CN101659890B - Deoxidating method for coal bed gas and catalyst - Google Patents

Deoxidating method for coal bed gas and catalyst Download PDF

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Publication number
CN101659890B
CN101659890B CN 200910195504 CN200910195504A CN101659890B CN 101659890 B CN101659890 B CN 101659890B CN 200910195504 CN200910195504 CN 200910195504 CN 200910195504 A CN200910195504 A CN 200910195504A CN 101659890 B CN101659890 B CN 101659890B
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coal bed
bed gas
catalyst
deoxidation
feso
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CN101659890A (en
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周霞萍
曹建勤
任国平
张钊
王杰
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The invention discloses a deoxidating method for coal bed gas, which comprises the following steps: under the action of a catalyst, the oxidation reaction is carried out on coal bed gas and a FeSO4 water solution, wherein the catalyst is a catalyst A, or the mixture of catalysts A and B; and the catalyst A is a ferrous metal and the catalyst B is one or a plurality of alkali metal hydroxides, alkaline-earth metal hydroxides, Zn(OH)2, NH4OH, H2NCH2CH2NH2 and NH2CH2CH2OH. The invention also discloses a catalyst. The method has mild reaction conditions and can deoxidate at normal temperature under normal pressure. The method has the advantages of high treatment load, short reaction time, high conversion rate and the like, and is a novel high-safety energy-saving environmental-protection technique for deoxidating coal bed gas.

Description

A kind of method of deoxidation of coal bed gas and a kind of catalyst
Technical field
The method of deoxidation that relates to a kind of coal bed gas that the present invention is concrete and a kind of catalyst.
Background technology
Coal bed gas is commonly called as " gas ", and main component is a methane, its calorific value 18.85MJ/M 3, approaching 2 times water-gas, 3 times producer gas is a kind of natural gas that is stored in the coal seam, new forms of energy.Make good use of the coal bed gas of extraction when mining, not only can ensure coal mining personnel's safety, avoid atmospheric environment is damaged, also can practice thrift the clean energy resource of a large amount of preciousnesses.
The difficulty of emptying gas utilization is its methane content 30-50%, and the concentration of oxygen is met naked light or high temperature heat source and is prone to the accident of blasting up to 8-12%.In order to make full use of coal bed gas resource, reduce its oxygen content, make its component be in the safe operation scope, present existing coal bed gas deoxidation method mainly contains: firing method (catalysis/noncatalytic combustion method), absorption method (transformation/alternating temperature absorption), hydrate etc.
The coal bed gas coke deoxidization method that patent 200610021720.1 adopts belongs to the firing method deoxidation.600-1000 ℃ of this method deoxidation temperature under the situation that reduces methane cracking to greatest extent, makes net value≤0.5% of combustion gas oxygen.The production-scale operation difficult point of this method is temperature control.
" a kind of catalytic conversion deoxidation method of coal bed gas " that patent 200810044237.4 is introduced also is the category that belongs to firing method.This method forms CO and H through the steam of adding and the part methane reaction in the coal bed gas 2And slough oxygen.It uses obstacle, and mainly still safety coefficient is not enough.
Technique compresses methane gas, separation of nitrogen and oxygen that patent 200510047624.X adopts transformation absorption to separate with film, its key technology still is in laboratory's stage, and application facet also has the cost problem of film.
Patent 200510073346.5 forms hydrate enrichment and accumulating in addition, still not mentioned deaerating effect with coal bed gas.
Summary of the invention
Technical problem to be solved by this invention is for the defective that temperature control in the method for deoxidation that overcomes existing coal bed gas is difficult, safety coefficient is lower, cost is more high, and a kind of method of deoxidation and a kind of catalyst of coal bed gas are provided.Method reaction condition of the present invention is gentle, can deoxygenation under normal temperature, normal pressure, and it is big to have a load of processing, and the reaction time is short, and the conversion ratio advantages of higher is the coal bed gas deoxidation new technology of a kind of safety, energy-saving and environmental protection.
The present invention relates to a kind of method of deoxidation of coal bed gas, it comprises the following step: under the effect of catalyst, with coal bed gas and FeSO 4The aqueous solution carries out oxidation reaction, gets final product; Wherein, described catalyst is a catalyst A, or the mixture of catalyst A and B; Catalyst A is a ferrous metal, and catalyst B is hydroxide, the Zn (OH) of alkali-metal hydroxide, alkaline-earth metal 2, NH 4OH, H 2NCH 2CH 2NH 2And NH 2CH 2CH 2Among the OH one or more.
Among the present invention, described ferrous metal is preferable is in iron wire, iron filings and the iron powder one or more, and described catalyst is hydroxide, the hydroxide of alkaline-earth metal, the Zn (OH) of B preferred as alkali 2And NH 4Among the OH one or more.That described alkali-metal hydroxide is preferable is NaOH and/or KOH, and that the oxyhydroxide of described alkaline-earth metal is preferable is Ca (OH) 2And/or Mg (OH) 2Described FeSO 4That the molar concentration of the aqueous solution is preferable is 0.0001～0.1mol/L, and that better is 0.001～0.01mol/L.
What described oxidation reaction was preferable carries out under the effect of the mixture of catalyst A and B, and what the weight ratio of A and B was preferable is 20: 1～2000: 1, and better is 50: 1～500: 1, and best is 100: 1～300: 1.
Among the present invention, what the temperature of described oxidation reaction was preferable is 10 ℃～50 ℃, and better is 20 ℃～30 ℃.That the pressure of oxidation reaction is preferable is 0.101～0.107MPa, and that better is 0.101～0.103MPa.What the oxygen content of described coal bed gas was preferable is percent by volume 8～12%, and what the coal bed gas of this moment and the mol ratio of catalyst were preferable is 1: 0.005～1: 0.05, and better is 1: 0.01～0.03; Coal bed gas and FeSO 4Mol ratio preferable be 1: 0.0001～1: 100, better is 1: 0.001-1: 0.105mol.
Among the present invention, the process of described method of deoxidation preferable as follows: with coal bed gas continuously through the fixed bed absorption tower, with FeSO 4Reactant aqueous solution gets final product.
In the oxygen of method of the present invention in removing coal bed gas, FeSO 4The oxidized by-product iron oxide yellow (Fe that also can generate 2O 3H 2O), can be used as pigment, coating is used for industries such as weaving, building.
The invention still further relates to a kind of catalyst, it is the mixture of catalyst A and B, and the selection of A and B and ratio are all ditto said.
Except that specified otherwise, reagent that the present invention relates to and raw material are all commercially available to be got.
Positive progressive effect of the present invention is:
1, method of the present invention can be through the temperature control deoxygenation of fixed bed absorption tower self-organizing ground, and the removal efficiency of oxygen reaches 88-98% in the coal bed gas of reaction back.
2, in the oxygen of method of the present invention in removing coal bed gas, go back by-product iron oxide yellow product, can be used as pigment, coating is used for industries such as weaving, building.
3, compared with prior art, method reaction condition of the present invention is gentle, can deoxygenation under normal temperature, normal pressure, and it is big to have a load of processing, and the reaction time is short, and the conversion ratio advantages of higher is the coal bed gas deoxidation new technology of a kind of safety, energy-saving and environmental protection.Under the situation that current oil, natural gas resource worsening shortages and environmental pollution constantly increase the weight of, method of the present invention can be developed the coal bed gas fuel of cleaning, cheap high heating value, therefore has a extensive future remarkable in economical benefits.
Description of drawings
Fig. 1～3rd utilizes method of the present invention, and the effect of coal bed gas before and after deoxidation be sketch map relatively.
Fig. 1 contains oxygen analysis chart (Agilent6820, CarboPLOT P7 chromatograph for the coal bed gas raw material among the embodiment 1～7; The 3rd peak is an oxygen, peak area 2329750m 2).
Fig. 2 is for carrying out coal bed gas analysis chart (Agilent6820, the CarboPLOTP7 chromatograph after the deoxidation among the embodiment 1; The 3rd peak is an oxygen, peak area 52496m 2, comparison diagram 1, the oxygen removal rate is 97.75%).
Fig. 3 is for carrying out coal bed gas analysis chart (Agilent6820, the CarboPLOTP7 chromatograph after the deoxidation among the embodiment 2; The 3rd peak is an oxygen, peak area 263486m 2, comparison diagram 1, the oxygen removal rate is 88.69%).
Fig. 4 is for carrying out coal bed gas analysis chart (Agilent6820, the CarboPLOTP7 chromatograph after the deoxidation among the embodiment 3; The 3rd peak is an oxygen).
The specific embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Embodiment 1
With the raw material coal bed gas with 3m 3The flow velocity of/min; Catalyst A (available from the iron powder commodity of Shanghai Ling Feng chemical industry Co., Ltd, iron content purity is Wt, 99%) and B catalyst (the NaOH commodity of Shanghai experiment reagent Co., Ltd are equipped with in entering; Purity Wt; 99%) fixed bed absorption tower, the weight ratio of A and B are 50: 1, coal bed gas consist of CH 450%, O 212%, N 230%, other component gas 8%.Coal bed gas: (A catalyst+B catalyst)=1: 0.003mol; Coal bed gas: FeSO 4=1: 0.105mol, FeSO 4The molar concentration of the aqueous solution is 0.1mol/L; Under 30 ℃ temperature, self-organizing ground temperature control deoxygenation under the normal pressure of 0.101MPa, the reaction back is in Agilent6820, and CarboPLOT P7 chromatograph carries out on-line analysis, obtains result shown in Figure 2, and the oxygen removal rate is 97.75%.
Embodiment 2
With the raw material coal bed gas with 200m 3The flow velocity of/hr, get into the design and assembly voluntarily that A and B catalyst are housed the fixed bed absorption tower (wherein, catalyst A is taken from the iron powder of company of Baoshan Iron and Steel Group and is considered to be worth doing, and iron content purity is Wt, 80%; Catalyst B is the carbide slag of Shanghai chemical industry for making chlorine and alkali Co., Ltd, contains calcium oxide 65%, magnesia 1.5%, and silica 8.2%, moisture and all the other compositions 25.3% use after the aquation); The weight ratio of A and B is 50: 1, and the composition of coal bed gas is with embodiment 1, coal bed gas: (A catalyst+B catalyst)=1: 0.001mol.Coal bed gas: FeSO 4=1: 0.100mol, FeSO 4The molar concentration of the aqueous solution is 0.1mol/L; Under 25 ℃ temperature, self-organizing ground temperature control deoxygenation under the normal pressure of 0.102MPa, the reaction back is in Agilent6820, and CarboPLOT P7 chromatograph carries out on-line analysis, obtains result shown in Figure 3, and the oxygen removal rate is 88.69%.
Embodiment 3
With the raw material coal bed gas with 1m 3The flow velocity of/min gets into the fixed bed absorption tower (with embodiment 1) that catalyst A (take from the bushel iron silk slag in school-run enterprise Seiko workshop, iron content purity is Wt, 85%) is housed.The composition of coal bed gas is the same.Coal bed gas: A catalyst=1: 0.3mol; Coal bed gas: FeSO 4=1: 0.05mol, FeSO 4The molar concentration of the aqueous solution is 0.1mol/L, under 50 ℃ temperature, and the reaction deoxygenation down of the normal pressure of 0.110MPa, on-line analysis oxygen removal rate as a result is 86.36% (see figure 4).The iron oxide pigment purity of by-product is 87.2Wt%.
Embodiment 4
With the raw material coal bed gas with 3m 3The flow velocity of/min gets into catalyst A (available from the iron powder commodity of Shanghai Ling Feng chemical industry Co., Ltd, iron content purity is Wt, 99%) and B catalyst (Zn (OH) is housed 2) the fixed bed absorption tower, the weight ratio of A and B is 50: 1, coal bed gas consist of CH 450%, O 28%, N 230%, other component gas 12%.Coal bed gas: (A catalyst+B catalyst)=1: 0.005mol; Coal bed gas: FeSO 4=1: 0.0001mol, FeSO 4The molar concentration of the aqueous solution is 0.0001mol/L; Under 50 ℃ temperature, self-organizing ground temperature control deoxygenation under the normal pressure of 0.103MPa, the oxygen removal rate is 97.00%.
Embodiment 5
With the raw material coal bed gas with 3m 3The flow velocity of/min gets into catalyst A (available from the iron powder commodity of Shanghai Ling Feng chemical industry Co., Ltd, iron content purity is Wt, 99%) and B catalyst (NH is housed 4OH and H 2NCH 2CH 2NH 2, both weight ratios 3: 1) the fixed bed absorption tower, the weight ratio of A and B is 2000: 1, coal bed gas consist of CH 450%, O 212%, N 230%, other component gas 8%.Coal bed gas: (A catalyst+B catalyst)=1: 0.05mol, FeSO 4The molar concentration of the aqueous solution is 0.1mol/L; Coal bed gas: FeSO 4=1: 100mol; Under 10 ℃ temperature, self-organizing ground temperature control deoxygenation under the normal pressure of 0.103MPa, the oxygen removal rate is 98.20%.
Embodiment 6
With the raw material coal bed gas with 3m 3The flow velocity of/min gets into catalyst A (available from the iron powder commodity of Shanghai Ling Feng chemical industry Co., Ltd, iron content purity is Wt, 99%) and B catalyst (KOH, Ca (OH) is housed 2And Mg (OH) 2, three's weight ratio 1: 1: 1) the fixed bed absorption tower, the weight ratio of A and B is 500: 1, coal bed gas consist of CH 450%, O 212%, N 230%, other component gas 8%.Coal bed gas: (A catalyst+B catalyst)=1: 0.05mol, FeSO 4The molar concentration of the aqueous solution is 0.1mol/L; Coal bed gas: FeSO 4=1: 100mol; Under 30 ℃ temperature, self-organizing ground temperature control deoxygenation under the normal pressure of 0.103MPa, the oxygen removal rate is 98.33%.
Embodiment 7
With the raw material coal bed gas with 3m 3The flow velocity of/min gets into catalyst A (available from the iron powder commodity of Shanghai Ling Feng chemical industry Co., Ltd, iron content purity is Wt, 99%) and B catalyst (NH is housed 2CH 2CH 2OH) fixed bed absorption tower, the weight ratio of A and B are 500: 1, coal bed gas consist of CH 450%, O 212%, N 230%, other component gas 8%.Coal bed gas: (A catalyst+B catalyst)=1: 0.05mol, FeSO 4The molar concentration of the aqueous solution is 0.1mol/L; Coal bed gas: FeSO 4=1: 100mol; Under 30 ℃ temperature, self-organizing ground temperature control deoxygenation under the normal pressure of 0.103MPa, the oxygen removal rate is 98.40%.

Claims (13)

1. the method for deoxidation of a coal bed gas is characterized in that comprising the following step: under the effect of catalyst, with coal bed gas and FeSO 4The aqueous solution carries out oxidation reaction, gets final product; Wherein, described catalyst is a catalyst A, or the mixture of catalyst A and B; Catalyst A is a ferrous metal, and catalyst B is hydroxide, the Zn (OH) of alkali-metal hydroxide, alkaline-earth metal 2, NH 4OH, H 2NCH 2CH 2NH 2And NH 2CH 2CH 2Among the OH one or more.
2. the method for deoxidation of coal bed gas as claimed in claim 1, it is characterized in that: described ferrous metal is one or more in iron wire, iron filings and the iron powder.
3. the method for deoxidation of coal bed gas as claimed in claim 1, it is characterized in that: described alkali-metal hydroxide is NaOH and/or KOH; The oxyhydroxide of described alkaline-earth metal is Ca (OH) 2And/or Mg (OH) 2
4. the method for deoxidation of coal bed gas as claimed in claim 1 is characterized in that: described FeSO 4The molar concentration of the aqueous solution is 0.0001～0.1mol/L.
5. the method for deoxidation of coal bed gas as claimed in claim 1, it is characterized in that: described oxidation reaction is carried out under the effect of the mixture of catalyst A and B, and the weight ratio of A and B is 20: 1～2000: 1.
6. the method for deoxidation of coal bed gas as claimed in claim 5, it is characterized in that: the weight ratio of described A and B is 50: 1～500: 1.
7. the method for deoxidation of coal bed gas as claimed in claim 1, it is characterized in that: the temperature of described oxidation reaction is 10 ℃～50 ℃; The pressure of oxidation reaction is 0.101～0.107MPa.
8. the method for deoxidation of coal bed gas as claimed in claim 7, it is characterized in that: the temperature of described oxidation reaction is 20 ℃～30 ℃; The pressure of oxidation reaction is 0.101～0.103MPa.
9. the method for deoxidation of coal bed gas as claimed in claim 1, it is characterized in that: the oxygen content of described coal bed gas is a percent by volume 8～12%, the mol ratio of coal bed gas and catalyst is 1: 0.005～1: 0.05.
10. the method for deoxidation of coal bed gas as claimed in claim 1, it is characterized in that: the oxygen content of described coal bed gas is 8～12%, coal bed gas and FeSO 4Mol ratio be 1: 0.0001～1: 100.
11. the method for deoxidation of coal bed gas as claimed in claim 10 is characterized in that: described coal bed gas and FeSO 4Mol ratio be 1: 0.001-1: 0.105.
12. a catalyst is characterized in that: it is the mixture of catalyst A and B, and the kind of A and B is claim 1～3 described in each roughly the same.
13. catalyst as claimed in claim 12 is characterized in that: the ratio of described A and B such as claim 5 or 6 are said.
CN 200910195504 2009-09-11 2009-09-11 Deoxidating method for coal bed gas and catalyst Expired - Fee Related CN101659890B (en)

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CN102533368B (en) * 2012-01-11 2013-09-18 东南大学 Method for deoxidizing coal bed gas through centrifugalization at low temperature and high speed
CN108441273B (en) * 2018-04-02 2019-12-24 东北大学 Oxygen-containing low-concentration combustible gas deoxidation method and deoxidation system

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101301611A (en) * 2008-07-07 2008-11-12 西南化工研究设计院 Sulfur-tolerance deoxidation catalyst and preparation and use thereof
CN101322942A (en) * 2008-07-29 2008-12-17 西南化工研究设计院 Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101301611A (en) * 2008-07-07 2008-11-12 西南化工研究设计院 Sulfur-tolerance deoxidation catalyst and preparation and use thereof
CN101322942A (en) * 2008-07-29 2008-12-17 西南化工研究设计院 Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications

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