CN102050471B - Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method - Google Patents
Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method Download PDFInfo
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- CN102050471B CN102050471B CN2010105324475A CN201010532447A CN102050471B CN 102050471 B CN102050471 B CN 102050471B CN 2010105324475 A CN2010105324475 A CN 2010105324475A CN 201010532447 A CN201010532447 A CN 201010532447A CN 102050471 B CN102050471 B CN 102050471B
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Abstract
The invention relates to a method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with a sodium formate method. The method comprises the following steps of: carrying out precise filtration and ultrafiltration on waste sodium hydrosulfite liquid with the sodium formate method to remove insoluble substances and granular impurities in the liquid; and then introducing the liquid into a nanofiltration device for nanofiltration separation, wherein after being evaporated and concentrated, an obtained nanofiltration permeate solution can be used as a raw material of the sodium hydrosulfite and returned to a sodium hydrosulfite production station, and can also be continuously evaporated, concentrated, crystallized, centrifuged and filtered to obtain a sodium formate product of which the purity is higher than 95 percent; and an obtained nanofiltration concentrated solution can be introduced into an evaporator for concentrating and then is crystallized, centrifuged and filtered to obtain a crude sodium sulfite product. The method has the technical advantages of no secondary pollution, high purity of the sodium formate, simple process and easiness for industrial realization, wherein the purity can be up to higher than 95 percent.
Description
Technical field
The present invention relates to the recovery method of sodium formiate and S-WAT in a kind of sodium formate method vat powder waste liquid, particularly a kind of employing nanofiltration carries out separation and purification to the vat powder waste liquid, produces the method for highly purified sodium formiate and thick S-WAT.
Background technology
At present, Domestic Insurance powder production technique has two kinds: zinc powder method and sodium formate method.The sodium formate method constant product quality, throughput is high, low cost of manufacture, the output of the vat powder that this method is produced accounts for 90% of national ultimate production.Sodium formate method is divided into soda processes and Sodium Pyrosulfite method again, the former usefulness more, this method produces a large amount of mother liquors when obtaining the vat powder product, mother liquor with in the caustic soda and after, through filter, drying obtains the S-WAT product; Methyl alcohol is wherein reclaimed in neutralizer rectifying in rectifying tower, contains 60-70% sodium formiate, 10-20% S-WAT and a spot of sodium sulfate, sodium-chlor and organism in the rectifying waste liquid.Because the purity of sodium formiate is lower in the waste liquid, utility value is little, so most of producer does not reclaim this part solution; But directly bury after it is concentrated; Or organism that will be wherein deals with slightly, waste liquid COD back up to standard discharged, or take advantage of the rainy day and discharge with rainwater; So both waste resource, again environment had been caused serious pollution.Usually, 1 ton of vat powder of every production produces 0.5-1.0 ton waste liquid approximately, therefore, the vat powder waste liquid is handled, and the sodium formiate and the S-WAT that reclaim wherein have important economy and social effect.
For solving the handling problem of sodium formate method vat powder waste liquid; Patent 96118152.4 adds sulfuric acid in waste liquid; Sodium formiate is converted into formic acid, and after with a kind of mixed extractant formic acid being extracted from solution then, layering obtains formic acid again; But the purity of product formic acid has only 85%, and still has the emission problem of raffinate after this method processing.Patent ZL03112293.0 takes pre-concentration, vacuum concentration, vacuum crystallization and method of extraction from the vat powder raffinate, to reclaim sodium formiate; Operating process is complicated; Need to add a large amount of methyl alcohol and make extraction agent; And the purity of the finished product sodium formiate has only 60-65%, and still has the emission problem of raffinate.
Summary of the invention
The recovery method that the purpose of this invention is to provide sodium formiate and S-WAT in a kind of sodium formate method vat powder waste liquid is used to solve material waste and the serious environmental pollution problem that sodium formate method vat powder discharging of waste liquid causes.
The recovery method of sodium formiate and S-WAT in the sodium formate method vat powder waste liquid may further comprise the steps:
(1) sodium formate method vat powder waste liquid at first removes by filter granule foreign through accurate filter and ultra-filtration equipment;
(2) removing waste liquid behind the granule foreign gets into nanofiltration system and carries out nanofiltration separation;
(3) nanofiltration sees through liquid and goes back to vat powder production workshop section as the raw material of vat powder, or through pervaporation, crystallization, filtration, obtains the sodium formiate product of purity more than 95%;
(4) the nanofiltration liquid concentrator obtains thick S-WAT product through pervaporation, crystallization, filtration.
Foregoing recovery method, preferred scheme be, before the filtration of step (1), with waste liquid the pH value be adjusted to 7-9.More preferably, with waste liquid the pH value be adjusted to 8-8.5.
Foregoing recovery method, preferably scheme is, and the molecular weight cut-off of ultra-filtration equipment ultra-filtration membrane is 2000-20000 in the said step (1), and the ultrafiltration temperature is 20-50 ℃.More preferably, molecular weight cut-off is 5000-15000, and the ultrafiltration temperature is 40-45 ℃.
Foregoing recovery method, preferably scheme is, and the molecular weight cut-off of nanofiltration system nf membrane is 150-300 in the said step (2), and service temperature is 20-50 ℃, and working pressure is 1-4MPa.More preferably, service temperature is 40-45 ℃, and working pressure is 2-3MPa.
The present invention relates to a kind of employing nanofiltration the vat powder waste liquid is carried out separation and purification, produce the method for highly purified sodium formiate and thick S-WAT.Its technical scheme main points are: with formic acid the pH value of sodium formate method vat powder waste liquid is adjusted to 7-9, passes through secondary filter, ultrafiltration then successively, remove wherein insolubles and granule foreign, get into nanofiltration device again and carry out nanofiltration separation.Nanofiltration sees through liquid through after the evaporation concentration, and the raw material that can be used as vat powder goes back to vat powder production workshop section, also can continue evaporation concentration, and crystallization then, centrifuging obtain the sodium formiate product of purity more than 95%.The nanofiltration liquid concentrator gets into vaporizer and concentrates, and then through crystallization, centrifuging, obtains thick S-WAT product.Sodium formate method vat powder waste liquid also can at first filter through flame filter press or whizzer before secondary filter, ultrafiltration, passes through accurate filter and ultra-filtration equipment then successively, gets into nanofiltration system at last and carries out nanofiltration separation.After seeing through liquid and imitating evaporation concentration through one, the raw material that can be used as vat powder goes back to vat powder production workshop section, also can continue evaporation concentration, and spinning then obtains the sodium formiate product of purity more than 95%; The nanofiltration liquid concentrator is imitated evaporation concentration through two, and is centrifugal then, obtains thick S-WAT product, and this product can be used as the raw material of material of construction water reducer.
Technical superiority of the present invention shows:
1. the solute in the vat powder production waste liquid all reclaims, and does not have waste liquid to discharge, and does not produce secondary pollution.
2. the water that goes out of the evaporator evaporation fresh process water that can be used as vat powder production workshop section is reused.
3. the purity of product sodium formiate is high, can reach more than 95%.
4. technology is simple, realizes easily in the industry.
Description of drawings
Fig. 1 is the production process schematic flow sheet that technical scheme of the present invention adopts.
The practical implementation method
Specify technical scheme of the present invention below in conjunction with embodiment and accompanying drawing, but protection domain is not limited thereto.
The recovery method of sodium formiate and S-WAT in the embodiment 1 sodium formate method vat powder waste liquid may further comprise the steps:
(1) sodium formate method vat powder waste liquid at first removes by filter granule foreign through accurate filter and ultra-filtration equipment; The molecular weight cut-off of ultra-filtration equipment ultra-filtration membrane is 5000, and the ultrafiltration temperature is 20 ℃.
(2) removing waste liquid behind the granule foreign gets into nanofiltration system and carries out nanofiltration separation; The molecular weight cut-off of nanofiltration system nf membrane is 150-300, and service temperature is 20 ℃, and working pressure is 4.0MPa.
(3) nanofiltration is gone back to vat powder production workshop section or through pervaporation, crystallization, filtration, is obtained the sodium formiate product of purity more than 95% through the raw material of liquid as vat powder;
(4) the nanofiltration liquid concentrator obtains thick S-WAT product through pervaporation, crystallization, filtration.
The recovery method of sodium formiate and S-WAT in the embodiment 2 sodium formate method vat powder waste liquids, step are with embodiment 1, but the ultrafiltration temperature is 50 ℃ in the said step (1); Service temperature in the said step (2) is 50 ℃, and working pressure is 1.0MPa.
The recovery method of sodium formiate and S-WAT in the embodiment 3 sodium formate method vat powder waste liquids, step are with embodiment 1, but the molecular weight cut-off of ultra-filtration equipment ultra-filtration membrane is 10000 in the said step (1), and the ultrafiltration temperature is 40 ℃; Said step (2) service temperature is 40 ℃, and working pressure is 2.0MPa.
The recovery method of sodium formiate and S-WAT in the embodiment 4 sodium formate method vat powder waste liquids, step is with embodiment 1, but the molecular weight cut-off of ultra-filtration membrane is 2000, the ultrafiltration temperature is 20 ℃.
The recovery method of sodium formiate and S-WAT in the embodiment 5 sodium formate method vat powder waste liquids, step is with embodiment 1, but the molecular weight cut-off of ultra-filtration membrane is 20000, the ultrafiltration temperature is 50 ℃.
Embodiment 6 contains sodium formiate 72g/L through measuring in certain sodium formate method vat powder waste liquid, and S-WAT and sodium sulfate is 21g/L altogether, sodium-chlor 5g/L, and the pH value of solution value is 11.1.
Utilize the recovery method of sodium formiate and S-WAT in the sodium formate method vat powder waste liquid of the present invention: the pH value of solution value is adjusted to 8.0 with formic acid; Solution passes through accurate filter and ultra-filtration equipment successively, and (molecular weight cut-off of ultra-filtration membrane is 5000; The ultrafiltration temperature is 40 ℃) remove wherein insolubles and granule foreign; Get into nanofiltration device (molecular weight cut-off of nf membrane is 150-300) then and carry out nanofiltration separation, 45 ℃ of service temperatures, working pressure 2.3MPa.Nanofiltration sees through liquid and carries out evaporation concentration, crystallization, centrifuging, obtains the sodium formiate product of purity 95.2%; The nanofiltration liquid concentrator carries out evaporation concentration, crystallization, centrifuging, obtains purity 72.1% S-WAT product.
Embodiment 7 contains sodium formiate 73g/L through measuring in certain sodium formate method vat powder waste liquid, and S-WAT and sodium sulfate is 20g/L altogether, sodium-chlor 4g/L, and the pH value of solution value is 12.2.
Utilize the recovery method of sodium formiate and S-WAT in the sodium formate method vat powder waste liquid of the present invention: the pH value of solution value is adjusted to 8.5 with formic acid; Solution passes through accurate filter and ultra-filtration equipment successively, and (molecular weight cut-off of ultra-filtration membrane is 15000; The ultrafiltration temperature is 45 ℃) remove wherein insolubles and granule foreign; Get into nanofiltration device (molecular weight cut-off of nf membrane is 150-300) then and carry out nanofiltration separation, 40 ℃ of service temperatures, working pressure 2.1MPa.Nanofiltration sees through liquid and carries out evaporation concentration, crystallization, centrifuging, obtains the sodium formiate product of purity 96.1%; Liquid concentrator carries out evaporation concentration, centrifugal, obtains purity 73.8% S-WAT product.
Claims (4)
1. the recovery method of sodium formiate and S-WAT in the sodium formate method vat powder waste liquid is characterized in that, may further comprise the steps:
(1) sodium formate method vat powder waste liquor PH value is adjusted to 7-9, removes by filter granule foreign through accurate filter and ultra-filtration equipment then, the molecular weight cut-off of said ultra-filtration equipment ultra-filtration membrane is 2000-20000, and the ultrafiltration temperature is 20-50 ℃;
(2) remove waste liquid behind the granule foreign and get into nanofiltration system and carry out nanofiltration separation, the molecular weight cut-off of nanofiltration system nf membrane is 150-300, and service temperature is 20-50 ℃, and working pressure is 1-4MPa;
(3) nanofiltration sees through liquid and goes back to vat powder production workshop section as the raw material of vat powder, or through pervaporation, crystallization, filtration, obtains the sodium formiate product of purity more than 95%;
(4) the nanofiltration liquid concentrator obtains thick S-WAT product through pervaporation, crystallization, filtration.
2. recovery method according to claim 1 is characterized in that, the pH value of waste liquid is adjusted to 8-8.5 in the step (1).
3. recovery method according to claim 1 is characterized in that, the molecular weight cut-off of ultra-filtration membrane is 5000-15000 in the step (1), and the ultrafiltration temperature is 40-45 ℃.
4. recovery method according to claim 1 is characterized in that, step (2) service temperature is 40-45 ℃, and working pressure is 2-3MPa.
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| CN2010105324475A CN102050471B (en) | 2010-11-05 | 2010-11-05 | Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method |
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| CN2010105324475A CN102050471B (en) | 2010-11-05 | 2010-11-05 | Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103058146A (en) * | 2011-12-17 | 2013-04-24 | 湖北宜化化工股份有限公司 | Method for recycling residues of sodium dithionite |
| CN102603090A (en) * | 2012-04-17 | 2012-07-25 | 常州大学 | Method and system for treating high-salinity amino acid waste water in aspartame industry |
| CN102616972B (en) * | 2012-04-17 | 2014-06-11 | 常州光辉生物科技有限公司 | Comprehensive recycling method and device for high-salt-content amino acid waste water |
| CN102746134A (en) * | 2012-07-13 | 2012-10-24 | 湖南中成化工有限公司 | Method for decreasing content of sodium chloride impurities in recovered sodium formate |
| CN103420533B (en) * | 2013-02-21 | 2015-12-09 | 宜兴统一环保科技有限公司 | A kind for the treatment of process of high concentrated organic wastewater |
| CN103483178B (en) * | 2013-08-29 | 2015-10-21 | 烟台大学 | The method of process waste residue in production of neopentyl glycol |
| CN103694101B (en) * | 2013-11-07 | 2015-08-19 | 济南大学 | A kind of method of comprehensive utilization of sodium hydrosulfite waste residue |
| CN103754896B (en) * | 2013-12-21 | 2016-06-15 | 中盐安徽红四方股份有限公司 | A kind of method extracting Natrii Sulfas in sodium hydrosulfite wastewater |
| CN103755048A (en) * | 2013-12-30 | 2014-04-30 | 中盐安徽红四方股份有限公司 | New sodium hydrosulfite wastewater treatment method |
| CN104710301B (en) * | 2014-04-29 | 2016-04-13 | 杨胜利 | The technique of sodium formiate is reclaimed in a kind of vat powder raffinate |
| CN104261434A (en) * | 2014-10-16 | 2015-01-07 | 烟台市金河保险粉厂有限公司 | Method for producing anhydrous sodium sulfite by utilizing crude methanol rectification residual liquid in production process of sodium hydrosulfite |
| CN104817480B (en) * | 2015-03-13 | 2017-04-19 | 济南大学 | Reuse of Bunte salt in sodium hydrosulfite waste residue |
| CN105967995B (en) * | 2016-05-16 | 2018-02-09 | 北京鑫佰利科技发展有限公司 | The method that embrane method prepares potassium formate |
| CN106186519A (en) * | 2016-07-22 | 2016-12-07 | 浙江嘉成化工有限公司 | A kind of processing method of sodium hydrosulfite wastewater |
| CN106706841B (en) * | 2016-12-13 | 2019-02-05 | 柳州化工股份有限公司 | The analysis method of sodium formate purity is recycled in sodium hydrosulfite production |
| CN107011160A (en) * | 2017-04-06 | 2017-08-04 | 济南大学 | The separation method of sodium formate in a kind of sodium hydrosulfite waste residue |
| CN113527086A (en) * | 2021-07-30 | 2021-10-22 | 湖北宜化化工股份有限公司 | Method for reducing residue generation amount in sodium hydrosulfite production process |
| CN116161681A (en) * | 2023-04-25 | 2023-05-26 | 北京高能时代环境技术股份有限公司 | Recycling treatment method and system for dangerous solid waste containing sodium bromide and sodium sulfite |
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| JP2001270844A (en) * | 2000-03-23 | 2001-10-02 | Mitsubishi Gas Chem Co Inc | Method for recovering sodium formate from production waste liquor of hydrosulfite |
| DE102004053090A1 (en) * | 2004-11-03 | 2006-05-04 | Basf Ag | Process for the preparation of sodium dithionite |
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