CN113845123A - Method for recovering potassium fluoborate from azolin intermediate wastewater - Google Patents
Method for recovering potassium fluoborate from azolin intermediate wastewater Download PDFInfo
- Publication number
- CN113845123A CN113845123A CN202111283629.8A CN202111283629A CN113845123A CN 113845123 A CN113845123 A CN 113845123A CN 202111283629 A CN202111283629 A CN 202111283629A CN 113845123 A CN113845123 A CN 113845123A
- Authority
- CN
- China
- Prior art keywords
- wastewater
- potassium
- fluorine
- potassium fluoborate
- recovering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 21
- 239000011591 potassium Substances 0.000 title claims abstract description 21
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N 1-Pyrroline Chemical compound C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- AEKNYBWUEYNWMJ-QWOOXDRHSA-N Pramiconazole Chemical compound O=C1N(C(C)C)CCN1C1=CC=C(N2CCN(CC2)C=2C=CC(OC[C@@H]3O[C@](CN4N=CN=C4)(CO3)C=3C(=CC(F)=CC=3)F)=CC=2)C=C1 AEKNYBWUEYNWMJ-QWOOXDRHSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000001103 potassium chloride Substances 0.000 claims abstract description 7
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- -1 fluorine ions Chemical class 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 21
- 239000011737 fluorine Substances 0.000 abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000005219 brazing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OFFFOVCCGHKJES-UHFFFAOYSA-N 4-methylthiadiazole Chemical compound CC1=CSN=N1 OFFFOVCCGHKJES-UHFFFAOYSA-N 0.000 description 1
- HSHGZXNAXBPPDL-HZGVNTEJSA-N 7beta-aminocephalosporanic acid Chemical compound S1CC(COC(=O)C)=C(C([O-])=O)N2C(=O)[C@@H]([NH3+])[C@@H]12 HSHGZXNAXBPPDL-HZGVNTEJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/121—Borates of alkali metal
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The invention discloses a method for recovering potassium fluoborate from azolin intermediate wastewater. The method is mainly used for recovering fluorine in the azoline intermediate wastewater. The recovery is carried out according to the following steps: adding an aqueous solution of inorganic base into the azoline intermediate wastewater, adjusting the pH value of the wastewater to be neutral, adding quantitative solid potassium chloride into the wastewater, stirring the mixture to react for a certain time, filtering and drying the mixture to obtain a target product, namely potassium fluoborate. The method reduces the content of fluorine ions in the fluorine-containing wastewater, simultaneously recycles the byproduct potassium fluoborate, reduces the treatment difficulty of the fluorine-containing wastewater, realizes the recycling of wastes, and is an effective case for promoting green chemistry.
Description
Technical Field
The invention relates to a method for recovering potassium fluoborate from azolin intermediate wastewater.
Technical Field
In the preparation process of ceftizolid acid, 7-aminocephalosporanic acid reacts with methyl thiadiazole, and BF is used3The complex catalyzes the synthesis of an intermediate. The catalyst adopted in the prior production process is BF3Complexes, BF3Difficult to recover and can only be hydrolyzed after the reaction, which makes the production waste liquid contain unreacted raw material, BF3And boric acid and about 5% F produced by hydrolysis-If the fluorine-containing waste liquid is not treated, the environment can be seriously polluted, the fluorine-containing waste liquid is directly discharged as waste water to be environment-friendly in the prior art, no reasonable treatment process is available, useful components in the waste water cannot be recovered, and the treatment cost is high.
Disclosure of Invention
The invention discloses a method for recovering potassium fluoborate from azolin intermediate wastewater. The method is mainly used for recovering fluorine in the azoline intermediate wastewater. The method reduces the content of fluorine ions in the fluorine-containing wastewater, simultaneously recycles the byproduct potassium fluoborate, reduces the treatment difficulty of the fluorine-containing wastewater, and realizes the recycling of wastes. The reaction formula is as follows:
the invention provides a method for recovering potassium fluoborate from azolin intermediate wastewater, which comprises the following steps:
(1) adding an aqueous solution of inorganic base into the azoline intermediate wastewater, adjusting the pH value of the wastewater to be neutral,
(2) adding crystallization auxiliary agent into the solution, stirring and reacting,
(3) filtering and drying to obtain the potassium fluoborate.
Wherein, in the method for recovering potassium fluoborate in the step (1), the inorganic alkali is selected from one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate, and sodium hydroxide and potassium hydroxide are preferred.
Wherein, in the method for recovering potassium fluoborate in the step (1), the concentration of the inorganic alkaline water solution is 0.2-1.0 mol/L.
Wherein the pH value is adjusted to be 6.5-7.5 in the step (1).
Wherein, the crystallization auxiliary agent in the step (2) is potassium chloride.
Wherein the stirring reaction time in the step (2) is 0.5-3 hours.
Wherein the stirring reaction in the step (2) is controlled at the temperature of 10-40 ℃, preferably 20-30 ℃.
Wherein the potassium fluoborate obtained in the step (3) is white to off-white solid, and the content is more than 95 percent.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) reduces the content of fluorinion in the fluorine-containing wastewater, and reduces the treatment cost of the fluorine-containing high-concentration wastewater by 20 percent compared with the prior art.
(2) Changing waste into valuable, realizing the recycling of the by-product potassium fluoborate and being used as a fluxing agent for hot welding and brazing.
Detailed Description
Example 1
Under the condition of stirring, controlling the temperature to be 23 ℃, dropwise adding 0.25mol/L sodium hydroxide solution into 1000mL of azoline intermediate wastewater (containing 5% of fluorine), adjusting the pH value to be 6.74, adding 34.0g of potassium chloride, slowly stirring for 30 minutes, filtering, reducing the fluorine content to 0.4%, sending the filtrate to environment-friendly treatment, washing a filter cake with 100mL of purified water, and drying to obtain 34.28g of white solid, wherein the purity of potassium fluoborate is 96.8% and the water content is 1.2%.
Example 2
Under the condition of stirring, controlling the temperature to be 28 ℃, dropwise adding 0.5mol/L sodium hydroxide solution into 1000mL of azoline intermediate wastewater (containing 5% of fluorine), adjusting the pH value to be 6.96, adding 33.1g of potassium chloride, slowly stirring for 45 minutes, filtering, reducing the fluorine content to be below 0.6%, carrying out environment-friendly treatment, washing a filter cake with 100mL of purified water, and drying to obtain 31.44g of white solid, wherein the purity of potassium fluoborate is 98.2% and the water content is 1.4%.
Example 3
Under the condition of stirring, controlling the temperature to be 42 ℃, dropwise adding 0.4mol/L potassium hydroxide solution into 1000mL of azoline intermediate wastewater (containing 5% of fluorine), adjusting the pH value to be 7.12, adding 34.4g of potassium chloride, slowly stirring for 30 minutes, filtering, reducing the fluorine content to 0.5%, sending the filtrate to environment-friendly treatment, washing a filter cake with 100mL of purified water, and drying to obtain 28.66g of white solid, wherein the purity of the potassium fluoborate is 97.6%, and the water content is 1.1%.
Example 4
Under the condition of stirring, controlling the temperature to be 45 ℃, dropwise adding 0.25mol/L sodium hydroxide solution into 1000mL of azoline intermediate wastewater (containing 5% of fluorine), adjusting the pH value to be 7.36, adding 30.3g of potassium chloride, slowly stirring for 60 minutes, filtering, reducing the fluorine content to 0.6%, sending to environment-friendly treatment, washing a filter cake with 100mL of purified water, and drying to obtain 27.47g of white solid, wherein the purity of potassium fluoborate is 98.8%, and the water content is 1.4%.
The recovered potassium fluoborate meets the welding quality requirements, is used as a fluxing agent for hot welding and brazing, and is sold to welding factories.
Claims (10)
1. A method for recovering potassium fluoborate from azolin intermediate wastewater comprises the following steps:
(1) adding an aqueous solution of inorganic base into the azoline intermediate wastewater, adjusting the pH value of the wastewater to be neutral,
(2) adding crystallization auxiliary agent into the solution, stirring and reacting,
(3) filtering and drying to obtain the potassium fluoborate.
2. The method according to claim 1, wherein the inorganic base in step (1) is selected from one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate.
3. The method according to claim 2, wherein the inorganic base in step (1) is selected from the group consisting of sodium hydroxide and potassium hydroxide.
4. The method according to claim 1, wherein the concentration of the aqueous inorganic base in the step (1) is 0.2 to 1.0 mol/L.
5. The method according to claim 1, wherein the pH is adjusted in step (1) to a range of 6.5 to 7.5.
6. The method according to claim 1, wherein the crystallization aid in step (2) is potassium chloride.
7. The method of claim 1, wherein the stirring reaction time in step (2) is 0.5 to 3 hours.
8. The method of claim 1, wherein the temperature of the stirring reaction in step (2) is controlled to be 10-40 ℃.
9. The method according to claim 8, wherein the stirring reaction in step (2) is controlled at a temperature of 20-30 ℃.
10. The method according to claim 1, wherein the potassium fluoroborate obtained in step (3) is a white to off-white solid having a content of 95% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111283629.8A CN113845123A (en) | 2021-11-01 | 2021-11-01 | Method for recovering potassium fluoborate from azolin intermediate wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111283629.8A CN113845123A (en) | 2021-11-01 | 2021-11-01 | Method for recovering potassium fluoborate from azolin intermediate wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113845123A true CN113845123A (en) | 2021-12-28 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111283629.8A Pending CN113845123A (en) | 2021-11-01 | 2021-11-01 | Method for recovering potassium fluoborate from azolin intermediate wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113845123A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114572993A (en) * | 2022-05-07 | 2022-06-03 | 齐鲁工业大学 | Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001040112A1 (en) * | 1999-12-03 | 2001-06-07 | Kemira Agro Oy | Production of two alkali metal salts by a combined ion exchange and crystallisation process |
| CN102963999A (en) * | 2012-10-08 | 2013-03-13 | 江苏德峰药业有限公司 | Technology for treatment of fluorine-boron-containing wastewater during Ceftezole acid preparation |
| CN109354034A (en) * | 2018-11-22 | 2019-02-19 | 山东罗欣药业集团股份有限公司 | A kind of fluorine-containing waste liquid borofluoride exchange crystallization recovery technology of cephalo |
-
2021
- 2021-11-01 CN CN202111283629.8A patent/CN113845123A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001040112A1 (en) * | 1999-12-03 | 2001-06-07 | Kemira Agro Oy | Production of two alkali metal salts by a combined ion exchange and crystallisation process |
| CN102963999A (en) * | 2012-10-08 | 2013-03-13 | 江苏德峰药业有限公司 | Technology for treatment of fluorine-boron-containing wastewater during Ceftezole acid preparation |
| CN109354034A (en) * | 2018-11-22 | 2019-02-19 | 山东罗欣药业集团股份有限公司 | A kind of fluorine-containing waste liquid borofluoride exchange crystallization recovery technology of cephalo |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114572993A (en) * | 2022-05-07 | 2022-06-03 | 齐鲁工业大学 | Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate |
| CN114572993B (en) * | 2022-05-07 | 2022-07-26 | 齐鲁工业大学 | Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate |
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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 |
Application publication date: 20211228 |
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| RJ01 | Rejection of invention patent application after publication |