CN103694101B - A kind of method of comprehensive utilization of sodium hydrosulfite waste residue - Google Patents
A kind of method of comprehensive utilization of sodium hydrosulfite waste residue Download PDFInfo
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- CN103694101B CN103694101B CN201310546542.4A CN201310546542A CN103694101B CN 103694101 B CN103694101 B CN 103694101B CN 201310546542 A CN201310546542 A CN 201310546542A CN 103694101 B CN103694101 B CN 103694101B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Abstract
The invention discloses a kind of method of comprehensive utilization of sodium hydrosulfite waste residue, (1) first adopts the method for underpressure distillation by the moisture removing in sodium hydrosulfite waste residue, can obtain ethylene glycol by underpressure distillation simultaneously; (2) complete for underpressure distillation remaining waste residue organic solvent is washed, obtain organic phase I and solid A; (3) according to solid different solubility in a solvent, sodium isethionate and sodium formiate can be obtained; (4) organic phase I is carried out vacuum distillation recovered solvent, can Thiodiglycol be obtained simultaneously.The waste residue produced in vat powder production process fully utilizes by the present invention, purifies and obtains four kinds of organic productss, brings economic benefit and social benefit while reducing enterprise's waste discharge to enterprise.
Description
Technical field
The present invention relates to the comprehensive utilization technique of the waste residue of the generation in the production of a kind of vat powder.The product of the high values such as ethylene glycol, sodium isethionate and Thiodiglycol can also be obtained while reclaiming sodium formiate by this technical finesse from waste residue.
Background technology
The main method of current domestic production vat powder is sodium formate method, the vat powder steady quality that this method is produced, and low cost of manufacture, throughput is high.The vat powder produced by the method accounts for 90% of national ultimate production.Main containing organism and a small amount of water such as sodium formiate, ethylene glycol, sodium isethionate, Thiodiglycols in the waste residue that the vat powder produced by the method is discharged.Do not have effective disposal and utilization method at present, it deposits or burning and burying by most company temporarily, so not only causes the waste of resource, also result in serious environmental pollution simultaneously.Therefore the waste residue produced in production vat powder process is fully utilized and there is important economic benefit and social benefit.
In order to solve the process problem of sodium hydrosulfite waste residue, patent CN1164527A passes through raffinate acidifying, sodium formiate is changed into formic acid, then utilize mixed solvent from wherein extracting formic acid, carry out again concentrating and obtain the aqueous formic acid that purity is 85%, but the method exists the emission pollution problem of raffinate, other products accounting for waste residue 60-70% fail to fully utilize.Patent CN102050471A adopts the steps such as ultrafiltration, nanofiltration, condensing crystal, centrifuging to reclaim sodium formiate and S-WAT.But other value products are all along with waste discharges in the lump in sodium hydrosulfite waste residue, cause the waste of resource and the pollution of environment.Wang Huai etc. (Chemical Industry in Guangzhou, 2012,40 (13), 133) utilize oxidative treatment sodium hydrosulfite wastewater, obtain certain effect, but COD are still very high.Gao Hong (Hefei College's journal, 2006,16 (3), 25) have studied a kind of vat powder process for cleanly preparing, first adopt to burn to waste residue and reclaim Sulfothiorine, then add hydrogen peroxide process organism, effectively reduce waste residue amount, but organic substance fails to fully utilize.Patent CN03112293.0 has invented a kind of method utilizing crude carbinol distillation residual liquid production sodium formiate in vat powder production process.Patent ZL200710164628.5 discloses and a kind ofly produces vat powder and add S-WAT after utilizing the method for its raffinate lignin co-production sodium sulfonate to be mixed with wooden sodium by raffinate, then formaldehyde is added, liquid feeding adjusting PH with base value again, obtains sodium lignosulfonate slurry after temperature reaction.Above-mentioned open source information is all different from the technology.
Summary of the invention
The object of the invention is to solve produce in vat powder production process liquid and waste slag produced.By the coupling of chemical separation process, realizing the comprehensive utilization of sodium hydrosulfite waste residue, is a kind of chemical technique turned waste into wealth.The Chemicals such as ethylene glycol, sodium isethionate and Thiodiglycol are obtained while can reclaiming sodium formiate from sodium hydrosulfite waste residue by present method, not only solve the serious environmental pollution that sodium hydrosulfite waste residue discharge causes and can also bring economic benefit for enterprise simultaneously, there is good environmental benefit and social benefit.
A method of comprehensive utilization for sodium hydrosulfite waste residue, is characterized in that, comprises the following steps:
(1) first adopt the method for underpressure distillation by the moisture removing in sodium hydrosulfite waste residue, obtain ethylene glycol by underpressure distillation simultaneously;
(2) after underpressure distillation completes, remaining solid slag organic solvent washs, and obtains organic phase I and solid A;
(3) adopt a kind of solvent or mixed solvent dissolved solids A, be separated and obtain hydroxyethylsulfonic acid sodium solution and sodium formiate solid.Distillation obtains sodium isethionate product;
(4) organic phase I is carried out vacuum distillation recovered solvent, can Thiodiglycol be obtained simultaneously.
Temperature in step (1) during underpressure distillation water is 10-60 DEG C, and pressure is 100-5000Pa, and preferable temperature is 50-60 DEG C, and pressure is 1500-2500Pa; Temperature during underpressure distillation ethylene glycol is 50-150 DEG C, and pressure is 50-3000Pa, and preferable temperature is 100-110 DEG C, and pressure is 500-800Pa.
When adopting organic solvent washing in step (2), the organic solvent adopted is the mixed solvent of one or more components in diethylene glycol dimethyl ether, isopropyl ether, ethyl formate, vinyl acetate resin, Isoamyl Acetate FCC, butylacetate, ethyl acetate, methyl ethyl diketone, methyl iso-butyl ketone (MIBK), acetone, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexanol, the solvent adopted and the ratio of waste residue are 1 ~ 10:1, and preferred ratio is 3 ~ 6:1; Temperature is 10-80 DEG C, preferable temperature 30 degree; The number of times of washing is 1-6 time, preferred 3-4 time.
When solid being separated in step (3), organic solvent is adopted to dissolve, the organic solvent adopted is the mixed solvent of one or more components in acetone, ethyl acetate, Virahol, methyl alcohol, ethanol, the solvent adopted and the ratio of waste residue are 1 ~ 10:1, and preferred proportion is 5 ~ 8:1; Temperature is 20-100 DEG C, and preferable temperature is 80-90 DEG C.
Temperature in step (4) during underpressure distillation organic solvent is 60-120 DEG C, and pressure is 10-5000Pa, and preferable temperature is 60-90 DEG C, and pressure is 1000-3000Pa; Temperature during underpressure distillation Thiodiglycol is 100-160 DEG C, and pressure is 50-5000Pa, and preferable temperature is 130-150 DEG C, and pressure is 100-200Pa.
Accompanying drawing explanation
Fig. 1 is sodium hydrosulfite waste residue comprehensive utilization process schema
Embodiment
Example 1: take 1000g sodium hydrosulfite waste residue and put into underpressure distillation still, open vacuum pump, adjustment vacuum tightness is about 2000Pa, controls oil bath Heating temperature and is about 80 DEG C, and distillation water outlet in 3 hours is complete, and the quality obtaining water is 98g.Close water receiving tank, open ethylene glycol receiving tank, adjustment vacuum tightness is 600Pa, and Heating temperature is upgraded to 100 DEG C, and distillation obtains colourless ethylene glycol, and the quality obtaining ethylene glycol is 100g, and purity is 99.5%.
Get the Virahol that volume ratio is 3:1: acetone mixed organic solvents 1500 milliliters is to upper step except to anhydrate and the waste residue of ethylene glycol washs, and the number of times of washing is 4 times, and the temperature of washing is 25-30 DEG C.Filtration obtains solid A498g, accounts for 50% of waste residue total amount.Filtrate merging is obtained organic phase I.
Get volume ratio be the Virahol of 5:1 and the mixed solvent of methyl alcohol to solid A process, the usage quantity of mixed organic solvents is 2500 milliliters, and the number of times of washing is 2 times, the temperature of washing is 80 DEG C, filter residue is sodium formiate 330g, and purity is 85%, can be used as the raw material reuse of vat powder.Filtrate distillating recovering solvent, is precipitated as sodium isethionate 160g, and purity is 99%.
Organic phase I is carried out air distillation recycling design, then underpressure distillation.Temperature during underpressure distillation organic solvent is 60 DEG C, and pressure is 3000Pa; Temperature during underpressure distillation Thiodiglycol is 140 DEG C, and pressure is 150Pa, obtains Thiodiglycol 186g, and purity is 99%.Distilling the organic solvent obtained can cycling and reutilization.
Example 2: take 1000g sodium hydrosulfite waste residue and put into underpressure distillation still, open vacuum pump, adjustment vacuum tightness is about 2000Pa, controls oil bath Heating temperature and is about 100 DEG C, and distillation water outlet in 1 hour is complete, and the quality obtaining water is 97.5g.Close water receiving tank, open ethylene glycol receiving tank, adjustment vacuum tightness is 600Pa, and Heating temperature is upgraded to 120 DEG C, and distillation obtains colourless ethylene glycol, and the quality obtaining ethylene glycol is 101g, and purity is 99%.
Get the Virahol that volume ratio is 2:1: acetone mixed organic solvents 1500 milliliters is to upper step except to anhydrate and the waste residue of ethylene glycol washs, and the usage quantity of mixed organic solvents is 3 times of slag quality, and the number of times of washing is 3 times, and the temperature of washing is 25 ~ 30 DEG C.Filtration obtains solid A495g.Filtrate merging is obtained organic phase I.
Get volume ratio be the Virahol of 8:1 and the mixed solvent of methyl alcohol to solid A process, the usage quantity of mixed organic solvents is 2500 milliliters, the number of times of washing is 3 times, and the temperature of washing is 90 DEG C, and filter residue is sodium formiate 320g, purity is 87%, can be used as the raw material reuse of vat powder.Filtrate distillating recovering solvent, is precipitated as sodium isethionate 165g, and purity is 98%.
Organic phase I is carried out underpressure distillation and reclaim organic solvent.Control temperature is 65 DEG C, and pressure is 2500Pa; Temperature during underpressure distillation Thiodiglycol is 150 DEG C, and pressure is 150Pa, obtains Thiodiglycol 188g, and purity is 98%.Distilling the organic solvent obtained can cycling and reutilization.
Claims (5)
1. a method of comprehensive utilization for sodium hydrosulfite waste residue, its feature comprises the following steps:
(1) first adopt the method for underpressure distillation by the moisture removing in sodium hydrosulfite waste residue, obtain ethylene glycol by underpressure distillation simultaneously;
(2) after underpressure distillation completes, remaining solid slag organic solvent washs, and obtains organic phase I and solid A;
(3) adopt a kind of solvent or mixed solvent dissolved solids A, be separated and obtain hydroxyethylsulfonic acid sodium solution and sodium formiate solid, distillation obtains sodium isethionate product;
(4) organic phase I is carried out vacuum distillation recovered solvent, can Thiodiglycol be obtained simultaneously.
2. method of comprehensive utilization according to claim 1, the temperature in step (1) during underpressure distillation water is 10-60 DEG C, and pressure is 100-5000Pa; Temperature during underpressure distillation ethylene glycol is 50-150 DEG C, and pressure is 50-3000Pa.
3. method of comprehensive utilization according to claim 1, when adopting organic solvent washing in step (2), the organic solvent adopted is the mixed solvent of one or more components in isopropyl ether, ethyl acetate, acetone, Virahol, and the solvent adopted and the ratio of waste residue are 1 ~ 10:1; Temperature is 10-30 DEG C; The number of times of washing is 1-6 time.
4. method of comprehensive utilization according to claim 1, when solid being separated in step (3), organic solvent is adopted to dissolve, the organic solvent adopted is the mixed solvent of one or more components in Virahol, methyl alcohol, ethanol, and the solvent adopted and the ratio of waste residue are 8 ~ 10:1; Temperature is 80-90 DEG C.
5. method of comprehensive utilization according to claim 1, the temperature in step (4) during underpressure distillation organic solvent is 60-120 DEG C, and pressure is 10-5000Pa; Temperature during underpressure distillation Thiodiglycol is 100-160 DEG C, and pressure is 50-5000Pa.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104817480B (en) * | 2015-03-13 | 2017-04-19 | 济南大学 | Reuse of Bunte salt in sodium hydrosulfite waste residue |
| 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 |
| CN114956986A (en) * | 2022-05-11 | 2022-08-30 | 湖北宜化化工股份有限公司 | Sodium hydrosulfite residue treatment method with high sodium formate recovery rate and low residue generation amount |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040012A (en) * | 1989-04-18 | 1990-02-28 | 老河口市石油化工总厂 | The recovery method of the processing of vat powder waste liquid and S-WAT and sodium-chlor |
| CN102050471A (en) * | 2010-11-05 | 2011-05-11 | 烟台大学 | Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040012A (en) * | 1989-04-18 | 1990-02-28 | 老河口市石油化工总厂 | The recovery method of the processing of vat powder waste liquid and S-WAT and sodium-chlor |
| CN102050471A (en) * | 2010-11-05 | 2011-05-11 | 烟台大学 | Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method |
| 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 |
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Inventor after: Liu Yu Inventor before: Sun Guoxin Inventor before: Liu Siyuan Inventor before: Sun Guojing |
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Effective date of registration: 20160727 Address after: 518000 Shenzhen, Guangdong province Nanshan District fun Village Patentee after: Shenzhen Gangchuang Building Material Co., Ltd. Address before: Central nanxinzhuang road Ji'nan Shandong province 250022 city University of Jinan No. 336 Patentee before: University of Jinan |