CN111517299A - Method for deep purification and dearsenification of industrial phosphoric acid - Google Patents
Method for deep purification and dearsenification of industrial phosphoric acid Download PDFInfo
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- CN111517299A CN111517299A CN202010583232.XA CN202010583232A CN111517299A CN 111517299 A CN111517299 A CN 111517299A CN 202010583232 A CN202010583232 A CN 202010583232A CN 111517299 A CN111517299 A CN 111517299A
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- Prior art keywords
- phosphoric acid
- dearsenification
- reaction
- coordination material
- coordination
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000000746 purification Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000012066 reaction slurry Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- NMRHZSSSJCTMME-UHFFFAOYSA-N OP(O)(O)=O.[AsH3] Chemical compound OP(O)(O)=O.[AsH3] NMRHZSSSJCTMME-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims 2
- 239000000825 pharmaceutical preparation Substances 0.000 claims 1
- 229940127557 pharmaceutical product Drugs 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 abstract description 21
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 21
- 239000012535 impurity Substances 0.000 abstract description 6
- 229940127554 medical product Drugs 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 description 37
- 239000000047 product Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 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 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry 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
- 239000002893 slag Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910052958 orpiment Inorganic materials 0.000 description 1
- 239000002245 particle Substances 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for deep evolution, purification and dearsenification of industrial phosphoric acid, which utilizes the characteristic that a strong coordination group of a new functional coordination material has strong affinity to small molecular impurities to apply the new functional coordination material to the deep purification and dearsenification of the industrial phosphoric acid. Mixing the new coordination material and industrial phosphoric acid according to a certain proportion, adjusting the stirring speed, reacting for 1-3 h at 40-80 ℃, filtering the reaction slurry through a microporous filter after the reaction is finished, wherein the filtered phosphoric acid is a deep purification dearsenification phosphoric acid product, and the dearsenification coordination material can be used for development and application of production raw materials of medical products after being treated by subsequent steps such as water washing and the like. The test result shows that the arsenic content in the industrial phosphoric acid can be reduced to below 300ppb, and the arsenic removal rate can reach more than 90%.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a novel method for deep purification and dearsenification of industrial phosphoric acid.
Background
At present, the wet-process phosphoric acid purification arsenic removal method comprises the following methods: 1. removing arsenic by chemical precipitation. Na2S can be used as a common dearsenization agent for dearsenization treatment of wet-process phosphoric acid. The principle is that H2S is generated by the reaction of Na2S and H3PO4, S2-in H2S and As3+ form As2S3 precipitate, and therefore the purpose of removing arsenic is achieved. However, the byproduct H2S can cause environmental pollution and seriously harm the life of operators. Sodium and sulfur plasma are introduced while arsenic is removed, so that the problem of new impurity pollution is brought to the deep purification of industrial phosphoric acid and the product quality. Meanwhile, arsenic slag generated after arsenic removal is in an irregular colloidal state and is suspended in concentrated phosphoric acid, and the arsenic slag is difficult to filter due to factors such as small particle size, wide distribution, low solid content and the like. 2. And (4) dearsenization by a crystallization method. The crystallization method is to separate out phosphoric acid or phosphate in the form of crystals from a system, and has the advantages of high efficiency, economy, small influence on the environment and the like compared with methods such as a chemical precipitation method, a solvent extraction method and the like, but the crystallization method is relatively complex to operate, and the complete separation of the crystallized crystals and a mother solution is difficult, which restricts the development of the technology to a certain extent. This way, it will be very time and labor consuming, affecting yield and productivity. 3. Ion exchange resin method. The ion exchange method is to treat wet-process phosphoric acid by using strong acid ion exchange resin to remove most of cationic impurities, but the method has the disadvantages of great difficulty in resin regeneration, low overall efficiency, large usage amount, high total cost and low market application prospect. 4. Electrodialysis method. The core equipment of the process is an ion exchange membrane, and impurities in the phosphoric acid solution are filtered under the stimulation of current by utilizing the selectivity of the ion exchange membrane to obtain the product. The method is still in a research stage at present, the main difficult points to be overcome are the selection of an ion exchange membrane and the influence of current density on the ion exchange process, the use environment is harsh, and the method can only be used for purifying dilute phosphoric acid at present. Has not been applied to industrial production on a large scale.
Disclosure of Invention
The invention aims to solve the problem of providing a new method for removing arsenic by wet-process purification of phosphoric acid aiming at the defects of the existing technique for removing arsenic by wet-process purification of phosphoric acid.
The above object of the present invention is achieved by the following technical solutions:
a new method for removing arsenic from phosphoric acid by wet purification is characterized in that arsenic in phosphoric acid is captured in a targeted manner through a coordination functional group of a new coordination material, so that the effect of deep purification and arsenic removal of industrial phosphoric acid is achieved; the method mainly comprises the following steps:
mixing a coordination material and industrial phosphoric acid according to a certain proportion, wherein the mass ratio of the coordination material to the industrial phosphoric acid is as follows: 1/1000-1/10000, wherein the coordination material is a porous functional coordination material, the loading capacity of functional groups is more than or equal to 0.9mmol/g, and the content of industrial purified arsenic phosphate is more than 1 ppm;
stirring and reacting for 0.1-10 h at 30-90 ℃, filtering the reaction slurry through a microporous filter after the reaction is finished, and obtaining the filtered phosphoric acid which is the deeply purified dearsenified phosphoric acid product. The product meets the food-grade phosphoric acid standard.
In the method, the coordination material adopted for dearsenization is a porous functional coordination material, and the loading capacity of the functional group is between 0.9 and 2.0 mmol/g.
In the method, the reaction stirring speed is controlled to be 200-300 r/min.
In the method, the temperature in the dearsenization reaction process is controlled to be 40-80 ℃.
In the method, the dearsenization reaction time, namely the retention time, is controlled to be 1-3 h.
The aperture of the filter element of the microporous filter is less than or equal to 50 mu m.
In the method, the coordination material after arsenic removal can be used for development and application of production raw materials of medical products after being washed by water and treated by conventional subsequent steps.
The inventor points out that: the functional coordination material of the invention has already applied for related invention patents, and the patent names are as follows: a compound and an adsorbing material synthesized by the compound are disclosed in the patent numbers: 201810147151.8.
the invention utilizes the characteristic that the functional coordination new material has stronger affinity to small molecular impurities to stably and efficiently capture arsenic in the wet-process purified phosphoric acid on the coordination new material so as to achieve the effect of efficiently and deeply removing arsenic. The novel functional coordination material belongs to a high-efficiency porous material, so that the wet-process purification phosphoric acid is optimized in flowing, the arsenic in the wet-process purification phosphoric acid can be removed to the maximum extent by the aid of the oversized surface area, other impurities cannot be introduced while the arsenic is removed, toxic and harmful gases cannot be generated, the operation is simple and safe, the occupied space of equipment is small, and the novel functional coordination material has good economic benefits and environmental benefits. The novel material is adopted to carry out the deep dearsenification of the wet-method purified phosphoric acid, and related literature reports are not seen yet, so that the technology has a good market application prospect.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Example 1.
Weighing 1g of new coordination material, mixing the new coordination material with industrial phosphoric acid according to the ratio of 1: 10000, and adjusting the stirring speed, wherein the reaction stirring speed is controlled at 300 r/min. The reaction time was controlled at 3h and the reaction temperature was controlled at 60 ℃. After the reaction is finished, the reaction slurry is filtered by a microporous filter, and the aperture of a filter element of the microporous filter is 50 mu m. The filtered phosphoric acid is a deep-purification dearsenified phosphoric acid product, the phosphoric acid is detected by ICP-MS, the arsenic content of the phosphoric acid is 206ppb, and the product meets the requirements of food-grade phosphoric acid standard (GB 1886.15-2015).
Example 2.
Weighing 1g of new coordination material, mixing the new coordination material with industrial phosphoric acid according to the ratio of 1: 1000, and adjusting the stirring speed, wherein the reaction stirring speed is controlled at 200 r/min. The reaction time was controlled to 2h and the reaction temperature was controlled to 80 ℃. After the reaction is finished, the reaction slurry is filtered by a microporous filter, and the aperture of a filter element of the microporous filter is 30 mu m. The filtered phosphoric acid is a deep-purification dearsenified phosphoric acid product, the phosphoric acid is detected by ICP-MS, the arsenic content of the phosphoric acid is 89ppb, and the product meets the requirements of food-grade phosphoric acid standard (GB 1886.15-2015).
Claims (7)
1. A method for deeply purifying and dearsenifying industrial phosphoric acid is characterized by comprising the following steps: the method mainly comprises the following steps:
mixing a coordination material and industrial phosphoric acid according to a certain proportion, wherein the mass ratio of the coordination material to the industrial phosphoric acid is as follows: 1/1000-1/10000, wherein the coordination material is a porous functional coordination material, the loading capacity of functional groups is more than or equal to 0.9mmol/g, and the content of industrial purified arsenic phosphate is more than 1 ppm;
stirring and reacting for 0.1-10 h at 30-90 ℃, filtering the reaction slurry through a microporous filter after the reaction is finished, and obtaining the filtered phosphoric acid which is the deeply purified dearsenified phosphoric acid product.
2. The method of claim 1, wherein the coordination material for dearsenification is a porous functional coordination material with a functional group loading of between 0.9 and 2.0 mmol/g.
3. The method of claim 1, wherein the reaction stirring speed is controlled to 200 to 300 r/min.
4. The method according to claim 1, wherein the temperature during the dearsenification reaction is controlled to be 40-80 ℃.
5. The method according to claim 1, wherein the dearsenification reaction time, i.e. the retention time, is controlled to be 1-3 h.
6. The method as claimed in claim 1, wherein after the reaction is completed, the filtration is carried out by means of microfiltration, the pore size of the filter element of the microfiltration machine being less than or equal to 50 μm.
7. The method according to claim 1, wherein the coordination material after dearsenification is used for development and application of raw materials for production of pharmaceutical products after being washed by water and treated by conventional subsequent steps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010583232.XA CN111517299A (en) | 2020-06-23 | 2020-06-23 | Method for deep purification and dearsenification of industrial phosphoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010583232.XA CN111517299A (en) | 2020-06-23 | 2020-06-23 | Method for deep purification and dearsenification of industrial phosphoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111517299A true CN111517299A (en) | 2020-08-11 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010583232.XA Pending CN111517299A (en) | 2020-06-23 | 2020-06-23 | Method for deep purification and dearsenification of industrial phosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111517299A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120009112A1 (en) * | 2010-07-09 | 2012-01-12 | Nippon Chemical Industrial Co., Ltd. | Method for preparing high-purity elemental phosphorus and method for preparing high-purity phosphoric acid |
| CN102992289A (en) * | 2012-12-27 | 2013-03-27 | 广西明利化工有限公司 | Method for producing food-grade phosphoric acid |
| CN103011111A (en) * | 2012-12-27 | 2013-04-03 | 广西明利化工有限公司 | Continuous arsenic removal reaction method |
| US9688559B1 (en) * | 2015-06-12 | 2017-06-27 | Pattison Sand Company | Multistage process for removal of phosphorus, fluoride, and arsenic species from water via complexation and solubility control |
| CN110142033A (en) * | 2018-02-12 | 2019-08-20 | 贵州金之键高科技材料有限公司 | A kind of compound and the adsorbent material using the compound synthesis |
-
2020
- 2020-06-23 CN CN202010583232.XA patent/CN111517299A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120009112A1 (en) * | 2010-07-09 | 2012-01-12 | Nippon Chemical Industrial Co., Ltd. | Method for preparing high-purity elemental phosphorus and method for preparing high-purity phosphoric acid |
| CN102992289A (en) * | 2012-12-27 | 2013-03-27 | 广西明利化工有限公司 | Method for producing food-grade phosphoric acid |
| CN103011111A (en) * | 2012-12-27 | 2013-04-03 | 广西明利化工有限公司 | Continuous arsenic removal reaction method |
| US9688559B1 (en) * | 2015-06-12 | 2017-06-27 | Pattison Sand Company | Multistage process for removal of phosphorus, fluoride, and arsenic species from water via complexation and solubility control |
| CN110142033A (en) * | 2018-02-12 | 2019-08-20 | 贵州金之键高科技材料有限公司 | A kind of compound and the adsorbent material using the compound synthesis |
Non-Patent Citations (1)
| Title |
|---|
| 李孟 等: "《给水处理原理》", 31 December 2013, 武汉理工大学出版社 * |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20200811 |