CN1903821B - 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
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- CN1903821B CN1903821B CN2006101068168A CN200610106816A CN1903821B CN 1903821 B CN1903821 B CN 1903821B CN 2006101068168 A CN2006101068168 A CN 2006101068168A CN 200610106816 A CN200610106816 A CN 200610106816A CN 1903821 B CN1903821 B CN 1903821B
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- sodium oxalate
- sodium
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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 Processes and apparatus of producing sodium oxalate by continuous dehydrogenation of sodium formate of the present invention belongs to organic chemistry filed, relates to the carboxylate salt preparation, is the production technique and the equipment of a kind of sodium oxalate and oxalic acid specifically.
At present, the technology of domestic production sodium oxalate is interrupter method, and its process is carried out in dehydrogenation at intermittence pot.Method is that heat with stove fire in the bottom of a pan with in exsiccant sodium formiate input dehydrogenation at the intermittence pot, and material heats up gradually; When temperature rose to about 310 ℃ of desorption temperature, the beginning dehydrogenation heated up simultaneously and accelerates; When temperature reached 400 ℃ of left and right sides, the rapid dehydrogenation of sodium formiate was because the certain embodiments heat release; Temperature of charge also sharply rises, and certain embodiments finishes immediately.After the cooling, manual work is shifted out product outside the pot, prepares to feed intake again.The advantage of this method is that equipment is simple, less investment.But because heating is irregular, be easy to thermolysis or carbonization near near the material the pot wall, secondly because the TRT is long, by product is many, and yield is low, has only 80% to 85% usually.Energy consumption and material loss are all bigger.In addition, high-temperature operation, work under hard conditions, labour intensity is big, sodium formiate and sodium oxalate have certain toxicity again.Dust from flying has great influence to workers ' health in operation.
Abroad in order to improve the dehydrogenation yield and to make the certain embodiments serialization, the chain continuous dehydrogenation device of employing, chain is processed by exotic materials, and purpose is to prevent the material adhesion.Material is divided uniformly with spray form through nozzle and is being about on 400～450 ℃ the chain through Heating temperature, the back dehydrogenation that heats up of being heated, and material is peeled off from chain subsequently, and dehydrogenation finishes, and chain continues cycle.The advantage of this method is to have realized the dehydrogenation serialization, has improved the dehydrogenation yield.Shortcoming is that facility investment is big, from such equipment of external introduction, needs 3,000 ten thousand yuan approximately.Because its chain is processed by exotic materials, up to the present, China can't prepare such equipment voluntarily simultaneously.
In order to improve the dehydrogenation yield; And realizing the certain embodiments serialization, the expert is all at the new-type dehydrogenation equipment of research both at home and abroad, from disclosed patent at present; Two types of representative continuous dehydrogenation Processes and apparatus are arranged, and one type is rotary drum continuous dehydrogenation Processes and apparatus.It is that material is uniformly sprayed through heating, has the drum surface of certain temperature, and material is realized dehydrogenation in drum surface; With scraper dehydrogenation product is removed from rotary drum then, rotary drum continuously rotates, with the serialization of implementation procedure; The advantage of this technology is to have realized the dehydrogenation serialization, and the dehydrogenation yield is increased, but shortcoming is the device structure complicacy; Require the equipment making precision high, be difficult in the industry realize the industriallization of being unrealized so far.Another kind of is the fluidized-bed continuous dehydrogenation, it be with the flue gas that forms after the gas-fired as thermal source, hot gas flow is from bottom to top through fluidized-bed, gas was scurried from the gap of material and with the material bed that blows off, thereby formed fluidized-bed.Material leaves fluidized-bed from tremie pipe after the dehydrogenation in fluidized-bed.The advantage of this method also is to have realized serialization; The dehydrogenation yield is improved, but shortcoming has three, first turndown ratio is little, not easy to operate; It two is to use the coal gas direct heating; Sulphur wherein has poisoning effect to certain embodiments, and it three is that the later product of dehydrogenation can not in time be lowered the temperature, and may cause material to decompose or carbonization.
The technology that double-circulation continuous dehydrogenation in triphase fluid bed is produced sodium oxalate is that the stack gas after nitrogen, air or the desulfurization is heated to 430 ℃～600 ℃ as heating agent, feeds through the bottom of gas blower from fluidized-bed, passes through fluidized-bed from bottom to top; Sodium formiate is melted in the fusion pot and is preheated to 200 ℃～250 ℃, then the sodium formiate of molten state is squeezed into fluidized-bed top with pressure pump; With under the spray form spray, with the high temperature gas flow counter current contact that rises, the residence time of sodium formiate in fluidized-bed was controlled in 20 seconds sodium formiate through shower nozzle in fluidized-bed, and the residence time of dehydrogenation product sodium oxalate in fluidized-bed was controlled in 10 seconds; The dehydrogenation product sodium oxalate is taken out of fluidized-bed rapidly by upstream and is got into successively and separates in cyclonic separator and the washing tower and cool off.The advantage of this method is on the basis of common fluidized-bed, to improve; Product after the dehydrogenation is taken out of fluidized-bed rapidly and is able to rapid cooling; Avoided the further decomposition of product; Further improved the yield of product, but a shortcoming has also been arranged, failed exactly thoroughly to solve owing to containing the safety-problems that a large amount of hydrogen bring in the dehydrogenation product.
The objective of the invention is to improve above-mentioned production technique, improve the dehydrogenation yield, and overcome the deficiency that above-mentioned technology exists, thereby a kind of Processes and apparatus of more safe and reliable producing sodium oxalate by continuous dehydrogenation of sodium formate is provided.
The object of the invention can be realized through following measure:
The Processes and apparatus of producing sodium oxalate by continuous dehydrogenation of sodium formate of the present invention is to be raw material with the sodium formiate, and continuous dehydrogenation prepares the novel process of sodium oxalate.The chemical formula of this reaction is following:
Be reflected between 310～450 ℃ and carry out, optimal reaction temperature and in the material temperature-rise period, especially is easy to produce side reaction about 300 ℃ about 420 ℃.
2HCOONa————→Na
2CO
3+CO↑+H
2↑
Thereby something must be done to that material is rapidly heated, and crosses 300 ℃ of these stages of the left and right sides rapidly, reaches about 420 ℃ of desorption temperatures with the short as far as possible time.In addition, certain embodiments is an exothermic process, and temperature of charge still can continue to rise after the dehydrogenation, and the sodium oxalate that generates after the dehydrogenation at high temperature decomposes and carbonization easily.So the product sodium oxalate after the dehydrogenation should leave high-temperature zone and cooling immediately immediately, just can avoid decomposing and carbonization.
The technology of producing sodium oxalate by continuous dehydrogenation of sodium formate; (1) with temperature be about 500 ℃ superheated vapour be heated to molten state; Temperature is that 260～280 ℃ sodium formiate gets into jet mixer simultaneously; The ratio of control superheated vapour and sodium formiate reaches about 420 ℃ mixed temperature, and in pipeline, carries out dehydrogenation reaction;
(2) the later mixture of dehydrogenation gets in the cyclonic separator and carries out gas solid separation; The sodium oxalate solid is discharged from the bottom; Hydrogen contacts with the sodium oxalate aqueous solution that gets off from top spray, makes behind its washing, purifying to discharge from top, and the sodium oxalate aqueous solution flows into the water-soluble liquid bath of sodium oxalate from the bottom.
A sodium oxalate aqueous solution part of (3) discharging from the cyclonic separator downtake is further processed to next workshop section, and another part is squeezed into cyclonic separator top by recycle pump and recycled after heat exchanger cooling.
The equipment of producing sodium oxalate by continuous dehydrogenation of sodium formate technology is: be made up of jet mixer (1), cyclonic separator (2), the water-soluble liquid bath of sodium oxalate (3), recycle pump (4); Jet mixer (1) is connected through pipeline and cyclonic separator (2); Cyclonic separator (2) is connected through pipeline and the water-soluble liquid bath of sodium oxalate (3), and the water-soluble liquid bath of sodium oxalate (3) is connected through pipeline and recycle pump (4).The inlet of recycle pump (4) is connected through pipeline and the water-soluble liquid bath of sodium oxalate (3), and outlet is connected through pipeline and cyclonic separator (2).
Advantage of the present invention:
1. realize serialization production, improved labour productivity, improved working condition and work situation;
2. because superheated vapour and sodium formiate liquid thorough mixing in jet mixer are rapidly heated, shorten the TRT, reduced the generation of by product, improved the yield of sodium oxalate;
3. the sodium formiate sodium oxalate Peng Song shape solid particulate that dehydrogenation generates later in pipeline is taken out of rapidly by air-flow, and gets into cooling rapidly in the cyclonic separator, has reduced the decomposition of sodium oxalate, has improved the yield of sodium oxalate;
4. adopted the circulation cooling of the sodium oxalate aqueous solution, when improving the sodium oxalate yield, washing, purifying hydrogen, the sodium oxalate aqueous solution can directly get into next workshop section, promptly plumbous chemical industry section has been omitted the sodium oxalate dissolution process.
5. adopt superheated vapour as heating medium, the total system three-waste free discharge, and, contain oxygen in the superheated vapour hardly because the mature technology of BW deoxygenation is arranged, thoroughly solved the safety-problems of hydrogen, for suitability for industrialized production provides safety control.
Description of drawings is following:
Accompanying drawing is a processing unit schematic diagram of the present invention, and wherein 1 is jet mixer, the 2nd, and cyclonic separator, the 3rd, the water-soluble liquid bath of sodium oxalate, the 4th, recycle pump.
Further comment through embodiment below in conjunction with accompanying drawing:
Produce 10000 tons of sodium oxalate production equipments per year, about 500 ℃ superheated vapours as heating agent, and are heated to molten state; Temperature is that 260～280 ℃ sodium formiate liquid gets into jet mixer simultaneously, in jet mixer, mixes the ratio of control superheated vapour and sodium formiate rapidly; Mixed temperature is reached about 420 ℃, and mixture carries out dehydrogenation reaction in pipeline, and the hydrogen that produces after the dehydrogenation mixes with water vapor; Thoroughly solved the security hidden trouble of hydrogen; The sodium oxalate of Peng Songzhuan after the dehydrogenation is taken out of the entering cyclonic separator rapidly by the mixed airflow of hydrogen and water vapor formation, and cyclonic separator is with the cooling of sodium oxalate aqueous solution circulated sprinkling, and the sodium oxalate aqueous solution that temperature is low gets off from top spray; The mixed gas that hydrogen and water vapor form is being carried the product sodium oxalate that produces after the dehydrogenation secretly from bottom to top; Through fully contact, and control the flow of the sodium oxalate aqueous solution well, make it that lucky total condensation of water vapor in mixed gas is got off to become water of condensation; The sodium oxalate that to wherein carry secretly simultaneously all is dissolved in the aqueous solution; Flow directly into the water-soluble liquid bath of sodium oxalate through downtake, a part is squeezed into cyclonic separator top by recycle pump and is recycled then, and another part is further processed to next workshop section.Hydrogen through washing, cooling, after purifying discharges from the cyclonic separator top that to send into gas holder for use.
Claims (2)
1. the technology of a producing sodium oxalate by continuous dehydrogenation of sodium formate; It is characterized in that: (1) is 500 ℃ superheated vapour with temperature and is heated to molten state; Temperature is that 260～280 ℃ sodium formiate gets into jet mixer simultaneously; The ratio of control superheated vapour and sodium formiate makes mixed temperature reach 420 ℃, and in pipeline, carries out dehydrogenation reaction; (2) the later mixture of dehydrogenation gets in the cyclonic separator and carries out gas solid separation; The sodium oxalate solid is discharged from the bottom; Hydrogen contacts with the sodium oxalate aqueous solution that gets off from top spray, makes behind its washing, purifying to discharge from top, and the sodium oxalate aqueous solution flows into the water-soluble liquid bath of sodium oxalate from the bottom; A sodium oxalate aqueous solution part of (3) discharging from the cyclonic separator downtake is further processed to next workshop section, and another part is squeezed into cyclonic separator top by recycle pump and recycled after heat exchanger cooling.
2. the equipment of the technology of the described a kind of producing sodium oxalate by continuous dehydrogenation of sodium formate of claim 1; It is characterized in that forming by jet mixer (1), cyclonic separator (2), the water-soluble liquid bath of sodium oxalate (3), recycle pump (4); Jet mixer (1) is connected through pipeline and cyclonic separator (2); Cyclonic separator (2) is connected through pipeline and the water-soluble liquid bath of sodium oxalate (3); The water-soluble liquid bath of sodium oxalate (3) is connected through pipeline and recycle pump (4), and the inlet of recycle pump (4) is connected through pipeline and the water-soluble liquid bath of sodium oxalate (3), and outlet is connected through pipeline and cyclonic separator (2).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
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| 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 |
| 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 |
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| 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 |
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| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
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