CN1903821A - Technology of producing sodium oxalate by continuous dehydrogenation of sodium formate and its equipment - Google Patents
Technology of producing sodium oxalate by continuous dehydrogenation of sodium formate and its equipment Download PDFInfo
- Publication number
- CN1903821A CN1903821A CN 200610106816 CN200610106816A CN1903821A CN 1903821 A CN1903821 A CN 1903821A CN 200610106816 CN200610106816 CN 200610106816 CN 200610106816 A CN200610106816 A CN 200610106816A CN 1903821 A CN1903821 A CN 1903821A
- Authority
- CN
- China
- Prior art keywords
- sodium oxalate
- sodium
- aqueous solution
- cyclone separator
- dehydrogenation
- 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
Abstract
The present invention relates to a process for producing sodium oxalate by using sodium formate through continuous dehydrogenation and its equipment. It is characterized by that said invention uses the superheated steam as heat-carrying body, said superheated steam can be used for directly heating molten sodium formate in the eductor mixer, the sodium formatted can be quickly heated in said eductor mixer, and can be quickly passed through the temperature zone in which the side reaction can be easily produced, and the product sodium oxalate obtained after the sodium formate is dehydrogenated can be driven by air flow and fed into the cyclone separator, and can be quickly cooled so as to prevent the sodium oxalate from being decomposed.
Description
The invention discloses a process and equipment for producing sodium oxalate by continuously dehydrogenating sodium formate, belongs to the field of organic chemistry, and relates to preparation of carboxylate, in particular to a process and equipment for producing sodium oxalate and oxalic acid.
At present, the domestic process for producing sodium oxalate is a batch method,and the process is carried out in a batch dehydrogenation pot. The method is that dry sodium formate is put into an intermittent dehydrogenation pot, the bottom of the pot is heated by fire, the material is heated gradually, when the temperature rises to about 310 ℃ of dehydrogenation temperature, dehydrogenation is started, the temperature rise is accelerated, when the temperature reaches about 400 ℃, the sodium formate is dehydrogenated rapidly, the material temperature also rises rapidly due to heat release in the dehydrogenation process, and then the dehydrogenation process is finished. After cooling, the product is manually moved out of the pot to prepare for feeding again. The method has the advantages of simple equipment and low investment. However, due to uneven heating, the material near the wall of the pot is easily decomposed or carbonized by overheating, and secondly, because the temperature rise time is too long, many byproducts are produced, and the yield is low, usually only 80% to 85%. The energy consumption and the material loss are both large. In addition, high-temperature operation, poor working conditions and high labor intensity, and sodium formate and sodium oxalate have certain toxicity. The dust flies upward in the operation, which has great influence on the health of workers.
In order to improve the dehydrogenation yield and ensure the continuous dehydrogenation process, a chain type continuous dehydrogenation device is adopted abroad, wherein the chain is made of special materials and aims to prevent the materials from being adhered. The material evenly spreads on the chain with the heating temperature of about 400-450 ℃ in a spraying manner through the nozzle, after being heated and heated, the material is dehydrogenated, and then the material is stripped from the chain, and after the dehydrogenation, the chain continuously and circularly runs. The method has the advantages of realizing dehydrogenation continuity and improving dehydrogenation yield. The disadvantage is that the investment of the equipment is large, and about 3000 ten thousand yuan is needed when one piece of equipment is introduced from abroad. Meanwhile, as the chain is made of special materials, the equipment cannot be prepared by China.
In order to improve the dehydrogenation yield and realize the continuous dehydrogenation process, experts at home and abroad research novel dehydrogenation equipment, and from the currently published patents, two representative continuous dehydrogenation processes and equipment exist, and one is a rotary drum continuous dehydrogenation process and equipment. The process is characterized in that materials are uniformly sprayed on the surface of a drum which is heated and has a certain temperature, the materials realize dehydrogenation on the surface of the drum, then a scraper is used for removing a dehydrogenation product from the drum, and the drum continuously rotates to realize process continuity. The other is continuous dehydrogenation in fluidized bed, which is formed by burning coal gas to form fume as heat source, passing hot gas through fluidized bed from bottom to top, and blowing gas from the material gap to separate material from bed layer. The material leaves the fluidized bed from the feed pipe after dehydrogenation in the fluidized bed. The method has the advantages of realizing the continuity and improving the dehydrogenation yield, but has three defects, namely small operation elasticity and difficult operation, directly heating by using coal gas, wherein sulfur has a poisoning effect on the dehydrogenation process, and finally, the product after dehydrogenation can not be cooled in time, so that the material can be decomposed or carbonized.
The process for producing sodium oxalate by double-circulation continuous dehydrogenation in a three-phase fluidized bed comprises the steps of heating nitrogen, air or desulfurized flue gas to 430-600 ℃ to serve as a heat-carrying medium, introducing the heat-carrying medium from the bottom of the fluidized bed through a blower, and passing the heat-carrying medium through the fluidized bed from bottom to top; melting sodium formate in a melting pot, preheating to 200-250 ℃, and pumping the molten sodium formate into the upper part of a fluidized bed by using a pressure pump; spraying sodium formate in a fluidized bed through a spray head in a spray manner, and making the sodium formate in countercurrent contact with rising high-temperature airflow, wherein the residence time of the sodium formate in the fluidized bed is controlled within 20 seconds, and the residence time of a dehydrogenation product sodium oxalate in the fluidized bed is controlled within 10 seconds; the dehydrogenated product sodium oxalate is carried out of the fluidized bed by the ascending gas flow and enters a cyclone separator and a washing tower in sequence for separation and cooling. The method has the advantages that the improvement is carried out on the basis of a common fluidized bed, the dehydrogenated product is quickly taken out of the fluidized bed and is quickly cooled, the further decomposition of the product is avoided, the yield of the product is further improved, but the method also has a defect that the safety problem caused by the large amount of hydrogen contained in the dehydrogenated product cannot be thoroughly solved.
The invention aims to improve the production process, improve the dehydrogenation yield and overcome the defects of the technology, thereby providing a safer and more reliable process and equipment for producing sodium oxalate by continuously dehydrogenating sodium formate.
The object of the invention can be achieved by the following measures:
the invention relates to a process and equipment for producing sodium oxalate by continuously dehydrogenating sodium formate, which is a new process for preparing sodium oxalate by continuously dehydrogenating sodium formate. The chemical formula for this reaction is as follows:
the reaction is carried out at 310-450 ℃, the optimal reaction temperature is about 420 ℃, and side reactions are easy to generate in the material heating process, particularly about 300 ℃.
Therefore, measures must be taken to rapidly raise the temperature of the material, rapidly pass through the stage of about 300 ℃ and reach the dehydrogenation temperature of about 420 ℃ in the shortest possible time. In addition, the dehydrogenation process is an exothermic process, the temperature of the material can still continuously rise after dehydrogenation, and sodium oxalate generated after dehydrogenation is easily decomposed and carbonized at high temperature. Therefore, the dehydrogenated product sodium oxalate should leave the high temperature zone immediately and be cooled immediately to avoid decomposition and carbonization.
The method comprises the following steps of (1) heating superheated steam at the temperature of about 500 ℃ and sodium formate at the temperature of 260-280 ℃ to a molten state in a jet mixer, controlling the proportion of the superheated steam and the sodium formate to enable the mixed temperature to reach about 420 ℃, and carrying out dehydrogenation reaction in a pipeline;
(2) and (3) the mixture after dehydrogenation enters a cyclone separator for gas-solid separation, sodium oxalate solid is discharged from the lower part, hydrogen is contacted with the sodium oxalate aqueous solution sprayed from the top part, the mixture is discharged fromthe upper part after being washed and purified, and the sodium oxalate aqueous solution flows into a sodium oxalate aqueous solution tank from the lower part.
(3) And one part of the sodium oxalate aqueous solution discharged from the downcomer of the cyclone separator is further processed in the next working section, and the other part of the sodium oxalate aqueous solution is cooled by a heat exchanger and then is pumped into the upper part of the cyclone separator by a circulating pump for recycling.
The equipment for producing sodium oxalate by continuously dehydrogenating sodium formate is as follows: the device is composed of a jet mixer (1), a cyclone separator (2), a sodium oxalate aqueous solution tank (3) and a circulating pump (4), wherein the jet mixer (1) is communicated with the cyclone separator (2) through a pipeline, the cyclone separator (2) is communicated with the sodium oxalate aqueous solution tank (3) through a pipeline, and the sodium oxalate aqueous solution tank (3) is communicated with the circulating pump (4) through a pipeline. The inlet of the circulating pump (4) is communicated with the sodium oxalate water solution tank (3) through a pipeline, and the outlet is communicated with the cyclone separator (2) through a pipeline.
The invention has the advantages that:
1. continuous production is realized, the labor productivity is improved, and the production conditions and the labor environment are improved;
2. because superheated steam and sodium formate liquid are fully mixed in the jet mixer and rapidly heated, the heating time is shortened, the generation of byproducts is reduced, and the yield of sodium oxalate is improved;
3. sodium oxalate puffed solid particles generated after sodium formate is dehydrogenated in a pipeline are rapidly carried out by airflow and enter a cycloneseparator for rapid cooling, so that the decomposition of sodium oxalate is reduced, and the yield of sodium oxalate is improved;
4. the method adopts the circulating cooling of the sodium oxalate aqueous solution, improves the yield of the sodium oxalate, washes and purifies the hydrogen, and the sodium oxalate aqueous solution can directly enter the next working section, namely the lead-melting working section, thereby omitting the sodium oxalate dissolving working procedure.
5. The superheated steam is used as a heating medium, the whole system has no three-waste discharge, and the superheated steam hardly contains oxygen due to the mature technology of deoxidizing water for a boiler, so that the safety problem of hydrogen is thoroughly solved, and the safety guarantee is provided for industrial production.
The drawings illustrate the following:
the attached drawing is a process equipment principle diagram of the invention, wherein 1 is a jet mixer, 2 is a cyclone separator, 3 is a sodium oxalate aqueous solution tank, and 4 is a circulating pump.
The following is further reviewed by way of example in conjunction with the accompanying drawings:
a10000 ton annual sodium oxalate production device takes superheated steam of about 500 ℃ as a heat-carrying medium, the superheated steam and sodium formate liquid which is heated to a molten state and the temperature of 260-280 ℃ enter a jet mixer simultaneously, the superheated steam and the sodium formate liquid are quickly mixed in the jet mixer, the proportion of the superheated steam and the sodium formate is controlled, the mixed temperature reaches about 420 ℃, the mixture is subjected to dehydrogenation reaction in a pipeline, hydrogen and water vapor generated after dehydrogenation are mixed, the potential safety hazard problem of the hydrogen is thoroughly solved, the dehydrogenated fluffy sodium oxalate is quickly brought out by mixed gas flow formed by the hydrogen and the water vapor to enter a cyclone separator, the cyclone separator is circularly sprayed and cooled by a sodium oxalate aqueous solution, the sodium oxalate aqueous solution with low temperature is sprayed from the top, the mixed gas formed by the hydrogen and the water vapor carries a product sodium oxalate generated after dehydrogenation from bottom to top, the product is fully contacted, and controlling the flow of the sodium oxalate aqueous solution to ensure that the sodium oxalate aqueous solution just completely condenses the water vapor in the mixed gas to form condensed water, simultaneously dissolving all the sodium oxalate carried in the condensed water in the aqueous solution, directly flowing into a sodium oxalate aqueous solution tank through a downcomer, then pumping a part of the condensed water into the upper part of the cyclone separator by a circulating pump for recycling, and further processing the other part of the condensed water to the next working section. The hydrogen after washing, cooling and purification is discharged from the top of the cyclone separator and sent into a gas holder for standby.
Claims (2)
1. A process for producing sodium oxalate by continuously dehydrogenating sodium formate is characterized by comprising the following steps: (1) the superheated steam is used as a heat carrier and enters the jet mixer together with the molten sodium formate, the sodium formate and the superheated steam are rapidly mixed in the jet mixer, and the temperature is rapidly increased to the optimal dehydrogenation temperature.
(2) The dehydrogenated product sodium oxalate is carried out of the high-temperature zone by airflow and enters a cyclone separator. The temperature of the hydrogen gas is rapidly reduced by the sodium oxalate aqueous solution, the sodium oxalate is completely dissolved in water to become the sodium oxalate aqueous solution, the sodium oxalate aqueous solution is discharged into a sodium oxalate aqueous solution tank, and the hydrogen gas is washed, cooled and purified and then is discharged from the upper part of the cyclone separator.
2. The equipment for the process for producing sodium oxalate by continuously dehydrogenating sodium formate according to claim 1, which is characterized by comprising a jet mixer (1), a cyclone separator (2), a sodium oxalate aqueous solution tank (3) and a circulating pump (4), wherein the jet mixer (1) is communicated with the cyclone separator (2) through a pipeline, the cyclone separator (2) is communicated with the sodium oxalate aqueous solution tank (3) through a pipeline, and the sodium oxalate aqueous solution tank (3) is communicated with the circulating pump (4) through a pipeline. The inlet of the circulating pump (4) is communicated with the sodium oxalate water solution tank (3) through a pipeline, and the outlet is communicated with the cyclone separator (2) through a pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101068168A CN1903821B (en) | 2006-08-01 | 2006-08-01 | Technology of producing sodium oxalate by continuous dehydrogenation of sodium formate and its equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101068168A CN1903821B (en) | 2006-08-01 | 2006-08-01 | Technology of producing sodium oxalate by continuous dehydrogenation of sodium formate and its equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1903821A true CN1903821A (en) | 2007-01-31 |
| CN1903821B CN1903821B (en) | 2012-05-23 |
Family
ID=37673203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101068168A Expired - Fee Related CN1903821B (en) | 2006-08-01 | 2006-08-01 | Technology of producing sodium oxalate by continuous dehydrogenation of sodium formate and its equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1903821B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462943B (en) * | 2009-01-08 | 2011-06-29 | 曹勇 | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate |
| CN102391099A (en) * | 2011-09-16 | 2012-03-28 | 罗田县富阳化肥有限公司 | Method and equipment for producing sodium oxalate through continuous dehydrogenation by two-fluid spraying |
| CN1948260B (en) * | 2006-09-26 | 2012-07-18 | 太原理工大学 | Technology of producing sodium oxalate by sodium formate spray dehydrogenation and its equipment |
| CN101823950B (en) * | 2009-03-03 | 2014-07-30 | 太原理工大学 | Process and equipment for producing sodium oxalate by utilizing synthesized tail gas continuous dehydrogenation |
| CN107216248A (en) * | 2017-06-29 | 2017-09-29 | 宁夏海纳川化工技术有限公司 | A kind of technique for producing sodium oxalate with polynary alcohol production byproduct sodium formate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244534C (en) * | 2002-11-22 | 2006-03-08 | 于学平 | Technological process for producing sodium oxalate by liquid-spraying type sodium formate dehydrogenation and use equipment |
-
2006
- 2006-08-01 CN CN2006101068168A patent/CN1903821B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948260B (en) * | 2006-09-26 | 2012-07-18 | 太原理工大学 | Technology of producing sodium oxalate by sodium formate spray dehydrogenation and its equipment |
| CN101462943B (en) * | 2009-01-08 | 2011-06-29 | 曹勇 | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate |
| CN101823950B (en) * | 2009-03-03 | 2014-07-30 | 太原理工大学 | Process and equipment for producing sodium oxalate by utilizing synthesized tail gas continuous dehydrogenation |
| CN102391099A (en) * | 2011-09-16 | 2012-03-28 | 罗田县富阳化肥有限公司 | Method and equipment for producing sodium oxalate through continuous dehydrogenation by two-fluid spraying |
| CN102391099B (en) * | 2011-09-16 | 2014-12-10 | 罗田县富阳化肥有限公司 | Method and equipment for producing sodium oxalate through continuous dehydrogenation by two-fluid spraying |
| CN107216248A (en) * | 2017-06-29 | 2017-09-29 | 宁夏海纳川化工技术有限公司 | A kind of technique for producing sodium oxalate with polynary alcohol production byproduct sodium formate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1903821B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106631759B (en) | A kind of system and method producing methacrylic acid coproducing methyl methacrylaldehyde | |
| CN1903821A (en) | Technology of producing sodium oxalate by continuous dehydrogenation of sodium formate and its equipment | |
| CN1927805A (en) | Process and apparatus of preparing sodium oxalate by superheated steam ejecting mixing fast heating-up continuous dehydrogenation | |
| CN106475010A (en) | A kind of devices and methods therefor of sodium formate synthesis | |
| CN1948260A (en) | Technology of producing sodium oxalate by sodium formate spray dehydrogenation and its equipment | |
| CN105084359B (en) | A kind of method that formic acid dehydration industry prepares high-purity CO | |
| CN1047381C (en) | sodium oxalate producing process and equipment through double-circulation continuous dehydrogenation in triphase fluid bed | |
| CN104096462A (en) | Novel technology for yellow phosphorus tail gas purification | |
| CN101077855A (en) | Technique and device for continuously dehydrogenating and producing sodium oxalate by dehydrogenation reaction remaining heat | |
| CN203639370U (en) | Continuous rectification system for m-toluic acid | |
| CN1765867A (en) | Sodium Diacetate production method | |
| CN107473943A (en) | A kind of preparation method of 2,6 orcin | |
| CN112573504A (en) | Continuous production process of mesocarbon microbeads | |
| CN110339585B (en) | Maleic anhydride device solvent dehydration drying treatment process and equipment | |
| CN100999462A (en) | Process and equipment of continuous dehydrogenating producing sodium oxalate by circulating fluidized bed | |
| CN105480948A (en) | Method and system for recycling by-product hydrogen chloride in fatty acid or fatty acyl chloride chlorination production process | |
| CN102391099B (en) | Method and equipment for producing sodium oxalate through continuous dehydrogenation by two-fluid spraying | |
| CN101954198A (en) | High-pressure dehydrating tower in process of continuously producing trimellitate | |
| CN210356589U (en) | Maleic anhydride device solvent recovery system | |
| CN106800507A (en) | A kind of solid-liquid separating method produced during sodium formate | |
| CN110304608B (en) | Method for preparing ozone and by-product phosphoric acid by liquid-phase oxidation of phosphorus sludge | |
| CN103030117B (en) | Recovering technology for waste acid | |
| CN102166505B (en) | Resorcinol alkali fusion workshop section reaction device and reaction technology thereof | |
| CN110339674A (en) | Maleic anhydride unit solvent recovering system | |
| CN206008100U (en) | A kind of acetone dewatering drying device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: TAIYUAN UNIV. OF TECHNOLOGY Free format text: FORMER OWNER: LI ANMIN Effective date: 20110418 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Anmin Inventor after: Zhao Zhijun Inventor after: Zhang Aihua Inventor after: Li Zhong Inventor after: Li Yuejun Inventor before: Li Anmin Inventor before: Li Yuejun |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: LI ANMIN LI YUEYUN TO: LI ANMIN ZHAO ZHIJUN ZHANG AIHUA LI ZHONG LI YUEYUN Free format text: CORRECT: ADDRESS; FROM: 030024 NO. 3, UNIT 2, BUILDING 12, EAST AREA, HONGFENG GARDEN, QIANFENG SOUTH ROAD, WANBOLIN DISTRICT, TAIYUAN CITY, SHANXI PROVINCE TO: 030000 NO. 79, YINGZE WEST STREET, TAIYUAN CITY, SHANXI PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20110418 Address after: 030000 West Street, Taiyuan, Shanxi, No. 79, No. Applicant after: Taiyuan University of Technology Address before: 030024, No. 2, unit 12, 3 floor, Hongfeng garden, Wan Feng South Road, Wan Berlin District, Shanxi, Taiyuan Applicant before: Li Anmin |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20120801 |