CA2120858A1 - Enhanced recovery of carbon dioxide from kiln gas by addition of cooled carbon dioxide - Google Patents

Enhanced recovery of carbon dioxide from kiln gas by addition of cooled carbon dioxide

Info

Publication number
CA2120858A1
CA2120858A1 CA002120858A CA2120858A CA2120858A1 CA 2120858 A1 CA2120858 A1 CA 2120858A1 CA 002120858 A CA002120858 A CA 002120858A CA 2120858 A CA2120858 A CA 2120858A CA 2120858 A1 CA2120858 A1 CA 2120858A1
Authority
CA
Canada
Prior art keywords
carbon dioxide
gaseous product
gas
method
high purity
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.)
Abandoned
Application number
CA002120858A
Other languages
French (fr)
Inventor
Ramachandran Krishnamurthy
Akhilesh Kapoor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BOC Group Inc
Original Assignee
BOC Group Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to US5387493A priority Critical
Priority to US08/053,874 priority
Application filed by BOC Group Inc filed Critical BOC Group Inc
Publication of CA2120858A1 publication Critical patent/CA2120858A1/en
Application status is Abandoned legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/50Carbon dioxide

Abstract

RECOVERY OF CARBON DIOXIDE FROM KILN GAS
ABSTRACT OF THE DISCLOSURE
High purity carbon dioxide-rich gas is produced from hot, carbon dioxide-rich kiln exhaust gas by cooling the exhaust gas by injecting carbon dioxide-rich gas, such as high purity carbon dioxide or previously cooled carbon dioxide-rich kiln exhaust gas into the exhaust gas to cool the gas, removing particulate impurities from the cooled exhaust gas and separating high purity carbon dioxide from the exhaust gas.

Description

930423CRR Attorney Docket No. 92A227 5 ~ ~ ~
~.

RECOVERY OF CARBON DIOXIDE EROM ~ILD GAS

FIELp OF ~ lNVEN~IQN

This invention relates to the recovery of carbon dio~ide from gas streams, and more particularly to the recovery of carbon dioxide from gaseous effluents from kilns.

BACKGROUND OF THE INVENTION ~-Certain inorganic substances, such as limestone (calcium carbonate) and dolemite ~magnesium carbonate) contain significant quantities of carbon dioxide in the form of carbonates. When these substances are subjected to high temperatures, such as in lime and cement manufacturing processes, the carbon dio~ide is liberated from the mineral and is generally released to the atmosphere. As part of the manufacturing process the feed material is heated, usually by directly firing a fuel, such as coal or coke or a liquid or gaseous hydrocarbon or misture of hydrocarbons into a kiln containing the mineral substance, thereby raising the temperature of the mineral substance to as high as 3000 F.
(about 1650 C.) or more, and the carbon dioside formed during the combustion is released to the atmosphere with the carbon dioside liberated from the mineral. Since the release of carbon dioside to the atmosphere contributes to the already overburdening ~greenhouse efect~, it would be desirable from an environmental standpoint to reduce the volume of carbon dioside ~ischarqes, such as those described above, to the atmosphere.

0312G ~ 2 0 8 ~ 8 Attorney Docket No. 92A227 Since high purity carbon dioxide is a valuable commodity, recovery of carbon dio~ide from kiln exhaust gases can provide an economic benefit, provided that the value of the recovered carbon dioxide exceeds the recovery cost. In general, it is economically feasible to recover carbon dioside from waste gas streams only when the concentration of carbon dio~ide in the waste gas streams is fairly high, ~uch as in the neighborhood of 40% by volume or more. The eshaust gas stream e~iting furnaces such as lime kilns contains up to 40% carbon dio~ide when the osidant is air, and up to 50% or more by volume carbon dio~ide when osygen-enriched air or pure osygen i8 used as the oxidant. Accordingly, it is worthwhile to undertake recovery of carbon dioxide from these gas streams.

E~haust gases from kilns contain ash and other fine solids which must be removed from the gases prior to their discharge from the plant. The fine solids are typically removed from the exhaust gas by filtration using fine filtering equipment such as baghouses. The baghouses contain glass fiber bags through which the eshaust gases pass, which results in the removal of fine particulates from the gases. However, because the kiln exhaust gases are very hot, typically as hot as 1000 C. or more, it is necessary that they be cooled prior to introduction into the filtering equipment. The hot kiln gases are usually cooled by injecting cool air into them soon after they exi~ the kiln. This rapidly cools the waste gases to temperatures at which they can be further cooled by passage through a water spray or directly introduced into a baghouse. Unfortuna~ely however, the introduc~ion of air into the kiln eshaust gas dilutes the carbon dioside therein, often to ~oncentrations of 20~ by volume or less. Cooling the exhaust gas with water is possible but is typically more espensive than direct gas cooling.

~ ince direct injection of a cool gas into a hot gas is an economical procedure for rapialy cooling the hot gas it would be desirable to continue to use this cooling method, but , .

930423CRR Attorney Docket No. 92A227 '0312G 21208~8 _ 3 _ :

~ithout decreasing the concentration of carbon dio~ide in the stream, so that recovery of the carbon dio~ide from the waste gas stream will remain economically attractive. The present invention accomplishes this goal by using cool carbon dioside as the heat exchange medium.

It is known to recover carbon dioside from waste gas streams from kilns. For e~ample, in Romanian Patent No. 91001, Barau et al. describes the recovery of carbon dioside from the eshaust gas of a rotary lime kiln. Steps to prevent unnecessary dilution of carbon dio~ide produced in lime kilns are also known. For instance, in Hungarian Patent No. T36257, Body et al. discloses a lime kiln furnace with a feed throat containing alternately operated locks.

~MMA~Y OF T~E_I~v~TIQ~

According to a broad embodiment of the invention high purity carbon dioside i8 produced by calcining a carbonate-containing mineral by combusting a high carbon content fuel with an oxidant in the presence of the mineral, thereby producing a hot carbon dio~ide-rich exhaust gas;
cooling the hot exhaust gas by injecting a cool carbon dioside-rich gas into the hot e~haust gas; optionally further cooling the gas by passing it through a water spray or by indirect heat exchange with a cool fluid; purifying the cooled eshaust gas to remove particulate impurities therefrom and separating carbon dio~ide ~rom the other components of the purified gas stream.

The invention is most advantageously applied to the production of carbon dio~ide by the calcination of a calcium carbonate-containing material, such as limestone or dolemite, in a kiln by burning a high carbon content solid, liquid or gaseous fuel, such as coal or coke, liquid hydrocarbons, or natural gas. Preferred fuels are coal and natural gas.

930423CRR 2~ 2 ~8~ Attorney Docket No. 92A227 Any oxygen-inert gas mi~tures, such as air, oxygen-enriched air, or oxygen-inert gas mi~tures can be used in the invention. The preferred oxidant is oxygen-enriched air.

Recovery of the high purity carbon dioxide from the purified exhaust gas may be accomplished by any procedure effective for separating carbon dioside from gas ~treams.
Typical carbon dioside separation procedures are adsorption, absorption, condensation and membrane separation. Preferred separation procedures are adsorp~ion and a~sorption, and the most preferred separation technique is adsorption, particularly pressure swing adsorption, using a zeolite adsorbent such as 13 X ~eolite.

In a preferred embodiment moisture is removed from the e~haust gas prior to carbon dio~ide recovery. The method of moisture removal is not critical, but in preferred embodiments moisture is removed by passing the e~haust gas through an adsorbent such as silica ~el or activated alumina, or mistures of these.

According to the most preferred embodiment of the invention high purity ~arbon dioside is produced by calcining limestone or dolemite, either alone or in the presence of other minerals, in a kiln using coal or natural gas as fuel and osygen-enriched air as osidant; the hot e~haust gas issuing from the ~iln is cooled by injecting previously cooled and purified eshaust gas into the hot e~haust gas; the cooled gas is purified to remove particulate impurities therefrom; and high purity carbon dioside is separated from the cooled and purifued gas stream by pressure swing adsorption using a zeolite adsorbent. If desired, moisture can be removed from the high purity carbon dio~ide product stream by, for eYample, passing it through a bed of silica gel or activated alumina adsorbent.

. ~ :

i, :

~ 93~0423CRR Attorney Docket No. 92A227 0312G 21 2 0 ~ .~ 8 f BRIEF DESCRIPTION OF THE DRAwINGS
Z
f Fig. 1 is a schematic representation of one embodiment of a Z system for producing high purity carbon dioxide by the process Z of the invention; and Z
Fig. 2 is a schematic representation of an alternate embodiment of a system for producing high purity carbon dioside by the process of the invention.

DETAILED DE$~RIPTION QF~ THE INVENTION

The invention can be practiced with any lime or cement manufacturing process in which zn inorganic carbonate-fnfntaining substance is calcined to remove carbon dio~ide by heating the substance by combusting a carbon-containing fuel with an oxidant in the presence of the inorganic substance.
fS'fuch processes include calcination of limestone or dolemite in the manufacture of lime and cement.

The process of the invention can be more completely understood from the following description considered witfh the appended drawings. Valves, lines and equipment not necessary for an understanding of the invention have been omitted from the drawings. Like reference characters desiqnate like or corresponding parts in different ~iews.

~ urning now to Fig. 1, illustrated therein iZfs a system for processing a carbonate-containing mineral substance by a preferred embodiment of the invention. The equipment comprising the ~ystem of Fig. 1 inncludes kiln 2, secondary eshaust g~fs cooler 4, gas purifier 6 and carbon diofside separator 8.

Xiln 2 may be any type of furnace in which mineral æubstances are calcined, fsuch as a rotary or vertical kiln.
Kiln 2 is equipped with carbonate-containing fill port, which !1~ :: . : . .
~: :

~, , . :

~f~f ~' ' ~' ' ' 2~2~8-~
930423CRR Attorney Docket No. 92A227 ., may be a hopper or the like, fuel line 12, o~idant feed line 14, carbonate-depleted outlet port 16 and e~haust gas line 18.

Exhaust gas line 18 connects to the gas inlet to eshaust gas cooler 4. Cooler 4 may be any type of cooler used for cooling hot gases. Preferred coolers are water spray coolers wherein a spray of cool water washes the hot gas passing through the cooler. During the waterwash some o the particulates entrained in the gas stream are washed from the qas and removed from cooler 4 through a cooling water discharge line (not illustrated). Cooler 4 may also be a heat exchanger ¦ through which a coolant, such as water passes in indirect I contact with the hot gases that are to be cooled. Cooler 4 is equipped with a cooled gas discharge line 20, which is I connected to gas purifier 6.
s i Gas purifier 6 may be any of the well-known types of filter means used to remove particulate matter from kiln eshaust gases, such as a bag house or an electrostatic precipitator.
Purifier 6 is provided with a clean gas discharge line 22, which connects to the inlet to carbon dioside separator 8. In ~ the embodiment illustrated in Fig. 1, a cooling gas recycle 3 line connects line 22 and line 18.

Carbon dioside separator 8 may be any unit conventionally used for the separation of carbon dioside from a gas stream.
Typical carbon ~io~ide separator~ include absorption systems containing an absorbent which absorbs carbon dioside but does not appreciably absorb the other gases present in the effluent stream, such as mono- di- and triethanolamine; adsorbent systems containing an adsorbent which adsorbs carbon dioside in preference to the other gas in the e~haust gas ~tream, such as zeolite and carbon molecul~r sieves, etc.; and condensing systems, which cool the gas sufficiently to condense carbon dio~ide but not the other components of the gas strPam. When separator 8 is an adsorber or a condenser it is preferable to remove moisture from the gas stream prior to carbon dio~ide !.~.

. 0312G 2 ~ 2 0 ~ ~ 8 Attorney Docket No. 92A227 separation; otherwise the water would be separated from the gas stream with the carbon dioside. Water removal can be effected by means of a dryer (not shown) which contains an adsorbent, such as silica gel or alumina which ~dsorbs moisture in preference to carbon dioside and the other components of the gas stream. When carbon dioside separator 8 is an adsorption system it may comprise a single adsorption bed, but usually comprises two or more adsorption beds operated in parallel and out of phase to provide substantially continous operationO

Carbon dio~ide separator 8 is provided with line 26 for removing the carbon dioxide-rich stream from the system and line 28 for removing the gas stream containing the other components of the kiln gas effluent, (predominantly nitrogen and argon). If nitrogen oxides or sulfur osides are present in the carbon dioside-rich gas stream from the kiln, they can be removed, if desired, prior to separation of carbon dioside from the exhaust gas stream.

The system of Fig. 1 is a preferred embodiment of the invention in that it permits relatively large guantities of cooled gas to be recirculated without diluting the kiln effluent with respect to carbon dioside content. The recycled qas can be introduced into line 18 by any suitable device, such as a dispersing nozzle.

In operation, a carbonate-containing mineral is calcined in kiln 2 by burning a fuel with an osidant in the presence of the mineral. The spent mineral is removed from the kiln through port 16 a~d a hot carbon dioside-rich eshaust gas is removed ~ through line 18. Upon esiting kiln 2 the hot exhaust gas is A mi~ed with cool recycle gas from line 24, and is thereby sooled. The cooled eshaust gas is passed through cooler 4 (if such a unit is employed) and then through filter 6, wherein particulate matter, such as flyash, is removed from the gas stream. The cleaned gas is nest divided into a recycle stream and a carbon dioside separator feed stream. A ~ubstantially j!

-',' " " ' : ', ' . ' :

' ''' ' '. .: ' ` : :
: ` '': ~:~ ' ` `
' ." . ~ ''' 930423CRR 2 12 0 8 ~i 8 Attorney Docket No. 92A227 1, pure carbon dio~ide product gas is withdrawn from separator 8 through line 26 and the remaining gas stream is vented to the atmosphere through line 28.

The system illustrated in Fig. 2 is similar to the system of Fig. 1, except that recycle line 30 replaces recycle line 24 of the Fig. 1 system. In the system of Fig. 2 a substantially pure carb~n dio~ide stream is recycled to line 18 to serve as a coolant for the hot gaseous effluent from kiln 2. This embodiment is particularly applicable when separator 8 is an adsorber or a condenser and has the advantage that the carbon dio~ide from separator 8 has additional cooling capacity because it is cooler than the gas in line 22 when separator 8 is an adsorber or condenser.

The fuel used to provide the heat for calcination of the carbonate-containing material can be any solid, liquid or gaseous fuel. The fuel is preferably a substance that is low in sulfur and nitrogen to avoid the production of sulfur and nitrogen oxideæ. Preferred fuels are coal, particularly low sulfur coal, and methane, because of their low cost, purity and ready availability.

Preferred osidants include air, osygen-enriched air or osygen-inert gas mixtures. Osygen-enriched air containing high concentrations of o~ygen is preferred because of its ready availa~ility, low cost and low nitrogen content. ~
~ :
Although the invention has been described with reference to -specific e~amples, variations of these are contemplated. For e~ample, other ~teps, ~uch as sulfur oside scrubbing, may be included in the process of the invention. Furthermore, zupplemental cooling with other gases, such ~ air, is within the purview of the invention. The scope of the invention is limited solely by the breadth of the appended claims.

s~j .s~

Claims (13)

1. A method of producing high purity carbon dioxide comprising the steps:
(a) combusting a carbonaceous fuel with an oxidant in the presence of an inorganic carbonate-containing substance, thereby producing a hot carbon dioxide-rich gaseous product, (b) cooling the hot carbon dioxide-rich gaseous product by injecting a carbon dioxide-rich gas into the hot gaseous product, (c) purifying the cooled gaseous product by removing particulate impurities therefrom, and (d) separating high purity carbon dioxide from the purified gaseous product.
2. The method of Claim 1, wherein said carbon dioxide-rich gas is the purified gaseous product of step (c) or the high purity carbon dioxide product of step (d).
3. The method of Claim 1, wherein the oxidant is air, oxygen-enriched air or oxygen.
4. The method of Claim 1, wherein the carbonaceous fuel is coal, natural gas, a liquid hydrocarbon or mixtures of these.
5. The method of Claim 4, wherein said oxidant is oxygen.
6. The method of Claim 1, wherein the inorganic carbonate-containing substance is selected from limestone, dolemite or mixtures of these.
7. The method of Claim 1 wherein the high purity carbon dioxide is separated from the purified gaseous product by adsorption, absorption, condensation or mixtures of these.
8. A method of producing high purity carbon dioxide comprising the steps:

(a) combusting a carbonaceous fuel with an oxidant selected from air, oxygen-enriched air or oxygen in the presence of a substance selected from limestone, dolemite or mixtures of these, thereby producing a hot carbon dioxide-rich gaseous product, (b) cooling the hot carbon dioxide-rich gaseous product by injecting thereinto part of the purified product of step (c), below, (c) purifying the cooled gaseous product by removing particulate impurities therefrom, (d) removing moisture from the purified cooled gaseous product, and (e) separating high purity carbon dioxide from the moisture-depleted gaseous product.
9. The method of Claim 8, wherein the carbon dioxide is separated from the gaseous product by a pressure swing adsorption process.
10. The method of Claim 9, wherein moisture removal is effected by passage of the purified cooled gaseous product through a bed of adsorbent selected from silica gel, activated alumina and mixtures of these.
11. The method of Claim 10, wherein said pressure swing adsorption process is carried out using 13 X zeolite.
12. The process of Claim 11, wherein the carbonaceous fuel is selected from coal and natural gas.
13. The process of Claim 12, wherein the oxidant is oxygen.
CA002120858A 1993-04-26 1994-04-08 Enhanced recovery of carbon dioxide from kiln gas by addition of cooled carbon dioxide Abandoned CA2120858A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US5387493A true 1993-04-26 1993-04-26
US08/053,874 1993-04-26

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WO2014151224A1 (en) * 2013-03-15 2014-09-25 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in cement processing
US9077007B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9556753B2 (en) 2013-09-30 2017-01-31 Exxonmobil Research And Engineering Company Power generation and CO2 capture with turbines in series
US9755258B2 (en) 2013-09-30 2017-09-05 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using solid oxide fuel cells
US9774053B2 (en) 2013-03-15 2017-09-26 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells

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WO2014151224A1 (en) * 2013-03-15 2014-09-25 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in cement processing
US9077007B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9077008B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9077005B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
US9077006B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US9178234B2 (en) 2013-03-15 2015-11-03 Exxonmobil Research And Engineering Company Integrated power generation using molten carbonate fuel cells
CN105143140A (en) * 2013-03-15 2015-12-09 埃克森美孚研究工程公司 Integration of molten carbonate fuel cells in cement processing
US9257711B2 (en) 2013-03-15 2016-02-09 Exxonmobil Research And Engineering Company Integrated carbon capture and chemical production using fuel cells
US9263755B2 (en) 2013-03-15 2016-02-16 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in iron and steel processing
US9343763B2 (en) 2013-03-15 2016-05-17 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells for synthesis of nitrogen compounds
US9343764B2 (en) 2013-03-15 2016-05-17 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in methanol synthesis
US9362580B2 (en) 2013-03-15 2016-06-07 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in a refinery setting
US9419295B2 (en) 2013-03-15 2016-08-16 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells at a reduced electrical efficiency
US9455463B2 (en) 2013-03-15 2016-09-27 Exxonmobil Research And Engineering Company Integrated electrical power and chemical production using fuel cells
US9520607B2 (en) 2013-03-15 2016-12-13 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells with fermentation processes
US9553321B2 (en) 2013-03-15 2017-01-24 Exxonmobile Research And Engineering Company Integrated power generation and carbon capture using fuel cells
CN105143140B (en) * 2013-03-15 2018-06-22 埃克森美孚研究工程公司 Molten carbonate fuel cell in the integrated process of the cement
US9647284B2 (en) 2013-03-15 2017-05-09 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
US9650246B2 (en) 2013-03-15 2017-05-16 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US9735440B2 (en) 2013-03-15 2017-08-15 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US9941534B2 (en) 2013-03-15 2018-04-10 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US9774053B2 (en) 2013-03-15 2017-09-26 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US9786939B2 (en) 2013-03-15 2017-10-10 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9923219B2 (en) 2013-03-15 2018-03-20 Exxonmobile Research And Engineering Company Integrated operation of molten carbonate fuel cells
US10093997B2 (en) 2013-03-15 2018-10-09 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in iron and steel processing
US9755258B2 (en) 2013-09-30 2017-09-05 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using solid oxide fuel cells
US9556753B2 (en) 2013-09-30 2017-01-31 Exxonmobil Research And Engineering Company Power generation and CO2 capture with turbines in series

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Publication number Publication date
AU6058294A (en) 1994-10-27
AU683242B2 (en) 1997-11-06

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