CN101161335B - A method for preparing carbon base catalyst for CH4 reforming to CO2 for synthesis gas reaction - Google Patents

A method for preparing carbon base catalyst for CH4 reforming to CO2 for synthesis gas reaction Download PDF

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Publication number
CN101161335B
CN101161335B CN2007101320238A CN200710132023A CN101161335B CN 101161335 B CN101161335 B CN 101161335B CN 2007101320238 A CN2007101320238 A CN 2007101320238A CN 200710132023 A CN200710132023 A CN 200710132023A CN 101161335 B CN101161335 B CN 101161335B
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earth metal
alkaline earth
metal compound
catalyst
base catalyst
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CN101161335A (en
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肖睿
李延兵
金保升
仲兆平
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Southeast University
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Southeast University
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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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention discloses a method for preparing the carbon-base catalyst in the reaction of CH4 reforming of CO2 to synthesis gas, in the method the ball mill is adopted to crush the primary coal to the particles with dimension below 80 mu m, then the primary coal particle is mixed with the alkaline earth metal compound, the mixing weight ration between the primary coal particle to the alkaline earth metal compound is: 1.5: 1 to 19: 1, the alkaline earth metal compound is added with the mode of mechanical mixing to prepare the mixture of primary coal particle and the alkaline earth metal compound, the prepared mixture is stirred to uniform and then is thermally decomposed at the condition of 900 to 1250 DEG C to that no volatilized share is separated, the massive carbon-base catalyst is prepared and is crushed to the needed granular size. When the catalyst is used in the reaction of CH4 reforming of CO2 to synthesis gas and at the condition that the same CH4 transformation efficiency is obtained, the carbon-base catalyst evidently reduces the reaction temperature and the stability of the catalyst is better comparing with the carbon catalyst without alkaline earth metal compound.

Description

A kind of CH 4Reformation CO 2The preparation method of the carbon base catalyst of preparing synthetic gas reaction
Technical field
The present invention relates to a kind of CH 4Reformation CO 2The preparation method of the carbon base catalyst of preparing synthetic gas reaction.Specifically, be a kind of that former coal particle and alkaline earth metal compound is mixed as to be applicable to CH 4Catalytic reforming CO 2The method of carbon base catalyst.
Background technology
Whole world natural gas in 2006 estimation proved reserves are 175.08 tcms, and buried depth is shallower than 2000 meters coal bed gas reserves and is about 240 tcms.Wherein Chinese coal bed gas aboundresources occupies the third place in the world.CH in natural gas and the coal bed gas 4Content is than higher, generally greater than 90%; China produces a large amount of coke-stove gas (coal pyrolysis gas), CH every year in addition 4Content is also 20%～30%.Rationally utilize and be rich in CH 4The main path that gas becomes synthesis gas is to transform CH 4Be H 2And CO.
Industrial main employing steam methane catalytic reforming process is produced synthesis gas at present, the H that this technology obtains 2: CO is 3: 1, but many processes that further transform for synthesis gas such as Fischer-Tropsch is synthetic and carbonylation etc. need lower H 2/ CO mol ratio.Methane reforming carbon dioxide preparing synthetic gas can be avoided this weak point, because the H of its generation 2: CO is 1: 1.To alleviating greenhouse effects that carbon dioxide causes, alleviating air environmental pollution, has crucial meaning simultaneously.
CH 4Catalytic reforming CO 2The catalyst of synthetic gas production process mainly contains two series: a class is a noble metal series, as rhodium, nail, platinum, iridium, palladium etc., wherein especially with catalytic performance the best of rhodium, but because its resource-constrained costs an arm and a leg, is unfavorable for industrial applying; Another kind of is transiting metal nickel, cobalt, iron etc., and wherein with catalytic activity the best of nickel, the catalytic performance of nickel is only second to Noble Metal Rhodium, and cheap.There are defectives such as coking deactivation and sintering in nickel-base catalyst, and its industrialization is restricted but at high temperature.
Proposed a kind of Pd/carbon catalyst or carbon base catalyst of utilizing among the Chinese invention patent CN 1974732A and made CH 4With CO 2The method of synthesis gas is produced in the reformation conversion reaction.Pd/carbon catalyst is meant coke for ferroalloy or metallurgical coke in this invention, and carbon base catalyst is meant that coke for ferroalloy or metallurgical coke are through flooding the catalyst of nickel ion modification.Compare noble metal catalyst and nickel-base catalyst, this Pd/carbon catalyst and carbon base catalyst have wide source, less expensive, and be difficult for coking deactivation, become CH 4Catalytic reforming CO 2Industrial applications is one of the most potential catalyst.
But be to use Pd/carbon catalyst to produce synthesis gas requirement reaction temperature at 1000～1250 ℃, this will consume a large amount of energy undoubtedly, improves the reactor cost, thereby financial cost increases.The invention discloses a kind of preparation method of novel carbon base catalyst.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of CH 4Reformation CO 2The preparation method of the carbon base catalyst of preparing synthetic gas reaction.In system Jiao's former coal particle, add alkaline earth metal compound, make the catalytic performance of coke in reforming reaction improve, thus energy savings and reduction reactor cost.And the present invention compares with the carbon base catalyst among the aforementioned patent of invention CN 1974732A, and manufacture craft is fairly simple.
Technical scheme: a kind of CH of the present invention 4Reformation CO 2The preparation method of the carbon base catalyst of preparing synthetic gas reaction is to have added alkaline earth metal compound in producing the former coal particle of coke; It is as follows that it produces step:
1.) adopt ball mill that raw coal is crushed to the following particle of 80 μ m, then former coal particle is mixed with alkaline earth metal compound, the part by weight that former coal particle mixes with alkaline earth metal compound is: 1.5: 1～19: 1, mode with mechanical mixture is added alkaline earth metal compound, make the mixture of former coal particle and alkaline earth metal compound
2.) with 1) mixture that makes of step stirs, and pyrolysis under 900～1250 ℃ of conditions then to there not being fugitive constituent to separate out, makes block carbon base catalyst,
3.) with 2) carbon base catalyst that makes of step is crushed to required granular size.
The described alkaline earth metal compound of said method is meant the oxide and the hydroxide of alkaline-earth metal.
The described alkaline-earth metal of said method is meant magnesium (Mg) and two kinds of metals of calcium (Ca).
When adding alkaline earth metal compound in system Jiao's former coal particle, former coal particle and alkaline earth metal compound mixing ratio are 1.5: 1～19: 1 (weight).
This invention scope of application is CH 4Reformation CO 2The preparing synthetic gas reaction.
Beneficial effect: compare with the Pd/carbon catalyst that does not add alkaline earth metal compound, under the identical situation of CH4 conversion ratio, can significantly reduce reaction temperature, cut down the consumption of energy by a relatively large margin.
The specific embodiment
Describe the present invention in detail below by embodiment,
1.) adopt ball mill that raw coal is crushed to the following particle of 80 μ m, then former coal particle is mixed with alkaline earth metal compound, the part by weight that former coal particle mixes with alkaline earth metal compound is: 1.5: 1～19: 1, mode with mechanical mixture is added alkaline earth metal compound, make the mixture of former coal particle and alkaline earth metal compound
2.) with 1) mixture that makes of step stirs, and pyrolysis under 900～1250 ℃ of conditions then to there not being fugitive constituent to separate out, makes block carbon base catalyst,
3.) with 2) carbon base catalyst that makes of step is crushed to required granular size.
Described alkaline-earth metal is meant magnesium metal or calcium.Described alkaline earth metal compound is meant the oxide and the hydroxide of magnesium metal or calcium.
When adding alkaline earth metal compound in system Jiao's former coal particle, former coal particle and alkaline earth metal compound mixing ratio are 1.5: 1～19: 1 (weight), preferred 4: 1～10: 1 (weight).
Embodiment 1
1) get the following Xuzhou bituminous particle of 47.5 gram 80 μ m, add 2.5 gram lime powders (or the oxide of magnesium metal or calcium and hydroxide), fully mix,
2) get 50 grams the 1st) mixture that makes of step, pyrolysis 40min under 900 ℃ of conditions, to there not being fugitive constituent to separate out,
3) get the 2nd) coke that makes of step, grind and filter out particle diameter and be 0.3～0.45 particle 10.8 grams, make catalyst A.
Embodiment 2
Get the following Xuzhou bituminous particle of 42.5 gram 80um, add 7.5 gram lime powders (or the oxide of magnesium metal or calcium and hydroxide), press (2) (3) one step process among the embodiment 1, make catalyst B.
Embodiment 3
Get the following Xuzhou bituminous particle of 37.5 gram 80um, add 12.5 gram lime powders (or the oxide of magnesium metal or calcium and hydroxide), press (2) (3) one step process among the embodiment 1, make catalyst C.
The catalyst that makes in the foregoing description is tested, be found that adding the catalyst catalytic performance that makes behind the alkaline earth metal compound improves, and is promptly reaching identical CH 4Under the conversion ratio situation, the reaction temperature that adding the catalyst that makes behind the alkaline earth metal compound needs is lower than the catalyst that does not add alkaline earth metal compound, and along with the rising of alkaline earth metal compound addition, the reaction temperature of requirement reduces.Catalyst quality 10.8g for example, reaction gas flow speed 80ml/min, wherein CH 4: CO 2: N 2=1: 1: 2, reach under 50% situation at the CH4 conversion ratio, the reaction temperature that does not add the coke catalyst needs of alkaline earth metal compound is approximately 976 ℃, and the reaction temperature that the catalyst that embodiment 1,2 and 3 makes needs is respectively 968 ℃, 946 ℃ and 923 ℃.This shows that the catalyst that adds the catalyst that makes behind the alkaline earth metal compound than not adding alkaline earth metal compound and making has reduced energy resource consumption.

Claims (1)

1. CH 4Reformation CO 2The preparation method of the carbon base catalyst of preparing synthetic gas reaction, it is as follows to it is characterized in that producing step:
1.) adopt ball mill that raw coal is crushed to the following particle of 80 μ m, then former coal particle is mixed with alkaline earth metal compound, the part by weight that former coal particle mixes with alkaline earth metal compound is: 1.5: 1～19: 1, mode with mechanical mixture is added alkaline earth metal compound, make the mixture of former coal particle and alkaline earth metal compound
2.) with 1) mixture that makes of step stirs, and pyrolysis under 900～1250 ℃ of conditions then to there not being fugitive constituent to separate out, makes block carbon base catalyst,
3.) with 2) carbon base catalyst that makes of step is crushed to required granular size;
Described alkaline-earth metal is meant magnesium metal or calcium; Described alkaline earth metal compound is meant the oxide and the hydroxide of magnesium metal or calcium.
CN2007101320238A 2007-09-07 2007-09-07 A method for preparing carbon base catalyst for CH4 reforming to CO2 for synthesis gas reaction Expired - Fee Related CN101161335B (en)

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CN104925754A (en) * 2015-05-20 2015-09-23 广西科技大学 Composite catalytic active agent

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1272454A (en) * 1999-04-30 2000-11-08 煤炭科学研究总院北京煤化学研究所 Production method of coal base mesopore active carbon
CN1974732A (en) * 2006-12-13 2007-06-06 太原理工大学 Process of preparing synthesized gas with gasified gas and pyrolyzed gas

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1272454A (en) * 1999-04-30 2000-11-08 煤炭科学研究总院北京煤化学研究所 Production method of coal base mesopore active carbon
CN1974732A (en) * 2006-12-13 2007-06-06 太原理工大学 Process of preparing synthesized gas with gasified gas and pyrolyzed gas

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张香兰等人.中孔炭的催化剂制备方法.炭素 2.2001,(2),22-25.
张香兰等人.中孔炭的催化剂制备方法.炭素 2.2001,(2),22-25. *

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