CN102233224A - Method for recovering CO2 from flue gas in cement rotary kiln - Google Patents
Method for recovering CO2 from flue gas in cement rotary kiln Download PDFInfo
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- CN102233224A CN102233224A CN2010101693131A CN201010169313A CN102233224A CN 102233224 A CN102233224 A CN 102233224A CN 2010101693131 A CN2010101693131 A CN 2010101693131A CN 201010169313 A CN201010169313 A CN 201010169313A CN 102233224 A CN102233224 A CN 102233224A
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- absorption
- flue gas
- regeneration
- reboiler
- gas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention discloses a method for recovering CO2 from flue gas in a cement rotary kiln. The method comprises the following steps: (1) the flue gas is cooled and washed; (2) the washed flue gas is transferred into an absorption tower from the bottom part to be contacted with an absorption barren solution which enters the absorption tower from the upper part, and the CO2 in the flue gas is absorbed by the absorption barren solution and then is discharged from the top of the absorption tower, wherein the absorption barren solution is prepared from the following components by weight percent: 15-20% of MEA (monoethanolamine), 0.5-1% of triethanolamine and the balance of water; (3) the absorption solution absorbed with the CO2 is transferred into a regeneration tower from the upper part to be contacted with water vapor generated from a reboiler at the lower part of the regeneration tower for stripping and desorbing the CO2, and then the absorption solution enters the reboiler; and (4) the absorption barren solution flows out of the reboiler, and regeneration gas discharged from the top of the regeneration tower is transferred into a subsequent working section. The method provided by the invention has the beneficial effects of avoiding carbamate, reaching the maximum absorbing capacity up to 1mol CO2/mol MEA, and solving the problems such as efficiency and corrosion resistance.
Description
Technical field
The present invention relates to CO
2Recovery technology.
Technical background
Cement is a kind of TPR gel material, has the hydraulicity and is not only can harden in water but also can hardened in air a kind of construction material, the history in existing 185 years so far.Cement and steel, timber, plastics are referred to as four big foundation engineering materials.Cement industry is the typical energy and resource dependent form industry, new type nonaqueous cement technology CO
2Emission source is mainly derived from the decomposition of calcium carbonate, the burning of fuel and the consumption of electric power, and proportion is respectively 62%, 34% and 4%.
In cement raw material, the proportioning of general lime stone accounts for 80%～85%, in finished cement, account for about 70%, so the calcium carbonate resource that production cement needs is very big, and the CO that discharges in the production process
2Also maximum, clinker burning is the core process of cement industry, need a large amount of heats by the raw material mature calcined material, it is main fuel that coal is almost all adopted in China cement plant, cement comprehensive energy consumption per ton on average is about 115kg mark coal, and is current in the important branch of industry of China, except coal electricity and steel industry, cement industry is the industry of CO2 emissions maximum in the production process, and CO
2Absorb integral body and be in the starting stage, so cement industry is accelerated development low-carbon economy, promoted CO
2Reduce discharging, develop CO
2Seizure and carbon sequestration technology have very important meaning.
Reclaim CO in enterprises such as coal-burning power plant, steel plant commonplace employing chemical solvent absorption method at present
2, the chemical solvent absorption rule is utilized carbon dioxide and a certain solvent chemically reactive, generates intermediate compound, and other gases not with this solvent reaction; Generate carbon dioxide and solvent again after the intermediate compound that generates decomposes in the another one device, solvent is recycled, and carbon dioxide is discharged continuously, thereby makes carbon dioxide and other mixed gas separation.The chemical solvent absorption method is again based on the EMA method of comparative maturity, it is solvent that the EMA method adopts monoethanolamine, monoethanolamine absorbs the carbon dioxide in the flue gas under cryogenic conditions (40-50 ℃), when solution heats then (100-120 ℃), carbon dioxide discharges from chemical solvent, so obtain the carbon dioxide of high concentration.
Traditional MEA process reclaims low fractional pressure carbon dioxide and has the serious technical problem of equipment corrosion, its main cause is that the carbaminate that generated by MEA and carbon dioxide reaction and the chemical degradation product of MEA are caused, though certain progress is being arranged aspect the anticorrisive agent exploitation, is failing to reduce the equipment corrosion aspect and thoroughly solve from reducing the MEA degraded.Kiln exit gas temperature in cement plant reaches 160 ℃ in addition, and dust contained flue gas concentration is big, can not directly handle, therefore at CO
2Must address the above problem in the removal process.
Summary of the invention
The purpose of this invention is to provide and a kind ofly from the cement rotary kiln flue gas, reclaim CO
2Method, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) flue gas is sent into water scrubber cooling washing, made flue-gas temperature be reduced to 40 ℃ by 160 ℃, and the flush away dust, the flue gas that does not contain dust produced through moisture separator again, to meet the requirement of MEA process smoke treatment;
(2) flue gas that does not contain dust after step (1) processing is sent into the absorption tower from the bottom, with the absorption lean solution counter current contacting that enters from top, absorption tower, the CO in the flue gas
2After being absorbed the lean solution absorption, discharge from the top, absorption tower;
Described absorption lean solution comprises following as components in weight percentage:
Monoethanolamine 15～20%
Triethanolamine 0.5～1%
Water surplus
Described flue gas is cement rotary kiln flue gas, wherein CO
2Volume content be 12～18%;
The absorption tower gas liquid ratio is 180～185, volume ratio, and preferred gas liquid ratio is 182, volume ratio; Absorbing temperature is 40 ℃.
Conventional packed tower or conventional plate column can be adopted in described absorption tower;
(3) absorbed CO
2The absorption liquid of quilt, (be called for short rich solution, down with), send into regenerator from top, the water vapour counter current contacting that produces with reboiler from the regenerator bottom is by stripping desorb CO
2, enter reboiler then, make CO wherein
2Further desorb;
During regeneration, regeneration temperature is 100～110 ℃, and regeneration pressure is 0.1～0.12Mpa;
(4) desorb CO
2After the absorption lean solution flow out by reboiler 4, enter the absorption tower after the cooling again, recycle;
The regeneration gas of discharging from the regenerator top, by condenser condenses, the condensed water of separating that is condensed is sent into reboiler, is rich in CO then
2Regeneration gas, be sent to follow-up workshop section.
The present invention has added triethanolamine in right amount on monoethanolamine solvent basis, can bring into play the advantage separately of two class hydramine, is guaranteeing CO
2Under the condition of fast Absorption, reduce the regeneration energy consumption of mixed amine, effectively prevented amine degradation, reduced the corrosion to equipment, compared with traditional MEA process, absorbability improves more than 25%, energy consumption reduces more than 30%, and operating cost reduces by 30% at least, is used to reclaim low dividing potential drop CO
2, especially recovery contains CO in the higher kiln exit gas of oxygen
2, have higher utility.
MEA (monoethanolamine) with the reaction mechanism of carbon dioxide is: in reclaiming the carbon dioxide process, MEA easily with generation chemical degradations such as oxygen, carbon dioxide, sulfide, thermal degradation also easily takes place, and causes that the main cause that MEA degraded loss increases is the oxidative degradation of oxygen and MEA.The degraded intermediate product of MEA and oxygen is mainly peroxide, and end product is an amion acetic acid etc., Yaos oxazolidine ketone etc. with the catabolite Zhu of carbon dioxide.The MEA degradation problem is that MEA process reclaims the insoluble technical barrier that carbon dioxide exists always, and MEA and carbon dioxide reaction generate more stable carbaminate, need more energy to decompose in regenerative process, and the energy consumption that causes regenerating is bigger.The corrosivity of carbamic acid salt pair equipment is stronger simultaneously, easily forms incrustation scale again.This shows that the MEA absorbing carbon dioxide has the advantages that absorption rate is fast, uptake is little, heap(ed) capacity is 0.5mol CO
2/ molMEA.
Triethanolamine can not generate carbaminate because of there not being unnecessary H atom, brings into play CO simultaneously in absorption process
2Catalytic action during hydrolysis, heap(ed) capacity are 1mol CO
2/ molMEA.Be characterized in not being subjected to thermodynamic (al) restriction, absorbability is strong, but absorption rate is lower.The two combination can solve efficient and corrosion resistant problem.
Traditional MEA process reclaims low fractional pressure carbon dioxide and has the serious technical problem of equipment corrosion, its main cause is that the carbaminate that generated by MEA and carbon dioxide reaction and the chemical degradation product of MEA are caused, though certain progress is being arranged aspect the anticorrisive agent exploitation, is failing to reduce the equipment corrosion aspect and thoroughly solve from reducing the MEA degraded.
Be expected to obtain bigger society and economic benefit:
(1) China produces 1,600,000,000 tons of cement cement industry year at present, if by 0.7 ton of CO of cement discharging per ton
2Meter, common property is given birth to CO
21,000,000,000 tons, so cement rotary kiln flue gas CO
2Recovery technology has the wide prospect that promotes the use, and brings the huge social benefit.
(2) carbon dioxide about 40% of whole world recovery at present is used to produce chemicals, and 35% is used for the oil field recovers the oil for 3 times, and 10% is used for refrigeration, and 5% is used for soda, and other application account for 10%, CO
2Be converted into available resources by environomental pollution source, can be enterprise and create good economic benefit, improve the capability of sustainable development of cement industry.
Description of drawings
Fig. 1 is a flow chart of the present invention.
Referring to Fig. 1, method of the present invention comprises the steps:
(1) flue gas is sent into water scrubber 1, made flue-gas temperature be reduced to 40 ℃ by 160 ℃, and the flush away dust;
(2) flue gas after step (1) processing is sent into absorption tower 2 from the bottom, with the absorption lean solution counter current contacting that 2 tops from the absorption tower enter, the CO in the flue gas
2After being absorbed the lean solution absorption, discharge from the top, absorption tower;
(3) absorbed CO
2The absorption liquid of quilt, (be called for short rich solution, down with), send into regenerator 3 from top, the water vapour counter current contacting that produces with reboiler 4 from regenerator 3 bottoms is by stripping desorb CO
2, enter reboiler 4 then, make CO wherein
2Further desorb;
(4) desorb CO
2After the absorption lean solution flow out by reboiler 4, enter absorption tower 2 after the cooling again, recycle;
The regeneration gas of discharging from regenerator 3 tops, by condenser 5 condensations, the condensed water of separating that is condensed is sent into reboiler 4, is rich in CO then
2Regeneration gas, be sent to follow-up workshop section.
The specific embodiment
Embodiment 1～15
Adopt the flow process of Fig. 1.Packed tower is adopted on the absorption tower, and the effective depth of filler is 4 meters; 160 ℃ of flue-gas temperatures.
Specifically see Table 1.Wherein running parameter is as follows:
Absorb the component and the percentage by weight of lean solution:
Embodiment 1～7:
Monoethanolamine 20%, triethanolamine 0.5%, water surplus
Embodiment 8～15
Monoethanolamine 15%, triethanolamine 1%, water surplus
Going into absorption tower lean solution amount is 0.0165m
3/ h, absorbing temperature is 40 ℃.
Regeneration temperature is 108 ℃, and regeneration pressure is 0.11Mpa;
Flue gas is the cement rotary kiln flue gas, CO
2Content is actual measured value;
The rate of recovery can be with the CO of fume emission greater than 86% with this understanding
2Recovery as content greater than 95% technical grade CO
2Product.
Table 1. kiln gas reclaims CO
2Test data
| Embodiment | Tolerance m 3/h | CO 2Content % (volume) | Purified gas CO 2Content % (volume) | Rate of recovery % | Regeneration tolerance m 3/h | Regeneration gas CO 2Content % (volume) |
| 1 | 3 | 15 | 1.4 | 91.9 | 0.4 | ?96.2 |
| 2 | 3 | 13.6 | 0.6 | 96.2 | 0.37 | ?95.6 |
| 3 | 3 | 13.8 | 0.2 | 98.7 | 0.43 | ?95.0 |
| 4 | 3 | 15.6 | 2.4 | 86.7 | 0.40 | ?95.0 |
| 5 | 3 | 16.2 | 2.2 | 88.4 | 0.40 | ?96.0 |
| 6 | 3 | 13.8 | 0.8 | 95.0 | 0.43 | ?95.0 |
| 7 | 3 | 13.8 | 0.6 | 96.2 | 0.40 | ?95.8 |
| 8 | 3 | 18.6 | 3 | 86.5 | 0.40 | ?96.0 |
| 9 | 3 | 13.8 | 0.6 | 96.2 | 0.37 | ?96.0 |
| 10 | 3 | 14 | 1 | 93.8 | 0.40 | ?95.0 |
| 11 | 3 | 13.6 | 1 | 93.6 | 0.38 | ?96.0 |
| 12 | 3 | 12 | 0.6 | 95.6 | 0.36 | ?95.0 |
| 13 | 3 | 13 | 1 | 93.2 | 0.40 | ?96.0 |
| 14 | 3 | 12.4 | 0.2 | 98.6 | 0.48 | ?95.0 |
| 15 | 3 | 12.6 | 0.2 | 98.6 | 0.46 | ?96.2 |
Result of the test shows, the CO in the kiln gas
2The rate of recovery reaches more than 86%, CO
2Content is not less than 95%, reaches the technical grade requirement.If Co., Ltd of Shanghai building material group 3.38 * 10
5m
3/ h kiln tail discharged flue gas is all carried out CO
2Reclaim, both can reduce CO
2Discharging, but the O of production products C again
2, meet the requirement of present national energy-saving and emission-reduction consumption reduction, realize remarkable economic efficiency and social benefit.
Claims (6)
1. from the cement rotary kiln flue gas, reclaim CO
2Method, it is characterized in that, comprise the steps:
(1) flue gas is sent into water scrubber cooling washing;
(2) flue gas that step (1) is obtained is sent into the absorption tower from the bottom, with the absorption lean solution counter current contacting that enters from top, absorption tower, the CO in the flue gas
2After being absorbed the lean solution absorption, discharge from the top, absorption tower;
Described absorption lean solution comprises following as components in weight percentage:
Monoethanolamine 15～20%
Triethanolamine 0.5～1%
Water surplus
(3) absorbed CO
2The absorption liquid of quilt is sent into regenerator from top, with the water vapour counter current contacting that produces from the reboiler of regenerator bottom, stripping desorb CO
2, enter reboiler then;
(4) desorb CO
2After the absorption lean solution flow out by reboiler, enter the absorption tower after the cooling again, recycle;
After the regeneration gas condensation of regenerator top discharge, be sent to follow-up workshop section.
2. method according to claim 1 is characterized in that, the absorption tower gas liquid ratio is 180～185.
3. method according to claim 2 is characterized in that, gas liquid ratio is 182.
4. method according to claim 1 is characterized in that, absorbing temperature is 40 ℃.
5. method according to claim 1 is characterized in that, during regeneration, regeneration temperature is 100～110 ℃, and regeneration pressure is 0.1～0.12Mpa.
6. according to each described method of claim 1～5, it is characterized in that described flue gas is cement rotary kiln flue gas, wherein CO
2Volume content be 12～18%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101693131A CN102233224A (en) | 2010-05-07 | 2010-05-07 | Method for recovering CO2 from flue gas in cement rotary kiln |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101693131A CN102233224A (en) | 2010-05-07 | 2010-05-07 | Method for recovering CO2 from flue gas in cement rotary kiln |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289207A (en) * | 2015-10-09 | 2016-02-03 | 西安交通大学 | Triethanolamine compound amine absorbent for capturing carbon dioxide |
| CN106731499A (en) * | 2016-12-23 | 2017-05-31 | 重庆耐德工业股份有限公司 | A kind of alkanolamine solution regeneration parsing control system and method |
| CN109731438A (en) * | 2019-03-22 | 2019-05-10 | 南京凯盛国际工程有限公司 | A kind of CO in white wine sludge recycling cement kiln flue gas2Method and system |
| CN110639335A (en) * | 2019-09-26 | 2020-01-03 | 江苏城乡建设职业学院 | Energy-saving method and system for regeneration tower in deep decarburization of natural gas |
| RU2751200C2 (en) * | 2018-12-05 | 2021-07-12 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for obtaining carbon dioxide for soda production by the ammonia method |
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| CN1872679A (en) * | 2006-06-05 | 2006-12-06 | 内蒙古蒙西纳米材料有限责任公司 | Method for preparing liquid carbon dioxide in foodstuff level by using tail gas of cement kiln |
| CN101417200A (en) * | 2007-10-22 | 2009-04-29 | 辽河石油勘探局 | Carbon dioxide, nitrogen gas recovering method in boiler flue gas |
-
2010
- 2010-05-07 CN CN2010101693131A patent/CN102233224A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872679A (en) * | 2006-06-05 | 2006-12-06 | 内蒙古蒙西纳米材料有限责任公司 | Method for preparing liquid carbon dioxide in foodstuff level by using tail gas of cement kiln |
| CN101417200A (en) * | 2007-10-22 | 2009-04-29 | 辽河石油勘探局 | Carbon dioxide, nitrogen gas recovering method in boiler flue gas |
Non-Patent Citations (1)
| Title |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289207A (en) * | 2015-10-09 | 2016-02-03 | 西安交通大学 | Triethanolamine compound amine absorbent for capturing carbon dioxide |
| CN106731499A (en) * | 2016-12-23 | 2017-05-31 | 重庆耐德工业股份有限公司 | A kind of alkanolamine solution regeneration parsing control system and method |
| RU2751200C2 (en) * | 2018-12-05 | 2021-07-12 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for obtaining carbon dioxide for soda production by the ammonia method |
| CN109731438A (en) * | 2019-03-22 | 2019-05-10 | 南京凯盛国际工程有限公司 | A kind of CO in white wine sludge recycling cement kiln flue gas2Method and system |
| CN109731438B (en) * | 2019-03-22 | 2024-02-20 | 中材国际智能科技有限公司 | Recovery of CO in cement kiln flue gas by white spirit sludge 2 Method and system of (2) |
| CN110639335A (en) * | 2019-09-26 | 2020-01-03 | 江苏城乡建设职业学院 | Energy-saving method and system for regeneration tower in deep decarburization of natural gas |
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