CN102451690B - Preparation method of substitute natural gas - Google Patents
Preparation method of substitute natural gas Download PDFInfo
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- CN102451690B CN102451690B CN201010526396.5A CN201010526396A CN102451690B CN 102451690 B CN102451690 B CN 102451690B CN 201010526396 A CN201010526396 A CN 201010526396A CN 102451690 B CN102451690 B CN 102451690B
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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 field, particularly a kind of synthesis gas or coke-stove gas are that raw material is prepared the method for substitute natural gas through methanation reaction.
Background technology
Substitute natural gas (SNG) refers to by CO, H
2or containing CO
2synthesis gas, coke-stove gas through methanation reaction, obtain methane mole percent at more than 90% gas, for substituting of natural gas, as compressed natural gas (CNG) vehicle fuel and domestic gas.The feature of China's energy resource structure is rich coal, oil starvation, weak breath, and greatly developing clean coal technology is the important component part of energy development strategy, therefore, with synthesis gas, coke-stove gas substitute natural gas processed, is one of effective way of supplemental natural gas shortage of resources.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 reaction 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 transition metal, and wherein the activity of Ni and Ru is best.Nickel-base catalyst has been able to the ripe ，Ru Denmark that applies in industrial methanation technology
methanation technology is produced two more than ten years at big plain in u.s.a gasworks for substitute natural gas.Nickel normally forms support type heterogeneous catalyst on carrier and is used to be distributed to, and carrier has the Al of comprising
2o
3, SiO
2, ZrO
2, TiO
2with the various oxides such as MgO, role is dispersed activity component on the one hand, reduces metal use amount, and on the other hand, carrier and active component form appropriate interaction, promotion catalyst activity.For the efficient substitute natural gas that obtains, improve as far as possible catalyst activity, extending 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 larger temperature difference, and this just requires catalyst to have good heat-resistant stability.For this reason, in many-sides such as catalyst promoter, carrier and preparation methods, be modified into as first-selection.As Chinese patent CN101733104A provides a kind of catalyst of methanation of carbon dioxide-containing synthesis gas, by metal active constituent, auxiliary agent and carrier form, synthesis gas H
2/ CO (mol ratio)=3～8, 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 comprised of active component Ni, auxiliary agent and alumina catalyst support, for the synthesis of the carbon dioxide methanation of gas preparing natural gas by methanation back segment.Chinese patent CN101716513A discloses a kind of catalyst of coal gasification completely methanated by synthesis gas, by rare earth oxide, be carrier, active component is Ni, and auxiliary agent is La, improved the heat-resisting quantity of catalyst, weak point is Ni content high (> 20wt%).European patent EP 1173277 discloses with rare earth oxide and rare earth perovskite-type oxides supported ni catalyst, 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, although by adding second, third kind of metal promoter or changing catalyst carrier, to improve methanation activity, stability.For example, but these catalyst still exist some defects: (1) methanation activity still needs to improve; (2) reaction velocity is still lower; (3) nickel loading is higher; (4) catalyst high-temperature stability still leaves some room for improvement etc.Easily there is strong interaction with active component in single oxide carrier, even form low activity species when high temperature, causes catalyst reduction in service life.The present invention finds to using perovskite type rare earth complex oxide as carrier loaded Ni catalyst, when alkali metal or alkaline-earth metal are auxiliary agent, can be under low Ni content, high reaction velocity, obtain high methanation activity, during high temperature not with active component generation strong effect, thereby make catalyst there is extraordinary high-temperature stability, improve the efficiency of synthesis gas or coke-stove gas production substitute natural gas.
Summary of the invention
The deficiency that the object of the invention is to avoid existing patent, provides a kind of thermal structure to stablize, is easy to disperse the perovskite composite oxide carrier of Ni active component, for the method for High-efficient Production substitute natural gas.
A kind of preparation method of substitute natural gas, it is characterized in that it is unstripped gas that the method be take synthesis gas or coke-stove gas, by 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 condition, through methanation reaction, obtain methane mole percent in more than 93% substitute natural gas; Described catalyst is comprised of active component Ni 1-30wt%, auxiliary agent 0.01-5wt%, carrier 60-90wt%; One or more in auxiliary agent WeiIAZu Huo IIA family; Carrier is perovskite composite oxides, one or more of rare earth metal and transition metal ,IIA Zu,Huo IIIA family, consists of.
One or more ，IA family metals in the catalyst promoter WeiIAZu Huo IIA family that the present invention adopts are that Na or K ，IIA family metal are Ca or Mg.
Catalyst carrier is perovskite composite oxides, one or more of rare earth metal and transition metal ,IIAZu Huo IIIA family, consists of, and rare earth metal is La, and transition metal is that Ti, Mn, Fe, CoHuoCu， IIA family metal are that SrHuoBa， IIIA family metal is Al.
H in unstripped gas
2with the mol ratio of CO be 2～8, CO
2mole percent is 0.05～50%.
Catalyst preparation of the present invention adopts conventional infusion process or the precipitation method, the conventional method that the preparation process of carrier also adopts perovskite-type material to prepare, be that citric acid complex method is (as document J.A.B.Bourzutschky, N.Homes, A.T.Bell, J.Catal.1990, described in 124,52-72) or coprecipitation (Zhu Hongfa, catalyst carrier preparation and application technology, 2002 Nian， petroleum industry publishing houses).
The present invention adopts catalyst as mentioned above, by methanation reaction, separated through pressure-variable adsorption or film with synthesis gas or coke-stove gas, can obtain methane mole percent higher than 93% high-quality substitute natural gas.Both can feed natural gas supply system, also can be for compressed natural gas, thus become the effective way of supplemental natural gas resource.
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.It is catalyst carrier that the present invention has used the stable RE perovskite based composite oxide of thermal structure, 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 volume flow of reactor that enters per hour divided by the quality of catalyst, represents the L/kgh of unit with GHSV.Below in conjunction with embodiment, the present invention is described in further detail, obviously this scope being not meant to limit the present invention.
Embodiment 1
The lanthanum cobalt perovskite of specific area 70 meters squared per gram of take is carrier, by nickel oxide percetage by weight on final catalyst be 10%, the magnesian percetage by weight of auxiliary agent is 1.5%, adopts nickel nitrate and magnesium nitrate aqueous solution infusion process to prepare Ni-Mg/LaCoO
3catalyst (catalyst A).14 millimeters of internal diameters, in the quartz glass reaction pipe of long 250 millimeters, load 5 grams of 20-40 object catalyst A, with reducing after 6 hours at 380 ℃ containing 10% hydrogen/nitrogen gaseous mixture of flow 500 ml/min, 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 ℃, using insert in beds thermocouple indication as reaction temperature, with synthesis gas, be that raw material carries out methanation reaction, wherein H
2/ CO (mole)=3, CO
2content 0.5% (mole), after reaction, gas composition and catalyst performance are listed in table 1.
Embodiment 2
The lanthanum iron perovskite of specific area 30 meters squared per gram of take is carrier, by nickel oxide percetage by weight on final catalyst be 10%, the percetage by weight of auxiliary agent potassium oxide is 1.0%, adopts nickel nitrate and the Alkitrate precipitation method to prepare Ni-K/LaFeO
3catalyst (catalyst B).By the method described in embodiment 1, carry out methanation and produce substitute natural gas, after reaction, gas composition and catalyst performance are listed in table 1.
Table 1 evaluating catalyst result *
*GHSV＝20000L/kg·h
Embodiment 3
The lanthanum aluminium perovskite of specific area 20 meters squared per gram of take is carrier, by nickel oxide percetage by weight on final catalyst be 5%, the percetage by weight of auxiliary agent calcium oxide is 2.0%, adopts nickel nitrate and the calcium nitrate aqueous solution precipitation method to prepare Ni-Ca/LaAlO
3catalyst (catalyst C).Take mole percent as H
260%, CO 20%, CO
25%, CH
4it is synthetic that 15% gas is that raw material carries out substitute natural gas, and catalyst loading amount is 30g, and after reaction, gas is through pressure-variable adsorption, and the methane mole percent that obtains substitute natural gas is 95%, and catalyst performance is listed in table 2.
Embodiment 4
The specific area 18 meters squared per gram lanthanum ferro-aluminum perovskites of take are carrier, adopt the preparation method identical with embodiment 1, and obtaining final catalyst oxidation nickel percetage by weight is 10%, the Ni-Mg/LaAl that the magnesian percetage by weight of auxiliary agent is 1.0%
0.8fe
0.2o
3catalyst (catalyst D).Take mole percent as H
276%, CO14%, CO
210% gas is raw material, carries out substitute natural gas and synthesizes, and after reaction, gas methane mole percent after pressure-variable adsorption is 96%, and catalyst performance is in Table 2.
Embodiment 5
The surface area 31 meters squared per gram lanthanum strontium cobalt perovskites of take are 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%, the Ni-Na/La that the percetage by weight of auxiliary agent sodium oxide molybdena is 1.0%
0.9sr
0.1coO
3catalyst (catalyst E).Take mole percent as H
256%, CO 12%, CO
28%, CH
426% gas is raw material, carries out substitute natural gas and synthesizes, and after reaction, gas methane mole percent after pressure-variable adsorption is 95%, and catalyst performance is in Table 2.
Embodiment 6
The lanthanum barium titanium perovskite of specific area 50 meters squared per gram of take is 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%, the Ni-Mg/La that the magnesian percetage by weight of auxiliary agent is 1.0%
0.9ba
0.1tiO
3catalyst (catalyst F).Take mole percent as H
276%, CO 20%, CO
24% gas is raw material, carries out substitute natural gas and synthesizes, and after reaction, gas methane mole percent after pressure-variable adsorption is 96%, and catalyst performance is in Table 2.
Embodiment 7
The lanthanum strontium copper cobalt perovskite of specific area 50 meters squared per gram of take is 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%, the Ni-K/La that the percetage by weight of auxiliary agent potassium oxide is 1.0%
0.8sr
0.2cu
0.4co
0.6o
3catalyst (catalyst G).Take mole percent as H
256%, CO 12%, CO
28%, CH
426% gas is raw material, carries out substitute natural gas and synthesizes, and after reaction, gas methane mole percent after pressure-variable adsorption is 95%, and catalyst performance is in Table 2.
Embodiment 8
Take mole percent as 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, after reaction reaches balance, is directly warming up to 700 ℃ by reactor, maintains two hours, then is cooled to 360 ℃, detects the rear gases methane concentration of catalyst performance and reaction.After 6 times, catalyst performance does not have marked change repeatedly, and CO conversion ratio still can be higher than 99.5%, and after reaction, gas methane mole percent after pressure-variable adsorption is 95%.
The contrast of table 2 evaluating catalyst result
Embodiment 9
Take mole percent as 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 gas with various air speed, and result is as shown in table 3.In air speed, during up to 45000L/kgh, CO conversion ratio still can be higher than 99.5%, methane mole percent 93% in gas after pressure-variable adsorption.
The impact of table 3 gas space velocity on reaction
Claims (2)
1. the preparation method of a substitute natural gas, it is characterized in that it is unstripped gas that the method be take synthesis gas or coke-stove gas, by 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 condition, through methanation reaction, obtain methane mole percent in more than 93% substitute natural gas; Described catalyst is comprised of active component Ni1-30wt%, auxiliary agent 0.01-5wt%, carrier 60-90wt%; One or more in auxiliary agent WeiIAZu Huo IIA family; Carrier is perovskite composite oxides, one or more of rare earth metal and transition metal ,IIA Zu,Huo IIIA family, consists of; Wherein one or more the ，IA family metals in catalyst promoter WeiIAZu Huo IIA family are that Na or K ，IIA family metal are Ca or Mg; Catalyst carrier is perovskite composite oxides, one or more of rare earth metal and transition metal ,IIAZu Huo IIIA family, consists of, and rare earth metal is La, and transition metal is that Ti, Mn, Fe, CoHuoCu， IIA family metal are that SrHuoBa， IIIA family metal is Al.
2. the method for claim 1, is characterized in that H in unstripped gas
2with the mol ratio of CO be 2～8, CO
2mole percent is 0.05～50%.
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| CN102757829B (en) * | 2012-07-25 | 2014-04-02 | 华北电力大学 | Synthetic gas methanation flow conversion periodic operation reaction device and application |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| AUPP607198A0 (en) * | 1998-09-21 | 1998-10-15 | University Of Queensland, The | Process and catalysts for the methanation of oxides of carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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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 |