CN111762920A - Method for reducing concentration of potassium ions in acetic acid waste liquid - Google Patents
Method for reducing concentration of potassium ions in acetic acid waste liquid Download PDFInfo
- Publication number
- CN111762920A CN111762920A CN202010702543.3A CN202010702543A CN111762920A CN 111762920 A CN111762920 A CN 111762920A CN 202010702543 A CN202010702543 A CN 202010702543A CN 111762920 A CN111762920 A CN 111762920A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- acetic acid
- concentration
- potassium ions
- acid waste
- 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.)
- Granted
Links
Classifications
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
Abstract
The invention relates to a method for reducing the concentration of potassium ions in acetic acid waste liquid, which comprises the following steps: 1) placing original acetic acid waste liquid A in a container, and introducing HCl gas in the stirring process; 2) stopping introducing HCl gas and standing for a certain time when the concentration of potassium ions in the acetic acid waste liquid is less than 4g/L to obtain waste liquid B; 3) filtering the waste liquid B to obtain filtrate C; 4) and introducing the filtrate C into a container filled with anion exchange resin for treatment, and reducing the concentration of Cl ions to obtain a waste liquid D treated by the anion exchange resin. The concentration of potassium ions in the waste liquid D treated by the method is less than 4g/L, the concentration of Cl ions is not more than 400ppm, the concentration of potassium ions in the waste liquid D is greatly reduced, the waste liquid D can be used as a rectification raw material, the stable operation of a rectification system is facilitated, the recovery rate of useful components (such as propionic acid) in the waste liquid is improved, the amount of the waste liquid is greatly reduced, and the environmental protection benefit is remarkable.
Description
Technical Field
The invention relates to the technical field of acetic acid synthesis, in particular to a method for reducing the concentration of potassium ions in acetic acid waste liquid.
Background
In the industrial process for synthesizing acetic acid by using methanol at low pressure and liquid phase, a germanium/iodine catalyst system is used, and the waste liquid of a finished product tower of a rectification system has complex components. The current treatment methods mainly comprise three methods: firstly, the waste liquid and the combustible gas are discharged by means of combustion, and due to the strong corrosivity of the waste liquid, the incinerator is difficult to select, high in failure rate after being put into use and not beneficial to environmental protection; secondly, the part of waste liquid is sold at low price, so that the current selling price is greatly reduced and the situation of unmanned purchase appears. With the increasingly strict environmental requirements, the two methods are gradually eliminated. And thirdly, rectification separation, wherein the waste liquid contains a large amount of potassium ions, the concentration of the potassium ions in the acetic acid waste liquid is usually 35-60g/L, heavy components containing the potassium ions in the rectification process easily cause pipeline blockage, and a rectification system is stopped when the heavy components contain the potassium ions seriously. Meanwhile, the rectification efficiency is low, and the recovery rate of acetic acid and propionic acid in the waste liquid is lower than 50%. Therefore, a method capable of reducing the concentration of potassium ions in the acetic acid waste liquid is urgently needed in the market.
Disclosure of Invention
The invention aims to provide a method for reducing the concentration of potassium ions in acetic acid waste liquid, which aims to solve the problems that the high concentration of potassium ions in the acetic acid waste liquid in the prior art easily causes pipeline blockage and even stops a rectification system.
In order to achieve the purpose, the method for reducing the concentration of potassium ions in the acetic acid waste liquid adopts the following technical scheme: a method for reducing the concentration of potassium ions in acetic acid waste liquid comprises the following steps:
1) placing original acetic acid waste liquid A in a container, and introducing HCl gas in the stirring process;
2) stopping introducing HCl gas and standing for a certain time when the concentration of potassium ions in the acetic acid waste liquid is less than 4g/L to obtain waste liquid B;
3) filtering the waste liquid B to obtain filtrate C;
4) and introducing the filtrate C into a container filled with anion exchange resin for treatment, and reducing the concentration of Cl ions to obtain a waste liquid D treated by the anion exchange resin.
The introduction speed of HCl in the step 1) is not more than 1.5L/h.
The standing time in the step 2) is 30-60 min.
The ratio of the molar weight of the HCl gas introduced in the step 1) to the molar weight of the potassium ions in the acetic acid waste liquid is 1.005-1.055.
The ratio of the molar weight of the HCl gas introduced in the step 1) to the molar weight of potassium ions in the acetic acid waste liquid is 1.005.
The anion exchange resin in the step 4) adopts Hydrogen Carbonate (HCO)3-) anion exchange resin.
Adsorbing saturated anion exchange resin with NaHCO3The solution and pure water are regenerated.
The regeneration flow rate is not more than 4L/h, the regeneration time is 10-30min, and then the pure water is used for backwashing for 10-30 min.
The invention has the beneficial effects that: the concentration of potassium ions in the waste liquid D treated by the method is less than 4g/L, the concentration of potassium ions in the waste liquid D is greatly reduced, the waste liquid D can be used as a rectification raw material, the stable operation of a rectification system is facilitated, the recovery rate of useful components (such as propionic acid) in the waste liquid is improved, the amount of the waste liquid is greatly reduced, and the environmental protection benefit is remarkable. The concentration of Cl ions in the treated waste liquid is not more than 400ppm, so that the corrosion effect of the waste liquid on equipment is reduced, and the corrosion effect on stainless steel equipment is generated when the concentration of the Cl ions in the solution is more than 400ppm, and the equipment is corroded in the forms of pit corrosion and stress corrosion.
Detailed Description
The embodiment of the method for reducing the concentration of potassium ions in the acetic acid waste liquid comprises the following steps:
1) placing original acetic acid waste liquid A in a container, and introducing HCl gas in the stirring process;
2) stopping introducing HCl gas and standing for a certain time when the concentration of potassium ions in the acetic acid waste liquid is less than 4g/L to obtain waste liquid B;
3) filtering the waste liquid B to obtain filtrate C;
4) and introducing the filtrate C into a container filled with anion exchange resin for treatment, and reducing the concentration of Cl ions to obtain a waste liquid D treated by the anion exchange resin.
The introduction speed of HCl in the step 1) is not more than 1.5L/h.
The stirring time in the step 1) is 5-10 min.
The standing time in the step 2) is 30-60 min.
The ratio of the molar weight of HCl gas introduced into the step 1) to the molar weight of potassium ions in the acetic acid waste liquid is 1.005-1.055, and 1.005 is preferably selected.
The anion exchange resin in the step 4) adopts Hydrogen Carbonate (HCO)3-) anion exchange resin.
Adsorbing saturated anion exchange resin with NaHCO3The solution and pure water are regenerated.
The regeneration flow rate is not more than 4L/h, the regeneration time is 10-30min, and then the pure water is used for backwashing for 10-30 min.
If the Cl ion concentration in the waste liquid D in the step 4) is not less than 400ppm, the resin filling amount or the treatment time needs to be increased until the requirement that the Cl ion concentration in the waste liquid D is not more than 400ppm is met.
Experimental example 1
At present, a certain acetic acid synthesis device in the west of Henan produces 20-30 tons of waste acid per day, wherein the content of acetic acid is about 30-35%, the content of propionic acid is 60-70%, and the concentration of potassium ions is 42 g/L. A rectification separation device is constructed on site, but because metal ions such as potassium ions have high concentration, pipelines are easy to block in the rectification process, and a rectification device cannot normally operate. The sample is taken for treatment, and the effect is good.
The acetic acid waste liquid 2L from this plant was stirred for 5 minutes in a closed vessel equipped with a stirrer. High-purity HCl gas was introduced into the closed vessel at a rate of 1.0L/hr while stirring. And (3) testing and analyzing the potassium ion concentration in the waste acid by adopting a flame photometry, stopping introducing HCl gas (the ratio of the molar weight of the introduced HCl gas to the molar weight of potassium ions in the acetic acid waste liquid is 1.005 by calculation) when the potassium ion concentration is 4g/L, and standing for 30 minutes. Obtaining waste liquid B. And filtering the B to obtain filtrate C. Introducing the filtrate C into a reactor filled with Hydrogen Carbonate (HCO)3 －) And (4) treating the mixture in a container of the anion exchange resin. The effluent D after the treatment of the exchange resin was obtained, and the Cl ion concentration in the effluent D was measured by ion chromatography to be 800 ppm. The resin loading was increased by 1.3 times the original loading and the Cl ion concentration was found to be 300 ppm. At the moment, the concentration of potassium ions in the waste liquid D is obviously reduced, the probability of pipeline blockage is greatly reduced, and the waste liquid D can be used as a rectification raw material.
After 22.1L of waste acid is treated, anion exchange resin is saturated by adsorption, and 8g/L NaHCO is used3The solution was regenerated at a regeneration flow rate of 4L/hr for a regeneration time of 10 minutes, and then backwashed with pure water for 10 minutes. The regenerated washing liquid goes to a sewage treatment system of an enterprise.
Experimental example 2
At present, a certain acetic acid synthesis device in south Henan produces 10-25 tons of waste acid per day, wherein the content of acetic acid is about 40-45%, the content of propionic acid is 50-60%, and the concentration of potassium ions is 58 g/L. The sample is taken for treatment, and the effect is good.
The acetic acid waste liquid 2L from this plant was stirred for 8 minutes in a closed vessel equipped with a stirrer. High-purity HCl gas was introduced into the closed vessel at a rate of 1.5L/hr with stirring. Testing and analyzing the potassium ion concentration in the waste acid by adopting a flame photometry method, stopping introducing HCl gas when the potassium ion concentration is 3.2g/L (by calculation, the ratio of the molar weight of the introduced HCl gas to the molar weight of potassium ions in the acetic acid waste liquid is 1.055, standing for 50 minutes to obtain waste liquid B, filtering B to obtain filtrate C, introducing the filtrate C into a solution containing Hydrogen Carbonate (HCO)3 －) And (4) treating the mixture in a container of the anion exchange resin. The effluent D after the treatment with the exchange resin was obtained, and the Cl ion concentration in the effluent D was measured by ion chromatography to be 330 ppm. At the moment, the concentration of potassium ions in the waste liquid D is obviously reduced, the probability of pipeline blockage is greatly reduced, and the waste liquid D can be used as a rectification raw material.
After 14.0L of waste acid is treated, anion exchange resin is saturated by adsorption, and 8g/L NaHCO is used3The solution was regenerated at a regeneration flow rate of 3.5L/hr for a regeneration time of 26 minutes, and then backwashed with pure water for 18 minutes. The regenerated washing liquid goes to a sewage treatment system of an enterprise.
Example 3
The acetic acid waste liquid sample of example 2 was used.
The acetic acid waste liquid 2L was stirred for 10 minutes in a closed vessel equipped with a stirrer. High-purity HCl gas was introduced into the closed vessel at a rate of 1.2L/hr with stirring. Analyzing potassium ion concentration in waste acid by flame photometry, stopping introducing HCl gas (calculated that the ratio of HCl gas introduction molar weight to potassium ion in acetic acid waste liquid is 1.021) when potassium ion concentration is 3.8g/L, standing for 60min to obtain waste liquid B, filtering to obtain filtrate C, introducing filtrate C into Hydrogen Carbonate (HCO) type solution3 －) And (4) treating the mixture in a container of the anion exchange resin. The effluent D after the treatment of the exchange resin was obtained, and the Cl ion concentration in the effluent D was measured by ion chromatography to be 390 ppm. At the moment, the concentration of potassium ions in the waste liquid D is obviously reduced, the probability of pipeline blockage is greatly reduced, and the waste liquid D can be used as a rectification raw material.
After 14.6L of waste acid is treated, anion exchange resin is saturated by adsorption, and 8g/L NaHCO is used3The solution was regenerated at a regeneration flow rate of 3.0L/hr for 30 minutes, and then backwashed with pure water for 30 minutes. The regenerated washing liquid goes to a sewage treatment system of an enterprise.
Claims (8)
1. A method for reducing the concentration of potassium ions in acetic acid waste liquid is characterized by comprising the following steps:
1) placing original acetic acid waste liquid A in a container, and introducing HCl gas in the stirring process;
2) stopping introducing HCl gas and standing for a certain time when the concentration of potassium ions in the acetic acid waste liquid is less than 4g/L to obtain waste liquid B;
3) filtering the waste liquid B to obtain filtrate C;
4) and introducing the filtrate C into a container filled with anion exchange resin for treatment, and reducing the concentration of Cl ions to obtain a waste liquid D treated by the anion exchange resin.
2. The method for reducing the concentration of potassium ions in acetic acid waste liquid according to claim 1, characterized in that: the introduction speed of HCl in the step 1) is not more than 1.5L/h.
3. The method for reducing the concentration of potassium ions in acetic acid waste liquid according to claim 1, characterized in that: the standing time in the step 2) is 30-60 min.
4. The method for reducing the concentration of potassium ions in acetic acid waste liquid according to claim 1, characterized in that: the ratio of the molar weight of the HCl gas introduced in the step 1) to the molar weight of the potassium ions in the acetic acid waste liquid is 1.005-1.055.
5. The method for reducing the concentration of potassium ions in acetic acid waste liquid according to claim 4, characterized in that: the ratio of the molar weight of the HCl gas introduced in the step 1) to the molar weight of potassium ions in the acetic acid waste liquid is 1.005.
6. The method for reducing the concentration of potassium ions in acetic acid waste liquid according to any one of claims 1 to 5, characterized in that: the anion exchange resin in the step 4) adopts Hydrogen Carbonate (HCO)3-) anion exchange resin.
7. The method for reducing the concentration of potassium ions in acetic acid waste liquid according to claim 6, characterized in that: adsorbing saturated anion exchange resin with NaHCO3The solution and pure water are regenerated.
8. The method for reducing the concentration of potassium ions in acetic acid waste liquid according to claim 7, characterized in that: the regeneration flow rate is not more than 4L/h, the regeneration time is 10-30min, and then the pure water is used for backwashing for 10-30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010702543.3A CN111762920B (en) | 2020-07-21 | 2020-07-21 | Method for reducing concentration of potassium ions in acetic acid waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010702543.3A CN111762920B (en) | 2020-07-21 | 2020-07-21 | Method for reducing concentration of potassium ions in acetic acid waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111762920A true CN111762920A (en) | 2020-10-13 |
| CN111762920B CN111762920B (en) | 2023-04-18 |
Family
ID=72728586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010702543.3A Active CN111762920B (en) | 2020-07-21 | 2020-07-21 | Method for reducing concentration of potassium ions in acetic acid waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111762920B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69906203D1 (en) * | 1998-09-08 | 2003-04-30 | Bp Chem Int Ltd | carbonylation |
| KR101204177B1 (en) * | 2011-10-12 | 2012-11-22 | (주)새빗켐 | Method for preparing potassium nitrate using a potassium hydroxide waste solution containing silicon compound and a waste solution containing nitric acid |
| CN107141213A (en) * | 2017-05-24 | 2017-09-08 | 北京三聚环保新材料股份有限公司 | A kind of method of acetic acid synthesis from methanol carbonylation |
| CN107311856A (en) * | 2017-08-13 | 2017-11-03 | 河南省煤气(集团)有限责任公司义马气化厂 | A kind of purification recovery system of acetic acid waste liquid |
| CN109053424A (en) * | 2018-10-31 | 2018-12-21 | 天津中福环保科技股份有限公司 | System and method of the field of new materials from multiple types acetic acid devil liquor recovery purification acetic acid |
| CN110183325A (en) * | 2019-05-07 | 2019-08-30 | 宜昌苏鹏科技有限公司 | A kind of the purification recovery process and device of acetic acid waste liquid |
| CN110357321A (en) * | 2018-04-10 | 2019-10-22 | 华东理工大学 | A method of extracting sylvite from waste water |
-
2020
- 2020-07-21 CN CN202010702543.3A patent/CN111762920B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69906203D1 (en) * | 1998-09-08 | 2003-04-30 | Bp Chem Int Ltd | carbonylation |
| KR101204177B1 (en) * | 2011-10-12 | 2012-11-22 | (주)새빗켐 | Method for preparing potassium nitrate using a potassium hydroxide waste solution containing silicon compound and a waste solution containing nitric acid |
| CN107141213A (en) * | 2017-05-24 | 2017-09-08 | 北京三聚环保新材料股份有限公司 | A kind of method of acetic acid synthesis from methanol carbonylation |
| CN107311856A (en) * | 2017-08-13 | 2017-11-03 | 河南省煤气(集团)有限责任公司义马气化厂 | A kind of purification recovery system of acetic acid waste liquid |
| CN110357321A (en) * | 2018-04-10 | 2019-10-22 | 华东理工大学 | A method of extracting sylvite from waste water |
| CN109053424A (en) * | 2018-10-31 | 2018-12-21 | 天津中福环保科技股份有限公司 | System and method of the field of new materials from multiple types acetic acid devil liquor recovery purification acetic acid |
| CN110183325A (en) * | 2019-05-07 | 2019-08-30 | 宜昌苏鹏科技有限公司 | A kind of the purification recovery process and device of acetic acid waste liquid |
Non-Patent Citations (1)
| Title |
|---|
| 张文峰: "醋酸废液中丙酸的回收", 《醋酸废液中丙酸的回收》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111762920B (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201446726A (en) | Methanol carbonylation system having absorber with multiple solvent options | |
| CN102417263B (en) | Method for processing wastewater from nitrochlorobenzene production | |
| CN101838064A (en) | Method for recycling manganese ion in electrolytic manganese production tail end wastewater | |
| JPS62191800A (en) | Method of processing waste water containing uranium and fluorine | |
| CN101838065B (en) | Method for recycling hexavalent chromium in electrolytic manganese production tail end wastewater | |
| CN101955158B (en) | Recovery treatment process of mercury-containing waste hydrochloric acid | |
| JPH1085743A (en) | Method and apparatus for treating water containing boron | |
| KR101814304B1 (en) | Anion exchanger, mixture of anion exchanger and cation exchanger, mixed bed comprising anion exchanger and cation exchanger, production processes therefor, and method for purifying aqueous hydrogen peroxide solution | |
| CN111392946A (en) | Method for recovering 1,3 cyclohexanedione from wastewater containing 1,3 cyclohexanedione | |
| CN111762920B (en) | Method for reducing concentration of potassium ions in acetic acid waste liquid | |
| JP2007527311A (en) | Biodegradation of oxyanions such as perchlorate ions on ion exchange resins. | |
| CN110668956B (en) | Method for desalting and purifying water phase through water washing extraction in RT base production process | |
| CN111995152A (en) | Method for treating high-concentration wastewater generated in synthesis of anisole from methyl sodium sulfate waste residue | |
| JP2013119487A (en) | Method for treating hydrosilicofluoric acid-containing liquid | |
| NL2029939B1 (en) | Treatment process for purifying chlorine-containing wastewater by crystallization of ammonium salt | |
| CN100417634C (en) | Method of separating and recovering fumaric acid and phthalic acid in fumaric acid preparation wastewater | |
| CN115282939A (en) | Method and system for recycling cobalt and manganese catalysts in high-selectivity iron-removing resin and PTA wastewater | |
| CN109607478A (en) | A kind of technique of step oxidation chlorination hydrogen and hydrogen fluoride gaseous mixture preparing chlorine gas | |
| WO1994020450A1 (en) | Process for the recovery of cyclohexanedicarboxylic acids | |
| JPS5827999B2 (en) | Wet oxidation treatment method for wastewater | |
| CN110548311A (en) | Treatment process for mixed solution containing benzoic acid and acid radical thereof and/or phthalic acid and acid radical thereof | |
| CN217103373U (en) | Mercury-containing wastewater treatment system in chloroethylene production | |
| CN1189408C (en) | Sulfonation effluent treating and resource recovering method for 1,2,4-acid producing process | |
| CN105565416A (en) | Treatment method of chlorobenzene apparatus wastewater | |
| CN213924582U (en) | Phenol purification process units |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |