CN114538396B - Process system and method for producing multi-quality yellow phosphorus and recycling fluorine resources thereof - Google Patents
Process system and method for producing multi-quality yellow phosphorus and recycling fluorine resources thereof Download PDFInfo
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- CN114538396B CN114538396B CN202210343961.7A CN202210343961A CN114538396B CN 114538396 B CN114538396 B CN 114538396B CN 202210343961 A CN202210343961 A CN 202210343961A CN 114538396 B CN114538396 B CN 114538396B
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- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 264
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 88
- 239000011737 fluorine Substances 0.000 title claims abstract description 86
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000001816 cooling Methods 0.000 claims abstract description 95
- 239000000428 dust Substances 0.000 claims abstract description 51
- 239000012267 brine Substances 0.000 claims abstract description 48
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000007670 refining Methods 0.000 claims abstract description 33
- 238000005192 partition Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 157
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 100
- 239000011698 potassium fluoride Substances 0.000 claims description 88
- 235000003270 potassium fluoride Nutrition 0.000 claims description 75
- 239000007788 liquid Substances 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 60
- 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 48
- 239000000047 product Substances 0.000 claims description 42
- 229910052785 arsenic Inorganic materials 0.000 claims description 38
- 239000013078 crystal Substances 0.000 claims description 35
- 239000012535 impurity Substances 0.000 claims description 34
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 32
- 239000002826 coolant Substances 0.000 claims description 32
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 31
- 239000011591 potassium Substances 0.000 claims description 31
- 229910052700 potassium Inorganic materials 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 239000002956 ash Substances 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- 238000005507 spraying Methods 0.000 claims description 19
- 230000005484 gravity Effects 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 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
- 239000010413 mother solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 238000010438 heat treatment 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
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000011555 saturated liquid Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 150000002221 fluorine Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 47
- 239000011574 phosphorus Substances 0.000 abstract description 47
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 47
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 15
- 239000012043 crude product Substances 0.000 abstract description 12
- 229940104869 fluorosilicate Drugs 0.000 abstract description 11
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- 239000000741 silica gel Substances 0.000 abstract description 4
- 229910002027 silica gel Inorganic materials 0.000 abstract description 4
- 229960004029 silicic acid Drugs 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 116
- 229960001866 silicon dioxide Drugs 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 12
- 235000011181 potassium carbonates Nutrition 0.000 description 11
- 238000011084 recovery Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 150000004673 fluoride salts Chemical class 0.000 description 8
- 239000002994 raw material Substances 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
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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
- 238000010977 unit operation Methods 0.000 description 4
- 230000032798 delamination Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- -1 potassium fluorosilicate Chemical compound 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 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
- 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 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000607479 Yersinia pestis Species 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Removal Of Specific Substances (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to the technical field of phosphorus chemical industry clean production, and particularly relates to a process system and a process method for producing multi-quality yellow phosphorus and recycling fluorine resources. 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 steps of first-stage or two-stage partition wall air cooling or water cooling, first-stage fluorine-containing brine direct contact cooling, first-stage cold water washing and the like, respectively collects yellow phosphorus crude products obtained by condensation at different temperature stages, and respectively obtains yellow phosphorus with different qualities through conventional refining. Fluoride-containing brine and SiF therein during contact and circulation with furnace gas 4 And (3) producing fluorosilicate precipitate by reaction, recovering fluorosilicate resources, and eliminating the generation of hydrated silica gel phosphorus mud and process wastewater.
Description
Technical Field
The invention belongs to the technical field of phosphorus chemical industry clean production, and particularly relates to a process system and a process method for producing multi-quality yellow phosphorus and recycling fluorine resources.
Background
At present, industrial yellow phosphorus is produced by adopting a method for reducing phosphide in the phosphate ore in a high-temperature yellow phosphorus electric furnace by utilizing phosphate ore, silica, coke and the like at home and abroad. The production process is that apatite in the phosphate ore is reduced by coke to form phosphorus steam (P) 2 ) Mixed gas (commonly called yellow phosphorus furnace gas) such as CO and the like enters a series three-stage direct water washing and cooling through an air duct to enable simple substance phosphorus steam in the furnace gas to be condensed into liquid yellow phosphorus (P) 4 ) And mixing to obtain coarse industrial yellow phosphorus, and refining to obtain industrial yellow phosphorus. At the same time, under the high temperature reducing atmosphere in the electric furnace, arsenate in the phosphate ore is reduced into simple substance arsenic, fluoride such as fluorapatite in the phosphate ore and silicon dioxide also react to produce SiF 4 And (3) gas. Under the general condition, the fluorine content in the phosphate ore is in 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 the furnace burden, and the acidity index is high, so that SiO in the furnace burden is obtained 2 When the content is increased, the gas phase escape rate of fluorine is higher, and when the acidity index is conventional, the escape rate of fluorine is about 10% -90%, and the rest fluorine remains in the phosphorous slag. Obviously, the yellow phosphorus furnace gas entering the electric furnace delivery pipe contains phosphorus steam, carbon monoxide, 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 process 4 The silicon dioxide colloid produced by hydrolysis is mixed with ash and yellow phosphorus, and the existence of the hydrated silicon dioxide colloid causes difficulty in separating the yellow phosphorus from the ash, so that the existing traditional yellow phosphorus technology inevitably generates a large amount of phosphorus mud with higher phosphorus content, directly influences the yield of yellow phosphorus products, not only causes resource waste, but also generates serious problems of water pollution, arsenic pollution of soil and the like.
The invention patent (CN 104276549B) fully utilizes the larger difference between condensing temperature and 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 elemental arsenic which is desublimated and separated out (or adsorbed on the dust), then the furnace gas is directly washed by water after being re-graded (section), the yellow phosphorus which is separated out by condensing is collected by the grading (section), and the yellow phosphorus products with different (arsenic-containing) qualities are obtained by refining respectively. In addition, the invention also proposes to use SiF 4 The hydrolysis reaction temperature is below 120 ℃, and dust and SiF are partially avoided through the step-by-step dust removal and cooling of furnace gas 4 Mixing of silica gel particles produced by hydrolysis with yellow phosphorus, it is evident that it is difficult to thoroughly eliminate SiF in the furnace gas in the case of direct contact of the furnace gas with water 4 The silicon dioxide hydration colloid generated by hydrolysis has a certain difficulty in controlling the industrial process and also has a small amount of phosphorus mud and an influence on the quality of yellow phosphorus. Moreover, the process method disclosed in the patent cannot solve the problem of recycling fluorine and silicon resources in the production process.
At present, the production capacity scale of the existing yellow phosphorus enterprises in China is large, the yellow phosphorus production process is simple, but the impurity content in the produced yellow phosphorus is high, particularly arsenic and silicon are contained, 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 generated, the yellow phosphorus belongs to the two-high industry, and the industrial technology is urgently needed to be upgraded. There are few studies at home and abroad on the technology for preparing yellow phosphorus with different qualities based on the control of the yellow phosphorus production process, but no related report is made on the technology for obtaining yellow phosphorus with different qualities and recovering 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 and silicon in the yellow phosphorus production process. Along with the stricter requirements of clean production, energy conservation and emission reduction in the chemical industry at home and abroad, the rising of the fluoride industry in recent years, the domestic and international markets have a great demand for fluorine resources, and the phosphorus ores of main phosphorus mineral sites such as the cloud and precious jaw have a higher fluorine content, obviously, the technology of easily removing impurities from yellow phosphorus based on process control and recycling fluorine resources in the yellow phosphorus is also gradually becoming an urgent need technology of yellow phosphorus production enterprises.
Disclosure of Invention
The invention aims at solving the problems that yellow phosphorus produced in the current industrial process has higher impurity content, and a large amount of production wastewater, phosphorus mud containing hydrated silica gel and a large amount of fluorine-silicon resources thereof cannot be effectively recycled, and the like, and provides a process method which is beneficial to the control of the yellow phosphorus production process and is convenient for recycling fluorine-silicon resources. The method is to leave a yellow phosphorus electric furnace (containing phosphorus steam, arsenic steam and SiF) in the yellow phosphorus production process 4 Dust and other gases), and then separating the high-temperature furnace gas into a first-stage or a second-stage partition wall air cooling or a partition wall water cooling, directly contacting with first-stage fluorine-containing brine for cooling, a first-stage cold water washing and the like, respectively collecting yellow phosphorus crude products obtained by condensation at different temperature stages, and respectively obtaining yellow phosphorus with different qualities by conventional refining. Fluoride-containing brine and SiF in furnace gas during cooling circulation 4 And (3) producing fluorosilicate precipitate by reaction, recovering fluorosilicate resources, and eliminating the generation of hydrated silica gel phosphorus mud and process wastewater.
In order to achieve the above purpose, the invention adopts the technical principle that: the method is characterized in that the principle of separating arsenic from yellow phosphorus is fully utilized by utilizing the temperature difference of saturated steam of the yellow phosphorus and the arsenic, the yellow phosphorus furnace gas with the temperature above 200 ℃ after most of arsenic dust impurities are removed by a dust remover is subjected to unit operation of air cooling or water cooling heat exchange by a first-stage or a second-stage partition wall, the temperature of the furnace gas is reduced to 95-120 ℃, according to the related data of related literature about the relation between the partial pressure of phosphorus steam in the yellow phosphorus furnace gas and the temperature, about 90% of phosphorus steam is condensed and separated out and is collected in a hot water tank in a segmented mode, and the low-arsenic industrial yellow phosphorus product can be obtained after conventional refining. Obviously, the partition cools SiF in the furnace gas 4 The method is not in direct contact with spray water, so that the influence of hydrolysis on refining and quality of yellow phosphorus is avoided (the existence of hydrated silicon dioxide colloid generated by hydrolysis causes difficulty in separating yellow phosphorus from ash, so that the existing traditional yellow phosphorus process inevitably generates 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 ore raw materials entering the furnace, so that the furnace outlet temperature of yellow phosphorus furnace gas is improved, and the dust removal operation before is facilitated. The furnace gas after cooling heat exchange treatment is passed through a fluoride salt water washing tower and contains KF or NaF and NH with a certain concentration 4 Fluoride-containing brine of fluoride such as F and HF is used as cooling absorption liquid, and the fluoride solution can absorb SiF in furnace gas 4 And can react with the water to produce fluorosilicate or fluorosilicic acid to inhibit SiF 4 And eliminates the interference of the hydrolysis to the refining operation of yellow phosphorus. Meanwhile, a way is provided for recycling fluorine and silicon resources.
Taking potassium fluoride aqueous solution as cooling absorption liquid as an example, the specific reaction is as follows:
SiF 4 +2KF＝K 2 SiF 6 ↓ (1)
K 2 SiF 6 ↓+H 2 O＝4HF+H 2 SiO 3 +2KF (in boiling water) (2)
K 2 SiF 6 +2K 2 CO 3 ＝6KF+SiO 2 ↓+2CO 2 ↑ (3)
2KF+Na 2 CO 3 ＝NaF↓+K 2 CO 3 (4)
To avoid SiF in furnace gas 4 The hydrated silicon dioxide colloid generated by hydrolysis interferes with the separation of ash and yellow phosphorus washed from furnace gas, and KF water solution with higher concentration can be prepared to be used as cooling absorption liquid for absorbing SiF in the furnace gas by utilizing higher solubility of KF in water 4 And react to generate K 2 SiF 6 Precipitation, e.g. reaction (1), of SiF inhibition 4 Effect of hydrolysis on refining 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 a small amount of ash is contained), and the upper layer of the liquid is a potassium fluoride dilute solution for recycling. Lower part(s)The layer is yellow phosphorus crude product, and can become yellow phosphorus product with higher purity after conventional refining treatment.
The cooling absorption liquid regeneration cycle and the recovery of fluorine and silicon resources. 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, so that the solid ash in the solid potassium fluosilicate can be removed by utilizing the characteristic. Thus, the recovered potassium fluosilicate hot solution is added with a certain amount of potassium carbonate or potassium bicarbonate and potassium hydroxide to be mixed, and reacted for a period of time at the temperature of 95-110 ℃, and the reaction is as in (3). Filtering to obtain silicon dioxide, and washing and refining to produce white carbon black; the liquid is KF saturated solution, the potassium fluoride product is obtained by cooling and crystallizing, part of crystallization mother liquor is concentrated in a circulating way, and the other part of crystallization mother liquor is used as a supplementing liquid of coolant-fluorine-containing brine.
If the economical problem of potassium salt is considered, the characteristic of slightly water-soluble sodium fluoride can be fully utilized, sodium carbonate or sodium bicarbonate and sodium hydroxide are added into the KF saturated solution to carry out displacement reaction (4), and the solution is cooled to normal temperature and filtered to obtain a sodium fluoride product; the filtrate is a potassium carbonate solution and can be used as a raw material for treating potassium fluosilicate in a recycling way.
In order to solve the technical problems, the invention adopts the following technical scheme: when the outlet temperature of furnace gas leaving a yellow phosphorus electric furnace in the yellow phosphorus production process is 220-300 ℃, firstly removing about 90% of dust impurities and sublimated arsenic dust from the furnace gas of the yellow phosphorus electric furnace through a dust remover, then sequentially entering the steps of primary or two-stage partition wall air cooling or partition wall water cooling, primary fluorine-containing brine direct contact cooling washing, primary cold water washing and the like, respectively collecting yellow phosphorus crude products obtained by condensation at different temperature stages, and respectively obtaining yellow phosphorus with different qualities through simple refining. Cooling SiF in fluoride salt water circulation and furnace gas 4 Reacting and recovering the fluorine-silicon resource in the reaction product. The scheme is as follows.
A process system for producing multi-quality yellow phosphorus and recycling fluorine resources thereof 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 partition 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 liquid discharge port arranged at the bottom, a cooling medium inlet and a cooling medium outlet, wherein the yellow phosphorus furnace gas outlet is communicated with the high-temperature material inlet, the cooling medium inlet is sequentially communicated with cooling medium conveying equipment and a cooling medium inlet pipe, the condensate liquid discharge port is communicated with a water seal yellow phosphorus collecting tank, the water seal 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 equipment, the cooling medium is normal-temperature air or water, and the partition wall cooling device is a partition wall air cooling device or a partition wall water cooling device and is a 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 header and a potassium fluoride solution collecting port arranged at the bottom, wherein 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 for yellow phosphorus, potassium fluosilicate precipitation and potassium fluoride, and the fluorine-containing brine collecting and precipitating tank is also communicated with the first spray header 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 blanking port and a second spray header, the first air outlet is communicated with the second air inlet, the bottom blanking port is communicated with a cold water collecting and circulating tank, the cold water collecting and circulating tank is provided with a high-purity yellow phosphorus collecting port, and the cold water collecting and circulating tank is also communicated with the second spray header through a cold water circulating pump.
Further, the system further comprises:
the feed inlet of the separating device is communicated with a conveying equipment pipeline of a mixed liquid collecting port of yellow phosphorus, potassium fluosilicate sediment and potassium fluoride, and the liquid outlet of the separating device is communicated with a gravity sedimentation liquid separator which is provided with a low-impurity yellow phosphorus collecting port;
One feed inlet of the reaction kettle is respectively communicated with a slag outlet of the separation device and a supernatant outlet of the gravity sedimentation liquid separator, and the other feed inlet of the reaction kettle is a potassium carbonate solution feed inlet;
the feed inlet of the filter is communicated with the discharge port of the reaction kettle, the discharge port of the filter is communicated with the potassium fluoride saturated liquid collecting port through a valve and is also sequentially communicated with an evaporation concentration cooling crystallizer and a centrifugal machine, the discharge port of the centrifugal machine is communicated with the potassium fluoride solution recycling port and is also communicated with the evaporation concentration cooling crystallizer through a valve, the filter is provided with a byproduct silicon dioxide collecting port, and the centrifugal machine is provided with a byproduct potassium fluoride crystal collecting port.
The cooling medium is normal temperature air or water, and the partition wall cooling device is a partition wall air cooling device or a partition wall water cooling device. The cooling medium conveying device 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:
the replacement reaction kettle is characterized in that one feed inlet of the replacement reaction kettle is communicated with the potassium fluoride saturated liquid collecting opening, the other feed inlet of the replacement reaction kettle is a sodium carbonate feed inlet, the discharge outlet of the replacement reaction kettle is sequentially communicated with a heat exchanger and a sodium fluoride filter, and the sodium fluoride filter is provided with a potassium carbonate solution collecting opening and a byproduct sodium fluoride crystal collecting opening.
The invention also provides a process method for producing the multi-quality yellow phosphorus and recovering fluorine resources thereof, which can be adopted for production by the system provided by the invention, and specifically comprises the following steps:
1) The yellow phosphorus electric furnace gas flowing out from the yellow phosphorus furnace gas inlet is at the temperature of more than 230 ℃, dust is removed in the dust remover, dust is separated, and the yellow phosphorus furnace gas with the temperature of more than 200 ℃ for removing dust impurities containing arsenic simple substances is obtained; 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 dust removal operation cannot be performed, the yellow phosphorus furnace gas is directly introduced into the fluorine-containing salt water spray tower for performing the operation of step 3) and subsequent steps.
2) Introducing the dust impurity removed yellow phosphorus furnace gas obtained in the step 1) and containing arsenic simple substance into the dividing wall heat exchange device, wherein the temperature is above 200 DEG CCooling, separating to obtain condensate and SiF-containing solution with temperature of 95-120deg.C 4 Collecting and refining condensate effluent to obtain low-arsenic industrial yellow phosphorus;
3) The SiF-containing material obtained in the step 2) is subjected to 4 Introducing furnace gas into the fluorine-containing brine spray tower for spraying, and flowing the obtained mixed solution of condensed and precipitated liquid yellow phosphorus, potassium fluosilicate precipitate and potassium fluoride into the fluorine-containing brine collecting and precipitating tank, wherein the mixture of liquid in the tank and precipitated crystal particles can be circulated to a first spray head for spraying by the fluorine-containing brine circulating pump, and SiF is removed 4 Wherein the spray liquid is 10-45% potassium fluoride solution, the temperature is 30-50 ℃, and SiF is removed 4 The temperature of the furnace gas is 50-60 ℃;
4) The SiF removal obtained in the step 3) is carried out 4 Introducing 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, dispersing the solid yellow phosphorus particles in cold water, discharging yellow phosphorus tail gas, precipitating and collecting the solid yellow phosphorus from the cold water dispersed with the yellow phosphorus particles, heating and refining the solid yellow phosphorus to obtain high-purity yellow phosphorus, and circulating the precipitate supernatant-cold water to a second spray header for spraying by the cold water circulating pump, wherein the temperature of the yellow phosphorus tail gas is 10-35 ℃.
Further, the method further comprises step 5):
5a) Introducing the liquid yellow phosphorus, potassium fluosilicate precipitate, ash and potassium fluoride mixed solution obtained in the step 3) into the separation device for filtering, and carrying out heat preservation, standing and layering on filtrate through the gravity sedimentation liquid separator to obtain low-impurity yellow phosphorus, wherein the low-impurity yellow phosphorus 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 dedusted, and the yellow phosphorus crude product obtained by directly carrying out the operation of the step 3) in the step 2) is refined to obtain industrial yellow phosphorus;
5b) Adding potassium fluosilicate crystals containing part of ash separated by the separation device into the reaction kettle, adding supernatant obtained by the gravity sedimentation liquid separator, heating to 100 ℃ to hydrolyze the crystals into solution, filtering to remove ash in the solution, adding potassium carbonate or a replacement mother solution (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 cooling and crystallizing the obtained near-saturated potassium fluoride solution by the evaporation concentration cooling crystallizer to separate potassium fluoride, dehydrating by the centrifugal machine to obtain a potassium fluoride crystal product, wherein the rest is crystallized mother liquor which is rich in potassium fluoride, one part of the crystallized mother liquor is used as a supplementing liquid of the cooling absorption liquid potassium fluoride solution, and the other part of the crystallized mother liquor is sent to the concentration cooling crystallizer for reuse.
Further, the method further comprises step 6): and (3) sending the hot nearly saturated potassium fluoride solution obtained in the step (5 b) into a displacement reaction kettle, adding sodium carbonate for displacement reaction, cooling to normal temperature through a 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 a displacement mother solution (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 through a dust remover (a multi-pipe cyclone dust remover, an electric dust remover and the like), calculating according to the partial pressure of phosphorus steam in the common furnace gas, wherein the dew point of the separated phosphorus steam is about 180 ℃, and when the temperature of the furnace gas after the dust remover is purified is above 200 ℃, the trapped dust does not contain simple substance phosphorus, but contains simple substance arsenic and is treated according to specifications.
The specific principle of the step 2) is as follows: and (3) cooling the yellow phosphorus furnace gas after removing most of arsenic dust impurities by a dust remover to above 200 ℃, adopting a one-stage or two-stage partition wall air-cooling or water-cooling heat exchanger to perform cooling unit operation, reducing the temperature of the furnace gas to 95-120 ℃, condensing and separating out most of phosphorus steam, collecting the phosphorus steam in a hot water tank at the bottom of the air-cooling heat exchanger, and then conventionally refining to obtain 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 is respectively prepared into general industrial yellow phosphorus and low-impurity yellow phosphorus through conventional refining. In addition, in order to reduce the resistance loss of the furnace gas system and prevent the blockage in the pipe, the heat exchanger adopts a single-pipe Cheng Lishi large-row pipe heat exchanger, and the height-diameter ratio is controlled; the cooling medium is air or water outside the pipe (shell pass), the blower or the water pump is used for forced transportation and countercurrent operation, the operation unit is provided with outlet hot air or hot water reflux branch pipes with adjustable flow, the temperature of the mixed inlet is improved, and the influence on the heat transfer effect and even the blockage caused by solidification of yellow phosphorus in the inlet local pipe due to supercooling of air or cold water in winter is prevented. The outlet air heated on the shell side of the heat exchanger is used for drying the ore raw material entering the furnace, thereby being beneficial to improving the tapping temperature of the yellow phosphorus furnace gas. The operation of the dust remover is convenient, and the precipitation of the phosphorus simple substance does not occur.
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 a fluoride-containing brine spray tower from the bottom, and is directly contacted with fluoride-containing brine sprayed from the top of the tower for cooling, and the temperature of the fluoride-containing brine is about 45 ℃. The spraying amount of the fluorine-containing brine is controlled to ensure that the furnace gas leaving the spray tower has the temperature of about 50-55 ℃, a liquid yellow phosphorus primary product is condensed and separated out, flows into a fluorine-containing brine collecting and precipitating tank together with the fluorine-containing brine and the reaction precipitate fluorosilicate from the bottom of the spray tower, after the mixture of liquid and crystal particles in the tank is recycled and sprayed for a period of time, the crystal particles of the fluorine-containing silicate grow up gradually and accumulate to a certain amount with the condensed liquid yellow phosphorus, then the liquid yellow phosphorus is discharged, the solid fluorosilicate (potassium or sodium) with larger particles is obtained by filtering, the filtrate is subjected to heat preservation and standing delamination, the yellow phosphorus crude product is obtained at the bottom, and the yellow phosphorus with higher purity can be obtained by conventional refining. The upper layer liquid is fluorine-containing salt solution. And (3) periodically supplementing a certain amount of fluoride salt to the fluoride salt circulating system to maintain the concentration of the fluoride salt in the brine circulating and spraying system. In this step, the main reaction is the above reaction (1).
The specific principle of the step 4) is as follows: the partial pressure of phosphorus steam in the furnace gas leaving the fluorine salt water spray tower is very low, but the impurity content is very low, the furnace gas with the temperature of about 50-60 ℃ enters the cold water spray tower from the bottom to be washed and cooled by clean water for spraying, and the spraying quantity of clear water is controlled, so that the temperature of the tail gas of the furnace gas is about 20 ℃; the yellow phosphorus obtained by condensation at the stage is little and is in a solid dispersion shape, the yellow phosphorus flows into a yellow phosphorus collecting water tank along with water from the bottom of the tower, the solid yellow phosphorus is deposited at the bottom of the collecting water tank and is discharged at regular intervals, and the yellow phosphorus is heated to a liquid state for refining, so that the yellow phosphorus with extremely high purity can be obtained. And finally, the rest tail gas is sent into a gas holder through a centrifugal fan.
The specific principle of the step 5) is as follows: adding the potassium fluosilicate separated by filtration into a reaction kettle, adding water or 3) the supernatant (fluoride-containing brine) in the step, heating to about 100 ℃ to hydrolyze the supernatant into a solution, filtering to remove ash in the solution, adding a certain amount of potassium carbonate or potassium bicarbonate and potassium hydroxide (or the replacement mother liquor for preparing sodium fluoride subsequently) to prepare a material with higher concentration, reacting for a period of time at 95-110 ℃, filtering to obtain silicon dioxide, and washing and refining to prepare white carbon black; the liquid is KF (near saturated) solution, potassium fluoride products are separated out by cooling crystallization or cooling crystallization after concentration, the rest is mother solution after crystallization, and the mother solution is still rich in potassium fluoride, one part is used as a supplementary solution of cooling absorption liquid, and the other part can be recycled to the front end of the reaction. 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 slight water solubility 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, substitution reaction is carried out, and the sodium fluoride product is obtained by filtering at normal temperature; the filtrate is a replacement mother liquor which mainly contains potassium carbonate and contains a small amount of slightly soluble sodium fluoride and potassium fluoride, and can be recycled as a reaction raw material for treating potassium fluosilicate. 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 sedimentation or centrifugal sedimentation.
According to the scheme, the fluorine-containing brine contains KF or NaF or NH with a certain concentration 4 F and HF 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 4 The concentration of the F aqueous solution is 0-15%, and the concentration of the HF aqueous solution is 0-15%.
According to the scheme, the mother solution after crystallization is the liquid left by separating out potassium fluoride crystals through cooling or concentrating and cooling of filtrate-potassium fluoride solution obtained by reacting potassium fluosilicate with potassium carbonate and filtering, wherein the liquid is still rich in potassium fluoride with a certain concentration.
According to the scheme, the replacement mother liquor is filtrate generated after the replacement reaction of potassium fluoride and sodium carbonate solution and the 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 the subsequent recycling is not negatively affected.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, the furnace gas leaving the yellow phosphorus electric furnace in the yellow phosphorus production process is directly subjected to the steps of dust removal, one-stage or two-stage air cooling, one-stage fluorine-containing brine washing, one-stage cold water washing, cooling and the like step by step, liquid yellow phosphorus crude products obtained by condensation at different temperature stages are respectively collected, and then different-quality yellow phosphorus products are respectively obtained through conventional refining, so that the influence of impurities such as arsenic and silicon in the furnace gas on the quality and yield of the yellow phosphorus is avoided, and the different requirements of downstream industries on the quality of various elemental phosphorus can be met. Meanwhile, the method is also beneficial to solving the problems of arsenic pollution, water pollution and the like which plague the phosphorus chemical industry.
2) The invention firstly adopts dividing wall heat exchange to cool and condense most yellow phosphorus steam for yellow phosphorus furnace gas, thereby avoiding SiF caused by adopting water washing to cool 4 The hydrated silicon dioxide colloid produced by hydrolysis has difficulty in separating subsequent yellow phosphorus from ash, and subsequent furnace gas adopts fluoride-containing brine to directly spray and cool, thereby realizing SiF in the furnace gas 4 The 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 phosphorite, thereby providing technical support for transformation and upgrading of the phosphorus chemical industry.
3) The invention is suitable for carrying out process design and technical 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 requirements.
Drawings
Fig. 1 is a schematic structural diagram of a system part adopted in the process method for producing multi-quality yellow phosphorus and recovering fluorine resources in embodiment 1 of the present invention.
Fig. 2 is a schematic diagram of the structure of a system portion employed in the fluorine resource recovery section in embodiment 1 of the present invention.
FIG. 3 is a schematic diagram of a system part used for sodium fluoride production and reuse of potassium salt thereof in example 2 of the present invention.
In fig. 1, 2 and 3:
1. the device comprises a dust remover, 2, an air-cooled heat exchanger, 3, a fluoride-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 fluoride-containing brine collecting and precipitating tank, 8, a cold water collecting and circulating tank, 9, cooling medium conveying equipment, 10, a fluoride-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 evaporative concentration cooling crystallizer, 17, a centrifuge, 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 collecting port, 107, a byproduct potassium fluoride crystal collecting port, 108, a sodium carbonate feed inlet, 109 and a byproduct sodium fluoride crystal collecting port;
201. a potassium fluoride solution recycling port, a mixed solution collecting port of 202, yellow phosphorus, potassium fluosilicate sediment and potassium fluoride, a mixed solution collecting port of 203 and a potassium fluoride saturated solution collecting port;
301. industrial yellow phosphorus collection port 302, low impurity yellow phosphorus collection port 303, high purity yellow phosphorus collection port.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present 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 time 7200 h) of an electric furnace (15000 KVA) with a yield of 7500 tons/year yellow phosphorus, wherein phosphorus ore entering the furnace contains 30.5 percent of phosphorus pentoxide, 2 percent of fluorine content and 20 percent of gas phase escape rate of fluorine,the ratio of raw materials and auxiliary materials and other operation conditions are the same as those of the conventional operation, and the discharge amount of the yellow phosphorus electric furnace is about 11000m 3 And/h, the temperature is about 250 ℃, the following yellow phosphorus production process control is carried out by adopting the process technology shown in fig. 1 and 2, and the specific steps comprise:
1) The yellow phosphorus furnace gas leaving the yellow phosphorus electric furnace is subjected to multi-pipe cyclone dust remover 1 to remove solid dust (including dust for adsorbing arsenic), so as to ensure that the dust trapped in an ash bucket of the dust remover 1 has certain fluidity, and the temperature of the purified furnace gas leaving the dust remover 1 is more than 220 ℃ after heat preservation treatment or yellow phosphorus tail gas burning supplement heat energy heat preservation. The dust enters a semi-closed ash bin 5.
2) The yellow phosphorus furnace gas after the dust remover 1 removes most of arsenic dust impurities is subjected to cooling unit operation by adopting an interstage wall type air cooling heat exchanger 2, the air cooling heat exchanger 2 is a single-tube Cheng Lishi large-row tube heat exchanger, the cooling medium is air from a cooling medium inlet tube 103 and is outside a tube (shell pass), and the cooling medium conveying equipment 9 is a blower, so that the temperature of the furnace gas is reduced to 100-110 ℃ through forced air supply and countercurrent operation. Most of the phosphorus vapor in the furnace gas is condensed and separated out and is collected in a water seal yellow phosphorus collecting tank 6 at the bottom of the air cooling heat exchanger, and the furnace gas is collected from an industrial yellow phosphorus collecting port 301 and then refined into low-arsenic industrial yellow phosphorus through a conventional process. The air cooling system is provided with an outlet hot air reflux branch pipe with adjustable flow, so that the temperature of mixed air inlet is improved, and the influence on heat transfer effect and even blockage caused by solidification of yellow phosphorus in a local pipe due to air supercooling is prevented. In addition, the temperature of the heated outlet air discharged from the cooling medium outlet 104 may be up to 110 ℃ or higher for drying the raw material charged into the furnace so as to raise the tapping temperature of the yellow phosphorus furnace gas.
3) The furnace gas leaving the lower part of the air-cooled heat exchanger 2 enters a fluorine-containing brine spray tower 3 from the bottom of the spray tower, and is directly contacted with 14% potassium fluoride solution sprayed from the top of the tower for cooling, and the temperature of the potassium fluoride solution is about 45 ℃. The spraying amount of the fluorine-containing brine is controlled to ensure that the temperature of furnace gas leaving the spray tower is about 55 ℃, liquid yellow phosphorus is condensed and separated, fluorosilicate precipitate and the rest potassium fluoride solution flow into a fluorine-containing brine collecting and precipitating tank 7 together, and the mixture of liquid and precipitated crystal particles in the tank is sprayed and used circularly by a fluorine-containing brine circulating pump 10. The potassium fluosilicate crystal particles grow up gradually and accumulate with the condensed liquid yellow phosphorus to a certain amount, then are discharged, the solid potassium fluosilicate with larger particles is obtained by filtering through a separation device 12 which is a plate filter, the filtrate is subjected to heat preservation and standing delamination through a gravity sedimentation liquid separator 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 through conventional refining. The upper liquid is a solution containing residual potassium fluoride and is used as a hydrolysis solution of potassium fluosilicate.
4) The furnace gas leaving the fluoride salt water spray tower 3 enters a cold water spray tower 4 from the bottom for water washing and cooling, clean water is adopted for spraying, and the spraying quantity of the 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 is little and is in a solid dispersion shape, and flows into the cold water collecting and circulating tank 8 along with water from the bottom of the tower, the solid yellow phosphorus is deposited 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 rest tail gas is sent to a tail gas cabinet from a yellow phosphorus tail gas outlet 102 through an exhaust fan.
5) Adding potassium fluosilicate crystals containing a small amount of ash separated by a plate filter into a reaction kettle 14, adding heavy force to precipitate supernatant (residual potassium fluoride solution) of a knockout 13, heating at 100 ℃ to hydrolyze the supernatant, adding a certain amount of potassium carbonate (or substitution mother liquor for preparing sodium fluoride later) to prepare a material with higher concentration, reacting for a period of time at 95-110 ℃, filtering the material by a filter 15, obtaining silicon dioxide at a silicon dioxide collecting port 106, and washing and refining to produce white carbon black; the liquid is KF (near saturation) solution, potassium fluoride is separated out through cooling crystallization of an evaporative concentration cooling crystallizer 16, dehydration is carried out by a centrifugal machine 17, and a potassium fluoride crystal product is obtained through collection of a byproduct potassium fluoride crystal collecting port 107. The rest is the mother solution after crystallization which is rich in potassium fluoride, one part of the mother solution is used as the replenishing solution of the potassium fluoride solution of the cooling absorption liquid, the replenishing solution can be obtained from the recycling port of the potassium fluoride solution, and the other part of the mother solution is sent to the cooled evaporation concentration cooling crystallizer 16 for use. Wherein, the cooling medium can also adopt air, the corresponding partition wall cooling device adopts a partition wall air cooling device, and the cooling medium conveying equipment is a blower.
The main product technical indexes of the method are as follows:
yellow phosphorus product technical index: the yield of each quality yellow phosphorus product accounts for 99% of the total phosphorus in the furnace gas leaving the yellow phosphorus electric furnace. Wherein the general industrial yellow phosphorus yield is 90 percent (accounting for the mass fraction of the total phosphorus product), the arsenic content is 64mg/kg, and no silicon impurity is contained; the yield of the yellow phosphorus with higher purity is 9 percent (accounting for the mass fraction of the total phosphorus product) and the arsenic content is 8.3mg/kg; the high-purity yellow phosphorus yield is 1.0 percent (accounting for the mass fraction of the obtained total phosphorus product), the arsenic content is less than 1.4mg/kg, and no silicon impurities are contained.
Fluorine resource recovery index: the recovery rate of fluorine resources accounts for 90% of the total gas-phase escaping amount from the yellow phosphorus electric furnace; about 99.1 kg of potassium fluoride product is produced as a byproduct of each ton of yellow phosphorus product.
Example 2
A process system and a method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof aim at a yellow phosphorus electric furnace production device (annual operation time number 7200 h) with a yield of 10000 tons/year, wherein phosphorus ore entering the furnace contains phosphorus pentoxide (P) 2 O 5 ) 29.8%, 3% fluorine content, 15% fluorine gas escape rate, and the raw and auxiliary materials are proportioned and other operating conditions the same as those of the conventional operation. The discharge amount of the yellow phosphorus electric furnace is about 14000m 3 About/h, at about 260 ℃, adopting the process technology shown in fig. 1, 2 and 3 to control the subsequent yellow phosphorus production process and recover fluorine resources, wherein the method comprises the following specific steps:
1) The dehydration leaving the yellow phosphorus electric furnace is subjected to solid dust removal by the electrostatic dust remover 1, and the temperature of the purified furnace gas leaving the dust remover 1 is controlled to be more than 220 ℃. The dust enters a semi-closed ash bin 5.
2) The dedusting yellow phosphorus furnace gas is subjected to cooling unit operation by adopting an interstage wall type water cooling heat exchanger 2 tube pass, the water cooling heat exchanger 2 is a single tube Cheng Lishi large-tube heat exchanger, the cooling medium conveying device 9 is a water pump, normal-temperature water is sent into the heat exchanger shell pass, countercurrent operation is carried out, 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 side and is 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 by a conventional method. The heated outlet hot water may be used for other purposes or recycled via a chilled water system cooling cycle.
3) The furnace gas leaving the lower part of the water-cooled heat exchanger 2 enters a fluorine-containing brine spray tower 3 from the bottom of the spray tower, is directly contacted with a mixed solution of 12 percent potassium fluoride and 1 percent sodium fluoride sprayed from the top of the spray tower for cooling, the spraying quantity of the potassium fluoride solution is controlled to ensure that the furnace gas leaving the spray tower has the temperature of about 50 ℃, liquid yellow phosphorus and fluorosilicate precipitate are condensed and separated, and the rest of potassium fluoride solution flows into a fluorine-containing brine collecting and precipitating tank 7 together, and the mixture of liquid and precipitated crystal particles in the tank is circularly sprayed by a fluorine-containing brine circulating pump 10 for use. After the fluorosilicate crystal particles grow up gradually and accumulate with the condensed liquid yellow phosphorus to a certain amount, discharging, filtering by a separating device 12 which is a plate filter to obtain solid potassium fluorosilicate with larger particles (containing a small amount of sodium fluorosilicate), and carrying out heat preservation, standing and layering on filtrate by a gravity sedimentation separator 13, wherein the bottom is a yellow phosphorus crude product, collecting from a low-impurity yellow phosphorus collecting port 302, and obtaining the yellow phosphorus with higher purity through 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 fluoride salt water spray tower 3 enters a cold water spray tower 4 from the bottom for water washing and cooling, clean water is adopted for spraying, and the spraying quantity of the 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 is little and is in a solid dispersion shape, and flows into the cold water collecting and circulating tank 8 along with water from the bottom of the tower, the solid yellow phosphorus is deposited 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 and is refined, and the high-purity yellow phosphorus can be obtained. Finally, the rest tail gas is sent to a tail gas cabinet from a yellow phosphorus tail gas outlet 102 through an exhaust fan.
5) Adding potassium (sodium) fluosilicate crystals separated by a plate filter into a reaction kettle 14, adding gravity to precipitate supernatant (residual potassium fluoride and a small amount of sodium fluoride solution) of a knockout 13, heating, 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 and refining to produce white carbon black; the liquid was a 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 step of filtering machine 15 is sent into a replacement reaction kettle 18 from a potassium fluoride saturated solution collecting port 203, metered sodium carbonate which is subjected to replacement reaction (4) with potassium fluoride in the kettle is added from a sodium carbonate feeding port to undergo replacement reaction, and then cooled to normal temperature by a heat exchanger 19 to be further crystallized, sodium fluoride is filtered by a filter 20 to obtain sodium fluoride crystal products, and the sodium fluoride crystal products are collected in a byproduct sodium fluoride crystal collecting port 109; the filtrate is a replacement mother liquor, which mainly contains potassium carbonate and can be used as a reaction raw material for treating potassium fluosilicate in a circulating way at a potassium carbonate solution feed inlet 105. The other conditions were the same as in example 1. The cooling medium can also adopt water, the corresponding partition wall cooling device adopts a partition 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:
yellow phosphorus product technical index: the yield of each quality yellow phosphorus product accounts for 99% of the total phosphorus in the furnace gas leaving the yellow phosphorus electric furnace. Wherein the general industrial yellow phosphorus yield is 85 percent (accounting for the mass fraction of the total phosphorus product), the arsenic content is 86mg/kg, and no silicon impurity is contained; the yield of the yellow phosphorus with higher purity is 14 percent (accounting for the mass fraction of the total phosphorus product) and the arsenic content is 13mg/kg; the high-purity yellow phosphorus yield is 1.0 percent (accounting for the mass fraction of the obtained total phosphorus product), the arsenic content is less than 1.5mg/kg, and no silicon impurities are contained.
Fluorine resource recovery index: the recovery rate of fluorine resources accounts for 90% of the total amount escaped from the yellow phosphorus electric furnace in a gas phase form; the byproduct sodium fluoride produced in the production of yellow phosphorus per ton is about 89.5 kg.
Example 3
A process system and a method for producing multi-quality yellow phosphorus and recovering fluorine resources thereof aim at a yellow phosphorus electric furnace production device (annual operation time number 7200 h) with a yield of 10000 tons/year, wherein phosphorus ore entering the furnace contains phosphorus pentoxide (P) 2 O 5 ) 29.8%, 3% fluorine content, 15% fluorine gas escape rate, and the raw and auxiliary materials are proportioned and other operating conditions the same as those of the conventional operation. The discharge amount of the yellow phosphorus electric furnace is about 14000m 3 About/h, at about 150deg.C, and adopting the process techniques shown in figures 1, 2 and 3 to control the subsequent yellow phosphorus production process and recover fluorine resources The receiving operation comprises the following specific steps:
1) The furnace gas at 150 ℃ enters the fluorine-containing brine spray tower 3 from the bottom of the yellow phosphorus furnace gas inlet 101, is cooled by direct contact with 18% potassium fluoride sprayed from the top of the tower, and controls the spraying amount of potassium fluoride solution to ensure that the furnace gas leaving the spray tower has the temperature of about 60 ℃, and liquid yellow phosphorus, fluorosilicate precipitate, ash and residual potassium fluoride solution are condensed and separated out to flow into a fluorine-containing brine collecting and precipitating tank 7 together, and the mixture of liquid and precipitated crystal particles in the tank is circularly sprayed by a fluorine-containing brine circulating pump 10 for use. The liquid potassium fluosilicate (containing a certain amount of large granular ash) is separated by a separating device 12 which is a three-phase centrifugal separator, the liquid is subjected to heat preservation and standing delamination by a gravity sedimentation separator 13, the yellow phosphorus crude product is at the bottom, and the yellow phosphorus crude product is collected from an impurity yellow phosphorus collecting port 302, and the general industrial yellow phosphorus can be obtained through conventional refining. The upper liquid is a solution containing residual potassium fluoride and is used as a hydrolysis solution of potassium fluosilicate.
2) The furnace gas leaving the fluoride salt water spray tower 3 enters a cold water spray tower 4 from the bottom for water washing and cooling, clean water is adopted for spraying, and the spraying quantity of the clean water is controlled, so that the temperature of the tail gas of the furnace gas is about 20 ℃; the condensed yellow phosphorus is little and in a solid dispersion shape, flows into the cold water collecting and circulating tank 8 along with water from the bottom of the tower, the solid yellow phosphorus is deposited 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 rest tail gas is sent to a tail gas cabinet from a yellow phosphorus tail gas outlet 102 through an exhaust fan.
3) Adding potassium fluosilicate crystals separated by a three-phase centrifugal separator into a reaction kettle 14, adding gravity to precipitate supernatant (residual potassium fluoride and a small amount of sodium fluoride solution) of a knockout 13, heating, 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 and refining to produce white carbon black; the liquid was a 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 step of filtering machine 15 is sent into a replacement reaction kettle 18 from a potassium fluoride saturated solution collecting port 203, metered sodium carbonate which is subjected to replacement reaction (4) with potassium fluoride in the kettle is added from a sodium carbonate feeding port to undergo replacement reaction, and then cooled to normal temperature by a heat exchanger 19 to be further crystallized, sodium fluoride is filtered by a filter 20 to obtain sodium fluoride crystal products, and the sodium fluoride crystal products are collected in a byproduct sodium fluoride crystal collecting port 109; the filtrate is a replacement mother liquor, which mainly contains potassium carbonate and can be used as a reaction raw material for treating potassium fluosilicate in a circulating way at a potassium carbonate solution feed inlet 105. The other conditions were the same as in example 1 and example 2.
The main product technical indexes of the method are as follows:
yellow phosphorus product technical index: the yield of each quality yellow phosphorus product was 97% of the total phosphorus in the furnace gas leaving the yellow phosphorus electric furnace. Wherein the general industrial yellow phosphorus yield is 98.5 percent (accounting for the mass fraction of the total phosphorus product), the arsenic content is 295mg/kg, and the product does not contain silicon impurities; the high-purity yellow phosphorus yield is 1.50 percent (accounting for the mass fraction of the obtained total phosphorus product), the arsenic content is below 12.5mg/kg, and no silicon impurities are contained.
Fluorine resource recovery index: the recovery rate of fluorine resources accounts for 89% of the total amount escaped from the yellow phosphorus electric furnace in a gas phase form; and the byproduct sodium fluoride produced in the production of yellow phosphorus per ton is about 88 kg.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A process system for producing multi-quality yellow phosphorus and recycling fluorine resources thereof 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, wherein the ash outlet is communicated with the semi-sealed ash bin (5);
the partition 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 liquid discharge port arranged at the bottom, a cooling medium inlet and a cooling medium outlet (104), wherein the yellow phosphorus furnace gas outlet is communicated with the high-temperature material inlet, the cooling medium inlet is sequentially communicated with cooling medium conveying equipment (9) and a cooling medium inlet pipe (103), the condensate liquid 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 equipment (9);
The fluorine-containing brine spray tower (3) is provided with a first air inlet, a first air outlet, a first spray header and a potassium fluoride solution recycling opening (201) arranged at the bottom, wherein the cooling material outlet is communicated with the first air inlet, the potassium fluoride solution recycling opening (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 opening (202) for yellow phosphorus, potassium fluosilicate precipitation and potassium fluoride, the fluorine-containing brine collecting and precipitating tank (7) is also communicated with the first spray header through a fluorine-containing brine circulating pump (10), fluorine salt in fluorine-containing brine is KF, and the concentration of KF is 3% -45%;
and a cold water spray tower (4) which is provided with a second air inlet, a yellow phosphorus tail gas outlet (102), a bottom blanking port and a second spray header, wherein the first air outlet is communicated with the second air inlet, the bottom blanking port is communicated with a cold water collecting and circulating tank (8), the cold water collecting and circulating tank (8) is provided with a high-purity yellow phosphorus collecting port (303), and the cold water collecting and circulating tank is also communicated with the second spray header through a cold water circulating pump (11).
2. The process system for producing multi-quality yellow phosphorus and recovering fluorine resources thereof according to claim 1, wherein the system further comprises:
The feed inlet of the separating device (12) is communicated with the mixed liquid collecting port (202) of yellow phosphorus, potassium fluosilicate sediment and potassium fluoride, the liquid outlet of the separating device is communicated with the gravity sedimentation liquid separator (13), and the gravity sedimentation liquid separator (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 sedimentation liquid separator (13), and the other feed inlet of the reaction kettle is a potassium carbonate solution feed inlet (105);
the filter (15), its feed inlet intercommunication discharge gate of reation kettle (14), its discharge gate pass through valve intercommunication potassium fluoride saturated liquid collection mouth (203) to still communicate evaporation concentration cooling crystallizer (16) and centrifuge (17) in proper order, the discharge gate of centrifuge (17) communicates potassium fluoride solution retrieval and utilization mouth (201), and still communicate through the valve evaporation concentration cooling crystallizer (16), filter (15) have by-product silica collection mouth (106), centrifuge (17) have by-product potassium fluoride crystal collection mouth (107).
3. The process system for producing multi-quality yellow phosphorus and recovering fluorine resources thereof according to claim 2, wherein the system further comprises:
The replacement reaction kettle (18), one feed inlet of which is communicated with the potassium fluoride saturated liquid collecting opening (203), the other feed inlet of which is a sodium carbonate feed inlet (108), and the discharge outlet of which is sequentially communicated with the heat exchanger (19) and the sodium fluoride filter (20), wherein the sodium fluoride filter (20) is provided with a potassium carbonate solution feed inlet (105) and a byproduct sodium fluoride crystal collecting opening (109).
4. A process system for producing multi-quality yellow phosphorus and recovering fluorine resources thereof according to claim 3, wherein: the cooling medium is normal-temperature air or water, the partition wall cooling device is a partition wall air cooling device or a partition 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, which is characterized by adopting the system of claim 4 for production, and specifically comprising the following steps:
1) Introducing yellow phosphorus electric furnace gas into the yellow phosphorus furnace gas inlet (101) at the temperature of more than 230 ℃, removing dust in the dust remover (1), separating the dust, and obtaining the yellow phosphorus furnace gas with the temperature of more than 200 ℃ for removing 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 in the range of 140-180 ℃, directly introducing the yellow phosphorus furnace gas into the fluorine-containing salt water spray tower (3) for carrying out the operation of the step 3) and the subsequent steps;
2) Introducing the removed yellow phosphorus furnace gas with the temperature above 200 ℃ and removed dust impurities containing arsenic simple substances obtained in the step 1) into the dividing wall cooling device for air cooling or water cooling, and separating to obtain condensed effluent and SiF containing SiF with the temperature of 95-120 DEG C 4 Collecting and refining condensate effluent to obtain low-arsenic industrial yellow phosphorus;
3) The SiF-containing material obtained in the step 2) is subjected to 4 Introducing furnace gas into the fluorine-containing brine spray tower (3) for spraying, and flowing the obtained mixed solution of condensed and precipitated liquid yellow phosphorus, potassium fluosilicate precipitate and potassium fluoride into the fluorine-containing brine collecting and precipitating tank (7), wherein the mixture of liquid and precipitated crystal particles in the tank can be recycled to the first spray head for spraying through the fluorine-containing brine circulating pump (10), and SiF is removed 4 Wherein the spray liquid is 3-45% potassium fluoride solution, the temperature is 30-50 ℃, siF is removed 4 The temperature of the furnace gas is 50-60 ℃;
4) The SiF removal obtained in the step 3) is carried out 4 Introducing furnace gas into the cold water spray tower (4) for water washing and cooling, condensing to obtain cold water mixed solution dispersed with solid yellow phosphorus, discharging yellow phosphorus tail gas, precipitating and separating the solid yellow phosphorus from the water mixed solution dispersed with solid yellow phosphorus, refining to obtain high-purity yellow phosphorus, and circulating the precipitate supernatant to a second spray header 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 multi-quality yellow phosphorus and recycling fluorine resources thereof according to claim 5, further comprising the step 5):
5a) Introducing the liquid yellow phosphorus, potassium fluosilicate precipitate, ash and potassium fluoride mixed solution obtained in the step 3) into the separation device (12) for separation, and carrying out heat preservation, standing and layering on the liquid through the gravity sedimentation liquid separator (13) to obtain low-impurity yellow phosphorus, wherein the low-impurity yellow phosphorus 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 dedusted, and the crude yellow phosphorus product obtained in the step 3) is directly subjected to the step 2) to be refined to obtain industrial yellow phosphorus;
5b) Adding potassium fluosilicate crystals containing part of ash separated by the separation device (12) and the supernatant obtained by adding the gravity sedimentation knockout (13) into the reaction kettle (14), heating to 100 ℃ to hydrolyze the potassium fluosilicate crystals into a solution, filtering to remove ash in the solution, adding 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, and washing and refining to produce white carbon black and obtain a nearly saturated potassium fluoride solution;
5c) And cooling and crystallizing the obtained near-saturated potassium fluoride solution by using the evaporation concentration cooling crystallizer (16) to separate potassium fluoride, dehydrating by using 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 supplementing solution of the potassium fluoride solution of the cooling absorption liquid, and the other part is sent to the evaporation concentration cooling crystallizer (16) for reuse.
7. The process for producing multi-quality yellow phosphorus and recycling fluorine resources thereof according to claim 6, further comprising the step 6): and (3) sending the hot nearly saturated potassium fluoride solution obtained in the step (5 b) into a displacement reaction kettle (18), adding sodium carbonate, sodium bicarbonate or sodium hydroxide for displacement reaction, cooling to normal temperature through a heat exchanger (19) for crystallization, and filtering through a sodium fluoride filter (20) to obtain a sodium fluoride crystal product, wherein the filtrate can be used as a displacement mother solution of sodium fluoride.
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| CN108190919A (en) * | 2018-02-26 | 2018-06-22 | 中南大学 | A kind of method that sodium fluoride is separated and recovered from acid fluorine-containing waste liquid |
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| CN108190919A (en) * | 2018-02-26 | 2018-06-22 | 中南大学 | A kind of method that sodium fluoride is separated and recovered from acid fluorine-containing waste liquid |
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