CN112875661A - Production method of electronic grade yellow phosphorus - Google Patents
Production method of electronic grade yellow phosphorus Download PDFInfo
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- CN112875661A CN112875661A CN202110178388.4A CN202110178388A CN112875661A CN 112875661 A CN112875661 A CN 112875661A CN 202110178388 A CN202110178388 A CN 202110178388A CN 112875661 A CN112875661 A CN 112875661A
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- yellow phosphorus
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- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 230000009920 chelation Effects 0.000 claims abstract description 3
- 238000010668 complexation reaction Methods 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 8
- 238000002955 isolation Methods 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 15
- 238000003860 storage Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 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 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/04—Purification of phosphorus
- C01B25/047—Purification of phosphorus of yellow phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to the technical field of phosphorus chemical industry, and particularly relates to a production method for removing impurities from yellow phosphorus and purifying the yellow phosphorus into electronic-grade yellow phosphorus. The method comprises the steps of mixing and stirring industrial yellow phosphorus and polyphosphoric acid under the condition of isolating oxygen, settling and separating to obtain electronic grade yellow phosphorus with the content of 99.999% -99.99999%, wherein the principle is that metal elements, semimetal elements and organic matters in the yellow phosphorus are removed by utilizing the complexation and chelation of the polyphosphoric acid to obtain ultrapure yellow phosphorus, and one or more strong oxidants such as hydrogen peroxide, nitric acid and sulfuric acid are added into the polyphosphoric acid. The recovery rate of the yellow phosphorus obtained by the production method of the invention reaches more than 94 percent, and the method has safe operation, simple flow, is beneficial to industrialization, and has practicability and good economic benefit.
Description
Technical Field
The invention belongs to the technical field of phosphorus chemical industry, and particularly relates to a production method for removing impurities from yellow phosphorus and purifying the yellow phosphorus into electronic-grade yellow phosphorus.
Background
Yellow phosphorus, also called white phosphorus, has molecular formula P4, molecular weight 124.08, relative density of 1.82(20 deg.C), melting point of 44.1 deg.C, boiling point of 280 deg.C, and is white to light yellow brittle waxy solid. Yellow phosphorusIs an important basic chemical raw material, industrial yellow phosphorus is produced by an electric furnace method, and the product purity is generally 99.95 percent. The yellow phosphorus contains more metal elements, semimetal elements and organic impurities, so that the application of the yellow phosphorus in the semiconductor industry and the electronic industry is influenced, and the requirement of the production of high-purity electronic grade phosphoric acid on the purity of raw materials cannot be met in the production of the electronic grade phosphoric acid. The yellow phosphorus mainly contains metal elements such as calcium, magnesium, iron, aluminum, potassium, sodium, titanium, vanadium, chromium, cadmium, copper, nickel, lead, tin, zinc, antimony, manganese, cobalt, gallium and the like, semimetal elements mainly contain silicon, sulfur, arsenic, bismuth, boron, carbon and the like, organic substances mainly contain phenols, anthracene, tar, polyatomic polycyclic aromatic hydrocarbon and the like (commonly called oil component), wherein the most impurities are arsenic and organic substances, the next most impurities are iron, nickel, copper, zinc and antimony, and the total content of other impurities is 10-9An order of magnitude. The high-purity electronic grade yellow phosphorus is mainly obtained by purifying industrial yellow phosphorus, and the purifying method mainly comprises a chemical purifying method and a physical purifying method. The chemical method is generally used for the refining process of low-arsenic yellow phosphorus, the arsenic removal rate is high, but impurity ions brought by chemical reagents are difficult to remove in the refining process, the process for separating the chemical reagents is complex and difficult, and devices for purifying the yellow phosphorus by the chemical method of an aqueous phase oxidation method or an organic solvent extraction method to reach the electronic grade requirement have the defects of more types of the added chemical reagents, more brought impurity ions, more washing times, large treatment capacity of residual liquid, complex separation process of the solvent, long flow, low recovery rate of phosphorus and the like. The electromagnetic method for preparing high-purity yellow phosphorus (electronic-grade yellow phosphorus) purely by adopting a physical method has no industrial device yet.
The high-purity yellow phosphorus refining technology in China is promoted and developed in recent years due to rapid development of the electronic industry, but the yield of the high-purity yellow phosphorus is far from meeting the requirement of the domestic market, the high-purity yellow phosphorus still depends on import, the proportion of industrial yellow phosphorus, intermediate products and final products in developed foreign industries is usually 1:3:5, 1:1.5:0.8 in China, a large-scale production device for the high-purity yellow phosphorus is not provided, the requirement of industrial development in China cannot be met, and the development of the low-cost, short-flow, safe and reliable high-purity yellow phosphorus production technology is the requirement of the phosphorus chemical industry at present.
Polyphosphoric acidThe acid is called PPA for short, also called polyphosphoric acid, and is a mixture of phosphoric acids with different polymerization degrees. The general molecular formula is as follows: hn+2PnO3n+1. The pure anhydrous polyphosphoric acid is colorless, transparent and sticky liquid at normal temperature, is easy to wet, can be mixed with water and hydrolyzed into orthophosphoric acid, and is not crystallized and corrosive. 115% of polyphosphoric acid containing 83.2% of P2O5The relative density was 2.09g/cm3The boiling point is 856 ℃. The density of phosphorus pentoxide with a content of 72.46% (100% polyphosphoric acid) was 1.87g/cm3(20 ℃ C.), a phosphorus pentoxide content of 86.96% (120% polyphosphoric acid) and a density of 2.099g/cm3(25℃)。
The polyphosphoric acid is mixed phosphoric acid consisting of orthophosphoric acid, various polymerized phosphoric acids and a small amount of metaphosphoric acid and polymetaphosphoric acid, compared with orthophosphoric acid, the polyphosphoric acid not only has different concentrations, but also has a plurality of special properties, and can be used as a catalyst, a complexing agent, a chelating agent and the like and also has the function of mixing an oxidizing agent. Polyphosphoric acid can complex and chelate metal elements and metal ions in solution, and organic matters form chelate so as to be stably present in acid.
Disclosure of Invention
The invention aims to solve the technical problems of long process, high risk, high investment, high cost, difficult operation and the like in the existing yellow phosphorus purification technology, provides a method for producing high-purity electronic-grade yellow phosphorus by combining physical purification and chemical purification of yellow phosphorus, and provides an electronic-grade yellow phosphorus phosphate raw material with low cost, short process, easy operation and good quality for industrially producing electronic-grade phosphoric acid.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the method is characterized in that industrial yellow phosphorus and polyphosphoric acid are mixed and stirred in a reactor under the condition of oxygen isolation, the characteristics of the complexation capacity and the chelation capacity of the polyphosphoric acid on metal elements and organic matters are utilized to complex and chelate the metal elements and the organic matters in the yellow phosphorus, and the density difference of two mediums of the polyphosphoric acid and the yellow phosphorus is utilized to carry out sedimentation separation on the mixture of the industrial yellow phosphorus and the polyphosphoric acid under the condition of oxygen isolation to obtain the ultra-pure electronic grade yellow phosphorus.
Preferably, the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 72.46-86.96 wt%, namely polyphosphoric acid with corresponding phosphoric acid concentration of 100-120 wt%, namely polyphosphoric acid molecular formula Hn+2PnO3n+1Wherein n is 1-14.
Preferably, a strong oxidant is added in the reaction of the industrial yellow phosphorus and the polyphosphoric acid, the mass of the strong oxidant is 0-20% of that of the polyphosphoric acid, and the mass of the strong oxidant is more preferably 1-20% of that of the polyphosphoric acid; more preferably, the strong oxidant is a strong oxidant such as peroxide, strong acid and the like, and more preferably, the strong oxidant is one or more of strong oxidants such as hydrogen peroxide, nitric acid, sulfuric acid and the like, so that the complexing and chelating time can be further shortened.
Preferably, the mass ratio of the industrial yellow phosphorus to the mixed polyphosphoric acid containing the strong oxidant is 1: 0.05-0.9.
Preferably, the reactor for industrial yellow phosphorus and polyphosphoric acid is a closed reactor isolated from air, such as a stirring reaction kettle, a tubular reactor, a micro-reactor and the like; more preferably, the oxygen-insulating condition is not only a closed reactor, but also includes insulating measures such as filling inert gas such as nitrogen, argon, helium and the like or mixed gas thereof, and also includes insulating measures such as vacuum pumping and the like.
Preferably, the mixing and stirring temperature of the industrial yellow phosphorus and the polyphosphoric acid is 45-80 ℃, and the mixing and stirring time is 0.5-3 h.
Preferably, the settling separation temperature of the industrial yellow phosphorus and the polyphosphoric acid is 45-80 ℃, and the settling separation time is 0.5-3 h.
Preferably, the method can remove more than 99% of impurities such as metal elements, semimetal elements, organic matters and the like in the industrial yellow phosphorus, the purity of the obtained electronic-grade yellow phosphorus is 99.999% -99.99999%, and the yield of the yellow phosphorus is 94% -99%.
Preferably, the specific operation of the method comprises the following steps:
(1) if the strong oxidant exists, uniformly mixing the polyphosphoric acid with a certain concentration and the strong oxidant with a certain concentration to obtain mixed polyphosphoric acid;
(2) under the condition of isolating oxygen, putting the mixed industrial yellow phosphorus and the polyphosphoric acid obtained in the step (1) into a reaction kettle according to a certain mass ratio (if the mixed industrial yellow phosphorus and the polyphosphoric acid do not contain a strong oxidant, putting the industrial yellow phosphorus and the polyphosphoric acid with a certain concentration into the reaction kettle according to a certain mass ratio), and stirring for a certain time at a certain temperature to obtain a mixture;
(3) and feeding the mixture into a separator under the condition of isolating oxygen, and settling and separating at a certain temperature for a certain time to obtain the electronic-grade yellow phosphorus.
The yellow phosphorus and the polyphosphoric acid are mutually insoluble, the density of the yellow phosphorus and the polyphosphoric acid is different, the density of the polyphosphoric acid is greater than that of the yellow phosphorus, and the polyphosphoric acid has good natural settling separation performance. Strong oxidants such as hydrogen peroxide, nitric acid, sulfuric acid and the like are added into polyphosphoric acid and do not react, phosphoric acid and oxides produced by the reaction of the oxidants and yellow phosphorus and impurities in the yellow phosphorus are only dissolved in the polyphosphoric acid or are chelated by the polyphosphoric acid, so that the method has better implementation and operability, short production flow, less investment and easy realization of industrialization, and has a promotion effect on the electronic grade yellow phosphorus and electronic grade phosphoric acid industry in China.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a production method of ultra-pure electronic grade yellow phosphorus, which utilizes the characteristic that polyphosphoric acid can be used as a catalyst, a complexing agent and a chelating agent, and the characteristic that polyphosphoric acid can complex and chelate metal elements, metal ions and organic matters in a solution to form a complex, a chelate and the like so as to stably exist in acid, and utilizes the characteristic that polyphosphoric acid can be mixed with a strengthening agent such as hydrogen peroxide, nitric acid, sulfuric acid and the like without changing the performances of the respective agents to remove impurities such as metal elements, semimetal elements, organic matters and the like in industrial yellow phosphorus. The method utilizes physical characteristics of substances and adopts mild chemical reaction measures, has better implementation and operability, short production flow, low investment cost, easy realization of industrialization, greatly reduces the operation risk, and has promotion effect on the industries of electronic grade yellow phosphorus and electronic grade phosphoric acid in China.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
Example 1:
a method for producing electronic grade yellow phosphorus comprises the following steps of mixing and stirring industrial yellow phosphorus and polyphosphoric acid in a reactor under the condition of oxygen isolation, complexing and chelating metal elements and organic matters in the yellow phosphorus by utilizing the characteristics of complexing ability and chelating ability of the polyphosphoric acid to the metal elements and the organic matters, and settling and separating a mixture of the industrial yellow phosphorus and the polyphosphoric acid under the condition of oxygen isolation by utilizing the density difference of two mediums of the polyphosphoric acid and the yellow phosphorus to obtain the ultra-pure electronic grade yellow phosphorus, wherein the specific operation steps are as follows:
(1) and uniformly mixing polyphosphoric acid with the concentration of 120% and hydrogen peroxide with the concentration of 50% in a stirring tank, wherein the mass of the added hydrogen peroxide is 20% of that of the polyphosphoric acid, so as to obtain the mixed polyphosphoric acid containing hydrogen peroxide. Wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 86.96%, namely polyphosphoric acid with corresponding phosphoric acid concentration of 120%, and the mass concentration of the mixed polyphosphoric acid is 100%;
(2) putting industrial yellow phosphorus and mixed polyphosphoric acid containing hydrogen peroxide into a stirring reaction kettle according to the mass ratio of 1:0.9 under the condition of nitrogen protection, and mixing and stirring for 3 hours at the temperature of 45 ℃; wherein, the purity of the industrial yellow phosphorus is 99.95 percent;
(3) after mixing and stirring are finished, conveying a mixture of polyphosphoric acid and yellow phosphorus to a settling separator with nitrogen protection, settling and separating for 3 hours at 60 ℃ under the nitrogen protection, conveying the separated yellow phosphorus to a yellow phosphorus storage tank by using a pump to obtain the ultra-pure electronic grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic grade yellow phosphorus is 99.9994%, and the yield is 97.6%.
Example 2:
a production method of electronic grade yellow phosphorus comprises the following specific operation steps:
(1) uniformly mixing polyphosphoric acid with the concentration of 115% and nitric acid with the concentration of 68% in a stirring tank, wherein the mass of the added nitric acid is 10% of that of the polyphosphoric acid, and obtaining mixed polyphosphoric acid containing nitric acid. Wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 83.32%, namely polyphosphoric acid with corresponding phosphoric acid concentration of 115%, and the mass concentration of the mixed polyphosphoric acid is 104.5%;
(2) putting industrial yellow phosphorus and mixed polyphosphoric acid containing nitric acid into a stirring reaction kettle according to the mass ratio of 1:0.10 under the protection of nitrogen, and mixing and stirring for 2 hours at 60 ℃; wherein, the content of industrial yellow phosphorus is 99.96 percent;
(3) after mixing and stirring are finished, conveying a mixture of polyphosphoric acid and yellow phosphorus to a settling separator with nitrogen protection, settling and separating for 3 hours at 60 ℃ under the nitrogen protection, conveying the separated yellow phosphorus to a yellow phosphorus storage tank by using a pump to obtain the ultra-pure electronic grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic grade yellow phosphorus is 99.99997%, and the yield is 98.4%. .
Example 3:
a production method of electronic grade yellow phosphorus comprises the following specific operation steps:
(1) and uniformly mixing polyphosphoric acid with the concentration of 100% and sulfuric acid with the concentration of 98% in a stirring tank, wherein the mass of the added sulfuric acid is 1% of that of the polyphosphoric acid, and obtaining the mixed polyphosphoric acid containing sulfuric acid. Wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 72.46 percent, namely polyphosphoric acid with corresponding phosphoric acid concentration of 100 percent; the mass concentration of the mixed polyphosphoric acid is 99 percent;
(2) putting industrial yellow phosphorus and mixed polyphosphoric acid containing sulfuric acid into a microreactor according to the mass ratio of 1:0.5 under the protection of nitrogen, and mixing and stirring for 0.5h at 80 ℃; wherein, the content of industrial yellow phosphorus is 99.94%;
(3) after mixing and stirring are finished, conveying a mixture of polyphosphoric acid and yellow phosphorus to a settling separator with nitrogen protection, settling and separating for 0.5h at 80 ℃ under the nitrogen protection, conveying the separated yellow phosphorus to a yellow phosphorus storage tank by using a pump to obtain the ultra-pure electronic grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic grade yellow phosphorus is 99.9995%, and the yield is 94%.
Example 4:
a production method of electronic grade yellow phosphorus comprises the following specific operation steps:
(1) conveying industrial yellow phosphorus and polyphosphoric acid into a microreactor according to a mass ratio of 1:0.6 under the protection of nitrogen, and reacting at 60 ℃; wherein, the content of industrial yellow phosphorus is 99.96 percent; wherein the polyphosphoric acid is polyphosphoric acid with phosphorus pentoxide content of 83.32%; i.e. polyphosphoric acid with a corresponding phosphoric acid concentration of 115%;
(2) conveying a mixture of polyphosphoric acid and yellow phosphorus from the microreactor into a settling separator with nitrogen protection, settling and separating for 2 hours at 60 ℃ under the nitrogen protection, conveying the separated yellow phosphorus into a yellow phosphorus storage tank by using a pump to obtain ultra-pure electronic-grade yellow phosphorus, wherein purified water in the yellow phosphorus storage tank plays a role in isolating oxygen, the purity of the electronic-grade yellow phosphorus is 99.9999%, and the yield is 98%. .
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A production method of electronic grade yellow phosphorus is characterized in that industrial yellow phosphorus and polyphosphoric acid are mixed and stirred in a reactor under the condition of oxygen isolation, the characteristics of the complexation capacity and the chelation capacity of the polyphosphoric acid on metal elements and organic matters are utilized to complex and chelate the metal elements and the organic matters in the yellow phosphorus, and the density difference of two mediums of the polyphosphoric acid and the yellow phosphorus is utilized to carry out sedimentation separation on the mixture of the industrial yellow phosphorus and the polyphosphoric acid under the condition of oxygen isolation to obtain the electronic grade yellow phosphorus.
2. The method for producing electronic grade yellow phosphorus according to claim 1, wherein an oxidant is further added in the reaction of the industrial yellow phosphorus and the polyphosphoric acid, and the mass of the oxidant is 0-20% of that of the polyphosphoric acid.
3. The method for producing electronic grade yellow phosphorus according to claim 2, wherein the oxidant is one or more of hydrogen peroxide, nitric acid or sulfuric acid.
4. The method for producing electronic grade yellow phosphorus according to claim 2, wherein the mass ratio of the industrial yellow phosphorus to the mixed polyphosphoric acid containing the oxidant is 1: 0.05-0.9.
5. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the polyphosphoric acid is polyphosphoric acid with a phosphoric acid mass concentration of 100-120%.
6. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the reactor for industrial yellow phosphorus and polyphosphoric acid is a closed reactor isolated from air, and comprises a stirring reaction kettle, a tubular reactor and a micro-reactor.
7. The method of claim 1, wherein the isolation of oxygen is performed by filling inert gas such as nitrogen, argon, helium, or a mixture thereof.
8. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the mixing and stirring temperature of the industrial yellow phosphorus and the polyphosphoric acid is 45-80 ℃, and the mixing and stirring time is 0.5-3 h.
9. The method for producing electronic grade yellow phosphorus according to claim 1, wherein the settling separation temperature of industrial yellow phosphorus and polyphosphoric acid is 45-80 ℃ and the settling separation time is 0.5-3 h.
10. The method for producing electronic grade yellow phosphorus according to any one of claims 1 to 9, characterized in that the method can remove more than 99% of metallic elements, semimetallic elements and organic impurities in industrial yellow phosphorus, and the obtained electronic grade yellow phosphorus has a purity of 99.999% -99.99999% and a yield of 94-99%.
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| CN101289175A (en) * | 2008-06-10 | 2008-10-22 | 昆明理工大学 | Process for removing organics in yellow phosphorus |
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| CN101289175A (en) * | 2008-06-10 | 2008-10-22 | 昆明理工大学 | Process for removing organics in yellow phosphorus |
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