CN117720571A - Tributyl phosphate product for efficient extraction and separation of phosphoric acid, synthesis method and application - Google Patents
Tributyl phosphate product for efficient extraction and separation of phosphoric acid, synthesis method and application Download PDFInfo
- Publication number
- CN117720571A CN117720571A CN202311146331.1A CN202311146331A CN117720571A CN 117720571 A CN117720571 A CN 117720571A CN 202311146331 A CN202311146331 A CN 202311146331A CN 117720571 A CN117720571 A CN 117720571A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- reaction
- tributyl phosphate
- separation
- phosphate product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 170
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000926 separation method Methods 0.000 title claims abstract description 92
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 85
- 238000000605 extraction Methods 0.000 title claims abstract description 45
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 238000009833 condensation Methods 0.000 claims abstract description 39
- 230000005494 condensation Effects 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006482 condensation reaction Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 239000012071 phase Substances 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 15
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000011133 lead Substances 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 23
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011949 solid catalyst Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 claims description 8
- CTGNCBOZEMOASL-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecylphosphonic acid Chemical compound OP(O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CTGNCBOZEMOASL-UHFFFAOYSA-N 0.000 claims description 7
- TXOZSRCVHASUCW-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropan-1-ol Chemical compound OC(F)CC(F)(F)F TXOZSRCVHASUCW-UHFFFAOYSA-N 0.000 claims description 7
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 7
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 7
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- CRUISIDZTHMGJT-UHFFFAOYSA-L zinc;dichloride;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Zn+2] CRUISIDZTHMGJT-UHFFFAOYSA-L 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 30
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 12
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 10
- -1 sodium alkoxide Chemical class 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 5
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- DFFDSQBEGQFJJU-UHFFFAOYSA-M butyl carbonate Chemical compound CCCCOC([O-])=O DFFDSQBEGQFJJU-UHFFFAOYSA-M 0.000 description 5
- DWSYMNWJOYKKCK-UHFFFAOYSA-N butyl diethyl phosphate Chemical compound CCCCOP(=O)(OCC)OCC DWSYMNWJOYKKCK-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000012747 synergistic agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 101100520660 Drosophila melanogaster Poc1 gene Proteins 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101100520662 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PBA1 gene Proteins 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a tributyl phosphate product for efficient extraction and separation of phosphoric acid, a synthesis method and application thereof, wherein the synthesis method comprises the following steps: the butanol solution and the phosphoric acid solution enter a homogenizing mixer to be uniformly mixed; the mixed feed liquid enters a first-stage condensation reactor, and a catalyst is added for a first-stage condensation reaction; then the reaction liquid enters a secondary condensation reactor to carry out secondary condensation reaction; filtering the reaction solution, separating phases, and removing water phase and solid impurities; and (3) the organic phase enters a rectification purification tower to carry out rectification purification, low-boiling-point substance impurities are removed, and tributyl phosphate products are obtained from tower bottom liquid. The tributyl phosphate product realizes that the extraction rate of phosphoric acid is more than or equal to 95%, the separation coefficient of phosphoric acid/chloride is more than or equal to 1000, and simultaneously, the metal elements such as manganese, aluminum, arsenic, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc and the like in phosphoric acid and other nonmetallic elements such as arsenic, fluorine, silicon and the like can be prevented from being extracted, so that the phosphoric acid is purified, and the separation coefficient of the metal elements and other nonmetallic elements is more than 100.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a tributyl phosphate product for efficient extraction and separation of phosphoric acid, a synthesis method and application.
Background
Tributyl phosphate is an extraction agent commonly used in industry and has important application in the field of extraction and separation of rare earth elements. Generally, the higher the purity of tributyl phosphate, the better its extraction separation performance. However, it has been reported that tributyl phosphate containing a trace amount of impurities exhibits a superior extraction separation effect when extracting and separating phosphoric acid from a chloride-phosphoric acid system using tributyl phosphate as an extractant, possibly due to a synergistic extraction effect of impurity components, compared to a high-purity reagent. Therefore, the search for the best production process and the synthesis of tributyl phosphate with the best performance are key to efficient extraction and separation of phosphoric acid.
Industrially, tributyl phosphate is generally synthesized by esterification reaction of butanol and phosphorus oxychloride:
POC1 3 +3C 4 H 9 OH→(C 4 H 9 O) 3 PO+3HC1。
in order to inhibit the reaction of hydrogen chloride generated in the reaction with butanol and tributyl phosphate to generate byproducts such as chlorobutane, the reaction temperature is usually required to be controlled to be very low and the vacuum degree is high, but the reaction results in a great loss of butanol and phosphorus oxychloride, and the yield of tributyl phosphate is difficult to exceed 80%. The current methods for improving the yield of tributyl phosphate are of two main types: reaction process control and reaction product purification. The reaction process control method comprises the following steps: (1) Sodium formate (or sodium acetate), butyl acetate and the like are added in advance to remove hydrogen chloride generated in the reaction process, but the reaction of removing HCl from sodium formate or sodium acetate only needs to occur in the presence of water, and the reaction process is to avoid the existence of water because phosphorus oxychloride reacts with water, so that the method of adding sodium formate or sodium acetate is not feasible. (2) The raw material replacement method is to replace n-butanol in the reaction raw material with sodium alkoxide to ensure that NaCl is generated in the reaction process without generating HCl and inhibit side reaction; (3) The multistage reaction process includes the first primary reaction of the material, the elimination of hydrogen chloride and the subsequent deep esterification.
When butyl acetate is used as Lewis base by the research technology limited company of the phosphorus industry in Yunnan cloud, and the mass ratio of the phosphorus oxychloride, butanol and butyl acetate is 1:4:3, not only the synthesis yield of tributyl phosphate reaches 90.2%, but also the hydrogen chloride removal rate reaches 77.6%, and the feeding amount can be reduced to the greatest extent, so that the recovery pressure is reduced. Through 2L amplification experiments, the preparation process is verified that the hydrogen chloride removal rate of 73-75 percent, the tributyl phosphate yield of 92-95 percent and the purity of 98.8 percent can be obtained.
The patent CN202010449986.6 proposes a preparation method for producing high-purity tributyl phosphate by utilizing a microchannel technology (the process flow chart is shown in figure 1), reaction materials are cooled in advance and then added into a mixed reaction tower for reaction, the mixed reaction liquid is subjected to a great deal of deacidification by an atomization spray deacidification tower, then the reaction liquid enters a microchannel and is subjected to deep esterification with strictly controlled temperature and then is received in a glass lining reaction kettle, and meanwhile, nitrogen is introduced into the mixed reaction tower and the glass lining reaction kettle so as to take away hydrogen chloride gas generated by the reaction, so that the forward progress of the esterification reaction is promoted.
Patent CN2017107337043 discloses a preparation method of tributyl phosphate, which comprises the following steps:
(1) Sequentially adding n-butanol, metallic sodium and a solvent into a reaction device, and then stirring and heating to reflux to generate a mixed solution containing sodium butoxide; separating hydrogen generated by the reaction by a separator in the reaction device; (2) Cooling the mixed solution containing sodium butoxide to 15+/-3 ℃, and dropwise adding phosphorus oxychloride into the reaction device to perform esterification reaction to generate a mixed solution containing tributyl phosphate; (3) And heating the mixed solution containing tributyl phosphate to 80+/-6 ℃ and preserving heat for 1+/-0.3 hours, then cooling to 20+/-5 ℃ again, and then filtering, decompressing, washing with water for the second time, distilling to remove alcohol and solvent to obtain tributyl phosphate. The preparation method can not produce hydrogen chloride gas in the reaction process, greatly improves the working environment, and effectively improves the yield and purity of tributyl phosphate.
Patent CN201410373134.8 proposes a preparation method of tributyl phosphate, which is to directly esterify butanol solution of sodium butoxide and phosphorus oxychloride to synthesize tributyl phosphate, and the preparation method comprises the following steps: firstly, alkali metal or alkali metal hydroxide reacts with butanol to prepare an alcoholate with the water content of less than 0.1%, phosphorus oxychloride is dropwise added into the alcoholate at the reaction temperature of 20-100 ℃, and the target product tributyl phosphate is obtained after the reaction is completed, and then the filtration and distillation are carried out. Compared with the traditional method, the method has the advantages of high tributyl phosphate yield, low raw material consumption and the like.
Patent CN201610276861.1 proposes a process for preparing tributyl phosphate by synthesizing alkali metal alcoholate by a cryogenic method, loading butanol and benzene into a four-mouth bottle, continuously introducing inert gas into the closed four-mouth bottle, adding an alkali metal hydroxide aqueous solution, stirring and heating to generate gas, feeding the gas into a condensation water splitting device upwards for liquid separation, refluxing an oil phase into the four-mouth bottle, stopping heating when the water content in a mixed liquid system is less than 0.1%, cooling and cooling, dropwise adding phosphorus oxychloride, stirring to fully react the alkali metal alcoholate with the phosphorus oxychloride, and sequentially washing with water or salt and distilling under reduced pressure to obtain the finished tributyl phosphate; compared with the traditional method, the method has the advantages of high product yield, low raw material consumption, obviously shortened dehydration time and good dehydration effect.
The feasibility of synthesizing tributyl phosphate by using the sodium alkoxide method through intermittent reaction is verified by a researcher experiment, and the experimental result shows that the synthesis of tributyl phosphate by using the sodium alkoxide method is feasible. By optimizing the reaction conditions, a better experimental result is obtained: firstly, n-butyl alcohol reacts with metal sodium to prepare 22% sodium butoxide solution, then, the esterification reaction is carried out by taking sodium butoxide and phosphorus oxychloride as raw materials, the tributyl phosphate yield is 93.0%, and the recovery rate of excessive n-butyl alcohol is 89.1%. On the basis of an experiment for synthesizing tributyl phosphate by using a batch method, the tributyl phosphate is synthesized by adopting a single-kettle continuous method and a two-kettle continuous method, and the suitable process conditions for synthesizing the tributyl phosphate by using the single-kettle continuous method are as follows: the reaction temperature is 40 ℃, the average residence time is 60min, and the molar ratio of phosphorus oxychloride to sodium butoxide is 1:3.1.
The reaction product purification method comprises the following steps: (1) The adsorption method uses different adsorbents to adsorb impurities generated in the production process, but the method has large demand on the adsorbents and high cost, and finally, the product yield is insufficient. (2) The neutralization method is that ammonia gas or 10% alkaline solution such as potassium carbonate or sodium carbonate is used for neutralization until the pH value is 7 after the esterification reaction is finished, the neutralized crude ester is subjected to reduced pressure distillation and crude dealcoholization, the acidity is made to meet the requirement by washing with water, then the reduced pressure distillation is carried out, and after low-boiling-point substances are separated, fractions of 150 ℃ (0.667 kPa) to 180 ℃ (1.333 kPa) are collected, thus obtaining the TBP product.
Patent CN2015103639863 proposes a preparation method of high-purity tributyl phosphate, washing a mixture obtained after n-butanol reacts with phosphorus oxychloride, standing for layering, removing most of hydrogen chloride to obtain a 20-25% hydrochloric acid solution, and neutralizing an organic phase with ammonia gas until the pH value is 7. And (3) standing for phase separation after neutralization, crystallizing the water phase, then carrying out solid-liquid separation to obtain ammonium chloride solid, recycling the mother solution, washing the organic phase by adding clear water, and controlling the pH value to be 6-7. The water phase is recycled. The crude ester layer after phase separation is dealcoholized at 7-15kPa and 80-110 ℃ to recover most butanol. Then adding water as entrainer, vacuum distilling at 7-15kPa and 80-110 deg.C, recovering butanol from distilled butanol and water mixture, and obtaining high-purity tributyl phosphate.
Compared with the reaction process control, the reaction product purification method needs to consume a large amount of alkali, tributyl phosphate is degraded due to the fact that the alkali concentration is locally too high in the neutralization process, a large amount of heat is released, energy consumption is increased, and generated potassium chloride, sodium chloride and ammonium chloride cannot be recycled, so that environmental pollution is caused. In addition, the vacuum distillation condition for purifying TBP is harsh, the energy consumption is high, the requirement on equipment is high, the production cost is high, and the technical and economic value of the process is low. At present, the yield of tributyl phosphate is lower than 85 percent, and the purity is not high. Therefore, the reaction process control method is relatively more economical and feasible, but the existing method also has various defects, such as sodium chloride solid generated in the reaction process of the sodium alkoxide method in the raw material replacement method, and the solid adhered with the organic matters can only be subjected to dangerous waste treatment, thereby generating secondary pollution. In addition, a large amount of hydrogen is generated in the reaction process of preparing sodium alkoxide, so that potential safety hazards exist. The acid binding method of butyl acetate and the like has the defects that HCl generated in the esterification reaction process cannot be thoroughly removed, and the unreacted complete acid binding agent also increases the difficulty of subsequent purification of tributyl phosphate. The multi-stage esterification method has the defects of long process flow and large equipment investment.
In summary, in the current process for producing tributyl phosphate by using n-butyl alcohol (sodium butoxide) and phosphorus oxychloride as raw materials, various problems of complex byproducts, dangerous waste and secondary pollution in the reaction process, high subsequent purification difficulty and the like exist obviously. In addition, when tributyl phosphate synthesized by the prior art is used for extracting and separating phosphoric acid from a chloride-phosphoric acid system, the extraction separation coefficient is not more than 200.
Disclosure of Invention
The invention provides a synthesis method of a tributyl phosphate product for efficient extraction and separation of phosphoric acid, which aims to overcome the defects of the existing tributyl phosphate production process and meet the requirements of efficient extraction and separation of tributyl phosphate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthesis method of tributyl phosphate product for efficient extraction and separation of phosphoric acid comprises the following steps:
(1) The butanol solution and the phosphoric acid solution which are reaction raw materials enter a homogenizing mixer to be uniformly mixed;
(2) The mixed feed liquid enters a first-stage condensation reactor, and a catalyst is added for a first-stage condensation reaction;
(3) After the primary condensation reaction, the reaction liquid enters a secondary condensation reactor to carry out secondary condensation reaction;
(4) Filtering the liquid discharged from the secondary condensation reactor, separating phases, and removing water phase and solid impurities;
(5) And (3) the organic phase enters a rectification purification tower to carry out rectification purification, low-boiling-point substance impurities are removed, and tributyl phosphate products are obtained from tower bottom liquid.
Wherein the butanol solution consists of n-butanol, isobutanol, methyl butyrate, 3-trifluoromethyl-3-amyl dibutyl alcohol and 1, 1-dimethyl-2, 3-tetrafluoropropanol, and the mass ratio of the n-butanol to the isobutanol to the methyl butyrate to the 3-trifluoromethyl-3-amyl dibutyl alcohol to the 1, 1-dimethyl-2, 3-tetrafluoropropanol is as follows: 1000:0 to 0.1:0 to 5:0 to 0.5:0 to 0.002; the mol ratio of the n-butyl alcohol to the phosphoric acid is 3-4: 1.
wherein the phosphoric acid solution consists of phosphoric acid, phosphorous acid and perfluoro-n-decyl phosphonic acid, and the mass ratio of the phosphoric acid to the phosphorous acid to the perfluoro-n-decyl phosphonic acid is 1000:0 to 0.6:0 to 0.002.
Wherein in the step (2), the primary condensation reactor is a fixed bed or fluidized bed reactor, the temperature in the reactor is 100-135 ℃, the reaction residence time is 30-60 min, nitrogen is introduced for protection, and the reaction pressure is 0.1-0.2 MPa.
In the step (2), the catalyst is prepared by compounding a liquid catalyst and a solid catalyst, wherein the liquid catalyst is any one or more of sulfuric acid, phosphoric acid and nitric acid, and the bulk catalyst is any one or more of aluminum trichloride, ferric trichloride and zinc trichloride; the mass of the liquid and solid catalyst is 5-10: 1, a step of; the total mass ratio of the catalyst to the reaction raw materials is 0.1-0.2: 100.
wherein in the step (3), the secondary condensation reactor is a fixed bed or a fluidized bed, the reaction temperature in the secondary condensation reactor is 100-135 ℃, the reaction residence time is 30-60 min, the nitrogen is protected, and the reaction pressure is 0.1-0.2 MPa.
Wherein in the step (5), the temperature of the tower bottom of the rectifying and purifying tower is controlled to be 150-160 ℃, the temperature of the tower top is 130-140 ℃, the pressure of the tower bottom is 20-40 kPa, and the pressure of the tower top is 10-20 kPa; and (3) recovering and treating the low-boiling-point organic matters distilled from the top of the purifying tower, and cooling tower bottom liquid to obtain a tributyl phosphate product.
A phosphate product for efficient extraction and separation of phosphoric acid, which is prepared by the synthesis method.
The application of the phosphate product in extraction and separation of phosphoric acid.
In the condensation reactor, the main reaction of n-butyl alcohol and phosphoric acid to produce tributyl phosphate is accompanied by the production of controllable n-butyl ether, butyl butyrate and other trace byproducts, and the trace byproduct esters can be used as a synergistic agent for extracting phosphoric acid from tributyl phosphate, and the synergistic agent can prevent metal elements such as manganese, aluminum, arsenic, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc and the like in the phosphoric acid and other nonmetallic elements such as arsenic, fluorine, silicon and the like from being extracted, so that the phosphoric acid is purified, and the separation coefficient of the metal elements and the other nonmetallic elements is more than 100.
The operation parameters of the rectifying and purifying tower are strictly controlled, and other low-boiling-point impurity organic matters except the synergistic agent are removed through distillation, so that tributyl phosphate products with the content of more than or equal to 95%, n-butyl ether of 0-0.04%, butyl butyrate of 0-0.028%, butyl carbonate of 0-0.003%, dibutyl phosphite of 0-0.279%, butyl formate of 0-0.009%, triisobutyl phosphate of 0-0.029%, 1-dimethyl-2, 3-tetrafluoropropyl dibutyl phosphate of 0-0.117%, diethyl butyl phosphate of 0-0.417%, 3-trifluoromethyl-3-amyl dibutyl phosphate of 0-2.082% and perfluoro-n-decyl phosphonate of 0-0.061% are obtained. When the tributyl phosphate product is used for extracting and separating phosphoric acid in a chloride-phosphoric acid system, the phosphoric acid extraction rate is more than or equal to 95%, and the separation coefficient is more than or equal to 1000.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The existing process for synthesizing tributyl phosphate by esterification reaction of n-butyl alcohol and phosphorus oxychloride is replaced, and the problem of side reaction of hydrogen chloride and tributyl phosphate is effectively avoided by adopting the process for generating tributyl phosphate by catalytic condensation of butyl alcohol and phosphoric acid.
(2) The main reaction product and the side reaction product are effectively controlled by regulating and controlling the components of the raw material liquid and controlling the condensation reaction condition, so that the yield of the main reaction is greatly improved, and the difficulty of subsequent purification of tributyl phosphate is reduced.
(3) The operating parameters such as temperature and pressure in the rectifying and purifying tower are strictly controlled, impurity components with low boiling points are removed according to the difference of the boiling points of impurity organic matters, synergistic extraction components beneficial to phosphoric acid extraction are reserved, and finally the tributyl phosphate product with high purity and high extraction performance is obtained. Compared with tributyl phosphate produced by the prior art, the tributyl phosphate synthesized by the method realizes that the phosphoric acid extraction rate is more than or equal to 95%, the phosphoric acid/chloride separation coefficient is more than or equal to 1000, and meanwhile, the metal elements such as manganese, aluminum, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc and the like in phosphoric acid and other nonmetallic elements such as arsenic, fluorine, silicon and the like can be prevented from being extracted, so that the phosphoric acid is purified, and the separation coefficient of the metal elements and the other nonmetallic elements is more than 100.
Drawings
FIG. 1 is a process flow diagram of the prior art patent CN 202010449986.6;
FIG. 2 is a process flow diagram of tributyl phosphate synthesis in the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with specific embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A process flow diagram for tributyl phosphate synthesis in the following examples is shown in FIG. 2.
Example 1
The embodiment provides a synthesis method of tributyl phosphate product for efficient extraction and separation of phosphoric acid, which comprises the following steps:
(1) The butanol solution and the phosphoric acid solution which are reaction raw materials enter a homogenizing mixer to be uniformly mixed; the butanol solution comprises the following components in percentage by mass: 0.1:0.5:0.002 of n-butanol, isobutanol, 3-trifluoromethyl-3-pentyldibutanol and 1, 1-dimethyl-2, 3-tetrafluoropropanol; the phosphoric acid solution comprises the following components in percentage by mass: 0.6 is composed of phosphoric acid and phosphorous acid, and the reaction mole ratio of the main raw material n-butanol to the phosphoric acid is 3:1
(2) The mixed feed liquid enters a first-stage condensation reactor, the first-stage condensation reactor is a fixed bed or fluidized bed reactor, and a catalyst is added for carrying out a first-stage condensation reaction; the temperature in the reactor is 100 ℃, the reaction residence time is 30min, nitrogen is introduced for protection, and the reaction pressure is 0.1MPa; the catalyst is prepared by compounding a liquid catalyst and a solid catalyst, wherein the liquid catalyst is a combination of sulfuric acid, phosphoric acid and nitric acid (the mass ratio is 5:2:1), and the solid catalyst is aluminum trichloride; the mass of the liquid and solid catalyst is 10:1, a step of; the total mass ratio of the catalyst to the reaction raw materials is 0.1:100.
(3) After the primary condensation reaction, the reaction liquid enters a secondary condensation reactor to carry out secondary condensation reaction; the secondary condensation reactor is a fixed bed or a fluidized bed, the reaction temperature in the secondary condensation reactor is 120 ℃, the reaction residence time is 30min, the nitrogen is protected, and the reaction pressure is 0.1MPa.
(4) Filtering the liquid discharged from the secondary condensation reactor, separating phases, and removing water phase and solid impurities;
(5) The organic phase enters a rectifying and purifying tower to carry out rectifying and purifying, the temperature of the tower bottom of the rectifying and purifying tower is controlled at 150 ℃, the temperature of the tower top is 130 ℃, the pressure of the tower bottom is 20kPa, and the pressure of the tower top is 10kPa; and (3) recovering and treating the low-boiling-point organic matters distilled from the top of the purifying tower, and cooling tower bottom liquid to obtain a tributyl phosphate product.
Tributyl phosphate content of 95.5%, n-butyl ether 0.04%, butyl butyrate 0.028%, butyl carbonate 0%, dibutyl phosphite 0.279%, butyl formate 0%, triisobutyl phosphate 0.021%, 1-dimethyl-2, 3-tetrafluoropropyl dibutyl phosphate 0.117%, diethyl butyl phosphate 0.417%, 3-trifluoromethyl-3-amyl dibutyl phosphate 2.082%, perfluoro n-decyl phosphonate 0%.
When the tributyl phosphate product is used for extracting and separating phosphoric acid in a chloride-phosphoric acid system, the phosphoric acid extraction rate is 95%, the separation coefficient is 1000, and meanwhile, the extraction of manganese, aluminum, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc and other non-metal elements such as arsenic, fluorine and silicon in the phosphoric acid is avoided, wherein the separation coefficient of manganese is 105, the separation coefficient of aluminum is 112, the separation coefficient of calcium is 104, the separation coefficient of copper is 106, the separation coefficient of iron is 107, the separation coefficient of potassium is 108, the separation coefficient of magnesium is 113, the separation coefficient of sodium is 114, the separation coefficient of lead is 104, the separation coefficient of zinc is 103, the separation coefficient of arsenic is 102, the separation coefficient of fluorine is 107, and the separation coefficient of silicon is 108.
Example 2
The embodiment provides a synthesis method of tributyl phosphate product for efficient extraction and separation of phosphoric acid, which comprises the following steps:
(1) The butanol solution and the phosphoric acid solution which are reaction raw materials enter a homogenizing mixer to be uniformly mixed; the butanol solution comprises the following components in percentage by mass: 5 n-butanol and methyl butyrate; the phosphoric acid solution comprises the following components in percentage by mass: 0.6:0.002 is composed of phosphoric acid, phosphorous acid and perfluoro-n-decyl phosphonic acid, and the mol ratio of the main raw material n-butanol to the phosphoric acid is 4:1.
(2) The mixed feed liquid enters a first-stage condensation reactor, the first-stage condensation reactor is a fixed bed or fluidized bed reactor, and a catalyst is added for carrying out a first-stage condensation reaction; the temperature in the reactor is 135 ℃, the reaction residence time is 60min, nitrogen is introduced for protection, the reaction pressure is 0.2MPa, and the butanol and phosphoric acid undergo condensation reaction to generate tributyl phosphate. Wherein the liquid catalyst is a combination of sulfuric acid and phosphoric acid (mass ratio of 4:1), the solid catalyst is a combination of aluminum trichloride, ferric trichloride and zinc trichloride (mass ratio of 5:2:1), and the mass ratio of the liquid catalyst to the solid catalyst is 5:1, a step of; the total mass ratio of the catalyst to the reaction raw materials is 0.2:100.
(3) After the primary condensation reaction, the reaction liquid enters a secondary condensation reactor to carry out secondary condensation reaction; the secondary condensation reactor is a fixed bed or a fluidized bed, the reaction temperature in the secondary condensation reactor is 135 ℃, the reaction residence time is 60min, the nitrogen is protected, and the reaction pressure is 0.2MPa.
(4) Filtering the liquid discharged from the secondary condensation reactor, separating phases, and removing water phase and solid impurities;
(5) The organic phase enters a purifying tower to remove low boiling point organic matters, the temperature of the tower bottom of the rectifying purifying tower is controlled at 160 ℃, the temperature of the tower top is 140 ℃, the pressure of the tower bottom is 40kPa, and the pressure of the tower top is 20kPa. Recovering and treating low boiling point organic matters distilled from the top of the purifying tower, and cooling tower bottom liquid to obtain tributyl phosphate products, wherein the tributyl phosphate products comprise 95% of tributyl phosphate, 0.025% of butyl butyrate, 0.003% of butyl carbonate, 0.258% of dibutyl phosphite, 0.009% of butyl formate, 0% of triisobutyl phosphate, 0% of 1, 1-dimethyl-2, 3-tetrafluoropropyl dibutyl phosphate, 0.408% of diethyl butyl phosphate, 0% of 3-trifluoromethyl-3-amyl dibutyl phosphate and 0.061% of perfluoro-n-decyl phosphonate. When the obtained tributyl phosphate product is used for extracting and separating phosphoric acid by a chloride-phosphoric acid system, the phosphoric acid extraction rate is 96%, and the separation coefficient is 1200; meanwhile, the extraction of manganese, aluminum, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc and other non-metal elements such as arsenic, fluorine, silicon and the like in phosphoric acid is avoided, wherein the separation coefficient of manganese is 104, the separation coefficient of aluminum is 102, the separation coefficient of calcium is 101, the separation coefficient of copper is 103, the separation coefficient of iron is 104, the separation coefficient of potassium is 106, the separation coefficient of magnesium is 107, the separation coefficient of sodium is 112, the separation coefficient of lead is 104, the separation coefficient of zinc is 106, the separation coefficient of arsenic is 107, the separation coefficient of fluorine is 105 and the separation coefficient of silicon is 107.
Example 3
The embodiment provides a synthesis method of tributyl phosphate product for efficient extraction and separation of phosphoric acid, which comprises the following steps:
(1) The butanol solution and the phosphoric acid solution which are reaction raw materials enter a homogenizing mixer to be uniformly mixed; the butanol solution comprises the following components in percentage by mass: 0.05:4:0.3:0.001 of n-butanol, isobutanol, methyl butyrate, 3-trifluoromethyl-3-pentyldibutanol and 1, 1-dimethyl-2, 3-tetrafluoropropanol; the phosphoric acid solution comprises the following components in percentage by mass: 0.001 is composed of phosphoric acid and perfluoro-n-decyl phosphonic acid; wherein the reaction mole ratio of the main raw material n-butanol to phosphoric acid is 3.5:1.
(2) The mixed feed liquid enters a first-stage condensation reactor, the first-stage condensation reactor is a fixed bed or fluidized bed reactor, a catalyst is added, and the total mass ratio of the catalyst to the reaction raw materials is 0.15:100, performing a primary condensation reaction; the temperature in the reactor is 120 ℃, the reaction residence time is 40min, nitrogen is introduced for protection, and the reaction pressure is 0.15MPa; the catalyst is prepared by compounding a liquid catalyst and a solid catalyst, wherein the liquid catalyst is sulfuric acid and nitric acid (mass ratio is 5:1), the solid catalyst is ferric trichloride, and the mass of the liquid catalyst and the solid catalyst is 8:1.
(3) After the primary condensation reaction, the reaction liquid enters a secondary condensation reactor to carry out secondary condensation reaction; the secondary condensation reactor is a fixed bed or a fluidized bed, the reaction temperature in the secondary reactor is 120 ℃, the reaction residence time is 40min, the nitrogen is protected, and the reaction pressure is 0.15MPa. .
(4) Filtering the liquid discharged from the secondary condensation reactor, separating phases, and removing water phase and solid impurities;
(5) The organic phase enters a purifying tower to remove low boiling point organic matters, the temperature of the tower bottom of the rectifying purifying tower is controlled at 155 ℃, the temperature of the tower top is 135 ℃, the pressure of the tower bottom is 30kPa, and the pressure of the tower top is 15kPa. Recovering and treating low boiling point organic matters distilled from the top of the purifying tower, and cooling tower bottom liquid to obtain tributyl phosphate products, wherein the tributyl phosphate products comprise 95% of tributyl phosphate, 0% of n-butyl ether, 0% of butyl butyrate, 0.002% of butyl carbonate, 0% of dibutyl phosphite, 0.006% of butyl formate, 0.02% of triisobutyl phosphate, 0.104% of 1, 1-dimethyl-2, 3-tetrafluoropropyl dibutyl phosphate, 0.40% of diethyl butyl phosphate, 1.06% of 3-trifluoromethyl-3-amyl dibutyl phosphate and 0.044% of perfluoro-n-decyl phosphonate. When the obtained tributyl phosphate product is used for extracting and separating phosphoric acid by a chloride-phosphoric acid system, the phosphoric acid extraction rate is 95.6%, and the separation coefficient is 1150; meanwhile, the extraction of manganese, aluminum, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc and other non-metal elements such as arsenic, fluorine, silicon and the like in phosphoric acid is avoided, wherein the separation coefficient of manganese is 104, the separation coefficient of aluminum is 107, the separation coefficient of calcium is 108, the separation coefficient of copper is 110, the separation coefficient of iron is 106, the separation coefficient of potassium is 107, the separation coefficient of magnesium is 108, the separation coefficient of sodium is 107, the separation coefficient of lead is 109, the separation coefficient of zinc is 110, the separation coefficient of arsenic is 112, the separation coefficient of fluorine is 106, and the separation coefficient of silicon is 105.
Example 4:
the embodiment provides a synthesis method of tributyl phosphate product for efficient extraction and separation of phosphoric acid, which comprises the following steps:
(1) The butanol solution and the phosphoric acid solution which are reaction raw materials enter a homogenizing mixer to be uniformly mixed; the butanol solution comprises the following components in percentage by mass: 0.05:4:0.3:0.001 of n-butanol, isobutanol, methyl butyrate, 3-trifluoromethyl-3-pentyldibutanol and 1, 1-dimethyl-2, 3-tetrafluoropropanol; the phosphoric acid solution comprises the following components in percentage by mass: 0.4:0.001 is composed of phosphoric acid, phosphorous acid and perfluoro-n-decyl phosphonic acid.
(2) The mixed feed liquid enters a first-stage condensation reactor, the first-stage condensation reactor is a fixed bed or fluidized bed reactor, and a catalyst is added for carrying out a first-stage condensation reaction; the temperature in the reactor is 120 ℃, the reaction residence time is 40min, and the total mass ratio of the catalyst to the reaction raw materials is 0.15:100; the liquid and solid compound catalyst is used as a reaction catalyst, nitrogen is introduced for protection, the reaction pressure is 0.15MPa, and butanol and phosphoric acid undergo condensation reaction to generate tributyl phosphate. Wherein the liquid catalyst is nitric acid, the solid catalyst is zinc trichloride, and the mass of the liquid and the solid catalyst is 8:1.
(3) After the primary condensation reaction, the reaction liquid enters a secondary condensation reactor to carry out secondary condensation reaction; the secondary condensation reactor is a fixed bed, the reaction temperature in the secondary reactor is 120 ℃, the reaction residence time is 40min, the nitrogen protection is adopted, and the reaction pressure is 0.15MPa.
(4) Filtering the liquid discharged from the secondary condensation reactor, separating phases, and removing water phase and solid impurities;
(5) The organic phase enters a purifying tower to remove low boiling point organic matters, the temperature of the tower bottom of the rectifying purifying tower is controlled at 155 ℃, the temperature of the tower top is 135 ℃, the pressure of the tower bottom is 30kPa, and the pressure of the tower top is 15kPa. Recovering and treating low boiling point organic matters distilled from the top of the purifying tower, and cooling tower bottom liquid to obtain tributyl phosphate products, wherein tributyl phosphate products with tributyl phosphate content of 96.3%, n-butyl ether of 0.01%, butyl butyrate of 0.015%, butyl carbonate of 0.001%, dibutyl phosphite of 0.11%, butyl formate of 0.004%, triisobutyl phosphate of 0.015%, 1-dimethyl-2, 3-tetrafluoropropyl dibutyl phosphate of 0.004%, diethyl butyl phosphate of 0.215%, 3-trifluoromethyl-3-amyl dibutyl phosphate of 1.98% and perfluoro-n-decyl phosphonate of 0.004% are obtained. When the obtained tributyl phosphate product is used for extracting and separating phosphoric acid by a chloride-phosphoric acid system, the phosphoric acid extraction rate is 96%, and the separation coefficient is 1300; meanwhile, the extraction of manganese, aluminum, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc and other non-metal elements such as arsenic, fluorine, silicon and the like in phosphoric acid is avoided, wherein the separation coefficient of manganese is 104, the separation coefficient of aluminum is 108, the separation coefficient of calcium is 109, the separation coefficient of copper is 110, the separation coefficient of iron is 111, the separation coefficient of potassium is 112, the separation coefficient of magnesium is 106, the separation coefficient of sodium is 108, the separation coefficient of lead is 107, the separation coefficient of zinc is 106, the separation coefficient of arsenic is 104, the separation coefficient of fluorine is 106, and the separation coefficient of silicon is 105.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The synthesis method of tributyl phosphate product for efficient extraction and separation of phosphoric acid is characterized by comprising the following steps:
(1) The butanol solution and the phosphoric acid solution which are reaction raw materials enter a homogenizing mixer to be uniformly mixed;
(2) The mixed feed liquid enters a first-stage condensation reactor, and a catalyst is added for a first-stage condensation reaction;
(3) After the primary condensation reaction, the reaction liquid enters a secondary condensation reactor to carry out secondary condensation reaction;
(4) Filtering the liquid discharged from the secondary condensation reactor, separating phases, and removing water phase and solid impurities;
(5) And (3) the organic phase enters a rectification purification tower to carry out rectification purification, low-boiling-point substance impurities are removed, and tributyl phosphate products are obtained from tower bottom liquid.
2. The method for synthesizing tributyl phosphate product for efficient extraction and separation of phosphoric acid according to claim 1, wherein the method comprises the following steps: the butanol solution consists of n-butanol, isobutanol, methyl butyrate, 3-trifluoromethyl-3-amyl dibutyl alcohol and 1, 1-dimethyl-2, 3-tetrafluoropropanol, wherein the mass ratio of the n-butanol to the isobutanol to the methyl butyrate to the 3-trifluoromethyl-3-amyl dibutyl alcohol to the 1, 1-dimethyl-2, 3-tetrafluoropropanol is as follows: 1000:0 to 0.1:0 to 5:0 to 0.5:0 to 0.002; the mol ratio of the n-butyl alcohol to the phosphoric acid is 3-4: 1.
3. the method for synthesizing tributyl phosphate product for efficient extraction and separation of phosphoric acid according to claim 1, wherein the method comprises the following steps: the phosphoric acid solution consists of phosphoric acid, phosphorous acid and perfluoro-n-decyl phosphonic acid, wherein the mass ratio of the phosphoric acid to the phosphorous acid to the perfluoro-n-decyl phosphonic acid is 1000:0 to 0.6:0 to 0.002.
4. The method for synthesizing tributyl phosphate product for efficient extraction and separation of phosphoric acid according to claim 1, wherein the method comprises the following steps: in the step (2), the primary condensation reactor is a fixed bed or fluidized bed reactor, the temperature in the reactor is 100-135 ℃, the reaction residence time is 30-60 min, nitrogen is introduced for protection, and the reaction pressure is 0.1-0.2 MPa.
5. The method for synthesizing tributyl phosphate product for efficient extraction and separation of phosphoric acid according to claim 1, wherein the method comprises the following steps: in the step (2), the catalyst is prepared by compounding a liquid catalyst and a solid catalyst, wherein the liquid catalyst is any one or more of sulfuric acid, phosphoric acid and nitric acid, and the bulk catalyst is any one or more of aluminum trichloride, ferric trichloride and zinc trichloride; the mass of the liquid and solid catalyst is 5-10: 1, a step of; the total mass ratio of the catalyst to the reaction raw materials is 0.1-0.2: 100.
6. the method for synthesizing tributyl phosphate product for efficient extraction and separation of phosphoric acid according to claim 1, wherein the method comprises the following steps: in the step (3), the secondary condensation reactor is a fixed bed or a fluidized bed, the reaction temperature in the secondary condensation reactor is 100-135 ℃, the reaction residence time is 30-60 min, the nitrogen is protected, and the reaction pressure is 0.1-0.2 MPa.
7. The method for synthesizing tributyl phosphate product for efficient extraction and separation of phosphoric acid according to claim 1, wherein the method comprises the following steps: in the step (5), the temperature of the tower bottom of the rectifying and purifying tower is controlled to be 150-160 ℃, the temperature of the tower top is 130-140 ℃, the pressure of the tower bottom is 20-40 kPa, and the pressure of the tower top is 10-20 kPa; and (3) recovering and treating the low-boiling-point organic matters distilled from the top of the purifying tower, and cooling tower bottom liquid to obtain a tributyl phosphate product.
8. A tributyl phosphate product for efficient extraction of phosphoric acid prepared by the synthetic method of any one of claims 1-7.
9. The use of tributyl phosphate product according to claim 8 in the extraction separation of phosphoric acid in a chloride-phosphoric acid system, wherein the phosphoric acid extraction rate is not less than 95%, the separation coefficient is not less than 1000, and at the same time, the extraction of metallic elements and other nonmetallic elements is avoided, and the separation coefficient of metallic elements and other nonmetallic elements is not less than 100.
10. The use according to claim 9, characterized in that: the metallic elements include manganese, aluminum, arsenic, calcium, copper, iron, potassium, magnesium, sodium, lead, zinc, and the other nonmetallic elements include arsenic, fluorine, and silicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311146331.1A CN117720571A (en) | 2023-09-06 | 2023-09-06 | Tributyl phosphate product for efficient extraction and separation of phosphoric acid, synthesis method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311146331.1A CN117720571A (en) | 2023-09-06 | 2023-09-06 | Tributyl phosphate product for efficient extraction and separation of phosphoric acid, synthesis method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117720571A true CN117720571A (en) | 2024-03-19 |
Family
ID=90198523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311146331.1A Pending CN117720571A (en) | 2023-09-06 | 2023-09-06 | Tributyl phosphate product for efficient extraction and separation of phosphoric acid, synthesis method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117720571A (en) |
-
2023
- 2023-09-06 CN CN202311146331.1A patent/CN117720571A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892666A (en) | Method for preparing high-purity tributyl phosphate | |
| CN115894229B (en) | Selective synthesis process of adipic acid monoethyl ester | |
| CN103213960A (en) | Method for producing phosphoric acid by decomposing low-grade phosphate rock with wet-process phosphoric acid | |
| CN109503410A (en) | The method of solvent DMF recycling in a kind of production of Sucralose | |
| CN114436229A (en) | Preparation method for preparing phosphoric acid and byproduct nitrophosphate fertilizer from phosphorite | |
| CN103130622B (en) | A kind of preparation method of trimethyl orthoformate | |
| CN116780013A (en) | Method for recycling electrolyte of waste lithium ion battery | |
| CN115557927A (en) | Preparation method of vinyl sulfate | |
| EP2305630B1 (en) | Process for recovering valued compounds from a stream derived from purification of methyl methacrylate | |
| KR20150119141A (en) | Method for preparing methyl lactate | |
| CN1156394C (en) | Method for producing fluoride and silicon dioxide | |
| CN117720571A (en) | Tributyl phosphate product for efficient extraction and separation of phosphoric acid, synthesis method and application | |
| CN116216647B (en) | Method for preparing anhydrous hydrogen fluoride green by using aqueous hydrofluoric acid through multistage sulfuric acid analysis method | |
| CN109134215B (en) | Production method for preparing trimethyl orthoformate by liquid metal sodium slag method | |
| CN1317268C (en) | 2,6-dimethylpyridine preparation method | |
| CN111606822A (en) | Method for recovering acidic DMF (dimethyl formamide) in sucralose production | |
| CN112047857B (en) | Preparation method of 6-aminocapronitrile | |
| CN1357545A (en) | Prepn of alpha-acetyl-gamma butyrolactone | |
| CN112661179B (en) | Preparation method of high-purity alumina | |
| CN111003699A (en) | Method for producing feed-grade calcium hydrophosphate and co-producing industrial-grade calcium chloride by hydrochloric acid method | |
| CN1209329C (en) | Method for producing double pentaerythritol | |
| CN103992199A (en) | Method for extracting highly pure beta-methylnaphthalene from coal tar wash oil | |
| CN111269110B (en) | Post-treatment method of pivalic acid synthesis reaction liquid | |
| CN113735152B (en) | Method for removing entrained alcohol in aluminum hydroxide slurry | |
| CN109179329B (en) | Deiodination method for producing anhydrous hydrogen fluoride from phosphoric acid by-product fluosilicic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |