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CN103861599A - Catalyst used for preparing substitute natural gas from coal, and preparation method thereof - Google Patents

Catalyst used for preparing substitute natural gas from coal, and preparation method thereof Download PDF

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Publication number
CN103861599A
CN103861599A CN201210546405.6A CN201210546405A CN103861599A CN 103861599 A CN103861599 A CN 103861599A CN 201210546405 A CN201210546405 A CN 201210546405A CN 103861599 A CN103861599 A CN 103861599A
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China
Prior art keywords
catalyst
preparation
auxiliary agent
natural gas
coal
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CN201210546405.6A
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Chinese (zh)
Inventor
吴学其
魏士新
蔡进
蔡成伟
檀结东
陈长新
张�杰
吴�琳
孟建
朱艳芳
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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Priority to CN201210546405.6A priority Critical patent/CN103861599A/en
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Abstract

The invention belongs to the technical field of methane synthetic catalyst, and relates to a catalyst used for preparing substitute natural gas from coal-based synthetic gas, and a preparation method thereof. The catalyst comprises 60 to 92wt% of a structural ingredient, 5 to 30wt% of an active ingredient, and 3 to 10wt% of an auxiliary agent; the active ingredient is nickel oxide; the structural ingredient is a magnesium aluminum composite oxide carrier. The preparation method comprises following steps: a nitrate solution of the active auxiliary agent is neutralized with one or a plurality of compounds selected from a hydroxide, a carbonate, a bicarbonate, or ammonium hydroxide, so as to obtain a precipitate, wherein the auxiliary agent is made from one or a plurality of ingredients selected from metallic oxides or metal salts of NiCa, Mg, Ba, K, Ce, La, Ti, and Zr; magnesium oxide and aluminium powder are mixed, and an obtained mixed suspension liquid is subjected to processing so as to obtain a colloid; the precipitate is mixed with the colloid, and an obtained mixed material is subjected to filtering, washing, roasting, moulding, roasting, dipping, and roasting so as to obtain the catalyst. The steps of the preparation method are simple; cost is low; obtained products possess excellent thermal stability; and carbon deposition is not easily induced at a high temperature with high CO content.

Description

A kind of coal substitute natural gas Catalysts and its preparation method processed
Technical field
The invention belongs to catalysis technical field, relate to a kind of preparation method of catalyst.The raw material of specifically being prepared by catalyst or intermediate product use colloid mill, make methane synthesizing catalyst have better activity, stability.
Background technology
Along with World Economics develops rapidly, population sharply increases, and energy-consuming constantly increases, and greenhouse gases and various discharge of poisonous waste increase sharply, and environment for human survival is subject to very big challenge.Under these circumstances, the natural gas energy resource cleaning, calorific value is high comes into one's own just day by day, and development gas industry becomes the optimal selection that countries in the world are improved environment and promoted sustainable economic development.The greenhouse gases that produce after combustion of natural gas only have coal 1/2, oil 2/3, pollution on the environment is far smaller than oil and coal.Calorific value of gas is 3000 much cards, and heating value of natural gas is up to 8500 kilocalories, and visible natural gas is a kind of energy of high-efficiency cleaning.
At present, natural gas proportion in world's primary energy is 24.3%.Due to the deficiency of China's natural gas resource and exploitation amount, natural gas proportion in primary energy is only 4% left and right, far below world average level.In recent years, along with " Shan gas is gone to the capital ", " in succession the building up and come into operation of the national combustion gas conveying engineering such as West-east Gas, the demand of natural gas is explosive growth.It is predicted, 2015, the demand of Natural Gas In China will reach 1700 ~ 2,100 hundred million Nm 3, and the gas production of the same period can only reach 1,400 hundred million Nm 3, insufficiency of supply-demand approximately 300 ~ 70,000,000,000 Nm 3.In order to solve the imbalance between supply and demand problem of China's natural gas, also actively utilize the natural gas resource of other countries of the world except the resource of basing on our country, also need to seek other alternative route.
Coal resources in China is relatively abundant, obtains synthesis gas carry out methane synthetic reaction by coal gasification, conversion, purification, can produce the substitute natural gas (Substitute Natural Gas is called for short SNG) of the defeated requirement of coincidence tube.Exploitation coal to SNG technology and then construction coal to SNG device, to solving the problem of complex utilization of coal resources, alleviate the present situation of Chinese Petroliferous shortage of resources, safeguards the energy security of China, realizes CO 2reduce discharging, protection of the environment is all significant, therefore Development of Coal preparing natural gas project is compeled as pressing as a fire singeing one's eyebrows.
Summary of the invention
The object of this invention is to provide a kind of Catalysts and its preparation method for preparing substitute natural gas by using coal based synthesis.
Catalyst of the present invention has the higher feature such as pyrolytic conversion activity and heat endurance.
The methanation catalyst of preparing substitute natural gas by using coal based synthesis of the present invention, it is characterized in that this catalyst comprises structural constituent, active component and auxiliary agent, active component is the nickel oxide of 5~30 wt %, auxiliary agent 3~10wt%, the Mg-Al composite oxide carrier that structural constituent is 60~92wt%.
The preferred content of active component nickel oxide is 7~20%; Auxiliary agent comprises one or more in rare earth oxide and alkaline-earth metal oxide, as CaO, MgO, BaO, K 2o, CeO 2, La 2o 3, TiO 2and ZrO 2in one or more, the wherein preferred La of the first auxiliary agent 2o 3, content 1~8wt%, the preferred BaO of the second auxiliary agent, content 0~4%; Complex carrier is made up of magnesia and aluminium oxide, and Mg/Al mol ratio is 1/3~3/1, preferably Mg/Al=1/1.
The preparation method of the methanation catalyst of described preparing substitute natural gas by using coal based synthesis, is characterized in that making as follows:
Figure 2012105464056100002DEST_PATH_IMAGE002
aluminium powder and magnesium oxide powder are added water and be uniformly mixed, mixed suspension is worn into colloid with colloid mill; by being dissolved in the aqueous solution according to one or more oxide or the salt in nickel nitrate and rare earth metal and/or the alkaline-earth metal of catalyst proportion of composing configuration, be configured to solution, then with alkali neutralization, be precipitated thing;
Figure DEST_PATH_IMAGE006
by step
Figure 870547DEST_PATH_IMAGE004
in precipitation remove impurity wherein by the method such as washing;
Figure DEST_PATH_IMAGE008
by step
Figure 884115DEST_PATH_IMAGE002
in colloid be added to step
Figure 850933DEST_PATH_IMAGE006
precipitation in, be uniformly mixed;
Figure DEST_PATH_IMAGE010
by step
Figure 294684DEST_PATH_IMAGE008
mixture filtration, oven dry, roasting, the granulation of middle gained, play the catalyst that obtains preparing synthetic natural gas by using coal derived synthesis after sheet moulding.
Described step
Figure 714164DEST_PATH_IMAGE002
ratio 1:3 ~ the 3:1 of middle aluminium powder and magnesium oxide powder.
Described step
Figure 268774DEST_PATH_IMAGE002
the milling time of middle suspension is 0.5-10 hour, preferably 0.5-3 hour.
Described step
Figure 824520DEST_PATH_IMAGE004
neutralization alkali used is one or more in hydroxide, carbonate, bicarbonate, ammoniacal liquor.
Described step
Figure 235910DEST_PATH_IMAGE004
after neutralization, the pH value of solution is 7.0-9.0, preferably 7.0-7.5.
The present invention has, and preparation process is simple, reduces the energy consumption in producing, thereby reduces costs.And having good heat-resistant stability, catalyst is difficult for the features such as carbon distribution under high temperature, high CO content.Meanwhile, catalyst also has good selective, and the conversion ratio of gas product can reach more than 99%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
Figure 142686DEST_PATH_IMAGE002
get 1000g aluminium powder and 1000g magnesia is poured in the container that 2000ml water is housed, be uniformly mixed, mixed suspension is worn into colloid, milling time 4 hours with colloid mill; get 400g nickel nitrate, 100g lanthanum nitrate and 2000ml water and be mixed with solution, then to be neutralized to pH value with sodium bicarbonate solution be 7.2;
Figure 973556DEST_PATH_IMAGE006
by step
Figure 555847DEST_PATH_IMAGE004
in precipitation use the method for deionized water washing to remove impurity wherein;
Figure 949919DEST_PATH_IMAGE008
by step
Figure 843401DEST_PATH_IMAGE002
in colloid be added to step
Figure 108160DEST_PATH_IMAGE006
precipitation in, be uniformly mixed; by step
Figure 742721DEST_PATH_IMAGE008
mixture filtration, oven dry, roasting, the granulation of middle gained, play the catalyst 1 that obtains preparing synthetic natural gas by using coal derived synthesis after sheet moulding.
 
Embodiment 2:
Figure 239561DEST_PATH_IMAGE002
get 800g aluminium powder and 1200g magnesia is poured in the container that 2000ml water is housed, be uniformly mixed, mixed suspension is worn into colloid, milling time 5 hours with colloid mill; get 400g nickel nitrate, 80g neodymium nitrate, 80g barium nitrate and 2000ml water and be mixed with solution, then with ammonia neutralization to pH value be 7.5;
Figure 548500DEST_PATH_IMAGE006
by step
Figure 917164DEST_PATH_IMAGE004
in precipitation use the method for deionized water washing to remove impurity wherein;
Figure 952116DEST_PATH_IMAGE008
by step
Figure 722626DEST_PATH_IMAGE002
in colloid be added to step
Figure 958567DEST_PATH_IMAGE006
precipitation in, be uniformly mixed;
Figure 814527DEST_PATH_IMAGE010
by step
Figure 650241DEST_PATH_IMAGE008
mixture filtration, oven dry, roasting, the granulation of middle gained, play the catalyst 2 that obtains preparing synthetic natural gas by using coal derived synthesis after sheet moulding.
Comparative example:
Figure 9678DEST_PATH_IMAGE002
get 800g aluminium powder and 1200g magnesia is poured in the container that 2000ml water is housed, be uniformly mixed,
Figure 275574DEST_PATH_IMAGE004
get 400g nickel nitrate 2000ml water and be mixed with solution, then to be neutralized to pH value with sodium bicarbonate solution be 7.2;
Figure 353252DEST_PATH_IMAGE006
by step in precipitation use the method for deionized water washing to remove impurity wherein;
Figure 475108DEST_PATH_IMAGE008
by step
Figure 911906DEST_PATH_IMAGE002
in suspension be added to step
Figure 476879DEST_PATH_IMAGE006
precipitation in, be uniformly mixed;
Figure 657325DEST_PATH_IMAGE010
by step
Figure 991354DEST_PATH_IMAGE008
mixture filtration, oven dry, roasting, the granulation of middle gained, play the catalyst 3 that obtains preparing synthetic natural gas by using coal derived synthesis after sheet moulding.
Embodiment 1, embodiment 2, the prepared catalyst of comparative example are carried out to activity rating.Activity rating condition is: test pressure is 3.0MPa, and in unstripped gas, CO concentration is 4%, CO 2concentration is 1%, and density of hydrogen is 17%, and beds inlet temperature is 300 DEG C.Acquired results is as following table:
? Catalyst 1 Catalyst 2 Comparative example 3
Conversion ratio (%) 100 100 98
C2, C3 content (%) 0 0 0.21
Find out that according to above table the good conversion ratio of this invention is with selective.

Claims (10)

1. a coal substitute natural gas catalyst processed, is characterized in that this catalyst comprises structural constituent, active component and auxiliary agent, and active component is the nickel oxide of 5~30 wt %, auxiliary agent 3~10wt%, the Mg-Al composite oxide carrier that structural constituent is 60~92wt%.
2. catalyst as claimed in claim 1, is characterized in that active component nickel oxide content is 7~20%.
3. catalyst as claimed in claim 1, is characterized in that auxiliary agent is CaO, MgO, BaO, K 2o, CeO 2, La 2o 3, TiO 2and ZrO 2in one or more.
4. catalyst as claimed in claim 3, is characterized in that the first auxiliary agent is La 2o 3, content 1~8wt%, the second auxiliary agent is BaO, content 0~4%.
5. catalyst as claimed in claim 1, is characterized in that composite oxide carrier is made up of magnesia and aluminium oxide, and Mg/Al mol ratio is 1/3~3/1.
6. the preparation method of catalyst as claimed in claim 1, is characterized in that making as follows:
Figure 2012105464056100001DEST_PATH_IMAGE001
aluminium powder and magnesium oxide powder are added water and be uniformly mixed, mixed suspension is worn into colloid with colloid mill; by being dissolved in the aqueous solution according to one or more oxide or the salt in nickel nitrate and rare earth metal and/or the alkaline-earth metal of catalyst proportion of composing configuration, be configured to solution, then with alkali neutralization, be precipitated thing;
Figure 2012105464056100001DEST_PATH_IMAGE003
by step
Figure 707268DEST_PATH_IMAGE002
in precipitation remove impurity wherein by the method such as washing;
Figure 930439DEST_PATH_IMAGE004
by step
Figure 136292DEST_PATH_IMAGE001
in colloid be added to step
Figure 128519DEST_PATH_IMAGE003
precipitation in, be uniformly mixed;
Figure DEST_PATH_IMAGE005
by step mixture filtration, oven dry, roasting, the granulation of middle gained, play the catalyst that obtains preparing synthetic natural gas by using coal derived synthesis after sheet moulding.
7. method for preparing catalyst as claimed in claim 6, is characterized in that step
Figure 206513DEST_PATH_IMAGE001
the ratio of middle aluminium powder and magnesium oxide powder is 1/3~3/1.
8. the preparation method of catalyst as claimed in claim 6, is characterized in that step
Figure 65927DEST_PATH_IMAGE001
the milling time of middle suspension is 0.5-10 hour.
9. the preparation method of catalyst as claimed in claim 6, is characterized in that step
Figure 443818DEST_PATH_IMAGE002
neutralization alkali used is one or more in hydroxide, carbonate, bicarbonate, ammoniacal liquor.
10. the preparation method of catalyst as claimed in claim 6, is characterized in that step
Figure 529717DEST_PATH_IMAGE002
after neutralization, the pH value of solution is 7.0-9.0.
CN201210546405.6A 2012-12-17 2012-12-17 Catalyst used for preparing substitute natural gas from coal, and preparation method thereof Pending CN103861599A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105562010A (en) * 2014-10-11 2016-05-11 中国石油化工股份有限公司 Preparation method of methane synthesis catalyst used for coal-to-gas
CN105727954A (en) * 2014-12-06 2016-07-06 中国石油化工股份有限公司 Preparation method of catalyst for synthetic gas to natural gas
CN106311352A (en) * 2015-06-19 2017-01-11 中国石油化工股份有限公司 Preparation method of catalyst carrier for preparing natural gas from coke-oven gas

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6034031A (en) * 1995-09-18 2000-03-07 Nec Corporation Catalyst material for use in producing substitute natural gas and method for producing substitute natural gas
CN101391218A (en) * 2008-10-31 2009-03-25 西南化工研究设计院 Coke-oven gas methanation catalyst and preparation method thereof
CN102500387A (en) * 2011-11-17 2012-06-20 中国石油化工股份有限公司 Catalyst for preparing substitute natural gas by using coal based synthesis gas, and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6034031A (en) * 1995-09-18 2000-03-07 Nec Corporation Catalyst material for use in producing substitute natural gas and method for producing substitute natural gas
CN101391218A (en) * 2008-10-31 2009-03-25 西南化工研究设计院 Coke-oven gas methanation catalyst and preparation method thereof
CN102500387A (en) * 2011-11-17 2012-06-20 中国石油化工股份有限公司 Catalyst for preparing substitute natural gas by using coal based synthesis gas, and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105562010A (en) * 2014-10-11 2016-05-11 中国石油化工股份有限公司 Preparation method of methane synthesis catalyst used for coal-to-gas
CN105562010B (en) * 2014-10-11 2019-02-22 中国石油化工股份有限公司 Preparation method for coal gas methane synthesizing catalyst
CN105727954A (en) * 2014-12-06 2016-07-06 中国石油化工股份有限公司 Preparation method of catalyst for synthetic gas to natural gas
CN105727954B (en) * 2014-12-06 2018-01-16 中国石油化工股份有限公司 A kind of preparation method of synthesis gas preparing natural gas catalyst
CN106311352A (en) * 2015-06-19 2017-01-11 中国石油化工股份有限公司 Preparation method of catalyst carrier for preparing natural gas from coke-oven gas
CN106311352B (en) * 2015-06-19 2019-06-04 中国石油化工股份有限公司 A kind of preparation method for oven gas preparing natural gas catalyst carrier

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Application publication date: 20140618