CN101250449A - Catalytic conversion deoxidation method of coal-bed gas - Google Patents

Catalytic conversion deoxidation method of coal-bed gas Download PDF

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Publication number
CN101250449A
CN101250449A CN 200810044237 CN200810044237A CN101250449A CN 101250449 A CN101250449 A CN 101250449A CN 200810044237 CN200810044237 CN 200810044237 CN 200810044237 A CN200810044237 A CN 200810044237A CN 101250449 A CN101250449 A CN 101250449A
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gas
coal
deoxidation
bed gas
catalytic conversion
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CN 200810044237
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陶鹏万
李泽军
吴且毅
韩续良
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Southwest Research and Desigin Institute of Chemical Industry
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Southwest Research and Desigin Institute of Chemical Industry
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Abstract

The invention discloses a coal bed gas catalysis conversion deoxidation method, which comprises pumping raw material coal bed gas into a deoxidation reactor to do catalysis conversion deoxidation reaction after desulfurizing. The invention is characterized in that water vapour is added in coal bed gas after coal bed gas is desulfurized, and mole ratio of water which is added and firedamp in coal bed gas is led to be H2O/CH4=0.2-0.5. Partial firedamp is conversed to be CO and H2 through adding a little amount of water in coal bed gas, the method increases heat quantity of output gas and improves cold air efficiency of output gas, which is suitable for the fields which have wider heat value adaptation to gas and need to be pressured to higher pressure.

Description

A kind of catalytic conversion deoxidation method of coal-bed gas
Technical field
The invention belongs to gas deoxygenation technology field, particularly the method for deoxidation in the coal-seam gas field.
Background technology
Coal-seam gas is coal mine associated gas, and methane content can be made fuel and also can make industrial chemicals up to more than 40% in the coal field coal-seam gas (CMM).
Coal-seam gas as fuel or the generating, positive delivery or is concentrated and must remove oxygen except directly because of containing oxygen, could guarantee the safe operation of subsequent handling like this.Notification number is the Chinese patent of CN 1330739 C, a kind of " producing the catalyticcombustion deoxidization process of methyl alcohol with coal mine mash gas " disclosed, it mainly utilizes methane and oxygen catalyticcombustion to take off oxygen, and its catalyzer is noble metal catalyst or calcium titanium type O composite metallic oxide catalyst.
Principal reaction formula in the above-mentioned Production by Catalytic Combustion Process deoxidation process is:
CH 4+2O 2＝CO 2+2H 2O-Q
Big calorimetric is emitted in this reaction.In this method, the combustion heat of methane becomes vapor recovery, can reach high energy utilization rate, is adoptable method to concentrated production high density methane of methane or LNG.
But the gas cold air efficiency of this method output (cold air efficiency η=output gas volume * output gas high heating value/(input gas volume * input gas high heating value)) is lower.Especially it is lower to contain its cold air efficiency of the high more coal-seam gas of oxygen.If byproduct steam utilizes difficulty, then its capacity usage ratio will obviously reduce.
Summary of the invention
The purpose of this invention is to provide the higher catalytic conversion deoxidation method of coal-bed gas of a kind of cold air efficiency, this method is applicable to that mainly gas need be forced into elevated pressures, to the coal-seam gas catalyzed conversion deoxidation of gas heating value scope adaptation than wide-range.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of catalytic conversion deoxidation method of coal-bed gas, its flow process as shown in Figure 1, carry out the catalyzed conversion deoxygenation with feeding in the deoxidation reactor behind the raw material coal seam qi exhaustion sulphur, it is characterized in that: add a small amount of water vapor in the coal-seam gas after desulfurization, make the water of adding and the methane mol ratio H in the coal-seam gas 2O/CH 4=0.2～0.5.
In deoxidation reactor, in the presence of catalyzer, part methane in the coal-seam gas and oxygen react and remove oxygen, emit big calorimetric simultaneously; Utilize this reaction heat to make part methane and water vapour reaction, change into carbon monoxide (CO) and hydrogen (H 2), can reclaim heat and byproduct steam by waste heat boiler, after cooling removed and anhydrates, required user was sent in compression.Following reaction promptly takes place in reaction process simultaneously:
CH 4+2O 2＝CO 2+2H 2O-Q
CH 4+H 2O＝CO+3H 2+Q
Back one reaction is thermo-negative reaction, and its heat is provided by the methane and the oxygen combustion heat.From reaction formula as can be known, 1 standard rice 3Methane can obtain 1 standard rice 3Carbon monoxide and 3 standard rices 3Hydrogen.CH 4, CO, H 2Three's high heating value is respectively 39.816MJ/Nm 3, 12.635MJ/Nm 3And 12.745MJ/Nm 3The total heat of output gas is 12.635 * 1+12.745 * 3=50.870MJ like this, and the heat of input gas is 39.816MJ.Obviously the heat of output gas has increased the 11.05MJ heat than input gas, has so just improved the cold air efficiency of output gas.
In the above-mentioned catalyzed conversion deoxygenation process, catalyzer is to adopt SiO 2Or Al 2O 3For the Ni series catalysts of carrier is excellent.Reaction pressure can be preferably 0.15MPa～0.60Mpa.Reactor inlet temperatures can be preferably 400 ℃～500 ℃.
Above-mentioned catalytic conversion deoxidation method is applicable to that methane concentration is the raw material coal-seam gas catalyzed conversion deoxidation more than 25% or 25%.
Compared with prior art, the invention has the beneficial effects as follows:
Catalytic conversion deoxidation method of coal-bed gas of the present invention is by adding a small amount of water vapor in coal-seam gas, making the part methane conversion is CO and H 2, increased the heat of exporting gas, improved the cold air efficiency of output gas.Increase owing to transform the volume of back output gas, the unit volume heat vale of mixture decreases, so the present invention is applicable to gas heating value is adapted to the field that broad and needs are forced into elevated pressures.
Description of drawings
Fig. 1 is the process flow diagram of catalytic conversion deoxidation method of coal-bed gas of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
The technical process of present embodiment catalytic conversion deoxidation method of coal-bed gas is as shown in Figure 1:
After raw material coal-seam gas 100NM3 desulfurization, add a small amount of water vapor, make H 2O/CH 4(mol ratio, down with)=0.3 feeds in the deoxidation reactor, with SiO 2Under the Ni series catalysts existence for carrier, carry out the catalyzed conversion deoxygenation;
The pressure of deoxygenation is 0.60MPa, and the deoxidation reactor inlet temperature is 400 ℃.
The composition of raw material coal-seam gas (vol%) is: CH 450%, O 210%, N 240%.
Reaction back gas outlet temperature is 650 ℃.
Reaction back dry gas is formed (vol%) and is: CH 425.73%, N 231.30%, H 229.57%, CO 8.37%, CO 25.03%.
Reaction back gas volume 127.8Nm 3, mixed gas calorific value (high heating value, down together) 15.07MJ/Nm 3
Cold air efficiency 96.74%.
The contriver carries out catalytic deoxidation reaction (except that not adding water vapour, all the other Step By Conditions are all identical) to the raw material coal-seam gas that does not add water vapour under the similarity condition and compares, and its cold air efficiency only is 90%.
Embodiment 2
The technical process of present embodiment catalytic conversion deoxidation method of coal-bed gas is as shown in Figure 1:
After raw material coal-seam gas 100NM3 desulfurization, add a small amount of water vapor, make H 2O/CH 4(mol ratio, down with)=0.2 feeds in the deoxidation reactor, with Al 2O 3Under the Ni series catalysts existence for carrier, carry out the catalyzed conversion deoxygenation;
The pressure of deoxygenation is 0.45MPa, and the deoxidation reactor inlet temperature is 400 ℃.
The composition of raw material coal-seam gas (vol%) is: CH 440%, O 212%, N 248%.
Reaction back gas outlet temperature is 693 ℃.
Reaction back dry gas is formed (vol%) and is: CH 414.66%, N 236.70%, H 232.72%, CO 12.64%, CO 23.28%.
Reaction back gas volume 130.9Nm 3, exit gas calorific value 11.60MJ/Nm 3
Cold air efficiency 95.35%.
The contriver carries out catalytic deoxidation reaction (except that not adding water vapour, all the other Step By Conditions are all identical) to the raw material coal-seam gas that does not add water vapour under the similarity condition and compares, and its cold air efficiency only is 85%.
Embodiment 3
The technical process of present embodiment catalytic conversion deoxidation method of coal-bed gas is as shown in Figure 1:
After raw material coal-seam gas 100NM3 desulfurization, add a small amount of water vapor, make H 2O/CH 4(mol ratio, down with)=0.5 feeds in the deoxidation reactor, with Al 2O 3Under the Ni series catalysts existence for carrier, carry out the catalyzed conversion deoxygenation;
The pressure of deoxygenation is 0.6MPa, and the deoxidation reactor inlet temperature is 400 ℃.
The composition of raw material coal-seam gas (vol%) is: CH 450%, O 210%, N 240%.
Reaction back gas outlet temperature is 632.6 ℃.
Reaction back dry gas is formed (vol%) and is: CH 424.93%, N 230.47%, H 231.45%, CO 6.72%, CO 26.63%.
Reaction back gas volume 131.3Nm 3, mixed gas calorific value (high heating value, down together) 14.78MJ/Nm 3
Cold air efficiency 97.5%.
The contriver carries out catalytic deoxidation reaction (except that not adding water vapour, all the other Step By Conditions are all identical) to the raw material coal-seam gas that does not add water vapour under the similarity condition and compares, and its cold air efficiency only is 90%.
Embodiment 4
The technical process of present embodiment catalytic conversion deoxidation method of coal-bed gas is as shown in Figure 1:
After raw material coal-seam gas 100NM3 desulfurization, add a small amount of water vapor, make H 2O/CH 4(mol ratio, down with)=0.3 feeds in the deoxidation reactor, with Al 2O 3Under the Ni series catalysts existence for carrier, carry out the catalyzed conversion deoxygenation;
The pressure of deoxygenation is 0.45MPa, and the deoxidation reactor inlet temperature is 400 ℃.
The composition of raw material coal-seam gas (vol%) is: CH 430%, O 214%, N 256%.
Reaction back gas outlet temperature is 749.7 ℃.
Reaction back dry gas is formed (vol%) and is: CH 44.18%, N 241.38%, H 236.46%, CO 14.80%, CO 23.18%.
Reaction back gas volume 135.3Nm 3, mixed gas calorific value (high heating value, down together) 8.18MJ/Nm 3
Cold air efficiency 92.7%.
The contriver carries out catalytic deoxidation reaction (except that not adding water vapour, all the other Step By Conditions are all identical) to the raw material coal-seam gas that does not add water vapour under the similarity condition and compares, and its cold air efficiency only is 76.7%.
Embodiment 5
The technical process of present embodiment catalytic conversion deoxidation method of coal-bed gas is as shown in Figure 1:
After raw material coal-seam gas 100NM3 desulfurization, add a small amount of water vapor, make H 2O/CH 4(mol ratio, down with)=0.3 feeds in the deoxidation reactor, with SiO 2Under the Ni series catalysts existence for carrier, carry out the catalyzed conversion deoxygenation;
The pressure of deoxygenation is 0.6MPa, and the deoxidation reactor inlet temperature is 500 ℃.
The composition of raw material coal-seam gas (vol%) is: CH 450%, O 210%, N 240%.
Reaction back gas outlet temperature is 670 ℃.
Reaction back dry gas is formed (vol%) and is: CH 423.64%, N 230.28%, H 231.88%, CO 9.82%, CO 24.38%.
Reaction back gas volume 132.1Nm 3, mixed gas calorific value (high heating value, down together) 14.71MJ/Nm 3
Cold air efficiency 97.65%.
The contriver carries out catalytic deoxidation reaction (except that not adding water vapour, all the other Step By Conditions are all identical) to the raw material coal-seam gas that does not add water vapour under the similarity condition and compares, and its cold air efficiency only is 90%.
Embodiment 6
The technical process of present embodiment catalytic conversion deoxidation method of coal-bed gas is as shown in Figure 1:
After raw material coal-seam gas 100NM3 desulfurization, add a small amount of water vapor, make H 2O/CH 4(mol ratio, down with)=0.5 feeds in the deoxidation reactor, with SiO 2Under the Ni series catalysts existence for carrier, carry out the catalyzed conversion deoxygenation;
The pressure of deoxygenation is 0.15MPa, and the deoxidation reactor inlet temperature is 400 ℃.
The composition of raw material coal-seam gas (vol%) is: CH 425%, O 215%, N 260%.
Reaction back gas outlet temperature is 828 ℃.
Reaction back dry gas is formed (vol%) and is: CH 40.05%, N 244.54%, H 236.90%, CO 14.89%, CO 23.62%.
Reaction back gas volume 134.6Nm 3, mixed gas calorific value (high heating value, down together) 6.602MJ/Nm 3
Cold air efficiency 89.3%.
The contriver carries out catalytic deoxidation reaction (except that not adding water vapour, all the other Step By Conditions are all identical) to the raw material coal-seam gas that does not add water vapour under the similarity condition and compares, and its cold air efficiency only is 70%.
From the correlation data of the foregoing description 1-6 as seen, catalytic conversion deoxidation method of coal-bed gas of the present invention has obviously increased the heat of output gas, has improved the cold air efficiency of output gas; Simultaneously, increase owing to transform the volume of back output gas, the unit volume heat vale of mixture decreases, so the present invention is applicable to gas heating value is adapted to the field that broad and needs are forced into elevated pressures.

Claims (5)

1. a catalytic conversion deoxidation method of coal-bed gas carries out the catalyzed conversion deoxygenation with feeding in the deoxidation reactor behind the raw material coal seam qi exhaustion sulphur, it is characterized in that: add water vapour in the coal-seam gas after desulfurization, make the water of adding and the methane mol ratio H in the coal-seam gas 2O/CH 4=0.2～0.5.
2. catalytic conversion deoxidation method of coal-bed gas according to claim 1 is characterized in that: the catalyzer that described catalyzed conversion deoxygenation adopts is with SiO 2Or Al 2O 3Ni series catalysts for carrier.
3. catalytic conversion deoxidation method of coal-bed gas according to claim 1 is characterized in that: the pressure of described catalyzed conversion deoxygenation is 0.15MPa～0.60Mpa.
4. catalytic conversion deoxidation method of coal-bed gas according to claim 1 is characterized in that: the inlet temperature of described deoxidation reactor is 400 ℃～500 ℃.
5. catalytic conversion deoxidation method of coal-bed gas according to claim 1 is characterized in that: the methane concentration of described raw material coal-seam gas is more than 25% or 25%.
CN 200810044237 2008-04-17 2008-04-17 Catalytic conversion deoxidation method of coal-bed gas Pending CN101250449A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102533368A (en) * 2012-01-11 2012-07-04 东南大学 Method for deoxidizing coal bed gas through centrifugalization at low temperature and high speed
CN101445755B (en) * 2008-12-22 2012-11-28 中国石油集团长城钻探工程有限公司 Method for purifying and liquefying coalbed gas
CN102839028A (en) * 2012-09-18 2012-12-26 新地能源工程技术有限公司 Energy-saving method of deoxidizing coalbed methane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101445755B (en) * 2008-12-22 2012-11-28 中国石油集团长城钻探工程有限公司 Method for purifying and liquefying coalbed gas
CN102533368A (en) * 2012-01-11 2012-07-04 东南大学 Method for deoxidizing coal bed gas through centrifugalization at low temperature and high speed
CN102839028A (en) * 2012-09-18 2012-12-26 新地能源工程技术有限公司 Energy-saving method of deoxidizing coalbed methane

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