CN103497265B - A kind of electron-level phosphoric acid refines the preparation method with resin sorbent - Google Patents
A kind of electron-level phosphoric acid refines the preparation method with resin sorbent Download PDFInfo
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- CN103497265B CN103497265B CN201310486139.7A CN201310486139A CN103497265B CN 103497265 B CN103497265 B CN 103497265B CN 201310486139 A CN201310486139 A CN 201310486139A CN 103497265 B CN103497265 B CN 103497265B
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Abstract
The invention provides refining resin sorbent of a kind of electron-level phosphoric acid and preparation method thereof.Described preparation technology adopts commercially available macropore Chloromethyl polystyrene and urotropine to carry out amination reaction, obtains primary amine groups resin, then by primary amine groups resin and difluoro Mono Chloro Acetic Acid (C
2hClF
2o
2) carry out carboxylic acid reaction, described resin sorbent can be obtained.Resin sorbent prepared by technique of the present invention has good adsorption effect, can remove the dominant cation impurity A s brought in phosphoric acid production simply efficiently
3+, Fe
3+, Ca
2+, Mg
2+, Cr
2+, K
+, Na
+with heavy metal, then through using the negative resin exchange resin adsorpting anion S0 of OH-type
4 2-, NO
3 -, Cl
-, the purity of electron-level phosphoric acid can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of resin sorbent, particularly a kind of electron-level phosphoric acid refines the preparation method with resin sorbent.
Background technology
Electron-level phosphoric acid belongs to high-purity phosphoric acid, and high-purity phosphoric acid is the ultra-pure chemical reagent of one that electron trade uses, and belongs to one of microelectronics chemical products, and a few countries such as the Jin You U.S., Japan, Korea S can be produced in the world at present.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, purifying must be carried out, reduce its foreign matter content further.
Thermal phosphoric acid is by Rock Phosphate (72Min BPL) under quartz exists, and with reductive coke in stove, the element phosphor obtained after Phosphate ore reduction is sublimed into steam condition effusion, then element phosphor burning is made it to be oxidized into Vanadium Pentoxide in FLAKES, absorbs and be hydrolyzed into phosphoric acid with water.Thermal phosphoric acid is higher relative to the few quality product of phosphoric acid by wet process foreign matter content, but in phosphorous acid production by BEP process, due to the impact of the various external factor such as yellow phosphorus raw materials quality and production technique, and the wherein impurity mainly As that brings into of yellow phosphorus raw material
3+and heavy metal, it is Fe that production environment affects the impurity brought into
3+, Ca
2+, Mg
2+, Cr
2+, K
+, Na
+, the major impurity therefore brought in usual 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 using strong-acid ion exchange resin to carry out phosphoric acid, this process is based on the H on H type Zeo-karb
+the metal ion in phosphoric acid can be replaced, and OH
-the negatively charged ion of type then can replace sulfate ion, chlorion and nitrate ion in phosphoric acid, thus reaches the object of purification.
Such as, Zhang Hongying is in " investigative test of ion-exchange purification removal of impurities preparing phosphoric acid " literary composition, provide a kind of technique making spent ion exchange resin purification of phosphoric acid, comprise and will be processed into the solution of dihydrogen phosphate by strong acid cation exchange resin column bed, the impurity absorption such as the calcium in solution, magnesium, barium are separated with phosphoric acid on resin, thus obtain the chemical pure phosphoric acid that content reaches 85%, but this process resin easy in inactivation, 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 problem to be difficult to solve at present, the adsorption effect of the resin sorbent such as, adopted in above prior art is undesirable, particularly undesirable to the taking-up effect of metal ion, thus electron-level phosphoric acid product cannot be obtained, 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 refining resin sorbent of a kind of electronic-grade (MOS level) phosphoric acid and preparation method thereof.
The present invention adopts commercially available macropore Chloromethyl polystyrene, through amination, macropore Chloromethyl polystyrene ball and urotropine is reacted, obtains primary amine groups resin, then by primary amine groups resin and difluoro Mono Chloro Acetic Acid (C
2hClF
2o
2) carry out carboxylic acid reaction, generate fluorine-containing aminocarboxylic acid type resin, i.e. resin sorbent of the present invention.
Described electron-level phosphoric acid refines the preparation method with resin sorbent, comprises the following steps:
1). amination reaction
Macropore Chloromethyl polystyrene and urotropine react, and obtain primary amine resin;
By weight, in stirring tank, 100 parts of macropore Chloromethyl polystyrene balls are added, 50-100 part urotropine (vulkacit H), 50-100 part water, preferably 60 parts of water; Be warming up to 60-100 DEG C to react, be preferably 80 DEG C; Insulation 5-15h, is preferably 10h; Filter, blowing is weighed, and obtains primary amine groups resin, and structural formula is shown in formula (1):
2). carboxylic acid reaction
By weight, in stirring tank, add step 1) 100 parts of primary amine groups resins, 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 DEG C to react, be preferably 60 DEG C; Insulation 30-100h, be preferably 40h, obtain the refining resin sorbent of electron-level phosphoric acid of the present invention, its sodium form 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 the selectivity of heavy metal ion is far above alkaline-earth metal and alkalimetal ion, and it is similar to EDTA to the selectivity of metal ion.Fluorine element hale electronics effect, the bond energy between carbonyl and-OH base is weakened, makes this resin all have good adsorption effect to the metal ion that valency is 1,2 and 3 valency, the dominant cation impurity A s that therefore can bring in selective removal phosphorous acid production by BEP
3+, Fe
3+, Ca
2+, Mg
2+, Cr
2+, K
+, Na
+and heavy metal, the phosphoric acid solution after resin sorbent process of the present invention re-uses OH
-the resin anion(R.A) exchange resin adsorpting anion S0 of type
4 2-, NO
3 -, Cl
-, namely can reach electronic-grade (MOS level) phosphoric acid purity.
Embodiment
Following examples are only further illustrate the present invention, are not restriction the scope of protection of the invention.
Macropore Chloromethyl polystyrene, 1%DVB is cross-linked, and Pu Zhen bio tech ltd, Shanghai produces.
Embodiment 1
1). amination reaction
Macropore Chloromethyl polystyrene and urotropine react, and obtain primary amine groups resin.
By weight, in stirring tank, 100 parts of macropore Chloromethyl polystyrene balls are added, 70 parts of vulkacit Hs, 60 parts of water; Be warming up to 80 DEG C to react; Insulation 10h, filter, blowing is weighed, and obtains primary amine groups resin;
2). carboxylic acid reaction
By weight, in stirring tank, add step 1) 100 parts of primary amine groups resins, 300 parts of difluoro Mono Chloro Acetic Acids, and 300 parts of water, be warming up to 60 DEG C and react; Insulation 40h, obtains 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 DEG C, 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 DEG C, 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 water weight part is 100, and temperature of reaction is 50 DEG C, 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 water weight part is 400, and temperature of reaction is 80 DEG C, 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 D001 Zeo-karb as sorbent material, Kairui Chemical Co., Ltd. produces, and production code member is KR-10.
Comparing embodiment 11
Use 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 φ 18mm*2000mm glass exchange column two, wet method loads resin sorbent prepared by 500mL technique of the present invention, industrial phosphoric acid is crossed post with the speed of 500mL/h, detects the mass percentage of metal ion in filtered solution, calculate metal ion total removal rate %.Herein, metal ion total removal rate %=(in raw material metal ion mass percentage-filtered solution in the mass percentage of metal ion) mass percentage × 100% of metal ion in/raw material.
Wherein, the impurity composition of industrial phosphoric acid is 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 | Metal ion total removal rate % |
| 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: product treatment industrial phosphoric acid metal ion total removal rate data 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 the dominant cation impurity A s brought in phosphoric acid production simply efficiently
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 using OH
-the resin anion(R.A) exchange resin adsorpting anion S0 of type
4 2-, NO
3 -, Cl
-, the purity of electron-level phosphoric acid can be obtained.Relative to common cation exchange resins such as D001,001*7 in prior art, resin sorbent advantages of good adsorption effect prepared by technique of the present invention, Metal Ion Selective Electrode clearance is high, corresponding prolongation in work-ing life, has good market outlook.
Claims (5)
1. electron-level phosphoric acid refines the preparation method with resin sorbent, and it is characterized in that, described preparation method comprises the following steps:
1) amination reaction
Macropore Chloromethyl polystyrene and vulkacit H react, and obtain primary amine groups resin;
By weight, in stirring tank, 100 parts of macropore Chloromethyl polystyrene balls are added, 50-100 part vulkacit H, 50-100 part water; Be warming up to 60-100 DEG C to react; Insulation 5-15h; Filter, blowing is weighed, and obtains primary amine groups resin, and structural formula is shown in formula (1):
2) carboxylic acid reaction
By weight, in stirring tank, add step 1) the described primary amine groups resin 100 parts that obtains, 200-400 part difluoro Mono Chloro Acetic Acid (C
2hClF
2o
2), and 100-400 part water; Be warming up to 50-80 DEG C to react; Insulation 30-100h, obtain the refining resin sorbent of described electron-level phosphoric acid, its sodium form product structure formula is shown in formula (2):
2. electron-level phosphoric acid according to claim 1 refines the preparation method with resin sorbent, it is characterized in that, step 1) in water be 60 parts, temperature of reaction is 80 DEG C, insulation 10h.
3. the electron-level phosphoric acid described in claim 1 or 2 refines the preparation method with resin sorbent, it is characterized in that, step 2) in water be 300 parts, temperature of reaction is 60 DEG C, insulation 40h.
4. the resin sorbent that in claim 1-3, arbitrary described preparation method prepares.
5. the application of resin sorbent described in claim 4 in refining electron-level phosphoric acid technique.
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| 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 |
| CN113101906B (en) * | 2021-05-14 | 2022-11-25 | 重庆大学 | Amino-functionalized polystyrene material and application thereof 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 |
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| DE10049807A1 (en) * | 2000-10-09 | 2002-04-18 | Bayer Ag | Use of monodisperse ion exchangers for arsenic / antimony removal |
| CN101691213B (en) * | 2009-10-10 | 2011-07-20 | 武汉工程大学 | Novel process for removing metal ions in wet-process phosphoric acid |
| CN103159888B (en) * | 2013-03-29 | 2015-08-05 | 南京大学 | Primary amine groups resin of a kind of acrylic acid series Large Copacity trapping cupric ion and preparation method thereof |
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Address after: 062451 Cangzhou City, Hebei Province Hejian City Gu Xian Xiang Xi Liu Zhuang Applicant after: Kai Rui environmental protection Science and Technology Co., Ltd. Address before: 062451, Hebei City, Cangzhou Province Hejian City West Zhuang Industrial Zone Applicant before: Kairui Chemical Co., Ltd. |
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