CN101638359B - Technology for producing oxalic acid by using tail gas of calcium carbide furnace - Google Patents
Technology for producing oxalic acid by using tail gas of calcium carbide furnace Download PDFInfo
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- CN101638359B CN101638359B CN2009101174391A CN200910117439A CN101638359B CN 101638359 B CN101638359 B CN 101638359B CN 2009101174391 A CN2009101174391 A CN 2009101174391A CN 200910117439 A CN200910117439 A CN 200910117439A CN 101638359 B CN101638359 B CN 101638359B
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- oxalic acid
- calcium carbide
- tail gas
- technology
- stove exhaust
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Abstract
The invention relates to a technology for producing oxalic acid by using tail gas of calcium carbide furnace, which is characterized in that the dust of the tail gas of a calcium carbide furnace is removed by a drying method and a wetting method; the tail gas is washed with alkali; coal tar is removed; and after CO purification treatment is finished, the tail gas is transmitted into an oxalic acid compounding device and reacts with sodium hydroxide. The technology emphasizes the purification of the tail gas of calcium carbide and provides raw material gas CO for producing an oxalic acid production system with high additional value by recycling and optimizing CO with high concentration in the tail gas of the calcium carbide. The technology has the following technical characteristics: the new source of raw material for producing oxalic acid is opened up; the CO in the tail gas of the calcium carbide furnace is fully recycled for converting the CO into an oxalic acid product with higher additional value; the production cost of the oxalic acid is reduced; the economic benefit of the product is enhanced; the cost for treating the pollution of the tail gas of the calcium carbide furnace is reduced; and the technology is beneficial to the establishment of the circular economic circle of the field.
Description
Technical field
The present invention relates to chemical technology field, particularly relate to a kind of technology of utilizing calcium carbide stove exhaust to produce oxalic acid.
Background technology
Oxalic acid, formal name used at school: oxalic acid, molecular formula: (COOH) 2, molecular weight: 126.07,
Proterties: anhydrous oxalic acid is the transparent crystallization or the white powder of no color or smell.Poisonous.In water-soluble, alcohol and the ether.Two water things also are clear crystals.Proportion 1.653,101 ℃ of fusing points, in the exsiccant air or heating the time then dry out and to become white powder.
Oxalic acid is organic acid dicarboxyl acids, also is one of strong acid in the organic acid.Then dry out with vitriol oil effect, be decomposed into carbonic acid gas and carbon monoxide.Oxalic acid also has reductibility, easily is oxidized to carbonic acid gas and water, plays neutralizing effect with bases, generates oxalate.
Oxalic acid on chemical industry in order to make tetramethylolmethane, cobalt oxalate, nickelous oxalate, alkalescent light green, iron and steel, soil analysis reagent set, chemical reagent etc.Dyestuff is as the colour developing dyeing auxiliaries fast.The SYNTHETIC OPTICAL WHITNER of straw, straw goods (oxalic acid has reductibility), iron rust pollution eliminator (oxalic acid and iron effect generate the ironic oxalate of solubility, are gone by washing easily, so the iron mark that can remove on the fabric to be infected with).
The CO sodium formate method is the main method of present domestic production oxalic acid.Sodium formate method is produced oxalic acid and is divided into plumbousization method and calcification again.Carbon monoxide is made sodium formiate through the sodium hydroxide solution absorption, obtain sodium oxalate through dehydrogenation again, the latter and lead sulfate (plumbousization method) effect generates lead oxalate, and post precipitation makes oxalic acid with sulfuric acid acidation again, and this technological process is a plumbousization method; Carbon monoxide absorbed through sodium hydroxide solution make sodium formiate, obtain sodium oxalate through dehydrogenation again, make oxalic acid with sulfuric acid acidation again after generating calcium oxalate precipitation with calcium hydroxide (calcification) effect, this technological process is a calcification.
The reaction equation of above-mentioned plumbousization method is as follows:
NaOH+CO——HCOONa
2HCOONa——(COONa)
2+H
2
(COONa)
2+PbSO
4——(COO)
2Pb+Na
2SO
4
(COO)
2Pb+H
2SO
4——H
2C
2O
4+PbSO
4
From above-mentioned introduction as can be seen: CO is the main production raw material of oxalic acid.CO is actually the intermediate raw material of necessity of Coal Chemical Industry, and its status is equivalent to the ethene of petrochemical complex.The most large chemical of deriving is synthetic ammonia and methyl alcohol at present, and the step preface that relates generally to is purification, desulfurization, conversion, decarburization and synthetic.
Can derive the more chemical of high added value by CO and methyl alcohol, petroleum chemicals especially, the infant industry of Xing Chenging is called Coal Chemical Engineering Industry thus.Such as, CO sodium formate method, CO coupling system oxalic acid and CO methyl alcohol system acetic acid, almost all having replaced in the world is the petrochemical complex route of raw material with ethene.Producing at present the required CO major part of oxalic acid and being is to extract the coal gas of raw material production from coke(oven)gas or with the coal, the cost height, and be subjected to the restriction of current energy scarcity.
Calcium carbide stove exhaust is the waste gas that produces in the calcium carbide production process.In the closed calcium carbide furnace production system, but about one ton of calcium carbide by-product of every product tail gas amount, 400 standard cubic meter, contain CO, H in the calcium carbide stove exhaust
2, CO
2, N
2, O
2Deng, wherein all CO gas more than 85%, as shown in table 1.At present, for the processing of calcium carbide stove exhaust, most of enterprises ignite the torch to burn, or introduce boiler and burn, so not only contaminate environment but also wasted valuable CO resource.
Table 1 calcium carbide stove exhaust main component %
| CO | H 2 | CO 2 | N 2 | O 2 |
| 85～95 | 1～2.5 | 1～1.5 | 5～20 | 1～1.5 |
Summary of the invention
Purpose of the present invention just is to overcome the defective of above-mentioned prior art, provide a kind of abundant recycling refuse energy to solve and be used for the in short supply of oxalic acid raw materials for production CO and restriction, reduce production costs, increase economic efficiency, and promote the added value of calcium carbide stove exhaust, realization recycling economy process utilizes calcium carbide stove exhaust to produce the technology of oxalic acid.
The present invention is achieved through the following technical solutions:
A kind of technology of utilizing calcium carbide stove exhaust to produce oxalic acid is characterized in that: with calcium carbide stove exhaust through dry method dust, wet dedusting, alkali cleaning removes coal tar, and sends in the oxalic acid synthesizer after the CO purification processes and react with sodium hydroxide;
Before dry method dust, at first calcium carbide stove exhaust is cooled to 220 ℃～250 ℃;
Above-mentioned dry method dust is to carry out in sack cleaner;
Above-mentioned wet dedusting is to carry out in water wash column;
Before carrying out alkali cleaning, tail gas need be pressurizeed;
Described alkali cleaning is to carry out in thionizer;
The described coal tar that removes is to carry out in the static decoking device;
It is to adopt pressure swing adsorption technique that described CO purifies.
The present invention focuses on the purification calcium carbide tail gas, by reclaiming, optimize the CO that utilizes the calcium carbide tail gas middle and high concentration, and the oxalic acid production system that has a high added value to the production gas CO that supplies raw materials.
The present invention has following technical characterstic:
1. the new raw material sources of oxalic acid production have been opened up;
2. fully recycle the CO in the calcium carbide stove exhaust, make it transform into the higher oxalate product of added value;
3. reduce the production cost of oxalic acid, improved the economic benefit of product;
4. reduce the cost of calcium carbide stove exhaust Pollution abatement, helped the foundation of this field recycling economy circle.
Description of drawings
Fig. 1 is a production technique block diagram of the present invention.
Embodiment
Specific embodiment of the present invention is:
About 600 ℃ high temperature calcium carbide stove exhaust from the closed calcium carbide furnace smoke exhaust pipe is drawn is cooled to 220 ℃～250 ℃ through the air cooling fly-ash separator, sends into the sack cleaner dedusting then, goes out behind the sack cleaner in the calcium carbide stove exhaust dustiness at 40mg/Nm
3Below.Send cooling dedusting water wash column further wet cooling dedusting again, the temperature that makes calcium carbide stove exhaust less than 45 ℃, particle concentration less than 1mg/Nm
3Below.Go out water wash column after behind the water droplet of carrying secretly in the knockout tower divided gas flow, introduce supercharger and make the pressure of gas bring up to the cabinet storage of 350 mmhg after pipeline is supplied gas.The calcium carbide stove exhaust after purifying that comes out from gas holder send thionizer after the pressurization of Roots's machine, carry out wet desulphurization.The sulphur content of gas send the static decoking device to deviate from coal tar contained in the gas less than 10mg/Nm after the desulfurization.Gas is introduced compressor from the static decoking device back of coming out, and send shift conversion step after gaseous tension is brought up to 0.8MPa, under the effect of catalyst, and portion C O and H
2O (gaseous state) reaction generates CO
2With H
2, the gas after the conversion is delivered to decarburization workshop section again, adopts pressure swing adsorption technique, deviates from the CO in the gas
2, make the H in the gas
2Send the oxalic acid production system about/CO=2.
Above-mentioned oxalic acid production system adopts oxalic acid production system conventional in the prior art, i.e. plumbousization method or calcification.
Claims (6)
1. a technology of utilizing calcium carbide stove exhaust to produce oxalic acid is characterized in that: at first calcium carbide stove exhaust is cooled to 220 ℃～250 ℃, dry method dust, wet dedusting, pressurization back alkali cleaning removes coal tar, sends into after the CO purification processes in the oxalic acid synthesizer and reacts with sodium hydroxide.
2. according to the described technology of utilizing calcium carbide stove exhaust to produce oxalic acid of claim 1, it is characterized in that: above-mentioned dry method dust is to carry out in sack cleaner.
3. according to the described technology of utilizing calcium carbide stove exhaust to produce oxalic acid of claim 1, it is characterized in that: above-mentioned wet dedusting is to carry out in water wash column.
4. according to the described technology of utilizing calcium carbide stove exhaust to produce oxalic acid of claim 1, it is characterized in that: described alkali cleaning is to carry out in thionizer.
5. according to the described technology of utilizing calcium carbide stove exhaust to produce oxalic acid of claim 1, it is characterized in that: described to remove coal tar be to carry out in the static decoking device.
6. according to the described technology of utilizing calcium carbide stove exhaust to produce oxalic acid of claim 1, it is characterized in that: it is to adopt pressure swing adsorption technique that described CO purifies.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101174391A CN101638359B (en) | 2009-09-04 | 2009-09-04 | Technology for producing oxalic acid by using tail gas of calcium carbide furnace |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101174391A CN101638359B (en) | 2009-09-04 | 2009-09-04 | Technology for producing oxalic acid by using tail gas of calcium carbide furnace |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101638359A CN101638359A (en) | 2010-02-03 |
| CN101638359B true CN101638359B (en) | 2011-12-21 |
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| CN2009101174391A Expired - Fee Related CN101638359B (en) | 2009-09-04 | 2009-09-04 | Technology for producing oxalic acid by using tail gas of calcium carbide furnace |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072945B (en) * | 2013-01-18 | 2015-03-11 | 东华工程科技股份有限公司 | Process for preparing ethanediol synthetic gas by non sulfur-tolerant shift of calcium carbide furnace gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456546A (en) * | 2003-03-18 | 2003-11-19 | 四川亚联高科技有限责任公司 | Method for preparing potassium formate and sodium formate from carbide furnace tail gas as raw material |
| CN1939840A (en) * | 2006-09-30 | 2007-04-04 | 宁夏英力特电力集团股份有限公司 | Tail gas treatment and reutilization for calcium carbide stove |
-
2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456546A (en) * | 2003-03-18 | 2003-11-19 | 四川亚联高科技有限责任公司 | Method for preparing potassium formate and sodium formate from carbide furnace tail gas as raw material |
| CN1939840A (en) * | 2006-09-30 | 2007-04-04 | 宁夏英力特电力集团股份有限公司 | Tail gas treatment and reutilization for calcium carbide stove |
Non-Patent Citations (1)
| Title |
|---|
| 马清祥等.电石炉气的综合利用.《聚氯乙烯》.2007,(第12期),40-42,45. * |
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