CN102876828B - Reducing gas purification process and system matched with gas-based shaft furnace - Google Patents
Reducing gas purification process and system matched with gas-based shaft furnace Download PDFInfo
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- CN102876828B CN102876828B CN201210364110.7A CN201210364110A CN102876828B CN 102876828 B CN102876828 B CN 102876828B CN 201210364110 A CN201210364110 A CN 201210364110A CN 102876828 B CN102876828 B CN 102876828B
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- desulfurization
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- 238000000746 purification Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000005261 decarburization Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000007906 compression Methods 0.000 claims abstract description 7
- 230000006835 compression Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000023556 desulfurization Effects 0.000 claims description 29
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 239000003245 coal Substances 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 abstract 3
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 abstract 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 100
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003034 coal gas Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
Abstract
The invention provides a reducing gas purification process and a system matched with a gas-based shaft furnace; the process comprises the following steps: desulfurating raw gas by a MDEA solution, performing cooling and gas-liquid separation, delivering the gas into a compressor for compression, performing a shift reaction with water vapor at a certain pressure and temperature, separating the liquid by a gas-liquid separator, then performing compression, mixing the shifted gas from the compressor with furnace top gas of a gas-based shaft furnace compressed by the compressor, performing desulfuration and decarburization by the MDEA solution to generate reducing gas, performing cooling and gas-liquid separation of the reducing gas, heating, performing iron reduction in the shaft furnace, performing purification and gas-liquid separation of the furnace top gas generated through a shaft furnace reaction, compressing the furnace top gas by the compressor, and repeating the processes after mixing with the shifted gas. The method of the invention is not only low in energy consumption, but also good in MDEA solution absorption effect, has less equipment corrosivity, makes full use of the furnace top gas of the shaft furnace, and solves both furnace top gas purification and cyclic utilization.
Description
Technical field
The present invention relates to a kind of gas purifying technique, particularly relate to a kind of reducing gas purification process supporting with gas-based shaft kiln and system.
Background technology
At present, the mode of external multiplex gas renormalizing reducing gas provides CO+H
2reducing gas, compared with abroad, owing to being subject to the restriction of natural gas source, China does not have large-scale shaft furnace process direct-reduced iron production plant so far.But rich coal resources in China, the level of resources utilization of coal is lower, if will carry out deep purifying desulfurization process after gasification as unstripped gas, then mixes with appropriate water vapour etc., enters shift converter and carries out transformationreation and can obtain H
2the H of/CO between 4.6-1.5
2with the gas mixture of CO.These gas mixtures can produce the reducing gas of sponge iron as direct-reduction, and have the advantages such as cheap.
Most sulfur-bearing in the gas of gasification, this operating mode will bring very adverse influence to the type selecting of gas compressor and operation, therefore require first to carry out raw gas desulfurization, then just can enter the process gas of gas-based shaft kiln as reduced iron through operations such as overdraft, CO conversion, fine de-sulfur, decarburizations.In raw gas sulfur removal technology, if take ammoniacal liquor liquid catalytic, modified ADA method, tannin process, KCA method etc., also the requirement of desulfurizing and purifying technique can be met, but the greatest drawback due to these sulfur methods is that solution Sulfur capacity is low, high and process broad-minded operating mode for sulphur content, there is the drawbacks such as solution circulated amount is large, manipulation strength is large, energy consumption is high.And the process such as raw gas desulfurization and follow-up fine de-sulfur, decarburization adopts different Technologies.This makes whole device flow process comparatively complicated, and operational administrative inconvenience, facility investment costly.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of reducing gas purification process supporting with gas-based shaft kiln and system, this invention solves the problems such as the manipulation strength existed in traditional sulfur method is large, energy consumption is high, and the device flow process complexity that the process need such as raw gas desulfurization and follow-up fine de-sulfur, decarburization adopts different Technologies and causes, the problems such as facility investment expense is high.And a kind of gas purifying technique supporting with gas-based shaft kiln reduced iron is provided, solves top gas purification and recycle simultaneously.
The object of the invention is to be achieved through the following technical solutions:
With the reducing gas purification process that gas-based shaft kiln is supporting, comprise the following steps:
(1) raw gas is after dedusting cooling, carries out desulfurization with N methyldiethanol amine (i.e. MDEA) solution;
(2) raw gas after desulfurization delivers to compressor compresses after cooling and gas-liquid separation;
(3) fully mix with water vapor through compressor gas out, carry out transformationreation, then after gas-liquid separator separates liquid, return compressor and compress;
(4) mix through the compressor gas-based shaft kiln top gas of conversion gas after compressing through compressor out, carry out desulfurization and decarburization with N methyldiethanol amine solution, generate reducing gas;
(5) reducing gas is after cooling and gas-liquid separation, and heat temperature raising, enters reduction shaft furnace iron;
(6) top gas through the generation of shaft furnace reaction passes through purification, gas-liquid separation, enters compressor compresses;
(7) top gas repeating step (the 4)-step (6) after compression.
The N methyldiethanol amine solution that described step (1) and described step (4) are discharged, flash tank is entered after mixing, carry out desulfurization regeneration, the N methyldiethanol amine solution after regeneration, after interchanger and solution cooler heat exchange, recycles in step (1) and step (4).
In described step (6), the reacted top gas of shaft furnace adopts N methyldiethanol amine solvent to purify.
In the reducing gas that described step (4) generates, H
2+ CO volume content more than 88%, H
2/ CO volume ratio can regulate between 4.6-1.5, oxidisability <5%, regulates pressure to be about 1.0MPa (G).
In described step (5), Heating temperature is 900 DEG C.
The scavenging process of described step (6) also comprises dedusting.
The system that the described reducing gas purification process supporting with gas-based shaft kiln is used, comprises gas maked coal unit, thick desulfurization unit, the first compressed element, converter unit, mixed cell, fine de-sulfur decarburization unit, heating unit, reduction shaft furnace unit, the second compressed element, wherein, described gas maked coal unit connects thick desulfurization unit successively, the first compressed element, converter unit, mixed cell, fine de-sulfur decarburization unit, heating unit, reduction shaft furnace unit, the second compressed element, mixed cell.
Described gas maked coal unit is connected with described heating unit.
Described second compressed element is connected with fine de-sulfur decarburization unit.
Described heating unit is tubular oven.
Technical scheme provided by the invention, in order to the convenience operating and manage, the thick desulfurization of coal gas and reducing gas desulfurization and decarburization is adopted all to carry out in the equipment adopting same Solvents N-methyl diethanolamine (MDEA), simultaneously the MDEA of desulfurization and the MDEA of desulfurization and decarburization shares a set of solution regeneration system, simultaneously due in vertical furnace top gas except the CO of reaction generation
2with outside water, still there is a large amount of CO and H
2do not participate in reaction, in order to improve the utilization ratio of reducing gas and improve economic performance, the purification process of shaft furnace furnace roof circulation gas also can be merged in purification system of the present invention, thus simplified system, saving energy consumption, the utilization ratio improving reducing gas, minimizing number of devices and investment.
Accompanying drawing explanation
Fig. 1 is reduction purification process flow sheet supporting with gas-based shaft kiln in the present invention
Embodiment
For better the present invention being described, below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described.
1. thick desulfurization: raw gas enters purification system after the technique such as dedusting, washing, with the MDEA solution counter current contact in tower in thionizer, makes most of H of gas mixture body weight
2s and part SO
2absorbed with COS.The raw gas (normal temperature) going out thionizer enters tower top water cooler, and be cooled to 40 DEG C by because absorbing the process gas heated up, process gas carries out gas-liquid separation, reclaims MDEA absorption liquid.Then process gas gas delivery compression.The rich solution of discharging at the bottom of thionizer, carries out desulfurization regeneration, and the MDEA solution after regeneration returns thionizer after interchanger and solution cooler heat exchange and decarbonizing tower recycles.
2. compress 1: compressor, by after gas compression to certain pressure, imports shift conversion step.
3. convert: gas compressor exit gas enters shift conversion step under certain pressure and temperature, entrained oil water in compression process is separated through water-and-oil separator, entering mixing tank together with water vapor makes steam fully mix with coal gas, the raw gas of about 65% enters heat exchanger, is that the heat exchange of entrance coal gas heats up with the conversion gas going out shift converter.Coal gas rises to 300-360 DEG C by 130 DEG C; Conversion gas is down to 150-180 DEG C by 400-350 DEG C.Then through water cooler, temperature is down to about 40 DEG C, then enters gas-liquid separator, returns gas compressor after separating technology phlegma, H in reducing gas after compressor pressure-raising
2/ CO is between 4.6-1.5.
4. mix: gas compressor outlet conversion gas exports reducing gas with shaft furnace furnace roof recycle gas compressor and mixes.The reducing gas that Sweet natural gas or coke-oven gas obtain exports reducing gas with shaft furnace furnace roof recycle gas compressor and mixes.
5. fine de-sulfur decarburization: enter air inlet oil eliminator after reducing gas that the conversion gas of gas maked coal exports with recycle gas compressor (or Sweet natural gas or the obtained reducing gas of coke-oven gas export reducing gas with shaft furnace furnace roof recycle gas compressor mix) mixes, laggard fine de-sulfur decarbonizing tower, reducing gas bottom in and top out, absorption liquid upper entering and lower leaving, counter current contact.Gas after decarburization by tower top out, enters tower top water cooler, reclaiming MDEA absorption liquid.Tubular oven (H is sent into after reducing gas upon mediation pressure after purification
2+ CO can reach more than 88%, H
2/ CO can regulate between 4.6-1.5, oxidisability <5%, and pressure is about 1.0MPa (G)) regulate after pressure and send process furnace.
6. diamond heating: for being heated to temperature ~ 900 DEG C of reduction shaft furnace iron to reducing gas.
7. compress 2: be entrained with 400 ~ 450 DEG C, iron ore dust through the reacted process gas of reduction shaft furnace and discharged by shaft furnace top, eject by shaft furnace the top gas come and enter water washing dedust tower, purified gas makes fuel through circulation gas gas-liquid separator small part as discharging pneumatic transmission process furnace, to maintain the inert gas balance of system, after major part boosts to certain pressure as circulation pneumatic transmission recycle gas compressor, send into the clean desulfurization and decarburization of MDEA together with fresh conversion gas.
Of the present invention have following beneficial effect:
1. reduce investment, reduce the difficulty of operation, removed by the most of sulphur in raw gas in advance before transformationreation, the e-quipment and pipe reducing conversion and decarbonization process, to the design requirements of material, decreases investment; MDEA stability of solution is good, does not degrade, and volatility is little, little to carbon steel equipment corrosion, low to hydrocarbon solubility; The purification of the thick desulfurization of coal gas, reducing gas desulfurization and decarburization and vertical furnace top gas all adopts same solvent MDEA, and MDEA desulfurization and MDEA desulfurization and decarburization share a set of solution regeneration system, have been convenient to operate and management.
2. multiple-effect removes performance, can remove H in a system simultaneously
2s, organosulfur, SO
2, COS, CO
2deng, and meet by-product CO in regeneration time-division other places reason
2gas product, H
2s is concentrated waits requirement.
3. degree of purification is high, purified gas total sulfur≤10mg/m
3, CO
2content≤1%.
4. solution receptivity is large, because MDEA is for CO
2, H
2s has superior absorptive character at low temperatures, has solution Sulfur capacity high compared with other purifying method, absorbs CO
2ability is high, and solution circulated amount is low, manipulation strength is large, energy consumption is high
5. reduce energy consumption, adopt the recycle of vertical furnace top gas, participate in the reaction of reduction shaft furnace iron, save the reducing gas needed for the identical taste iron ore of reduction unit mass, thus save consumption of coal.
From above-mentioned analysis, the gas purifying technique that the present invention uses saves technology investment and running cost, and the recycle of vertical furnace top gas simultaneously reduces energy consumption.Whole technique is that environmental protection and energy saving are feasible technically.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (2)
1. a reducing gas purification process supporting with gas-based shaft kiln, is characterized in that, comprise the following steps:
(1) raw gas is after dedusting cooling, carries out desulfurization, the N methyldiethanol amine solution of discharge with N methyldiethanol amine solution, flash tank is entered after mixing, carry out desulfurization regeneration, the N methyldiethanol amine solution after regeneration after interchanger and solution cooler heat exchange, recycle;
(2) raw gas after desulfurization delivers to compressor compresses after cooling and gas-liquid separation;
(3) fully mix with water vapor through compressor gas out, carry out transformationreation, then after gas-liquid separator separates liquid, return compressor and compress;
(4) mix through the compressor gas-based shaft kiln top gas of conversion gas after compressing through compressor out, desulfurization and decarburization is carried out with N methyldiethanol amine solution, generate reducing gas, the N methyldiethanol amine solution of discharging, enters flash tank after mixing, carries out desulfurization regeneration, N methyldiethanol amine solution after regeneration is after interchanger and solution cooler heat exchange, recycle, in reducing gas, H
2+ CO volume content more than 88%, H
2the volume ratio of/CO regulates between 4.6-1.5, oxidisability <5%, and adjustment pressure is 1.0MPa (G);
(5) reducing gas is after cooling and gas-liquid separation, and carry out heat temperature raising at process furnace, Heating temperature is 900 DEG C and enters reduction shaft furnace iron;
(6) top gas through the generation of shaft furnace reaction passes through purification, dedusting, gas-liquid separation, enter compressor compresses, the top gas of the generation that small part is reacted through shaft furnace makes fuel as discharging process furnace described in pneumatic transmission, all the other major parts send into the clean desulfurization and decarburization of N methyldiethanol amine solution after boosting to certain pressure as circulation pneumatic transmission recycle gas compressor together with fresh conversion gas, and the reacted top gas of shaft furnace adopts N methyldiethanol amine solvent to purify;
(7) top gas repeating step (the 4)-step (6) after compression.
2. the system that the reducing gas purification process supporting with gas-based shaft kiln according to claim 1 is used, is characterized in that, comprise gas maked coal unit, thick desulfurization unit, first compressed element, converter unit, mixed cell, fine de-sulfur decarburization unit, heating unit, reduction shaft furnace unit, the second compressed element, wherein, described gas maked coal unit connects thick desulfurization unit successively, the first compressed element, converter unit, mixed cell, fine de-sulfur decarburization unit, heating unit, reduction shaft furnace unit, second compressed element, mixed cell; Described gas maked coal unit is connected with described heating unit; Described second compressed element is connected with fine de-sulfur decarburization unit; Described heating unit is tubular oven.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103381331A (en) * | 2013-08-01 | 2013-11-06 | 中石化南京工程有限公司 | Method and device for treating hydrogen sulfide in sulfur recovery tail gas |
| CN104030243B (en) * | 2014-06-20 | 2016-04-20 | 北京神雾环境能源科技集团股份有限公司 | The system and method for a kind of gas-based shaft kiln system reducing gas purification and vent gas treatment |
| CN106702065A (en) * | 2016-12-20 | 2017-05-24 | 江苏省冶金设计院有限公司 | Novel system and novel method for preparing sponge iron through gas-based shaft kiln |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597663A (en) * | 2009-06-30 | 2009-12-09 | 上海锅炉厂有限公司 | A kind of energy recovery system for preparing sponge iron by gasification of high-pressure pulverized coal and method |
| CN202786159U (en) * | 2012-09-26 | 2013-03-13 | 北京神雾环境能源科技集团股份有限公司 | Reducing gas purification system matched with air base shaft furnace |
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| CN102424876B (en) * | 2011-12-26 | 2013-07-24 | 重钢西昌矿业有限公司 | Non-blast-furnace iron making process for directly reducing vanadium titanomagnetite through gas-based shaft furnace |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597663A (en) * | 2009-06-30 | 2009-12-09 | 上海锅炉厂有限公司 | A kind of energy recovery system for preparing sponge iron by gasification of high-pressure pulverized coal and method |
| CN202786159U (en) * | 2012-09-26 | 2013-03-13 | 北京神雾环境能源科技集团股份有限公司 | Reducing gas purification system matched with air base shaft furnace |
Non-Patent Citations (1)
| Title |
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| 真空膜蒸馏法再生烟气脱硫废液的实验研究;韩永嘉等;《环境工程》;20100430;第28卷(第2期);第91页右栏第2段-第92页左栏第1段 * |
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