CN102451690A - Preparation method of substitute natural gas - Google Patents
Preparation method of substitute natural gas Download PDFInfo
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- CN102451690A CN102451690A CN2010105263965A CN201010526396A CN102451690A CN 102451690 A CN102451690 A CN 102451690A CN 2010105263965 A CN2010105263965 A CN 2010105263965A CN 201010526396 A CN201010526396 A CN 201010526396A CN 102451690 A CN102451690 A CN 102451690A
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Abstract
The invention discloses a method for preparing a substitute natural gas from synthesis gas or coke oven gas by methanation reaction. In the method, the substitute natural gas in which the molar percentage of methane is more than 93% is obtained by the methanation reaction in a fixed bed reactor containing a methanation catalyst on the conditions that the reaction temperature is 250-750 DEG C, the reaction pressure is 0.1-6.0 Mpa and the total airspeed of feed gas is 500-50000h<-1>, wherein the feed gas can be synthesis gas or coke oven gas. Compared with the existing process, the method disclosed by the invention can be carried out at a higher airspeed, thus a higher methane space-time yield can be obtained.
Description
Technical field
The invention belongs to synthesis gas and coke-stove gas utilizes the field, particularly a kind of synthesis gas or coke-stove gas are raw material prepares substitute natural gas through methanation reaction method.
Background technology
Substitute natural gas (SNG) is meant by CO, H
2Or contain CO
2Synthesis gas, coke-stove gas obtain the methane mole percent at the gas more than 90% through methanation reaction, be used for substituting of natural gas, like compressed natural gas (CNG) vehicle fuel and domestic gas.The characteristics of China's energy resource structure are rich coal, oil starvation, weak breath, and greatly developing clean coal technology is the important component part of energy development strategy, therefore, is one of effective way of supplemental natural gas shortage of resources with synthesis gas, coke-stove gas system substitute natural gas.The key reaction of SNG process is CO, CO
2Methanation, that is: CO+H
2→ CH
4+ H
2O (Δ H
298 o=-206kJ/mol), CO
2+ H
2→ CH
4+ H
2O (Δ H
298 o=-165kJ/mol).This be reflected at synthetic ammonia hydrogen remove oxycarbide commercial Application for many years, research in recent years shows, in hydrogen-rich gas, selecting methanation to remove CO also will have potential application.Methanation reaction is the strong exothermic process of a catalytic hydrogenation, and generally acknowledged catalyst activity component is a transition metal, and wherein Ni and Ru's is active best.Nickel-base catalyst has been able to ripe the application in industrial methanation technology, be used for substitute natural gas like Denmark
methanation technology at the big plain in u.s.a gasworks and produce two more than ten years.Nickel normally uses to be distributed to formation support type heterogeneous catalyst on the carrier, and carrier has the Al of comprising
2O
3, SiO
2, ZrO
2, TiO
2With various oxides such as MgO, role is the dispersed activity component on the one hand, reduces the metal use amount, and on the other hand, carrier and active component form the interaction of appropriateness, the promotion catalyst activity.Be the efficient substitute natural gas that obtains, improve catalyst activity as far as possible, prolong catalyst and become one of target that people pursue service life.In addition, for the methanation reaction of strong heat release, reactor is imported and exported has the bigger temperature difference, and this just requires catalyst to have good heat-resistant stability.For this reason, be modified in many-sides such as catalyst promoter, carrier and preparation methods and be first-selection.Provide a kind of carbonated synthesis gas to carry out the catalyst of methanation like Chinese patent CN101733104A, by metal active constituent, auxiliary agent and carrier are formed, synthesis gas H
2/ CO (mol ratio)=3～8, the CO conversion ratio is the highest by 90.5%, and methane selectively is the highest by 92.2%, and weak point is the lower (1000-8000h of reaction velocity
-1).Chinese patent CN101757928A discloses a kind of carbon dioxide methanation catalyst and preparation method thereof, and catalyst is made up of active component Ni, auxiliary agent and alumina catalyst support, is used for the carbon dioxide methanation of synthesis gas preparing natural gas by methanation back segment.Chinese patent CN101716513A discloses a kind of catalyst of coal gasification completely methanated by synthesis gas, is carrier by rare earth oxide, and active component is Ni, and auxiliary agent is La, has improved the heat-resisting quantity of catalyst, weak point be Ni content high (＞20wt%).European patent EP 1173277 discloses with rare earth oxide and the oxide carried Ni catalyst of RE perovskite type, catalyzed carbon oxide methanation reaction, and weak point is the lower (10000h of air speed
-1), activity is also not high enough.In disclosed patent, though through adding second, third kind metal promoter or changing catalyst carrier, to improve methanation activity, stability.But these catalyst still exist some defectives, and for example: (1) methanation activity still need improve; (2) reaction velocity is still lower; (3) nickel loading is higher; (4) the catalyst high-temperature stability still leaves some room for improvement or the like.Strong interaction easily takes place with active component in single oxide carrier when high temperature, even forms the low activity species, causes catalyst reduction in service life.The present invention finds with perovskite type rare earth complex oxide as carrier loaded Ni catalyst; When alkali metal or alkaline-earth metal are auxiliary agent; Can under low Ni content, high reaction velocity, obtain high methanation activity, during high temperature not with active component generation strong effect; Thereby make catalyst have extraordinary high-temperature stability, improve the efficient of synthesis gas or coke-stove gas production substitute natural gas.
Summary of the invention
The objective of the invention is to avoid the deficiency of existing patent, provide a kind of thermal structure to stablize, be easy to disperse the perovskite composite oxide carrier of Ni active component, be used for the method for High-efficient Production substitute natural gas.
A kind of preparation method of substitute natural gas; It is characterized in that this method is a unstripped gas with synthesis gas or coke-stove gas, through the fixed bed reactors of methanation catalyst are housed, 250～750 ℃ of reaction temperatures; Reaction pressure 0.1～6.0Mpa, the total air speed 500～50000h of unstripped gas
-1Under the condition, obtain the methane mole percent in the substitute natural gas more than 93% through methanation reaction; Described catalyst is made up of active component Ni 1-30wt%, auxiliary agent 0.01-5wt%, carrier 60-90wt%; Auxiliary agent is one or more in IA family or the IIA family; Carrier is a perovskite composite oxides, is made up of one or more of rare earth metal and transition metal, IIA family or IIIA family.
The catalyst promoter that the present invention adopts is one or more in IA family or the IIA family, and IA family metal is Na or K, and IIA family metal is Ca or Mg.
Catalyst carrier is a perovskite composite oxides, is made up of one or more of rare earth metal and transition metal, IIA family or IIIA family, and rare earth metal is La, and transition metal is Ti, Mn, Fe, Co or Cu, and IIA family metal is Sr or Ba, and IIIA family metal is Al.
H in the unstripped gas
2With the mol ratio of CO be 2～8, CO
2Mole percent is 0.05～50%.
Preparation of Catalyst of the present invention adopts the conventional infusion process or the precipitation method, and the preparation process of carrier also adopts the conventional method of perovskite-type material preparation, and promptly citric acid complex method is (like document J.A.B.Bourzutschky; N.Homes, A.T.Bell, J.Catal.1990; 124, described in the 52-72) or coprecipitation (Zhu Hongfa, catalyst carrier preparation and application technology; 2002, petroleum industry publishing house).
The present invention adopts catalyst as stated, passes through methanation reaction with synthesis gas or coke-stove gas, separates through transformation absorption or film, can obtain the methane mole percent and be higher than 93% high-quality substitute natural gas.Both can infeed the natural gas supply system, also can be used for compressed natural gas, thereby become supplemental natural gas resources effective approach.
The present invention has the following advantages: the present invention compares with existing process and can under higher air speed condition, operate; Thereby obtain higher methane space-time yield; The production efficiency that is substitute natural gas is higher, and the nickel loading of catalyst is lower simultaneously, effectively reduces disposable input and operating cost.The present invention has used the stable RE perovskite based composite oxide of thermal structure to be catalyst carrier, makes catalyst have better heat-resistant stability, has effectively improved the operating flexibility that substitute natural gas is produced.
The specific embodiment
Reaction velocity of the present invention is defined as the reacting gas raw material and per hour gets into the quality of the volume flow of reactor divided by catalyst, representes the L/kgh of unit with GHSV.Below in conjunction with embodiment the present invention is done further detailed description, obviously this scope that is not meant to limit the present invention.
Embodiment 1
Lanthanum cobalt perovskite with specific area 70 meters squared per gram is a carrier, by nickel oxide percetage by weight on the final catalyst be 10%, the magnesian percetage by weight of auxiliary agent is 1.5%, adopts nickel nitrate and magnesium nitrate aqueous solution immersion process for preparing Ni-Mg/LaCoO
3Catalyst (catalyst A).14 millimeters of internal diameters; Filling 5 gram 20-40 purpose catalyst A in long 250 millimeters the quartz glass reaction pipe; With flow 500 ml/min contain 10% hydrogen/nitrogen gaseous mixture 380 ℃ the reduction 6 hours after; Be cooled to room temperature, be transferred in the stainless steel reactor of 18 millimeters of internal diameters, 300 millimeters of length.Reactor is warming up to 350 ℃, indicates as reaction temperature, use synthesis gas to carry out methanation reaction, wherein H as raw material with the thermocouple that inserts in beds
2/ CO (mole)=3, CO
2Content 0.5% (mole), reaction back gas composition and catalyst performance are listed in table 1.
Embodiment 2
Lanthanum iron perovskite with specific area 30 meters squared per gram is a carrier, by nickel oxide percetage by weight on the final catalyst be 10%, the percetage by weight of auxiliary agent potassium oxide is 1.0%, adopts the nickel nitrate and the potassium nitrate aqueous solution precipitation method to prepare Ni-K/LaFeO
3Catalyst (catalyst B).Carry out methanation by embodiment 1 described method and produce substitute natural gas, reaction back gas composition and catalyst performance are listed in table 1.
Table 1 evaluating catalyst is * as a result
*GHSV＝20000L/kg·h
Embodiment 3
Lanthanum aluminium perovskite with specific area 20 meters squared per gram is a carrier, by nickel oxide percetage by weight on the final catalyst be 5%, the percetage by weight of auxiliary agent calcium oxide is 2.0%, adopts the nickel nitrate and the calcium nitrate aqueous solution precipitation method to prepare Ni-Ca/LaAlO
3Catalyst (catalyst C).With the mole percent is H
260%, CO 20%, CO
25%, CH
4It is synthetic that 15% gas is that raw material carries out substitute natural gas, and the catalyst loading amount is 30g, and reaction back gas adsorbs through transformation, and the methane mole percent that obtains substitute natural gas is 95%, and catalyst performance is listed in table 2.
Embodiment 4
With specific area 18 meters squared per gram lanthanum ferro-aluminum perovskites is carrier, adopts the preparation method identical with embodiment 1, and obtaining final catalyst oxidation nickel percetage by weight is 10%, and the magnesian percetage by weight of auxiliary agent is 1.0% Ni-Mg/LaAl
0.8Fe
0.2O
3Catalyst (catalyst D).With the mole percent is H
276%, CO14%, CO
210% gas is raw material, carries out substitute natural gas and synthesizes, and gas methane mole percent after transformation absorption in reaction back is 96%, and catalyst performance is seen table 2.
Embodiment 5
With surface area 31 meters squared per gram lanthanum strontium cobalt perovskites is carrier; Adopt the preparation method identical with embodiment 3; Difference is to replace calcium nitrate with sodium nitrate, and obtaining final catalyst oxidation nickel percetage by weight is 10%, and the percetage by weight of auxiliary agent sodium oxide molybdena is 1.0% Ni-Na/La
0.9Sr
0.1CoO
3Catalyst (catalyst E).With the mole percent is H
256%, CO 12%, CO
28%, CH
426% gas is raw material, carries out substitute natural gas and synthesizes, and gas methane mole percent after transformation absorption in reaction back is 95%, and catalyst performance is seen table 2.
Embodiment 6
Lanthanum barium titanium perovskite with specific area 50 meters squared per gram is a carrier; Adopt the preparation method identical with embodiment 3; Difference is to replace calcium nitrate with magnesium nitrate, and obtaining final catalyst oxidation nickel percetage by weight is 10%, and the magnesian percetage by weight of auxiliary agent is 1.0% Ni-Mg/La
0.9Ba
0.1TiO
3Catalyst (catalyst F).With the mole percent is H
276%, CO 20%, CO
24% gas is raw material, carries out substitute natural gas and synthesizes, and gas methane mole percent after transformation absorption in reaction back is 96%, and catalyst performance is seen table 2.
Embodiment 7
Lanthanum strontium copper cobalt perovskite with specific area 50 meters squared per gram is a carrier; Adopt the preparation method identical with embodiment 3; Difference is to replace calcium nitrate with potassium nitrate, and obtaining final catalyst oxidation nickel percetage by weight is 12%, and the percetage by weight of auxiliary agent potassium oxide is 1.0% Ni-K/La
0.8Sr
0.2Cu
0.4Co
0.6O
3Catalyst (catalyst G).With the mole percent is H
256%, CO 12%, CO
28%, CH
426% gas is raw material, carries out substitute natural gas and synthesizes, and gas methane mole percent after transformation absorption in reaction back is 95%, and catalyst performance is seen table 2.
Embodiment 8
With the mole percent is H
256%, CO 12%, CO
28%, CH
426% gas is the resistance to elevated temperatures of raw material evaluate catalysts D.360 ℃ of reaction temperatures, pressure 1.0MPa, under the condition of the total air speed 25000L/kgh of gas, reaction reaches after the balance, and reactor directly is warming up to 700 ℃, keeps two hours, is cooled to 360 ℃ again, detects catalyst performance and reaction back gases methane concentration.After 6 times, catalyst performance does not have marked change repeatedly, and the CO conversion ratio still can be higher than 99.5%, and gas methane mole percent after transformation absorption in reaction back is 95%.
Table 2 evaluating catalyst result contrast
Embodiment 9
With the mole percent is H
260%, CO 20%, CO
25%, CH
415% gas is raw material, and filling 10g catalyst G 350～390 ℃ of reaction temperatures, carries out methanation reaction under pressure 2.0MPa and the gas with various air speed, and the result is as shown in table 3.During up to 45000L/kgh, the CO conversion ratio still can be higher than 99.5% in air speed, methane mole percent 93% in the gas of transformation absorption back.
Table 3 gas space velocity is to the influence of reaction
Claims (4)
1. the preparation method of a substitute natural gas; It is characterized in that this method is a unstripped gas with synthesis gas or coke-stove gas, through the fixed bed reactors of methanation catalyst are housed, 250～750 ℃ of reaction temperatures; Reaction pressure 0.1～6.0Mpa, the total air speed 500～50000h of unstripped gas
-1Under the condition, obtain the methane mole percent in the substitute natural gas more than 93% through methanation reaction; Described catalyst is made up of active component Ni 1-30wt%, auxiliary agent 0.01-5wt%, carrier 60-90wt%; Auxiliary agent is one or more in IA family or the IIA family; Carrier is a perovskite composite oxides, is made up of one or more of rare earth metal and transition metal, IIA family or IIIA family.
2. the method for claim 1 is characterized in that catalyst promoter is one or more in IA family or the IIA family, and IA family metal is Na or K, and IIA family metal is Ca or Mg.
3. the method for claim 1; It is characterized in that catalyst carrier is a perovskite composite oxides; Be made up of one or more of rare earth metal and transition metal, IIA family or IIIA family, rare earth metal is La, and transition metal is Ti, Mn, Fe, Co or Cu; IIA family metal is Sr or Ba, and IIIA family metal is Al.
4. the method for claim 1 is characterized in that H in the unstripped gas
2With the mol ratio of CO be 2～8, CO
2Mole percent is 0.05～50%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757829A (en) * | 2012-07-25 | 2012-10-31 | 华北电力大学 | Synthetic gas methanation flow conversion periodic operation reaction device and application |
| CN102757830A (en) * | 2012-07-25 | 2012-10-31 | 华北电力大学 | Reversed flow cycle operation reaction device for methanation of synthesis gas and application thereof |
| CN109745991A (en) * | 2018-12-13 | 2019-05-14 | 大连海事大学 | The preparation method and application of O composite metallic oxide catalyst for coal gasification |
| CN115837275A (en) * | 2022-11-04 | 2023-03-24 | 天津大学 | Perovskite type high-entropy oxide and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000016901A1 (en) * | 1998-09-21 | 2000-03-30 | The University Of Queensland | Process and catalysts for the methanation of oxides of carbon |
| CN101538011A (en) * | 2007-11-21 | 2009-09-23 | 艾尼股份公司 | Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses |
| CN101733104A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for methanation of carbon dioxide-containing synthesis gas, preparation method and application |
-
2010
- 2010-10-29 CN CN201010526396.5A patent/CN102451690B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000016901A1 (en) * | 1998-09-21 | 2000-03-30 | The University Of Queensland | Process and catalysts for the methanation of oxides of carbon |
| CN101538011A (en) * | 2007-11-21 | 2009-09-23 | 艾尼股份公司 | Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses |
| CN101733104A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for methanation of carbon dioxide-containing synthesis gas, preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757829A (en) * | 2012-07-25 | 2012-10-31 | 华北电力大学 | Synthetic gas methanation flow conversion periodic operation reaction device and application |
| CN102757830A (en) * | 2012-07-25 | 2012-10-31 | 华北电力大学 | Reversed flow cycle operation reaction device for methanation of synthesis gas and application thereof |
| CN102757830B (en) * | 2012-07-25 | 2014-01-08 | 华北电力大学 | Reversed flow cycle operation reaction device for methanation of synthesis gas and application thereof |
| CN109745991A (en) * | 2018-12-13 | 2019-05-14 | 大连海事大学 | The preparation method and application of O composite metallic oxide catalyst for coal gasification |
| CN115837275A (en) * | 2022-11-04 | 2023-03-24 | 天津大学 | Perovskite type high-entropy oxide and preparation method and application thereof |
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| CN102451690B (en) | 2014-01-15 |
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Effective date of registration: 20191018 Address after: 215699 building 30, Yangtze River International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu Province Patentee after: Jiangsu Huachang new material technology research Co., Ltd Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences |