CN103694101A - Comprehensive utilization method of sodium hydrosulfite waste residue - Google Patents
Comprehensive utilization method of sodium hydrosulfite waste residue Download PDFInfo
- Publication number
- CN103694101A CN103694101A CN201310546542.4A CN201310546542A CN103694101A CN 103694101 A CN103694101 A CN 103694101A CN 201310546542 A CN201310546542 A CN 201310546542A CN 103694101 A CN103694101 A CN 103694101A
- Authority
- CN
- China
- Prior art keywords
- temperature
- waste residue
- solvent
- pressure
- comprehensive utilization
- 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
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a comprehensive utilization method of sodium hydrosulfite waste residue. The comprehensive utilization method comprises that: (1) a vacuum distillation method is adopted to remove water in sodium hydrosulfite waste residue and concurrently obtain ethylene glycol; (2) the remaining waste residue obtained from vacuum distillation is washed by using an organic solvent to obtain an organic phase I and a solid A; (3) according to different solubilities of the solid in the solvent, sodium isethionate and sodium formate can be obtained; and (4) the organic phase I is subjected to vacuum distillation to recover the solvent and concurrently obtain thiodiglycol. According to the invention, the waste residue produced in the sodium hydrosulfite production process is subjected to comprehensive utilization and is purified to obtain four organic products, such that enterprise waste emission is reduced while economic benefits and social benefits are brought to enterprises.
Description
Technical field
The present invention relates to the comprehensive utilization technique of the waste residue of the generation in a kind of vat powder production.When reclaiming sodium formiate by this technical finesse from waste residue, can also obtain the product of the high values such as ethylene glycol, sodium isethionate and Thiodiglycol.
Background technology
The main method of domestic production vat powder is sodium formate method at present, the vat powder steady quality that this method is produced, and low cost of manufacture, throughput is high.The vat powder of producing by the method accounts for 90% of national ultimate production.In the waste residue that the vat powder of producing by the method is discharged, mainly contain organism and a small amount of water such as sodium formiate, ethylene glycol, sodium isethionate, Thiodiglycol.There is no at present effective disposal and utilization method, most company deposits it or burning and burying temporarily, so not only causes the waste of resource, has also caused serious environmental pollution simultaneously.Therefore the waste residue producing in production vat powder process is fully utilized and has important economic benefit and social benefit.
In order to solve the processing problem of vat powder waste residue, patent CN1164527A passes through raffinate acidifying, sodium formiate is changed into formic acid, then utilize mixed solvent from wherein extracting formic acid, concentrating and obtaining purity is 85% aqueous formic acid, yet the method exists the emission pollution problem of raffinate, other products that account 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 in vat powder waste residue, other value products are all along with waste discharges in the lump, caused the waste of resource and the pollution of environment.Wang Huai etc. (Chemical Industry in Guangzhou, 2012,40(13), and 133) utilize oxidative treatment vat powder waste water, obtain certain effect, but COD is still very high.Gao Hong (Hefei College's journal, 2006,16(3), 25) studied a kind of vat powder process for cleanly preparing, waste residue has first been adopted to burn and reclaim Sulfothiorine, then added hydrogen peroxide and process organism, effectively reduce waste residue amount, but organic substance fails to fully utilize.Patent CN03112293.0 has invented a kind of method that in vat powder production process, thick methanol rectified raffinate is produced sodium formiate of utilizing.Patent ZL200710164628.5 discloses and has a kind ofly added S-WAT after producing vat powder and utilizing the method for its raffinate coproduction sodium lignosulfonate that raffinate is mixed with wooden sodium, then add formaldehyde, liquid feeding adjusting PH with base value, obtains sodium lignosulfonate slurry after temperature reaction again.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, realize the comprehensive utilization of vat powder waste residue, be a kind of chemical technique turning waste into wealth.When can reclaim sodium formiate from vat powder waste residue by present method, obtain the Chemicals such as ethylene glycol, sodium isethionate and Thiodiglycol, not only solved the serious environmental pollution that vat powder waste sludge discharge causes and can also, for enterprise brings economic benefit, have there is good environmental benefit and social benefit simultaneously.
A method of comprehensive utilization for vat powder waste residue, is characterized in that, comprises the following steps:
(1) first adopt the method for underpressure distillation that the moisture in vat powder waste residue is removed, by underpressure distillation, obtain ethylene glycol simultaneously;
(2) after underpressure distillation completes, remaining solid slag washs with organic solvent, obtains organic phase I and solid A;
(3) adopt a kind of solvent or mixed solvent dissolved solids A, separation obtains hydroxyethylsulfonic acid sodium solution and sodium formiate solid.Distillation obtains sodium isethionate product;
(4) organic phase I is carried out to vacuum distillation recovered solvent, can obtain Thiodiglycol simultaneously.
Temperature during the middle underpressure distillation water of step (1) is 10-60 ℃, and pressure is 100-5000Pa, and preferably temperature is 50-60 ℃, and pressure is 1500-2500Pa; Temperature during underpressure distillation ethylene glycol is 50-150 ℃, and pressure is 50-3000Pa, and preferably temperature is 100-110 ℃, and pressure is 500-800Pa.
While adopting organic solvent washing in step (2), the organic solvent adopting 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 adopting and the ratio of waste residue are 1～10:1, and preferred ratio is 3～6:1; Temperature is 10-80 ℃, preferably temperature 30 degree; The number of times of washing is 1-6 time, preferably 3-4 time.
While solid being carried out to separation in step (3), adopt organic solvent to dissolve, the organic solvent adopting is the mixed solvent of one or more components in water, acetone, ethyl acetate, Virahol, methyl alcohol, ethanol, the solvent adopting and the ratio of waste residue are 1～10:1, and preferred proportion is 5～8:1; Temperature is 20-100 ℃, and preferably temperature is 80-90 ℃.
Temperature during the middle underpressure distillation organic solvent of step (4) is 60-120 ℃, and pressure is 10-5000Pa, and preferably temperature is 60-90 ℃, and pressure is 1000-3000Pa; Temperature during underpressure distillation Thiodiglycol is 100-160 ℃, and pressure is 50-5000Pa, and preferably temperature is 130-150 ℃, and pressure is 100-200Pa.
Accompanying drawing explanation
Fig. 1 is vat powder waste reside comprehensive utilization process flow sheet
Embodiment
Example 1: take 1000g vat powder waste residue and put into underpressure distillation still, open vacuum pump, regulating vacuum tightness is 2000Pa left and right, controls oil bath Heating temperature and is about 80 ℃, and distillation water outlet in 3 hours is complete, and the quality that obtains water is 98g.Close water receiving tank, open ethylene glycol receiving tank, adjusting vacuum tightness is 600Pa, and Heating temperature is upgraded to 100 ℃, and distillation obtains colourless ethylene glycol, and the quality that obtains ethylene glycol is 100g, and purity is 99.5%.
Get the Virahol that volume ratio is 3:1: 1500 milliliters of acetone mixed organic solvents are to upper step except anhydrating 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 ℃.Filtration obtains solid A498g, accounts for 50% of waste residue total amount.Filtrate merging is obtained to organic phase I.
Getting volume ratio is that the Virahol of 5:1 and the mixed solvent of methyl alcohol are processed solid A, and 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 ℃, 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 to air distillation and reclaim solvent, then underpressure distillation.Temperature during underpressure distillation organic solvent is 60 ℃, and pressure is 3000Pa; Temperature during underpressure distillation Thiodiglycol is 140 ℃, and pressure is 150Pa, obtains Thiodiglycol 186g, and purity is 99%.The organic solvent that distillation obtains can cycling and reutilization.
Example 2: take 1000g vat powder waste residue and put into underpressure distillation still, open vacuum pump, regulating vacuum tightness is 2000Pa left and right, controls oil bath Heating temperature and is about 100 ℃, and distillation water outlet in 1 hour is complete, and the quality that obtains water is 97.5g.Close water receiving tank, open ethylene glycol receiving tank, adjusting vacuum tightness is 600Pa, and Heating temperature is upgraded to 120 ℃, and distillation obtains colourless ethylene glycol, and the quality that obtains ethylene glycol is 101g, and purity is 99%.
Get the Virahol that volume ratio is 2:1: 1500 milliliters of acetone mixed organic solvents to upper step except anhydrating and the waste residue of ethylene glycol washs, the usage quantity of mixed organic solvents is slag quality 3 times, the number of times of washing is 3 times, the temperature of washing is 25～30 ℃.Filtration obtains solid A495g.Filtrate merging is obtained to organic phase I.
Getting volume ratio is that the Virahol of 8:1 and the mixed solvent of methyl alcohol are processed solid A, and 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 ℃, 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 to underpressure distillation and reclaim organic solvent.Controlling temperature is 65 ℃, and pressure is 2500Pa; Temperature during underpressure distillation Thiodiglycol is 150 ℃, and pressure is 150Pa, obtains Thiodiglycol 188g, and purity is 98%.The organic solvent that distillation obtains can cycling and reutilization.
Claims (5)
1. a method of comprehensive utilization for vat powder waste residue, is characterized in that, comprises the following steps:
(1) first adopt the method for underpressure distillation that the moisture in vat powder waste residue is removed, by underpressure distillation, obtain ethylene glycol simultaneously;
(2) after underpressure distillation completes, remaining solid slag washs with organic solvent, obtains organic phase I and solid A;
(3) adopt a kind of solvent or mixed solvent dissolved solids A, separation obtains hydroxyethylsulfonic acid sodium solution and sodium formiate solid, and distillation obtains sodium isethionate product;
(4) organic phase I is carried out to vacuum distillation recovered solvent, can obtain Thiodiglycol simultaneously.
2. method of comprehensive utilization according to claim 1, the temperature in step (1) during underpressure distillation water is 10-60 ℃, and pressure is 100-5000Pa, and preferably temperature is 50-60 ℃, and pressure is 1500-2500Pa; Temperature during underpressure distillation ethylene glycol is 50-150 ℃, and pressure is 50-3000Pa, and preferably temperature is 100-110 ℃, and pressure is 500-800Pa.
3. method of comprehensive utilization according to claim 1, while adopting organic solvent washing in step (2), the organic solvent adopting 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 adopting and the ratio of waste residue are 1～10:1, and preferred ratio is 3:1; Temperature is 10-80 ℃, preferably temperature 30 degree; The number of times of washing is 1-6 time, preferably 3-4 time.
4. method of comprehensive utilization according to claim 1, while solid being carried out to separation in step (3), adopt organic solvent to dissolve, the organic solvent adopting is the mixed solvent of one or more components in water, acetone, ethyl acetate, Virahol, methyl alcohol, ethanol, the solvent adopting and the ratio of waste residue are 8～10:1, and preferred proportion is 8:1; Temperature is 20-100 ℃, and preferably temperature is 80-90 ℃.
5. method of comprehensive utilization according to claim 1, the temperature in step (4) during underpressure distillation organic solvent is 60-120 ℃, and pressure is 10-5000Pa, and preferably temperature is 60-90 ℃, and pressure is 1000-3000Pa; Temperature during underpressure distillation Thiodiglycol is 100-160 ℃, and pressure is 50-5000Pa, and preferably temperature is 130-150 ℃, and pressure is 100-200Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310546542.4A CN103694101B (en) | 2013-11-07 | 2013-11-07 | A kind of method of comprehensive utilization of sodium hydrosulfite waste residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310546542.4A CN103694101B (en) | 2013-11-07 | 2013-11-07 | A kind of method of comprehensive utilization of sodium hydrosulfite waste residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103694101A true CN103694101A (en) | 2014-04-02 |
| CN103694101B CN103694101B (en) | 2015-08-19 |
Family
ID=50355795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310546542.4A Active CN103694101B (en) | 2013-11-07 | 2013-11-07 | A kind of method of comprehensive utilization of sodium hydrosulfite waste residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103694101B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710301A (en) * | 2014-04-29 | 2015-06-17 | 杨胜利 | Process for recovering sodium formate from sodium hydrosulfite raffinate |
| CN104817480A (en) * | 2015-03-13 | 2015-08-05 | 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 |
-
2013
- 2013-11-07 CN CN201310546542.4A patent/CN103694101B/en active Active
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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710301A (en) * | 2014-04-29 | 2015-06-17 | 杨胜利 | Process for recovering sodium formate from sodium hydrosulfite raffinate |
| CN104817480A (en) * | 2015-03-13 | 2015-08-05 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103694101B (en) | 2015-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103694101B (en) | A kind of method of comprehensive utilization of sodium hydrosulfite waste residue | |
| CN102050471B (en) | Method for recycling sodium formate and sodium sulfite from waste sodium hydrosulfite liquid with sodium formate method | |
| CN103254064B (en) | A kind of preparation method of forulic acid | |
| CN107987036A (en) | A kind of propylene oxide process | |
| CN105237394A (en) | Preparation method of diisobutyl phthalate | |
| CN104628664A (en) | Method for continuously producing benzotriazole | |
| CN101712712A (en) | Method for preparing 16-dehydropregnenolone acetate by multistage filtration and recrystallization | |
| CN103466873B (en) | A kind of process is containing the method for high-concentration phenol, ammonia sewage | |
| CN102643611B (en) | High-efficiency energy-saving low-cost high-quality rosin production process and production line equipment | |
| CN101870639A (en) | Method for producing kelp mannitol with low energy consumption | |
| CN109825359B (en) | Method for preparing bio-based lubricating oil by using papermaking black liquor and special production device | |
| JP2013208108A (en) | Method for recovering acid, method for manufacturing sugar liquid and method of fermentation | |
| CN204058303U (en) | A kind of purifying plant of sodium formiate | |
| CN204039299U (en) | A kind of purifying plant of high-purity sodium formate | |
| CN104163525B (en) | A kind of bromination prepares the processing method producing waste water of bromamine acid sodium salt | |
| CN216629750U (en) | System for separate pentaerythritol and calcium formate from pentaerythritol mother liquor | |
| CN107337308B (en) | Device and process for extracting glycerin from epoxy resin device high-salinity wastewater concentrated solution | |
| CN101597268B (en) | Processing method of mother liquor of ainothiazoly loximate | |
| CN113968782A (en) | Method for removing impurities in recycled acetic acid | |
| CN111039894A (en) | Method for producing DM (direct methanol gasoline) by utilizing recycled rubber accelerator M waste | |
| CN104892406A (en) | Industrialized preparation method of 2-carboxyl-3-naphthalene formic acid | |
| CN210030513U (en) | Extraction and dehydration system in trioxymethylene production process | |
| CN114684956B (en) | Membrane separation method for recycling sorbic acid in sorbic acid wastewater | |
| CN117088757A (en) | Preparation method of D-chiro-inositol | |
| CN219186478U (en) | Lactic acid nanofiltration membrane treatment system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Yu Inventor before: Sun Guoxin Inventor before: Liu Siyuan Inventor before: Sun Guojing |
|
| COR | Change of bibliographic data | ||
| TR01 | Transfer of patent right |
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 |