CN103497265A - Method for preparing resin adsorbent for refining electronic grade phosphoric acid - Google Patents
Method for preparing resin adsorbent for refining electronic grade phosphoric acid Download PDFInfo
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- CN103497265A CN103497265A CN201310486139.7A CN201310486139A CN103497265A CN 103497265 A CN103497265 A CN 103497265A CN 201310486139 A CN201310486139 A CN 201310486139A CN 103497265 A CN103497265 A CN 103497265A
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- phosphoric acid
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- electron
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000007670 refining Methods 0.000 title claims abstract description 13
- 239000003463 adsorbent Substances 0.000 title abstract 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- OAWAZQITIZDJRB-UHFFFAOYSA-N 2-chloro-2,2-difluoroacetic acid Chemical compound OC(=O)C(F)(F)Cl OAWAZQITIZDJRB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 10
- 229920002223 polystyrene Polymers 0.000 claims abstract description 10
- 238000005576 amination reaction Methods 0.000 claims abstract description 5
- 239000002594 sorbent Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 150000001450 anions Chemical class 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 3
- -1 As<3+> Substances 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract 4
- 230000002745 absorbent Effects 0.000 abstract 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract 1
- 210000001691 amnion Anatomy 0.000 abstract 1
- 238000006473 carboxylation reaction Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 14
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical class OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a resin absorbent for refining electronic grade phosphoric acid and a method for preparing the resin adsorbent. The method includes enabling commercially available macroporous chloromethyleted polystyrene and commercially available urotropine to carry out amination so as to obtain amino-based resin; enabling the amnion-based resin and difluoro-chloroacetic acid (C<2>HClF<2>O<2>) to carry out carboxylation reaction so as to obtain the resin absorbent. The resin absorbent and the method have the advantages that the resin absorbent is excellent in adsorption effect, main cation impurities such as As<3+>, Fe<3+>, Ca<2+>, Mg<2+>, Cr<2+>, K<+>, Na<+> and metal which are brought into phosphoric acid production can be easily and efficiently removed, and SO<4><2->, NO<3><-> and Cl<-> anions can be adsorbed by OH<-> anion resin and exchange resin, so that the electronic grade phosphoric acid with the required purity can be acquired.
Description
Technical field
The present invention relates to a kind of preparation method of resin sorbent, particularly the refining preparation method with resin sorbent of a kind of electron-level phosphoric acid.
Background technology
Electron-level phosphoric acid belongs to high-purity phosphoric acid, and high-purity phosphoric acid is a kind of ultra-pure chemical reagent that electron trade is used, and belongs to one of microelectronics chemistry product, only has in the world at present a few countries such as the U.S., Japan, Korea S to produce.Electron-level phosphoric acid is widely used in the microelectronics industry such as super large-scale integration, big screen LCD, is mainly used in wet-cleaned and the wet etching of chip.And the thermal phosphoric acid of current industrial production to be applied to electronic industry, and must carry out purifying, further reduce its foreign matter content.
Thermal phosphoric acid be by Rock Phosphate (72Min BPL) under quartz exists, in stove, with the coke reduction, the element phosphor obtained after Phosphate ore reduction is sublimed into steam condition and overflows, then the element phosphor burning is made it to be oxidized into Vanadium Pentoxide in FLAKES, water absorbs and is hydrolyzed into phosphoric acid.Thermal phosphoric acid is higher with respect to the few quality product of phosphoric acid by wet process foreign matter content, but, in the thermal phosphoric acid production process, due to the impact of the various external factor such as yellow phosphorus raw materials quality and production technique, the impurity that wherein the yellow phosphorus raw material is brought into is mainly As
3+and heavy metal, the impurity that the production environment impact is brought into is Fe
3+, Ca
2+, Mg
2+, Cr
2+, K
+, Na
+, the major impurity of bringing in therefore common phosphoric acid production comprises As
3+, Fe
3+, Ca
2+, Mg
2+, Cr
2+, K
+, Na
+and heavy metal, and S0
4 2-, NO
3 -, Cl
-deng negatively charged ion.
In prior art, the main refinement treatment of using strong-acid ion exchange resin to carry out phosphoric acid, the H+ that this processing is based on H type Zeo-karb can replace the metal ion in phosphoric acid, the negatively charged ion of OH-type can replace sulfate ion, chlorion and the nitrate ion in phosphoric acid, thereby reaches the purpose of purification.
For example, Zhang Hongying is in " investigative test of ion-exchange purification removal of impurities preparing phosphoric acid " literary composition, a kind of technique that makes the spent ion exchange resin purification of phosphoric acid is provided, comprise that the solution that will be processed into dihydrogen phosphate is by the strong acid cation exchange resin column bed, make the impurity absorption such as calcium in solution, magnesium, barium on resin and separate with phosphoric acid, reach 85% chemical pure phosphoric acid thereby obtain content, but the easy inactivation of this process resin, work-ing life is short.
In sum, using ion exchange method refining crude phosphoric acid to obtain high-purity phosphoric acid still has a lot of technical problems to be difficult to solve at present, for example the adsorption effect of the resin sorbent of above available technology adopting is undesirable, particularly undesirable to the taking-up effect of metal ion, thereby can't obtain the electron-level phosphoric acid product, so be difficult to so far carry out suitability for industrialized production.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of electronic-grade (MOS level) phosphoric acid refining with resin sorbent and preparation method thereof.
The present invention adopts commercially available macropore chloromethyl polystyrene, through amination, macropore chloromethyl polystyrene spheres is reacted with urotropine, obtains the primary amine groups resin, then by primary amine groups resin and difluoro Mono Chloro Acetic Acid (C
2hClF
2o
2) carry out the carboxylic acid reaction, generate fluorine-containing aminocarboxylic acid type resin, i.e. resin sorbent of the present invention.
The refining preparation method with resin sorbent of described electron-level phosphoric acid comprises the following steps:
1). amination reaction
Macropore chloromethyl polystyrene reacts with urotropine, obtains primary amine resin;
By weight, add 100 parts of macropore chloromethyl polystyrene spheres in stirring tank, 50-100 part urotropine (vulkacit H), 50-100 part water, preferably 60 parts of water; Be warming up to 60-100 ℃ and reacted, be preferably 80 ℃; Insulation 5-15h, be preferably 10h; Filter, blowing is weighed, and obtains the primary amine groups resin, and structural formula is shown in formula (1):
2). the carboxylic acid reaction
By weight, add 100 parts of primary amine groups resins of step 1) in stirring tank, 200-400 part difluoro Mono Chloro Acetic Acid (C
2hClF
2o
2), and 100-400 part water, be preferably 300 parts of water; Be warming up to 50-80 ℃ and reacted, be preferably 60 ℃; Insulation 30-100h, be preferably 40h, obtains that electron-level phosphoric acid of the present invention is refining uses resin sorbent, and its sodium type product structure formula is shown in formula (2):
Beneficial effect of the present invention:
Resin sorbent of the present invention is a kind of resin of fluorine-containing imine oxalic acid functional group, and to the selectivity of heavy metal ion, far above alkaline-earth metal and alkalimetal ion, its selectivity to metal ion is similar to EDTA.Fluorine element hale the electronics effect, make carbonyl and-bond energy between the OH base weakens, and makes the metal ion that this resin is 1,2 and 3 valencys to valency all have good adsorption effect, the main cation impurity As brought in therefore can the production of selective removal thermal phosphoric acid
3+, Fe
3+, Ca
2+, Mg
2+, Cr
2+, K
+, Na
+and heavy metal, the phosphoric acid solution after resin sorbent of the present invention is processed re-uses the resin anion(R.A) exchange resin adsorpting anion S0 of OH-type
4 2-, NO
3 -, Cl
-, can reach electronic-grade (MOS level) phosphoric acid purity.
Embodiment
Following examples are only to further illustrate the present invention, are not the restriction the scope of protection of the invention.
Macropore chloromethyl polystyrene, 1%DVB is crosslinked, and the bio tech ltd production of shaking is composed in Shanghai.
Embodiment 1
1). amination reaction
Macropore chloromethyl polystyrene reacts with urotropine, obtains the primary amine groups resin.
By weight, add 100 parts of macropore chloromethyl polystyrene spheres in stirring tank, 70 parts of vulkacit Hs, 60 parts of water; Being warming up to 80 ℃ is reacted; Insulation 10h, filter, and blowing is weighed, and obtains the primary amine groups resin;
2). the carboxylic acid reaction
By weight, add 100 parts of primary amine groups resins of step 1) in stirring tank, 300 parts of difluoro Mono Chloro Acetic Acids, and 300 parts of water, be warming up to 60 ℃ and reacted; Insulation 40h, obtain product of the present invention.Be numbered KR-1.
Embodiment 2
In step 1, water and vulkacit H weight part are 50, and temperature of reaction is 60 ℃, insulation 5h; The other the same as in Example 1.Products obtained therefrom is numbered KR-2.
Embodiment 3
In step 1, water and vulkacit H weight part are 100, and temperature of reaction is 100 ℃, insulation 15h the other the same as in Example 1.Products obtained therefrom is numbered KR-3.
Embodiment 4
In step 2, difluoro Mono Chloro Acetic Acid weight part is 200, and the water weight part is 100, and temperature of reaction is 50 ℃, insulation 30h; The other the same as in Example 1.Products obtained therefrom is numbered KR-4.
Embodiment 5
In step 2, difluoro Mono Chloro Acetic Acid weight part is 200, and the water weight part is 400, and temperature of reaction is 80 ℃, insulation 100h; The other the same as in Example 2.Products obtained therefrom is numbered KR-5.
Embodiment 6
In step 2, difluoro Mono Chloro Acetic Acid weight part is 200, the other the same as in Example 3.Products obtained therefrom is numbered KR-6.
Embodiment 7
In step 2, difluoro Mono Chloro Acetic Acid weight part is 400, the other the same as in Example 1.Products obtained therefrom is numbered KR-7.
Embodiment 8
In step 2, difluoro Mono Chloro Acetic Acid weight part is 400, the other the same as in Example 2.Products obtained therefrom is numbered KR-8.
Embodiment 9
In step 2, difluoro Mono Chloro Acetic Acid weight part is 400, the other the same as in Example 3.Products obtained therefrom is numbered KR-9.
Comparing embodiment 10
Use the D001 Zeo-karb as sorbent material, Kairui Chemical Co., Ltd. produces, and production code member is KR-10.
Comparing embodiment 11
Use the 001*7 Zeo-karb as sorbent material, Kairui Chemical Co., Ltd. produces, and production code member is KR-11.
Embodiment 12
Cross the experiment of post adsorbing metal ions
Get two of φ 18mm*2000mm glass exchange columns, the wet method resin sorbent prepared by 500mL technique of the present invention of packing into, industrial phosphoric acid is crossed to post with the speed of 500mL/h, detect the quality percentage composition of metal ion in filtered solution, calculate the total clearance % of metal ion.Herein, the quality percentage composition of metal ion * 100% in the quality percentage composition of metal ion in the quality percentage composition-filtered solution of metal ion in the total clearance %=(of metal ion raw material)/raw material.
Wherein, the impurity of industrial phosphoric acid forms in Table 1:
| Element | Al | As | Ca | Fe | Ga | Li | Mg | Heavy metal |
| Content % | 0.38 | 27 | 28 | 6.8 | 1.7 | 7.9 | 12 | 1.1 |
Table 1: industrial phosphoric acid impurity forms
Detected result is in Table 2:
| Numbering | The total clearance % of metal ion |
| KR-1 | 97 |
| KR-2 | 99 |
| KR-3 | 96 |
| KR-4 | 91 |
| KR-5 | 92 |
| KR-6 | 94 |
| KR-7 | 99 |
| KR-8 | 99 |
| KR-9 | 97 |
| KR-10 | 67 |
| KR-11 | 43 |
Table 2: the total clearance data of product treatment industrial phosphoric acid metal ion of the present invention
Visible by above-mentioned post adsorption experiment excessively, resin sorbent prepared by technique of the present invention has good adsorption effect, can remove simply efficiently the main cation impurity As brought in phosphoric acid production
3+, Fe
3+, Ca
2+, Mg
2+, Cr
2+, K
+, Na
+and heavy metal, the phosphoric acid solution after the resin sorbent prepared by technique of the present invention absorption is again through being used the resin anion(R.A) exchange resin adsorpting anion S0 of OH-type
4 2-, NO
3 -, Cl
-, purity that can electron gain level phosphoric acid.With respect to D001 in prior art, the common cation exchange resins such as 001*7, resin sorbent advantages of good adsorption effect prepared by technique of the present invention, the Metal Ion Selective Electrode clearance is high, and corresponding prolongation in work-ing life, have market outlook preferably.
Claims (5)
1. the refining preparation method with resin sorbent of electron-level phosphoric acid, is characterized in that, described preparation method comprises the following steps:
1) amination reaction
Macropore chloromethyl polystyrene reacts with vulkacit H, obtains the primary amine groups resin;
By weight, add 100 parts of macropore chloromethyl polystyrene spheres in stirring tank, 50-100 part vulkacit H, 50-100 part water; Being warming up to 60-100 ℃ is reacted; Insulation 5-15h; Filter, blowing is weighed, and obtains the primary amine groups resin, and structural formula is shown in formula (1):
2) carboxylic acid reaction
By weight, add 100 parts of primary amine groups resins of step 1) in stirring tank, 200-400 part difluoro Mono Chloro Acetic Acid (C
2hClF
2o
2), and 100-400 part water; Being warming up to 50-80 ℃ is reacted; Insulation 30-100h, obtain that described electron-level phosphoric acid is refining uses resin sorbent, and its sodium type product structure formula is shown in formula (2):
2. the refining preparation method with resin sorbent of electron-level phosphoric acid claimed in claim 1, is characterized in that, in step 1), water is 60 parts, and temperature of reaction is 80 ℃, insulation 10h.
3. the refining preparation method with resin sorbent of the described electron-level phosphoric acid of claim 1 or 2, is characterized in that step 2) in water be 300 parts, temperature of reaction is 60 ℃, insulation 40h.
4. the resin sorbent that in claim 1-3, arbitrary described preparation method prepares.
5. the application of the described resin sorbent of claim 4 in refining electron-level phosphoric acid technique.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109399591A (en) * | 2018-12-26 | 2019-03-01 | 江苏新宏大集团有限公司 | A kind of preparation method of purification of wet process phosphoric acid |
| CN113101906A (en) * | 2021-05-14 | 2021-07-13 | 重庆恩斯特龙通用航空技术研究院有限公司 | Amino functionalized polystyrene material and its application in adsorption of methyl orange |
| CN113546446A (en) * | 2021-07-28 | 2021-10-26 | 江西东江环保技术有限公司 | Method for recovering copper in BCC synthetic mother liquor by using cationic resin |
| CN116332151A (en) * | 2023-04-14 | 2023-06-27 | 衢州市九洲化工有限公司 | A kind of preparation method of sodium difluorophosphate |
| CN116356349A (en) * | 2023-04-17 | 2023-06-30 | 华东理工大学 | A method for preparing electronic-grade phosphoric acid and regenerating resin in situ by combining resin-electrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109399591A (en) * | 2018-12-26 | 2019-03-01 | 江苏新宏大集团有限公司 | A kind of preparation method of purification of wet process phosphoric acid |
| CN109399591B (en) * | 2018-12-26 | 2021-06-29 | 江苏新宏大集团有限公司 | Preparation method of purified wet-process phosphoric acid |
| CN113101906A (en) * | 2021-05-14 | 2021-07-13 | 重庆恩斯特龙通用航空技术研究院有限公司 | Amino functionalized polystyrene material and its application in adsorption of methyl orange |
| CN113546446A (en) * | 2021-07-28 | 2021-10-26 | 江西东江环保技术有限公司 | Method for recovering copper in BCC synthetic mother liquor by using cationic resin |
| CN116332151A (en) * | 2023-04-14 | 2023-06-27 | 衢州市九洲化工有限公司 | A kind of preparation method of sodium difluorophosphate |
| CN116356349A (en) * | 2023-04-17 | 2023-06-30 | 华东理工大学 | A method for preparing electronic-grade phosphoric acid and regenerating resin in situ by combining resin-electrolysis |
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