phosphorus contains arsenic and silicon, the quality of the yellow phosphorus cannot meet the requirements of industry downstream industries on high-quality yellow phosphorus, a large amount of phosphorus mud and process wastewater are produced, and the yellow phosphorus production method belongs to the industry of 'two high' and needs to be upgraded in the industry technology urgently. The research for preparing the yellow phosphorus with different qualities based on the control of the yellow phosphorus production process is little at home and abroad, and the technology for obtaining the yellow phosphorus with different qualities and recycling the fluorine resources in the yellow phosphorus based on the adoption of different cooling modes and the simple control of the transfer of impurities and fluorine silicon in the yellow phosphorus production process has not been reported. With the increasingly strict requirements for clean production, energy conservation and emission reduction of the chemical industry at home and abroad and the rise of the fluorine chemical industry in recent years, the demands for fluorine resources in domestic and international markets are strong, and the fluorine content of phosphorite in main phosphorite production places such as Yunobuo and the like is high, obviously, the technology for easily removing impurities from yellow phosphorus and recycling fluorine resources in yellow phosphorus based on process control is gradually an urgent technology for yellow phosphorus production enterprises.
Disclosure of Invention
The invention aims to provide a process method which is beneficial to the control of the production process of yellow phosphorus and is convenient for recovering fluorine and silicon resources in the yellow phosphorus, aiming at the problems that the content of impurities in the yellow phosphorus produced in the current industrial process is high, the generation of mass production wastewater and phosphorus mud containing hydrated silica gel cannot be avoided, and a large amount of fluorine and silicon resources cannot be effectively recovered. The method is to leave a yellow phosphorus electric furnace (containing phosphorus steam, arsenic steam and SiF) in the yellow phosphorus production process4Dust and other gases), then performing one-stage or two-stage partition wall air cooling or partition wall water cooling, one-stage fluorine-containing brine direct contact cooling, one-stage cold water washing and the like, and respectivelyCollecting yellow phosphorus crude products obtained by condensation at different temperature stages, and respectively obtaining yellow phosphorus with different qualities by conventional refining. The fluorine-containing brine and SiF in furnace gas in the cooling circulation process4The fluosilicate precipitate is produced by reaction, the fluosilicate resource is recovered, and the generation of phosphorus mud containing hydrated silica gel and process wastewater is eliminated.
In order to achieve the purpose, the invention adopts the technical principle that: the principle of fully utilizing the temperature difference of saturated steam of yellow phosphorus and arsenic to realize the separation of arsenic and yellow phosphorus is adopted, the yellow phosphorus furnace gas with the temperature of more than 200 ℃ after most of arsenic-containing dust impurities are removed by a dust remover is operated by a unit of primary or secondary partition wall air cooling or primary partition wall water cooling heat exchange, the temperature of the furnace gas is reduced to 95-120 ℃, the temperature can be calculated according to related data of related documents about the relationship between the partial pressure of phosphorus steam in the yellow phosphorus furnace gas and the temperature, about 90 percent of phosphorus steam is condensed and separated out and is collected in a hot water tank in a segmented manner, and the low-arsenic industrial yellow phosphorus product can be obtained after conventional refining. Obviously, the partition cooling causes the SiF in the furnace gas4The method does not directly contact spray water, and avoids the influence of hydrolysis on yellow phosphorus refining and quality (the separation of yellow phosphorus and ash is difficult due to the existence of hydrated silicon dioxide colloid generated by hydrolysis, so that the conventional yellow phosphorus process can not avoid the generation of a large amount of phosphorus mud to influence the yield of yellow phosphorus products). In addition, the air heated in the air cooling process is used for drying the ore raw materials entering the furnace, so that the discharging temperature of the yellow phosphorus furnace gas is favorably improved, and the dust removal operation is favorably performed. The furnace gas after cooling and heat exchange treatment passes through a fluorine-containing brine washing tower and contains KF or NaF and NH with certain concentration4Fluoride-containing salt water of F, HF and other fluorides as cooling absorption liquid capable of absorbing SiF in furnace gas4And can react with the silicon to produce fluorosilicate or fluosilicic acid to inhibit SiF4The interference of the hydrolysis on the yellow phosphorus refining operation is eliminated. Meanwhile, a way is provided for the recovery of fluorine and silicon resources.
Taking potassium fluoride water solution as an example of cooling absorption liquid, the specific reaction is as follows:
SiF4+2KF＝K2SiF6↓ (1)
K2SiF6↓+H2O＝4HF+H2SiO3+2KF (in boiling water) (2)
K2SiF6+2K2CO3＝6KF+SiO2↓+2CO2↑ (3)
2KF+Na2CO3＝NaF↓+K2CO3 (4)
To avoid SiF in the furnace gas4The hydrated silicon dioxide colloid generated by hydrolysis causes interference to the separation of ash and yellow phosphorus washed from furnace gas, and by utilizing the higher solubility of KF in water, a KF water solution with higher concentration can be prepared to be used as a cooling absorption liquid to absorb SiF in the furnace gas4And react to form K2 SiF6Precipitation, as in reaction (1), inhibits SiF4Influence of hydrolysis on refining and separation of yellow phosphorus. In addition, the condensed liquid yellow phosphorus is discharged together with the cooling absorption liquid, solid-liquid separation is carried out to obtain solid precipitated potassium fluosilicate (or containing a small amount of ash), and the upper layer of the liquid is a diluted potassium fluoride solution for recycling. The lower layer is yellow phosphorus crude product which can be made into yellow phosphorus product with higher purity after conventional refining treatment.
Cooling absorption liquid regeneration circulation and fluorine and silicon resource recovery. The solid potassium fluosilicate separated by solid-liquid separation is easy to hydrolyze in water at about 100 ℃, such as reaction (2), and the silicic acid is only dissolved in hydrofluoric acid solution, and the solid ash in the silicic acid can be removed by utilizing the characteristic. Therefore, adding a certain amount of potassium carbonate or potassium bicarbonate and potassium hydroxide into the recovered potassium fluosilicate hot solution, mixing, and reacting for a period of time at the temperature of 95-110 ℃, wherein the reaction is as shown in (3). Filtering to obtain silicon dioxide, washing and refining to produce white carbon black; the liquid is KF saturated solution, the potassium fluoride product is obtained by cooling crystallization, part of crystallization mother liquor is circularly concentrated, and the other part of crystallization mother liquor is used as a supplementary liquid of coolant-fluorine-containing saline water.
If the economic problem of using potassium salt is considered, the characteristic of slightly soluble water of sodium fluoride can be fully utilized, sodium carbonate or sodium bicarbonate and sodium hydroxide are added into the KF saturated solution to carry out a replacement reaction (4), and the solution is cooled to normal temperature and filtered to obtain a sodium fluoride product; the filtrate is potassium carbonate solution which can be used as raw material for treating potassium fluosilicate for recycling.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a yellow phosphorus production and fluorine resource recovery process method, when the furnace gas outlet temperature leaving the yellow phosphorus electric furnace in the yellow phosphorus production process is 220-300 ℃, firstly, the furnace gas of the yellow phosphorus electric furnace is dedusted to remove about 90% of dust impurities and arsenic dust which is desublimated, then the furnace gas is sequentially subjected to one-stage or two-stage partition wall air cooling or partition wall water cooling, one-stage fluorine-containing brine direct contact cooling washing, one-stage cold water washing and other steps, yellow phosphorus crude products which are obtained by condensation in different temperature stages are respectively collected, and then yellow phosphorus with different qualities is obtained by simple refining. Cooling the fluorine brine circulation and the SiF in the furnace gas4Reacting and recovering the fluorosilicone resource. The scheme is as follows.
A multi-quality yellow phosphorus production and fluorine resource recovery process system comprises:
the dust remover is provided with a yellow phosphorus furnace gas inlet, a yellow phosphorus furnace gas outlet and an ash outlet arranged at the bottom, and the ash outlet is communicated with the semi-sealed ash bin;
the dividing wall cooling device is provided with a high-temperature material inlet arranged at the top, a cooling material outlet arranged at the lower part, a condensate discharge port arranged at the bottom, a cooling medium inlet and a cooling medium outlet, the yellow phosphorus furnace gas outlet is communicated with the high-temperature material inlet, the cooling medium inlet is sequentially communicated with a cooling medium conveying device and a cooling medium inlet pipe, the condensate discharge port is communicated with a water-sealed yellow phosphorus collecting tank, the water-sealed yellow phosphorus collecting tank is provided with an industrial yellow phosphorus collecting port, the cooling medium outlet is also communicated with the cooling medium conveying device, the cooling medium is normal-temperature air or water, correspondingly, the dividing wall cooling device is a dividing wall air cooling device or a dividing wall water cooling device, and the cooling medium conveying device is an air blower or a water pump;
the fluorine-containing brine spray tower is provided with a first air inlet, a first air outlet, a first spray head and a potassium fluoride solution collecting port arranged at the bottom, the cooling material outlet is communicated with the first air inlet, the potassium fluoride solution collecting port is communicated with a fluorine-containing brine collecting and precipitating tank, the fluorine-containing brine collecting and precipitating tank is provided with a mixed solution collecting port of yellow phosphorus, potassium fluosilicate precipitate and potassium fluoride, and the fluorine-containing brine collecting and precipitating tank is also communicated with the first spray head through a fluorine-containing brine circulating pump;
and the cold water spray tower is provided with a second air inlet, a yellow phosphorus tail gas outlet, a bottom feed opening and a second spray head, the first air outlet is communicated with the second air inlet, the bottom feed opening is communicated with a cold water collecting and circulating groove, the cold water collecting and circulating groove is provided with a high-purity yellow phosphorus collecting opening, and the cold water collecting and circulating groove is also communicated with the second spray head through a cold water circulating pump.
Further, the system further comprises:
a feed inlet of the separation device is communicated with a pipeline of conveying equipment of a mixed liquid collecting port of the yellow phosphorus, potassium fluosilicate sediment and potassium fluoride, a liquid outlet of the separation device is communicated with a gravity settling knockout, and the gravity settling knockout is provided with a low-impurity yellow phosphorus collecting port;
one feed inlet of the reaction kettle is respectively communicated with the slag outlet of the separation device and the supernatant outlet of the gravity settling liquid separator, and the other feed inlet of the reaction kettle is a potassium carbonate solution feed inlet;
the filter, its feed inlet intercommunication reation kettle's discharge gate, its discharge gate pass through valve intercommunication potassium fluoride saturated liquid and collect the mouth to still communicate evaporative concentration cooling crystallizer and centrifuge in proper order, centrifuge's discharge gate intercommunication potassium fluoride solution retrieval and utilization mouth, and still pass through valve intercommunication evaporative concentration cooling crystallizer, the filter has byproduct silicon dioxide and collects the mouth, centrifuge has byproduct potassium fluoride crystal and collects the mouth.
The cooling medium is normal temperature air or water, and correspondingly, the dividing wall cooling device is a dividing wall air cooling device or a dividing wall water cooling device. The cooling medium conveying equipment is a blower or a water pump. The separation device is a plate filter or a three-phase centrifugal separator.
Further, the system further comprises:
and one feed inlet of the displacement reaction kettle is communicated with the potassium fluoride saturated liquid collecting port, the other feed inlet of the displacement reaction kettle is a sodium carbonate feed inlet, a discharge outlet of the displacement reaction kettle is sequentially communicated with the heat exchanger and the sodium fluoride filter, and the sodium fluoride filter is provided with a potassium carbonate solution collecting port and a byproduct sodium fluoride crystal collecting port.
The invention also provides a process method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof, which can adopt the system provided by the invention to produce and specifically comprises the following steps:
1) the temperature of the yellow phosphorus electric furnace gas flowing out from the yellow phosphorus furnace gas inlet is above 230 ℃, dust is removed in the dust remover, dust is separated, and the yellow phosphorus furnace gas with the temperature of above 200 ℃ and the dust impurities containing arsenic simple substances removed is obtained; and when the temperature of the yellow phosphorus furnace gas introduced from the yellow phosphorus furnace gas inlet is 140-180 ℃, part of gaseous phosphorus is condensed and separated out, and the dust removal operation cannot be performed, directly introducing the yellow phosphorus furnace gas into the fluorine-containing salt water spray tower to perform the operation of the step 3) and the subsequent steps.
2) Introducing the yellow phosphorus-removing furnace gas which is obtained in the step 1) and is used for removing the dust impurities containing the arsenic simple substance and has the temperature of more than 200 ℃ into the partition wall heat exchange device for cooling, separating to obtain condensed discharge liquid and SiF containing the arsenic simple substance and having the temperature of 95-120 DEG C4Furnace gas, collecting and refining the condensate effluent to obtain low-arsenic industrial yellow phosphorus;
3) the SiF-containing material obtained in the step 2)4Furnace gas is introduced into the fluorine-containing brine spray tower for spraying, the obtained mixed liquid of condensed and separated liquid yellow phosphorus, potassium fluosilicate precipitate and potassium fluoride flows into the fluorine-containing brine collecting and precipitating tank, the mixture of liquid and precipitated crystal particles in the tank can be circulated to the first spray header for spraying through the fluorine-containing brine circulating pump, and simultaneously SiF is removed4Wherein the spray liquid is 10-45% potassium fluoride solution, the temperature is 30-50 ℃, and SiF is removed4The temperature of furnace gas is 50-60 ℃;
4) removing SiF obtained in the step 3)4Introducing the furnace gas into the cold water spray tower for water washing and cooling, condensing a small amount of gaseous yellow phosphorus remained in the furnace gas into solid yellow phosphorus particles to be dispersed in cold water, simultaneously discharging yellow phosphorus tail gas, and precipitating and collecting the cold water dispersed with the yellow phosphorus particlesAfter solid yellow phosphorus is collected, the yellow phosphorus is heated and refined to obtain high-purity yellow phosphorus, and supernatant liquid, namely cold water, of the precipitate is circulated to a second spray header by a cold water circulating pump for spraying, wherein the temperature of the yellow phosphorus tail gas is 10-35 ℃.
Further, the method also comprises a step 5):
5a) introducing the mixed liquid of the liquid yellow phosphorus obtained in the step 3), potassium fluosilicate precipitate, ash and potassium fluoride into the separation device for filtering, and then carrying out heat preservation, standing and layering on the filtrate by the gravity settling knockout to obtain low-impurity yellow phosphorus which can be refined to obtain high-purity yellow phosphorus; the yellow phosphorus furnace gas with the temperature of 140-180 ℃ in the step 1) is not subjected to dust removal, and the yellow phosphorus crude product obtained by directly performing the operation of the step 3) in the step 2) is refined to obtain industrial yellow phosphorus;
5b) putting potassium fluosilicate crystals containing part of ash separated by the separation device into the reaction kettle, adding a supernatant obtained by the gravity settling liquid separator, heating to 100 ℃ to hydrolyze the potassium fluosilicate crystals into a solution, filtering to remove the ash in the solution, adding potassium carbonate or a replacement mother liquor (mainly containing potassium carbonate or potassium bicarbonate) of sodium fluoride obtained subsequently to prepare a high-concentration material, reacting at 95-110 ℃, filtering by the filter to obtain silicon dioxide, washing and refining to produce white carbon black, and obtaining a nearly saturated potassium fluoride solution;
5c) and (3) cooling and crystallizing the obtained nearly saturated potassium fluoride solution through the evaporation concentration cooling crystallizer to separate out potassium fluoride, dehydrating the solution through the centrifuge to obtain a potassium fluoride crystal product, wherein the rest is crystallized mother liquor rich in potassium fluoride, one part is used as a supplement liquid of a cooling absorption liquid potassium fluoride solution, and the other part is sent to the concentration cooling crystallizer for use.
Further, the method further comprises step 6): and (b) feeding the hot nearly saturated potassium fluoride solution obtained in the step 5b) into the replacement reaction kettle, adding sodium carbonate to perform replacement reaction, cooling to normal temperature through the heat exchanger for crystallization, and filtering through a sodium fluoride filter to obtain a sodium fluoride crystal product, wherein the filtrate can be used as the replacement mother liquor (mainly containing potassium carbonate or potassium bicarbonate) of the sodium fluoride.
The specific principle of the step 1) is as follows: firstly, removing about 90% of dust impurities containing arsenic simple substances from yellow phosphorus electric furnace gas by a dust remover (a multi-pipe cyclone dust remover or an electric dust remover and the like), calculating according to the partial pressure of phosphorus steam in the furnace gas, wherein the dew point of phosphorus steam precipitation is about 180 ℃, and when the temperature of the furnace gas is more than 200 ℃ after the furnace gas is purified by the dust remover, the trapped dust does not contain simple substances of phosphorus, but contains simple substances of arsenic, and the dust is treated according to the standard.
The specific principle of the step 2) is as follows: and (3) performing cooling unit operation on the yellow phosphorus furnace gas after most of arsenic-containing dust impurities are removed by the dust remover at the temperature of over 200 ℃, adopting a one-stage or two-stage dividing wall air-cooled or water-cooled heat exchanger to reduce the temperature of the furnace gas to 95-120 ℃, condensing and separating most phosphorus steam, collecting the phosphorus steam in a hot water tank at the bottom of the air-cooled heat exchanger, and conventionally refining the phosphorus steam into low-arsenic industrial yellow phosphorus. If two-stage air cooling is adopted, the yellow phosphorus condensate is respectively collected in a hot water tank and then respectively refined into common industrial yellow phosphorus and low-impurity yellow phosphorus by conventional method. In addition, in order to reduce resistance loss of a furnace gas system and prevent blockage in the tube, the heat exchanger adopts a single-pass vertical large tubular heat exchanger, and the height-diameter ratio is controlled; the cooling medium is air or water which is fed outside the tube (shell pass), the blower or water pump is used for forced conveying, the counter-flow operation is carried out, the operation unit is also provided with an outlet hot air or hot water backflow branch pipe with adjustable flow, the temperature of a mixed inlet is improved, and the influence on the heat transfer effect and even the blockage caused by yellow phosphorus solidification in the local pipe of the inlet due to supercooling of air or cold water in winter is prevented. The outlet air heated on the shell pass of the heat exchanger is used for drying the ore raw materials entering the furnace, and is beneficial to improving the discharging temperature of the yellow phosphorus furnace gas. The operation of the dust remover is convenient, and no phosphorus is precipitated.
The specific principle of the step 3) is as follows: the temperature of furnace gas leaving the lower part of the air-cooled heat exchanger is about 110 ℃, the furnace gas enters the fluorine-containing salt water spray tower from the bottom and is directly contacted with the fluorine-containing salt water sprayed from the top of the spray tower for cooling, and the temperature of the fluorine-containing salt water is about 45 ℃. Controlling the spraying amount of fluorine-containing salt water to enable the temperature of furnace gas leaving a spray tower to be about 50-55 ℃, condensing to separate out a liquid yellow phosphorus primary product, enabling the condensed liquid yellow phosphorus primary product to flow into a fluorine-containing salt water collecting and precipitating tank together with fluorine salt water and reaction precipitate fluosilicate, recycling and spraying a mixture of liquid and crystal particles in the tank for a period of time, discharging the mixture after fluosilicate crystal particles grow gradually and accumulate to a certain amount with the condensed liquid yellow phosphorus, filtering to obtain large-particle solid fluosilicate (potassium or sodium), preserving the temperature of filtrate and standing for layering, wherein the bottom of the filtrate is a yellow phosphorus primary product, and the yellow phosphorus with higher purity can be obtained through conventional refining. The supernatant is a fluorine-containing salt solution. The circulating system of the fluorine-containing brine is periodically supplemented with a certain amount of fluorine salt to maintain the concentration of the fluorine-containing salt in the circulating spraying system of the brine. In this step, the main reaction is the above reaction (1).
The specific principle of the step 4) is as follows: the partial pressure ratio of phosphorus steam in furnace gas leaving the villiaumite spray tower is very low, but the impurity content is also very low, the furnace gas at the temperature of about 50-60 ℃ enters a cold water spray tower from the bottom for washing and cooling, clean water is adopted for spraying, and the spraying amount of clean water is controlled, so that the temperature of the tail gas of the furnace gas is about 20 ℃; the yellow phosphorus obtained by condensation in this stage is little and in a solid dispersion state, flows into the yellow phosphorus collection water tank along with water from the bottom of the tower, is deposited at the bottom of the collection water tank, is periodically discharged, is heated to a liquid state for refining, and can obtain the yellow phosphorus with extremely high purity. And finally, the residual tail gas is sent into a gas holder through a centrifugal fan.
The specific principle of the step 5) is as follows: putting the filtered and separated potassium fluosilicate into a reaction kettle, adding water or 3) heating the supernatant (fluorine-containing saline water) at about 100 ℃ to hydrolyze the potassium fluosilicate into a solution, filtering to remove ash in the solution, adding a certain amount of potassium carbonate or potassium bicarbonate and potassium hydroxide (or displacement mother liquor for subsequently preparing sodium fluoride) to prepare a material with higher concentration, reacting for a period of time at 95-110 ℃, filtering to obtain silicon dioxide, washing and refining to produce white carbon black; the liquid is KF (approaching saturation) solution, the potassium fluoride product is separated out by cooling crystallization or cooling crystallization after concentration, the rest is mother liquor after crystallization, the mother liquor is still rich in potassium fluoride, one part is used as supplement liquid of cooling absorption liquid, and the other part can be circulated to the front end of the reaction for application. In this step, the main reactions are the above-mentioned reaction (2) and reaction (3).
The specific principle of the step 6) is as follows: if sodium fluoride is used as a final product in the recovery process, the characteristics of good water solubility of potassium fluoride and slightly soluble water of sodium fluoride can be fully utilized, sodium carbonate or sodium bicarbonate and sodium hydroxide are added into the hot KF saturated solution obtained by filtering to perform a replacement reaction, and a sodium fluoride product is obtained by filtering at normal temperature; the filtrate is a replacement mother liquor which mainly contains potassium carbonate and a small amount of slightly soluble sodium fluoride and potassium fluoride and can be used as a reaction raw material for treating potassium fluosilicate for recycling. In this step, the main reaction is the above reaction (4).
According to the scheme, the conventional refining treatment of the yellow phosphorus comprises the separation procedures of water rinsing, gravity settling or centrifugal settling and the like.
According to the scheme, the fluorine-containing brine contains KF or NaF and NH with certain concentration4F, HF and other fluoride single-component aqueous solution or mixed solution of two or more components, wherein the concentration of KF aqueous solution is 3-45%, the concentration of NaF aqueous solution is 0-5%, and NH is4The concentration of the F aqueous solution is 0-15 percent, and the concentration of the HF aqueous solution is 0-15 percent.
According to the scheme, the crystallized mother liquor is the residual liquor obtained by reacting potassium fluosilicate with potassium carbonate and filtering the obtained filtrate, namely potassium fluoride solution, and cooling or concentrating and cooling the filtrate to separate out potassium fluoride crystals, wherein the potassium fluoride crystals are still rich in potassium fluoride with a certain concentration.
According to the scheme, the replacement mother liquor is a filtrate generated after potassium fluoride and a sodium carbonate solution are subjected to replacement reaction and temperature reduction filtration, wherein the main component is potassium carbonate, and a small amount of slightly soluble sodium fluoride and potassium fluoride are contained, so that no negative influence is generated on subsequent recycling.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention directly adopts the steps of dust removal, primary or secondary air cooling, primary fluorine-containing salt water washing, primary cold water washing, temperature reduction and the like to the furnace gas leaving the yellow phosphorus electric furnace in the yellow phosphorus production process step by step, respectively collects liquid yellow phosphorus crude products obtained by condensation in different temperature stages, and then obtains yellow phosphorus products with different qualities through conventional refining, thereby avoiding the influence of impurities such as arsenic, silicon and the like in the furnace gas on the quality and yield of yellow phosphorus and meeting the different requirements of downstream industries on the quality of various elemental phosphorus. Meanwhile, the method is also helpful to solve the problems of arsenic pollution, water pollution and the like which are puzzling the phosphorus chemical industry.
2) The invention provides that the temperature of yellow phosphorus furnace gas is reduced by adopting dividing wall heat exchange to condense most of yellow phosphorus steam, thereby avoiding SiF caused by adopting water washing for temperature reduction4The hydrated silicon dioxide colloid generated by hydrolysis has difficulty in separating the subsequent yellow phosphorus and ash, and the subsequent furnace gas adopts fluorine-containing saline water to directly spray and cool, thereby realizing the purpose of separating the SiF in the furnace gas4The absorption reaction not only eliminates the generation of phosphorus mud, but also improves the yield of yellow phosphorus products, and can recover fluorine and silicon resources in the phosphorus ore, thereby providing technical support for transformation and upgrading of phosphorus chemical industry.
3) The invention is suitable for carrying out process design and technology upgrading and reconstruction on a production device with the production capacity of 5000-30000 tons/year of a single yellow phosphorus electric furnace, and the related production process and operation are simple, thereby meeting the actual production requirement.
Drawings
FIG. 1 is a schematic structural diagram of a system part adopted in a process for producing multi-quality yellow phosphorus and recovering fluorine resources thereof in example 1 of the present invention.
Fig. 2 is a schematic structural view of a system part employed in a fluorine resource recovery part according to embodiment 1 of the present invention.
FIG. 3 is a schematic diagram showing the structure of the system part for producing sodium fluoride and recycling potassium salt thereof according to example 2 of the present invention.
In the attached figures 1, 2 and 3:
1. the device comprises a dust remover, 2, an air-cooled heat exchanger, 3, a fluorine-containing brine spray tower, 4, a cold water spray tower, 5, a semi-sealed ash bin, 6, a water-sealed yellow phosphorus collecting tank, 7, a fluorine-containing brine collecting and precipitating tank, 8, a cold water collecting and circulating tank, 9, cooling medium conveying equipment, 10, a fluorine-containing brine circulating pump, 11, a cold water circulating pump, 12, a separating device, 13, a gravity settling knockout, 14, a reaction kettle, 15, a filter, 16, an evaporation concentration cooling crystallizer, 17, a centrifugal machine, 18, a replacement reaction kettle, 19, a heat exchanger, 20 and a sodium fluoride filter;
101. a yellow phosphorus furnace gas inlet 102, a yellow phosphorus tail gas outlet 103, a cooling medium inlet pipe 104, a cooling medium outlet 105, a potassium carbonate solution feed inlet 106, a silicon dioxide collection port 107, a byproduct potassium fluoride crystal collection port 108, a sodium carbonate feed inlet 109 and a byproduct sodium fluoride crystal collection port;
201. a potassium fluoride solution recycling port, a mixed solution collecting port of 202, yellow phosphorus, potassium fluosilicate precipitate and potassium fluoride, and a potassium fluoride saturated solution collecting port of 203;
301. an industrial yellow phosphorus collection port 302, a low-impurity yellow phosphorus collection port 303 and a high-purity yellow phosphorus collection port.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A process system and a method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof aim at a production device (annual operation hours 7200h) of a yellow phosphorus electric furnace (15000KVA) with a certain yield of 7500 tons/year, wherein the phosphorus ore fed into the furnace contains 30.5 percent of phosphorus pentoxide, 2 percent of fluorine, 20 percent of gas-phase escape rate of fluorine, the proportion of raw materials and auxiliary materials and other operation conditions are the same as the conventional operation, and the gas output of the yellow phosphorus electric furnace is about 11000m3The temperature is about 250 ℃, the subsequent yellow phosphorus production process control is carried out by adopting the process technology shown in figure 1 and figure 2, and the specific steps comprise:
1) the yellow phosphorus furnace gas leaving the yellow phosphorus electric furnace is treated by a multi-pipe cyclone dust collector 1 to remove solid dust (including dust for absorbing arsenic), in order to ensure that the dust collected in an ash hopper of the dust collector 1 has certain fluidity, the dust collector 1 is subjected to heat preservation treatment or heat preservation by supplementing heat energy by combusting yellow phosphorus tail gas, and the temperature of the purified furnace gas leaving the dust collector 1 is more than 220 ℃. The dust enters a semi-closed ash bin 5.
2) And (2) performing cooling unit operation on the yellow phosphorus furnace gas after most of arsenic-containing dust impurities are removed by the dust remover 1 by adopting a primary dividing wall type air-cooled heat exchanger 2, wherein the air-cooled heat exchanger 2 is a single-tube-pass vertical large tubular heat exchanger, a cooling medium of the air-cooled heat exchanger is an air outlet tube (shell pass) from a cooling medium inlet tube 103, a cooling medium conveying device 9 is an air blower, and forced air supply and countercurrent operation are performed to reduce the temperature of the furnace gas to 100-110 ℃. Most phosphorus vapor in the furnace gas is condensed and separated out and collected in a water-sealed yellow phosphorus collecting tank 6 at the bottom of the air-cooled heat exchanger, and is collected from an industrial yellow phosphorus collecting port 301 and then is refined into low-arsenic industrial yellow phosphorus by a conventional method. The air cooling system is provided with an outlet hot air backflow branch pipe with adjustable flow, the mixed air inlet temperature is improved, and the influence of yellow phosphorus solidification in a local pipe caused by air supercooling on the heat transfer effect and even blockage is prevented. In addition, the heated outlet air discharged from the cooling medium outlet 104 can reach a temperature of more than 110 ℃, and is used for drying the raw materials entering the furnace so as to improve the discharging temperature of the yellow phosphorus furnace gas.
3) The furnace gas leaving the lower part of the air-cooled heat exchanger 2 enters the fluorine-containing salt water spray tower 3 from the bottom of the spray tower and is directly contacted with a 14 percent potassium fluoride solution sprayed from the top of the spray tower for cooling, and the temperature of the potassium fluoride-containing solution is about 45 ℃. Controlling the spraying amount of the fluorine-containing salt water to ensure that the temperature of furnace gas leaving the spray tower is about 55 ℃, condensing to separate out liquid yellow phosphorus, depositing fluosilicate and residual potassium fluoride solution to flow into a fluorine-containing salt water collecting and depositing tank 7 together, and circularly spraying the mixture of liquid in the tank and deposited crystal particles by a fluorine-containing salt water circulating pump 10 for use. After potassium fluosilicate crystal particles grow gradually and accumulate to a certain amount with condensed liquid yellow phosphorus, the potassium fluosilicate crystal particles are discharged, solid potassium fluosilicate with larger particles is obtained by filtering through a separating device 12 which is a plate filter, filtrate is subjected to heat preservation and standing layering through a gravity settling knockout 13, crude yellow phosphorus is arranged at the bottom and is collected from a low-impurity yellow phosphorus collecting port 302, and high-purity yellow phosphorus can be obtained through conventional refining. The upper layer liquid is a solution containing residual potassium fluoride and is used as a hydrolysis solution of potassium fluosilicate.
4) The furnace gas leaving the fluorine salt water spray tower 3 enters a cold water spray tower 4 from the bottom for washing and cooling, clean water is adopted for spraying, and the spraying amount of clean water is controlled, so that the temperature of the tail gas of the furnace gas is about 20 ℃; little yellow phosphorus obtained by condensation is in a solid dispersion state, flows into the cold water collecting and circulating tank 8 along with water from the bottom of the tower, deposits the solid yellow phosphorus at the bottom of the cold water collecting and circulating tank 8, is periodically discharged from the high-purity yellow phosphorus collecting port 303, and is heated to be in a liquid state for refining, so that the yellow phosphorus with extremely high purity can be obtained. Finally, the residual tail gas is sent into a tail gas cabinet from a yellow phosphorus tail gas outlet 102 through an exhaust fan.
5) Putting potassium fluosilicate crystals containing a small amount of ash separated by a plate filter into a reaction kettle 14, heating the supernatant (residual potassium fluoride solution) of a gravity settling liquid separator 13 at 100 ℃ to hydrolyze the potassium fluosilicate crystals, adding a certain amount of potassium carbonate (or replacement mother liquor for subsequently preparing sodium fluoride) to prepare a material with higher concentration, reacting for a period of time at 95-110 ℃, filtering by a filter 15, obtaining silicon dioxide at a silicon dioxide collecting port 106, washing and refining to produce white carbon black; the liquid is KF (nearly saturated) solution, potassium fluoride is separated out by temperature reduction crystallization of an evaporation concentration temperature reduction crystallizer 16, and the potassium fluoride crystal product is obtained by dehydration of a centrifuge 17 and collection at a byproduct potassium fluoride crystal collection port 107. The rest is mother liquor which is rich in potassium fluoride after crystallization, one part of the mother liquor is used as a supplement liquid of a cooling absorption liquid potassium fluoride solution and can be obtained from a potassium fluoride solution recycling port, and the other part of the mother liquor is sent to a cooled evaporation concentration cooling crystallizer 16 for reuse. The cooling medium can also adopt air, the corresponding dividing wall cooling device adopts a dividing wall air cooling device, and the cooling medium conveying equipment is a blower.
The main product technical indexes of the method are as follows:
the technical indexes of the yellow phosphorus product are as follows: the yield of each quality of yellow phosphorus product was 99% of the total phosphorus in the furnace gas leaving the yellow phosphorus electric furnace. Wherein the yield of the general industrial yellow phosphorus is 90 percent (accounting for the mass fraction of the obtained total phosphorus products), the arsenic content is 64mg/kg, and the product does not contain silicon impurities; the yield of the yellow phosphorus with higher purity is 9 percent (accounting for the mass fraction of the obtained total phosphorus products), and the arsenic content is 8.3 mg/kg; the yield of the high-purity yellow phosphorus is 1.0 percent (accounting for the mass fraction of the total phosphorus products), the arsenic content is less than 1.4mg/kg, and the high-purity yellow phosphorus does not contain silicon impurities.
Fluorine resource recovery index: the recovery rate of fluorine resources accounts for 90 percent of the total amount of gas phase escaping from the yellow phosphorus electric furnace; the byproduct potassium fluoride product of each ton of yellow phosphorus product is about 99.1 kg.
Example 2
A multi-quality yellow phosphorus production and fluorine resource recovery process system and method, which aims at a yellow phosphorus electric furnace production device (annual operation hours 7200h) with a certain yield of 10000 tons/year, wherein the phosphorus ore fed into the furnace contains phosphorus pentoxide (P)2O5) 29.8%, fluorine content 3%, gas phase evolution of fluorineThe rate is 15%, and the proportion of raw materials and auxiliary materials and other operating conditions are the same as those of the conventional operation. The discharge gas quantity of the yellow phosphorus electric furnace is about 14000m3About/h, the temperature is about 260 ℃, the subsequent yellow phosphorus production process control and fluorine resource recovery operation are carried out by adopting the process technology shown in figure 1, figure 2 and figure 3, and the specific steps comprise:
1) the dehydration leaving the yellow phosphorus electric furnace removes solid dust through an electrostatic dust remover 1, and the temperature of the purified furnace gas leaving the dust remover 1 is controlled to be above 220 ℃. The dust enters a semi-closed ash bin 5.
2) And (3) performing cooling unit operation on the dust-removed yellow phosphorus furnace gas by adopting a primary dividing wall type water cooling heat exchanger 2 tube pass, wherein the water cooling heat exchanger 2 is a single-tube-pass vertical large-array tube heat exchanger, the cooling medium conveying equipment 9 is a water pump, normal-temperature water is fed into the shell pass of the heat exchanger, and the countercurrent operation is performed, and the water quantity is controlled to reduce the temperature of the furnace gas to 110-120 ℃. The phosphorus steam is condensed and separated out in the tube pass and collected in a hot water tank 6 at the bottom of the water-cooled heat exchanger 2, and then is refined into low-arsenic industrial yellow phosphorus 301 in a conventional way. The heated outlet hot water can be used for other purposes or can be cooled and recycled by a cold water system.
3) Furnace gas leaving the lower part of the water-cooled heat exchanger 2 enters a fluorine-containing salt water spray tower 3 from the bottom of the spray tower, directly contacts with a mixed solution of 12% potassium fluoride and 1% sodium fluoride sprayed from the top of the spray tower for cooling, the spray amount of the potassium fluoride solution is controlled to ensure that the temperature of the furnace gas leaving the spray tower is about 50 ℃, liquid yellow phosphorus and fluorosilicate precipitate are condensed and separated out, the residual potassium fluoride solution flows into a fluorine-containing salt water collection and precipitation tank 7 together, and the mixture of liquid and precipitated crystal particles in the tank is recycled and sprayed by a fluorine-containing salt water circulating pump 10. After the fluosilicate crystal particles gradually grow up and accumulate to a certain amount with the condensed liquid yellow phosphorus, the liquid yellow phosphorus is discharged, the liquid yellow phosphorus is filtered by a separating device 12 which is a plate filter to obtain solid potassium fluosilicate (containing a small amount of sodium fluosilicate) with larger particles, the filtrate is subjected to heat preservation, standing and layering by a gravity settling knockout 13, the bottom is a yellow phosphorus crude product, the yellow phosphorus crude product is collected from a low-impurity yellow phosphorus collecting port 302, and the yellow phosphorus with higher purity can be obtained by conventional refining. The upper liquid is a solution containing residual potassium fluoride (and sodium fluoride) and is used as a hydrolysis solution of potassium fluosilicate.
4) The furnace gas leaving the fluorine salt water spray tower 3 enters a cold water spray tower 4 from the bottom for washing and cooling, clean water is adopted for spraying, and the spraying amount of clean water is controlled, so that the temperature of the tail gas of the furnace gas is about 20 ℃; little yellow phosphorus obtained by condensation is in a solid dispersion state, flows into the cold water collecting and circulating tank 8 along with water from the bottom of the tower, deposits the solid yellow phosphorus at the bottom of the cold water collecting and circulating tank 8, is periodically discharged from the high-purity yellow phosphorus collecting port 303, is heated to a liquid state for refining, and can obtain the yellow phosphorus with extremely high purity. Finally, the residual tail gas is sent into a tail gas cabinet from a yellow phosphorus tail gas outlet 102 through an exhaust fan.
5) Putting potassium (sodium) fluosilicate crystals separated by a plate filter into a reaction kettle 14, heating supernatant (residual potassium fluoride and a small amount of sodium fluoride solution) of a gravity precipitation knockout 13, adding a certain amount of replacement mother liquor for subsequent preparation of sodium fluoride) to prepare a material with higher concentration, reacting for a period of time at 95-110 ℃, filtering by a filter 15, obtaining silicon dioxide at a silicon dioxide collecting port 106, and washing, refining and producing white carbon black; the liquid is potassium fluoride solution (containing a small amount of sodium fluoride).
6) As shown in fig. 3, the hot potassium fluoride solution (containing a small amount of sodium fluoride) obtained by filtering in the filter 15 in the above step is sent into a replacement reaction kettle 18 from a potassium fluoride saturated solution collecting port 203, a metered amount of sodium carbonate which has a replacement reaction (4) with potassium fluoride in the kettle is added from a sodium carbonate feed port to perform a replacement reaction, and then is cooled to normal temperature by a heat exchanger 19 to further crystallize, and sodium fluoride is filtered by a filter 20 to obtain a sodium fluoride crystal product which is collected at a byproduct sodium fluoride crystal collecting port 109; the filtrate is a replacement mother liquor, wherein the replacement mother liquor mainly contains potassium carbonate and can be recycled at a potassium carbonate solution feeding port 105 as a reaction raw material for treating potassium fluosilicate. The other conditions were the same as in example 1. Wherein, the cooling medium can also adopt water, the corresponding dividing wall cooling device adopts a dividing wall water cooling device, and the cooling medium conveying equipment is a water pump.
The main product technical indexes of the method are as follows:
the technical indexes of the yellow phosphorus product are as follows: the yield of each quality of yellow phosphorus product was 99% of the total phosphorus in the furnace gas leaving the yellow phosphorus electric furnace. Wherein the yield of the general industrial yellow phosphorus is 85 percent (accounting for the mass fraction of the obtained total phosphorus products), the arsenic content is 86mg/kg, and the product does not contain silicon impurities; the yield of the yellow phosphorus with higher purity is 14 percent (accounting for the mass fraction of the obtained total phosphorus products), and the arsenic content is 13 mg/kg; the yield of the high-purity yellow phosphorus is 1.0 percent (accounting for the mass fraction of the total phosphorus products), the arsenic content is less than 1.5mg/kg, and the yellow phosphorus does not contain silicon impurities.
Fluorine resource recovery index: the recovery rate of fluorine resources accounts for 90 percent of the total amount of the fluorine resources escaping from the yellow phosphorus electric furnace in a gas phase form; the byproduct sodium fluoride in each ton of yellow phosphorus product is about 89.5 kg.
Example 3
A multi-quality yellow phosphorus production and fluorine resource recovery process system and method, which aims at a yellow phosphorus electric furnace production device (annual operation hours 7200h) with a certain yield of 10000 tons/year, wherein the phosphorus ore fed into the furnace contains phosphorus pentoxide (P)2O5) 29.8 percent, 3 percent of fluorine content and 15 percent of gas phase escape rate of fluorine, and the proportion of raw materials and auxiliary materials and other operating conditions are the same as those of the conventional operation. The discharge gas quantity of the yellow phosphorus electric furnace is about 14000m3About/h, the temperature is about 150 ℃, the subsequent yellow phosphorus production process control and fluorine resource recovery operation are carried out by adopting the process technology shown in figure 1, figure 2 and figure 3, and the specific steps comprise:
1) furnace gas with the temperature of 150 ℃ enters a fluorine-containing saline water spray tower 3 from the bottom of a yellow phosphorus furnace gas inlet 101, is directly contacted with 18 percent potassium fluoride sprayed from the top of the tower for cooling, the spraying amount of a potassium fluoride solution is controlled to ensure that the temperature of the furnace gas leaving the spray tower is about 60 ℃, liquid yellow phosphorus, fluorosilicate precipitate, ash and residual potassium fluoride solution which are condensed and separated out flow into a fluorine-containing saline water collection and precipitation tank 7 together, and the mixture of liquid in the tank and precipitated crystal particles is recycled and sprayed by a fluorine-containing saline water circulating pump 10. After fluorosilicate crystal particles gradually accumulate and grow up and accumulate to a certain amount with condensed liquid yellow phosphorus and ash, the fluorosilicate crystal particles are discharged, solid potassium fluosilicate (containing a certain amount of large-particle ash) is obtained through separation by a separation device 12 of a three-phase centrifugal separator, liquid is subjected to heat preservation and standing layering by a gravity settling liquid distributor 13, a yellow phosphorus crude product is arranged at the bottom, and the yellow phosphorus crude product is collected from an impurity yellow phosphorus collection port 302 and can be obtained through conventional refining. The upper layer liquid is a solution containing residual potassium fluoride and is used as a hydrolysis solution of potassium fluosilicate.
2) The furnace gas leaving the fluorine salt water spray tower 3 enters a cold water spray tower 4 from the bottom for washing and cooling, clean water is adopted for spraying, and the spraying amount of clean water is controlled, so that the temperature of the tail gas of the furnace gas is about 20 ℃; little yellow phosphorus obtained by condensation is in a solid dispersion state, flows into the cold water collecting and circulating tank 8 along with water from the bottom of the tower, deposits the solid yellow phosphorus at the bottom of the cold water collecting and circulating tank 8, is periodically discharged from the high-purity yellow phosphorus collecting port 303, and is heated to a liquid state for refining, so that the high-purity yellow phosphorus can be obtained. Finally, the residual tail gas is sent into a tail gas cabinet from a yellow phosphorus tail gas outlet 102 through an exhaust fan.
3) Putting potassium fluosilicate crystals separated by a three-phase centrifugal separator into a reaction kettle 14, heating supernatant (residual potassium fluoride and a small amount of sodium fluoride solution) of a gravity precipitation knockout 13, adding a certain amount of replacement mother liquor for subsequent preparation of sodium fluoride) to prepare a material with higher concentration, reacting for a period of time at 95-110 ℃, filtering by a filter 15, obtaining silicon dioxide at a silicon dioxide collection port 106, and washing and refining to produce white carbon black; the liquid is potassium fluoride solution (containing a small amount of sodium fluoride).
4) As shown in fig. 3, the hot potassium fluoride solution (containing a small amount of sodium fluoride) obtained by filtering in the filter 15 in the above step is sent into a replacement reaction kettle 18 from a potassium fluoride saturated solution collecting port 203, a metered amount of sodium carbonate which has a replacement reaction (4) with potassium fluoride in the kettle is added from a sodium carbonate feed port to perform a replacement reaction, and then is cooled to normal temperature by a heat exchanger 19 to further crystallize, and sodium fluoride is filtered by a filter 20 to obtain a sodium fluoride crystal product which is collected at a byproduct sodium fluoride crystal collecting port 109; the filtrate is a replacement mother liquor, wherein the replacement mother liquor mainly contains potassium carbonate and can be recycled at a potassium carbonate solution feeding port 105 as a reaction raw material for treating potassium fluosilicate. The other conditions were the same as in examples 1 and 2.
The main product technical indexes of the method are as follows:
the technical indexes of the yellow phosphorus product are as follows: the yield of each quality of yellow phosphorus product was 97% of the total phosphorus in the furnace gas leaving the yellow phosphorus electric furnace. Wherein the yield of the general industrial yellow phosphorus is 98.5 percent (accounting for the mass fraction of the obtained total phosphorus products), the arsenic content is 295mg/kg, and the product does not contain silicon impurities; the yield of the high-purity yellow phosphorus is 1.50 percent (accounting for the mass fraction of the total phosphorus products), the arsenic content is less than 12.5mg/kg, and the high-purity yellow phosphorus does not contain silicon impurities.
Fluorine resource recovery index: the recovery rate of fluorine resources accounts for 89% of the total amount of the fluorine resources escaping from the yellow phosphorus electric furnace in a gas phase form; the byproduct sodium fluoride of each ton of yellow phosphorus product is about 88 kg.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A multi-quality yellow phosphorus production and fluorine resource recovery process system is characterized by comprising the following steps:
the dust remover (1) is provided with a yellow phosphorus furnace gas inlet (101), a yellow phosphorus furnace gas outlet and an ash outlet arranged at the bottom, and the ash outlet is communicated with the semi-sealed ash bin (5);
the dividing wall cooling device is provided with a high-temperature material inlet arranged at the top, a cooling material outlet arranged at the lower part, a condensate discharge port arranged at the bottom, a cooling medium inlet and a cooling medium outlet (104), the yellow phosphorus furnace gas outlet is communicated with the high-temperature material inlet, the cooling medium inlet is sequentially communicated with a cooling medium conveying device (9) and a cooling medium inlet pipe (103), the condensate discharge port is communicated with a water-sealed yellow phosphorus collecting tank (6), the water-sealed yellow phosphorus collecting tank (6) is provided with an industrial yellow phosphorus collecting port (301), and the cooling medium outlet (104) is also communicated with the cooling medium conveying device (9);
the fluorine-containing brine spray tower (3) is provided with a first air inlet, a first air outlet, a first spray head and a potassium fluoride solution collecting port (201) arranged at the bottom, the cooling material outlet is communicated with the first air inlet, the potassium fluoride solution collecting port (201) is communicated with a fluorine-containing brine collecting and precipitating tank (7), the fluorine-containing brine collecting and precipitating tank (7) is provided with a mixed solution collecting port (202) for yellow phosphorus, potassium fluosilicate precipitate and potassium fluoride, and the fluorine-containing brine collecting and precipitating tank (7) is also communicated with the first spray head through a fluorine-containing brine circulating pump (10);
and the cold water spray tower (4) is provided with a second air inlet, a yellow phosphorus tail gas outlet (102), a bottom feed opening and a second spray head, the first air outlet is communicated with the second air inlet, the bottom feed opening is communicated with the cold water collecting and circulating groove (8), the cold water collecting and circulating groove (8) is provided with a high-purity yellow phosphorus collecting opening (303), and is also communicated with the second spray head through a cold water circulating pump (11).
2. The process system for producing high-quality yellow phosphorus and recovering fluorine resources thereof according to claim 1, wherein the system further comprises:
a feed inlet of the separation device (12) is communicated with a mixed liquid collecting port (202) of the yellow phosphorus, the potassium fluosilicate precipitate and the potassium fluoride, a liquid outlet of the separation device is communicated with a gravity settling knockout (13), and the gravity settling knockout (13) is provided with a low-impurity yellow phosphorus collecting port (302);
one feed inlet of the reaction kettle (14) is respectively communicated with a slag outlet of the separation device (12) and a supernatant outlet of the gravity settling liquid separator (13), and the other feed inlet of the reaction kettle is a potassium carbonate solution feed inlet (105);
filter (15), its feed inlet intercommunication the discharge gate of reation kettle (14), its discharge gate passes through valve intercommunication potassium fluoride saturated liquid and collects mouth (203) to still communicate evaporative concentration cooling crystallizer (16) and centrifuge (17) in proper order, the discharge gate intercommunication potassium fluoride solution retrieval and utilization mouth (201) of centrifuge (17) is and still communicates through the valve evaporative concentration cooling crystallizer (16), filter (15) have by-product silicon dioxide and collect mouth (106), centrifuge (17) have by-product potassium fluoride crystal and collect mouth (107).
3. The process system for producing high-quality yellow phosphorus and recovering fluorine resources thereof according to claim 2, wherein the system further comprises:
and one feed inlet of the displacement reaction kettle (18) is communicated with the potassium fluoride saturated liquid collecting port (203), the other feed inlet of the displacement reaction kettle is a sodium carbonate feed inlet (108), the discharge outlet of the displacement reaction kettle is sequentially communicated with a heat exchanger (19) and a sodium fluoride filter (20), and the sodium fluoride filter (20) is provided with a potassium carbonate solution collecting port (105) and a byproduct sodium fluoride crystal collecting port (109).
4. The process system for producing high-quality yellow phosphorus and recovering fluorine resources thereof according to any one of claims 1 to 3, wherein: the cooling medium is normal temperature air or water, correspondingly, the dividing wall cooling device is a dividing wall air cooling device or a dividing wall water cooling device, and the cooling medium conveying equipment (9) is a blower or a water pump; the separation device (12) is a plate filter or a three-phase centrifugal separator.
5. A process method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof is characterized in that the system of any one of claims 1 to 4 is adopted for production, and the process method specifically comprises the following steps:
1) introducing yellow phosphorus electric furnace gas from the yellow phosphorus furnace gas inlet (101) at the temperature of more than 230 ℃, removing dust in the dust remover (1), separating dust, and obtaining yellow phosphorus-removed furnace gas with the temperature of more than 200 ℃ and without dust impurities containing arsenic simple substances; when the temperature of the yellow phosphorus furnace gas introduced from the yellow phosphorus furnace gas inlet (101) is 140-180 ℃, directly introducing the yellow phosphorus furnace gas into the fluorine-containing saline water spray tower (3) to carry out the step 3) and the subsequent steps;
2) introducing the yellow phosphorus-removing furnace gas which is obtained in the step 1) and is used for removing the dust impurities containing the arsenic simple substance and has the temperature of more than 200 ℃ into the partition wall cooling device for air cooling or water cooling, and separating to obtain condensed discharge liquid and SiF containing the arsenic simple substance and having the temperature of 95-120 DEG C4Furnace gas, collecting and refining the condensation effluent to obtain low-arsenic industrial yellow phosphorus;
3) the SiF-containing material obtained in the step 2)4Furnace gas is introduced into the fluorine-containing brine spray tower (3) for spraying, the obtained mixed liquid of liquid yellow phosphorus precipitated by condensation, potassium fluosilicate precipitate and potassium fluoride flows into the fluorine-containing brine collection and precipitation tank (7), the mixture of liquid in the tank and precipitated crystal particles can be circulated to the first spray header for spraying through the fluorine-containing brine circulating pump (10), and simultaneously SiF is removed4Wherein the spray liquid is 3-45% potassium fluoride solution, the temperature is 30-50 ℃, and SiF is removed4The temperature of furnace gas is 50-60 ℃;
4) will step withThe SiF removal obtained in step 3)4The furnace gas is introduced into the cold water spray tower (4) for washing and cooling, the cold water mixed liquid dispersed with solid yellow phosphorus is obtained by condensation, meanwhile, yellow phosphorus tail gas is discharged, the water mixed liquid dispersed with the solid yellow phosphorus is precipitated and separated to obtain the solid yellow phosphorus, the yellow phosphorus is refined to obtain high-purity yellow phosphorus, and the supernatant fluid of the precipitate is circulated to a second spray head for spraying by the cold water circulating pump (11), wherein the temperature of the yellow phosphorus tail gas is 10-35 ℃.
6. The process for producing high-quality yellow phosphorus and recovering fluorine resources thereof according to claim 5, further comprising the step 5):
5a) introducing the mixed liquid of the liquid yellow phosphorus, the potassium fluosilicate precipitate, the ash and the potassium fluoride obtained in the step 3) into the separation device (12) for separation, and then carrying out heat preservation, standing and layering on the liquid by the gravity settling knockout (13) to obtain low-impurity yellow phosphorus which can be refined to obtain high-purity yellow phosphorus; in the step 1), the yellow phosphorus furnace gas with the temperature of 140-180 ℃ is not subjected to dust removal, and in the step 2), the obtained yellow phosphorus crude product operated in the step 3) is directly refined to obtain industrial yellow phosphorus;
5b) putting the potassium fluosilicate crystal containing part of ash separated by the separation device (12) into the reaction kettle (14), adding a supernatant obtained by the gravity settling liquid separator (13), heating to 100 ℃ to hydrolyze the potassium fluosilicate crystal into a solution, filtering to remove the ash, adding a replacement mother liquor of potassium carbonate or sodium fluoride to prepare a high-concentration material, reacting at 95-110 ℃, filtering by the filter (15) to obtain silicon dioxide, washing and refining to produce white carbon black, and obtaining a nearly saturated potassium fluoride solution;
5c) and (3) cooling and crystallizing the obtained nearly saturated potassium fluoride solution through the concentration cooling crystallizer (16) to separate out potassium fluoride, dehydrating the solution through the centrifugal machine (17) to obtain a potassium fluoride crystal product, wherein the rest is crystallized mother solution rich in potassium fluoride, one part is used as a supplement solution of a cooling absorption solution potassium fluoride solution, and the other part is sent to the evaporation concentration cooling crystallizer (16) for reuse.
7. The process for producing high-quality yellow phosphorus and recovering fluorine resources thereof according to claim 6, further comprising the step 6): feeding the hot nearly saturated potassium fluoride solution obtained in the step 5b) into the replacement reaction kettle (18), adding sodium carbonate, sodium bicarbonate or sodium hydroxide to perform replacement reaction, cooling to normal temperature through the heat exchanger (19) for crystallization, filtering through the sodium fluoride filter (20) to obtain a sodium fluoride crystal product, wherein the filtrate can be used as the replacement mother liquor of the sodium fluoride.
8. The process for the production of high-quality yellow phosphorus and the recovery of fluorine resources thereof according to any one of claims 5 to 7, wherein: the fluorine salt in the fluorine-containing brine is selected from KF, NaF and NH4F or HF, fluoride-containing brine, the concentration of KF is 3-45%, the concentration of NaF is 0-5%, and NH4The concentration of F is 0-15%, and the concentration of HF is 0-15%.
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| CN104276549A (en) * | 2014-09-29 | 2015-01-14 | 武汉工程大学 | Low-impurity yellow phosphorus production method based on yellow phosphorus production technological process control |
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| CN104276549A (en) * | 2014-09-29 | 2015-01-14 | 武汉工程大学 | Low-impurity yellow phosphorus production method based on yellow phosphorus production technological process control |
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