CN101322942B - Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications - Google Patents
Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications Download PDFInfo
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- CN101322942B CN101322942B CN2008100456659A CN200810045665A CN101322942B CN 101322942 B CN101322942 B CN 101322942B CN 2008100456659 A CN2008100456659 A CN 2008100456659A CN 200810045665 A CN200810045665 A CN 200810045665A CN 101322942 B CN101322942 B CN 101322942B
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Abstract
The invention discloses a deoxidizing catalyst for a coal-seam gas containing oxygen and a preparation method as well as an application thereof. The deoxidizing catalyst of the invention consists of an active component, an active auxiliary and a porous carrier. The active component is the compound of Co; the active auxiliary is one or more compounds of Mn, Fe, Zn and Cu; the porous carrier is one or more of aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, silicon oxide, a phosphor-aluminium molecular sieve, an A-typed molecular sieve, an X-typed molecular sieve, a Y-typed molecular sieve, a mordenite, a ZSM-5 zeolite, diatomaceous earth, kaolinite, natural clay, aluminum silicate and magnesium silicate; calculated by oxide, the weight percentage of the active component is 1 to 60 percent; the weight percentage of the active auxiliary is 1 to 50 percent; the rest is the carrier. The catalyst of the invention has certain sulfur-resistance performance, is applicable to the deoxidization treatment of coal-seam gas with an oxygen content of 3 to 6 percent (V/V) and is capable of causing the oxygen content in the coal-seam gas to be lower than 0.5 percent by deoxidization.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of oxygen-containing coal bed gas deoxidation catalyst and preparation method thereof and the application in oxygen-containing coal bed gas deoxidation thereof.
Background technology
Coal bed gas is present in the coal seam in a large number, belongs to unconventional natural gas; It is the one of the main reasons that causes the colliery down-hole accident.In fact coal bed gas is a kind of calorific value height, and free of contamination new forms of energy can be used as fuel used to generate electricity, process fuel, industrial chemicals and resident living fuel etc.China causes the huge environmental pressure and the wasting of resources to about 300 billion cubic meters of airborne release coal bed gas every year.Coal bed gas is rationally fully utilized, can remedy China's energy shortage.The recycling of coal bed gas simultaneously also helps the protection ring border, and the greenhouse effects of methane are more than 20 times of CO2, and a large amount of coal bed gas enters atmosphere and aggravated Global Greenhouse Effect.Therefore, the poor efficiency of coal bed gas had both caused the significant wastage of resource, had increased the weight of environmental pollution again.
Southnest China Chemical Engineering Inst., Ministry of Chemical Industry discloses a kind of method of utilizing pressure swing adsorption method separation and concentration methane from coal bed gas in the Chinese patent ZL85103557 " methane in the pressure swing adsorption method enrichment coal mine mash gas " of application in 1985.Generally speaking, the oxygen content of methane discharging waste gas in concentrating purification process also is concentrated raising, owing to inevitably contain 5～15% methane in the waste gas, cause exhaust gas discharged to be in the explosion limit scope of methane, in the discharging waste gas pipe, all the time exist the danger of blast, this makes this The Application of Technology be restricted, thereby to carry out deoxidation treatment before coal bed gas comprehensive utilization be very necessary.
Present adoptable coal bed gas deoxidation method mainly contains catalytic deoxidation method (ZL02113628.9) and coke deoxidization method (ZL02113627.0,200610021720.1) etc., these two kinds of methods all can effectively be reduced to the oxygen content in the coal bed gas below 0.5%, propose the safety operation of dense process to guarantee subsequent technique.
Employed catalyst was noble metal catalysts such as Pt or Pd during Chinese patent ZL02113628.9 " produced the catalytic combustion deoxidization process of methyl alcohol with coal mine mash gas ", the advantage of this type of catalyst is the catalytic activity height, reaction temperature is lower, oxygen after the deoxidation in the gas can eliminate substantially, technological operation is easy, equipment is simple, is convenient to automatic control.Weak point is that catalyst costs an arm and a leg, contain sulfide in the coal bed gas simultaneously, thereby toxic effect causes catalysqt deactivation and sulphur is to noble metal, therefore will carry out desulfurization before deoxidation earlier carries out deoxygenation again, cause the deoxidation cost to increase like this, caused the disposal cost of coal bed gas catalytic deoxidation higher.
Coal bed gas coke method deoxidation (ZL02113627.0,200610021720.1) is under hot conditions, is rich in oxygen and coke gasification reaction in the methane gas, thereby while part methane and oxygen reaction reach the purpose of deoxidation.The advantage of coke method deoxidation is about 70% oxygen and coke gasification reaction, 30% oxygen and methane reaction, so the loss of methane is less.The disposal cost of this method is lower than precious metal catalyst deoxidation method.But shortcoming is this method and wants the coke resource of consume valuable that the consuming cost of coke is about about 50% of whole service expense.In addition the deoxidation of coke method its add Jiao, the labour intensity of slagging tap is big, ambient dust is bigger, and has the sulfide of variform in the coke.
In view of precious metal catalyst deoxidation and coke method deoxidation shortcoming separately, develop a kind of base metal oxygen-containing coal bed gas deoxidation catalyst and be undoubtedly a kind of optimal selection, have very big market prospects simultaneously.
Summary of the invention
The objective of the invention is in order to overcome above shortcomings in the prior art, a kind of new base metal oxygen-containing coal bed gas deoxidation catalyst is provided.
Another object of the present invention provides the preparation method of above-mentioned oxygen-containing coal bed gas deoxidation catalyst.
The 3rd purpose of the present invention provides the application of this oxygen-containing coal bed gas deoxidation catalyst in oxygen-containing coal bed gas deoxidation, making coalbed methane containing oxygen need not to carry out earlier desulfurization handles, can directly enter deoxidation in the deoxidation reactor, thereby reduce disposal cost, and simplify processing step.
Dehydrogenation catalyst of the present invention is by active component, coagent and porous carrier are formed, described active component is the compound of cobalt, described coagent is a manganese, iron, zinc, in the copper compound one or more, described porous carrier is selected from aluminium oxide, titanium oxide, zirconia, magnesia, calcium oxide, silica, phosphate aluminium molecular sieve, A type molecular sieve, X type molecular sieve, Y zeolite, modenite, the ZSM-5 zeolite, diatomite, kaolin, natural clay, alumina silicate, in the magnesium silicate one or more, in oxide, the weight percentage of active component is 1～60%, the weight percentage of coagent is 1～50%, and all the other are carrier.
Described active component is any one in cobalt oxide, cobalt acetate, cobalt nitrate, cobalt chloride or the cobaltous sulfate.
Described coagent is selected from the oxide of manganese, iron, zinc, copper or in the soluble-salt one or more.
Described coagent is selected from any one or a few in nitrate, chloride or the sulfate of manganese, iron, zinc, copper.
The preparation method of oxygen-containing coal bed gas deoxidation catalyst of the present invention may further comprise the steps:
(1) active component and coagent are mixed with the aqueous solution;
(2) porous carrier is immersed in the aqueous solution of step (1) preparation, flooded 6～12 hours down in normal temperature;
(3) with the mixture of step (2) gained by roller forming or extruded moulding, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours can make oxygen-containing coal bed gas deoxidation catalyst of the present invention.
Coalbed methane containing oxygen catalyst of the present invention also can be prepared as follows:
(1) coagent compound and porous carrier are mixed in proportion;
(2) mixture with step (1) passes through compressing tablet, spin or extruded moulding, makes the oxygen-containing coal bed gas deoxidation catalyst precursor;
(3) active component is made into the aqueous solution, with this solution impregnation or the oxygen-containing coal bed gas deoxidation catalyst precursor that makes of spraying step (2), in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make oxygen-containing coal bed gas deoxidation catalyst.
Coalbed methane containing oxygen of the present invention also can be prepared as follows:
(1) active constituent compound and porous carrier are mixed in proportion;
(2) mixture that step (1) is made makes the oxygen-containing coal bed gas deoxidation catalyst precursor by compressing tablet, spin or extruded moulding;
(3) coagent is mixed with the aqueous solution, with the catalyst precarsor of this solution impregnation or spraying step (2), in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make oxygen-containing coal bed gas deoxidation catalyst.
The moulding of above-mentioned oxygen-containing coal bed gas deoxidation catalyst can be made multiple shapes such as spherical, strip, column, sheet, ring-type.
Oxygen-containing coal bed gas deoxidation catalyst of the present invention is the deoxidation treatment of the coal bed gas of 1～12% (V/V) applicable to oxygen content, be specially adapted to oxygen content and be the deoxidation treatment of 3～6% coal bed gas, can regulate the oxygen content that enters reactor, unstripped gas air speed 1000～6000h during deoxidation treatment by regulating circulating air
-1, reaction temperature is 200～750 ℃, reaction temperature is preferably 300～650 ℃, the oxygen content in the coal bed gas can be taken off after the reaction to less than 0.5%.
Key reaction in the deoxidation process of coalbed methane containing oxygen is:
CH
4+2O
2→CO
2+2H
2O
A small amount of methane generation cracking under the high temperature:
CH
4→C+2H
2
Following reaction further takes place again in charcoal and hydrogen that methane cracking produces:
2C+O
2→2CO
2CO+O
2→2CO
2
2H
2+O
2→2H
2O
Because methane and oxygen reaction are strong exothermal reactions, the adiabatic temperature rise of per 1% oxygen and methane reaction heat release is at 90～100 ℃, when oxygen content is higher in the raw material coal bed gas, can be by in the unstripped gas of the cooled gas of cyclic part deoxidation to the deoxidation, adjusting enters the oxygen content of reactor to optimum range, thereby effectively reaction temperature is controlled in the optimum range, coalbed methane containing oxygen catalytic deoxidation range of reaction temperature is 200～750 ℃.
Reaction velocity in the above-mentioned deoxidation reactor can be preferably 1000～6000h
-1
Compared with prior art, the invention has the beneficial effects as follows:
(1) compare with noble metal catalyst catalytic deoxidation method, coalbed methane containing oxygen catalytic deoxidation process of the present invention is owing to select non-precious metal catalyst for use, and the catalyst price declines to a great extent; The used coalbed methane containing oxygen catalyst of the present invention simultaneously has certain sulfur tolerance, the coal bed gas sulfur content≤10mg/m in general colliery
3, can be with the method without pre-desulfurization, thereby saved the expense of pre-desulfurization link;
(2) compare with the coke deoxidization method, because coalbed methane containing oxygen catalytic deoxidation process of the present invention does not need to consume coke resource owing to the methane reaction in oxygen and the coal bed gas, but energy savings; And technological process of the present invention is easier, and easy and simple to handle, equipment is simple, is convenient to automatic control, and its operating cost descends about 1/3rd than coke method;
(3) compare with the coke deoxidization method, though coalbed methane containing oxygen catalytic deoxidation process of the present invention will consume a small amount of methane, thereby the methane total amount slightly reduces after making deoxidation, but the oxygen content after the deoxidation in the coal bed gas has reduced to below 0.5%, the total gas flow in back that dewaters reduces to some extent, thus after the deoxidation in the gas component relative amount of methane change little; Simultaneously, though methane is lost, generate CO owing to behind the methane oxidation
2And H
2O can obtain heat, produces the part waste hot steam, can make other purposes.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, in the embodiment of the invention in the oxygen-containing coal bed gas deoxidation catalyst percentage composition of each component be weight percentage.
Embodiment 1
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 1% active component, 50% coagent and 49% carrier, active component is that to be equivalent to cobalt oxide in the catalyst be 1% cobalt nitrate, coagent is that to be equivalent to manganese dioxide be that 10% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 30% copper sulphate is formed, carrier is 49% aluminium oxide, is named doc1.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 3.9g cobalt nitrate hexahydrate (being equivalent to the 1g cobalt oxide), 29g four water manganese nitrates (being equivalent to 10g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 94g cupric sulfate pentahydrate (being equivalent to the 30g cupric oxide) are dissolved in the 100g water, are made into the aqueous solution;
(2) the 49g aluminium oxide is immersed in the aqueous solution of step (1) configuration, normal temperature flooded 6 hours down;
(3) with the mixture extruded moulding of step (2), 120 ℃ dry 1 hour down, 500 ℃ of following roastings 4 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst doc1 of present embodiment.
Embodiment 2
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 60% active component, 1% coagent and 39% carrier, active component is that to be equivalent to cobalt oxide content in the catalyst be 60% cobalt acetate, coagent is that to be equivalent to ferric oxide content be 1% ferrous sulfate, carrier is that the zirconia of 20% titanium oxide and 19% is formed, and is named doc2.
(1) 199g Cobalt diacetate tetrahydrate (being equivalent to the 60g cobalt oxide), 20g titanium oxide and 19g zirconia are fully mixed, extruded moulding, 120 ℃ dry 2 hours down, 400 ℃ of following roastings 5 hours promptly make catalyst precarsor;
(2) 3.5g ferrous sulfate heptahydrate (being equivalent to the 1g di-iron trioxide) is dissolved in the 50g water, is made into the aqueous solution;
(3) catalyst precarsor that step (1) made immerses in the solution of step (2) preparation, and normal temperature is dipping 12 hours down, 120 ℃ dry 1 hour down, 500 ℃ of following roastings 4 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst doc2 of present embodiment.
Embodiment 3
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 30% active component, 30% coagent and 40% carrier, active component is that to be equivalent to cobalt oxide be 30% cobalt chloride, coagent is that to be equivalent to manganese dioxide be 5% manganese chloride and to be equivalent to zinc oxide be that 25% zinc nitrate is formed, carrier is formed by the A type molecular sieve of 10% magnesia, 10% calcium oxide, 10% silica and 10%, is named doc3.
(1) A type molecular sieve with 11.4g tetrahydrate manganese chloride (being equivalent to 5g manganese dioxide), 91.7g zinc nitrate hexahydrate (being equivalent to 25g zinc oxide) and 10g magnesia, 10g calcium oxide, 10g silica and 10g fully mixes, roller forming, drying is 1.5 hours under 120 ℃, 450 ℃ of following roastings 4.5 hours make catalyst precarsor;
(2) 95.2g CoCL2 (being equivalent to the 30g cobalt oxide) is dissolved in the 150g water, is made into the aqueous solution;
(3) catalyst precarsor of step (1) is immersed in the solution of step (2), normal temperature is dipping 10 hours down, 120 ℃ dry 2 hours down, 480 ℃ of following roastings 4 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment.
Embodiment 4
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 6% active component, 45% coagent and 49% carrier, active component is a cobalt oxide, coagent is that 5% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 30% copper sulphate is formed by being equivalent to manganese dioxide, carrier is made up of 9% phosphate aluminium molecular sieve, 10%X type molecular sieve, 10%Y type molecular sieve, 10% modenite, 10% diatomite, is named doc4.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 6g cobalt oxide, 9g phosphate aluminium molecular sieve, 10g X type molecular sieve, 10g Y zeolite, 10g modenite, 10g diatomite are mixed;
(2) with the mixture extruded moulding, 120 ℃ dry 2 hours down, catalyst precarsor is made in 500 ℃ of following roastings 1.5 hours;
(3) 14.5g four water manganese nitrates (being equivalent to 5g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 94g cupric sulfate pentahydrate (being equivalent to the 30g cupric oxide) are dissolved in the 100g water, be made into the aqueous solution, the catalyst precarsor that makes with this solution spraying step (2), drying is 2 hours under 120 ℃, 480 ℃ of following roastings 4 hours promptly make oxygen-containing coal bed gas deoxidation catalyst doc4.
Embodiment 5
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 16% active component, 40% coagent and 44% carrier, active component is that to be equivalent to cobalt oxide be 16% cobaltous sulfate, coagent is that to be equivalent to manganese dioxide be that 10% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 20% copper sulphate is formed, carrier is 44% alumina silicate, is named doc5.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 59.9g cobalt sulfate (being equivalent to the 16g cobalt oxide), 29g four water manganese nitrates (being equivalent to 10g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 62.5g cupric sulfate pentahydrate (being equivalent to the 20g cupric oxide) are dissolved in the 150g water, are made into the aqueous solution;
(2) the 44g alumina silicate is immersed in the aqueous solution of step (1) configuration, normal temperature flooded 6 hours down;
(3) with the mixture extruded moulding of step (2), 120 ℃ dry 1 hour down, 400 ℃ of following roastings 5 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst doc5 of present embodiment.
Embodiment 6
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 20% active component, 40% coagent and 40% carrier, active component is that to be equivalent to cobalt oxide be 20% cobalt nitrate, coagent is that to be equivalent to manganese dioxide be that 10% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 20% copper sulphate is formed, carrier is made up of 10%ZSM-5 zeolite, 10% kaolin, 10% natural clay, 10% magnesium silicate, is named doc6.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 29g four water manganese nitrates (being equivalent to 10g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 62.5g cupric sulfate pentahydrate (being equivalent to the 20g cupric oxide), 10g ZSM-5 zeolite, 10g kaolin, 10g natural clay, 10g magnesium silicate are mixed;
(2) with the mixture extruded moulding, 120 ℃ dry 2 hours down, catalyst precarsor is made in 500 ℃ of following roastings 2 hours;
(3) 78g cobalt nitrate hexahydrate (being equivalent to the 20g cobalt oxide) is dissolved in the 100g water, be made into the aqueous solution, with the catalyst precarsor that this solution spraying step (2) makes, drying is 1 hour under 120 ℃, 1500 ℃ of following roastings 4 hours promptly make oxygen-containing coal bed gas deoxidation catalyst doc6.
Embodiment 7
Present embodiment is the application of oxygen-containing coal bed gas deoxidation catalyst of the present invention in the deoxidation treatment of coalbed methane containing oxygen.
Directly send in deoxidation reactor after by the preheater preheating raw material coalbed methane containing oxygen, under normal pressure, uniform temperature and air speed condition, in beds, methane in the coal bed gas and oxygen reaction generate carbon dioxide and water, simultaneously a spot of methane generation cracking produces charcoal and hydrogen, charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal bed gas.
Methane and oxygen reaction are strong exothermal reaction, and per 1% oxygen and methane reaction liberated heat adiabatic temperature rise are 95～100 ℃, therefore, for the unlikely too high methane cracking loss that causes of control reaction temperature, need the unstripped gas Control for Oxygen Content 3～6%.When raw material coal bed gas oxygen content is higher than 6%, can be by in the raw material coal bed gas of the cooled coal bed gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen content to optimum range, thereby reach the purpose of deoxidation and temperature control.
Different model catalyst activity property testing concrete outcome sees Table 1, and the unstripped gas oxygen content is 3～6% (V/V), sulfur content 3～10mg/m
3, methane content is 70～85%, all the other are nitrogen, unstripped gas air speed 1000～6000h
-1, the catalytic deoxidation reaction temperature is 300～650 ℃, loaded catalyst 100ml.
Table 1
| The catalyst numbering | Unstripped gas oxygen content % | Unstripped gas total sulfur content mg/m 3 | Deoxidation temperature ℃ | Unstripped gas air speed h -1 | Tail gas oxygen content % |
| doc1 | 3.01 | 3.0 | 650 | 4000 | 0.35 |
| doc2 | 6.02 | 6.4 | 300 | 6000 | 0.22 |
| doc3 | 3.52 | 3.5 | 500 | 3000 | 0.15 |
| doc4 | 4.62 | 7.5 | 450 | 4000 | 0.18 |
| doc5 | 4.05 | 4.2 | 380 | 3000 | 0.12 |
| doc6 | 5.15 | 10.0 | 495 | 1000 | 0.08 |
Claims (4)
1. the application of oxygen-containing coal bed gas deoxidation catalyst in coalbed methane containing oxygen, it is characterized in that: described oxygen-containing coal bed gas deoxidation catalyst is applied to the deoxidation treatment that oxygen content is the coal bed gas of 3-6%, and the unstripped gas air speed is 1000-6000h
-1The temperature of catalyst deoxygenation is 300-650 ℃, described oxygen-containing coal bed gas deoxidation catalyst is by active component, coagent and porous carrier are formed, described active component is the compound of cobalt, described coagent is a manganese, iron, zinc, in the copper compound one or more, described porous carrier is selected from aluminium oxide, titanium oxide, zirconia, magnesia, calcium oxide, silica, phosphate aluminium molecular sieve, A type molecular sieve, X type molecular sieve, Y zeolite, modenite, the ZSM-5 zeolite, diatomite, kaolin, natural clay, alumina silicate, in the magnesium silicate one or more, in oxide, the weight percentage of active component is 1-60%, the weight percentage of coagent is 1-50%, and all the other are carrier.
2. the application of oxygen-containing coal bed gas deoxidation catalyst according to claim 1 in coalbed methane containing oxygen is characterized in that: the active component of described oxygen-containing coal bed gas deoxidation catalyst is any one in cobalt oxide, cobalt acetate, cobalt nitrate, cobalt chloride or the cobaltous sulfate.
3. the application of oxygen-containing coal bed gas deoxidation catalyst according to claim 1 in coalbed methane containing oxygen is characterized in that: the coagent of described oxygen-containing coal bed gas deoxidation catalyst is selected from the oxide of manganese, iron, zinc, copper or in the soluble-salt one or more.
4. the application of oxygen-containing coal bed gas deoxidation catalyst according to claim 1 in coalbed methane containing oxygen is characterized in that: the coagent of described oxygen-containing coal bed gas deoxidation catalyst is selected from any one or a few in nitrate, chloride or the sulfate of manganese, iron, zinc, copper.
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| CN101664679B (en) * | 2009-11-17 | 2012-09-12 | 中国科学院大连化学物理研究所 | Coal bed gas deoxidation catalyst as well as preparation method and application thereof |
| CN101659890B (en) * | 2009-09-11 | 2012-12-26 | 华东理工大学 | Deoxidating method for coal bed gas and catalyst |
| CN102266768B (en) * | 2010-07-29 | 2012-12-26 | 西南化工研究设计院有限公司 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
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| CN102433181B (en) * | 2010-09-29 | 2014-03-12 | 中国石油化工股份有限公司 | Catalytic deoxidation method for coalbed gas in coal mine area |
| CN102321494B (en) * | 2011-05-24 | 2013-11-27 | 北京惟泰安全设备有限公司 | Coal bed gas separating system and process |
| CN102321493B (en) * | 2011-05-24 | 2013-11-27 | 北京惟泰安全设备有限公司 | Coal bed gas separating system and process utilizing catalyst to deoxidize |
| CN102229829B (en) * | 2011-05-24 | 2014-01-22 | 北京惟泰安全设备有限公司 | Separation system and process for coal bed gas |
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| JP2021512782A (en) * | 2018-02-12 | 2021-05-20 | ランザテク，インコーポレイテッド | Integrated process for filtering components from gas stream |
| CN111889106B (en) * | 2019-05-05 | 2022-08-12 | 中国石油化工股份有限公司 | Compound and preparation method and application thereof |
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