CN1087656C - Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use - Google Patents
Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use Download PDFInfo
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- CN1087656C CN1087656C CN96115391A CN96115391A CN1087656C CN 1087656 C CN1087656 C CN 1087656C CN 96115391 A CN96115391 A CN 96115391A CN 96115391 A CN96115391 A CN 96115391A CN 1087656 C CN1087656 C CN 1087656C
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Abstract
The present invention relates to a supported type or non-supported type metallic oxide catalyst used for a new reaction process directly preparing synthetic gas by the reaction of low-carbon alkane and carbon dioxide, which uses Ni as an active constituent and uses K or/and Fe as auxiliary agents. In the catalytic reaction, the low-carbon alkane and the carbon dioxide can be converted to the synthetic gas with high conversion rate, the conversion rate of the alkane is 95%, and the conversion rate of the carbon dioxide is 75%. The catalyst can be used for directly producing the synthetic gas by the reaction of carbon dioxide and a large amount of low-carbon alkane such as methane, ethane, propane, etc. contained in natural gas or oil field gas or low-carbon alkane such as methane, ethane, etc. contained in catalytic cracking dry gas. The reaction process has the advantages of simple technological process and convenient operation; the reaction process is suitable for application in industrial production.
Description
The present invention relates to (the CO+H of a kind of low-carbon alkanes and the direct preparing synthetic gas of carbon dioxide reaction
2) new process and the Ni System Catalyst that provides for this process.
With a large amount of exploitations of petroleum resources with worsening shortages and natural gas resource, the carbon dioxide of by-product increases considerably simultaneously, impel people to continually develop new technology path to make full use of oil, carbon resource in natural gas and the carbon dioxide, especially for the making full use of of the catalytic cracked dry gas after the petroleum cracking, caused people's great attention and keen interest.Once propose a kind of technology (Chinese patent publication number CN1031072.A) that is used for catalytic cracked dry gas ethene and producing phenylethane from alkylation of benzene as the present inventor and can make full use of ethylene production ethylbenzene wherein.In addition, the present inventor has invented again ethane, the catalyst that the new process of propane and carbon dioxide reaction system ethene and the corresponding Cr of containing element are active component (Chinese patent application number: 95111951.5).Utilize this technology the ethane in the catalytic cracked dry gas can be converted into ethene, and then produce ethylbenzene with benzene alkylation, also can be with the ethane in natural gas or the casing-head gas, low-carbon alkanes such as propane are converted into ethene and are used.For the methane utilization in natural gas or the casing-head gas, chemists have also invented a little new technology paths, have invented a kind of Pt catalyst as GB P 2240284, and methane and carbon dioxide reaction can directly be produced synthesis gas; USP5068057 also provides a kind of Al
2O
3Or SiO
2Loaded Pt and Pd catalyst are with the new process of low-carbon alkanes such as methane and carbon dioxide reaction preparing synthetic gas; The Ni catalyst of EP483795 invention also can be with CH
4Produce synthesis gas with carbon dioxide reaction.But adopt the catalyst of precious metal element preparation to cost an arm and a leg, and utilize the catalyst of Ni for active component, activity of being reported and selectivity are not high, still can not be suitable for suitability for industrialized production.
The purpose of this invention is to provide a kind of by the rare low-carbon alkanes (CH in low-carbon alkanes or the catalytic cracked dry gas
4-C
5H
12) directly produce synthesis gas new reaction process and contain Ni new system catalyst for what this process provided with carbon dioxide reaction.This process is used general fixed-bed process device, has characteristics simple to operate, stable, is easy to the superiority of suitability for industrialized production; Not only can be by this new process with methane, ethane or propane or its gaseous mixture and carbon dioxide reaction are produced synthesis gas, and can make full use of the carbon resource production synthesis gas in the carbon dioxide, and the production industrial chemicals that is used.
The present invention contains Ni metallic catalyst or its supported catalyst for what low-carbon alkanes and carbon dioxide reaction produced that synthesis gas provides, and its active component is Ni, is supported on SiO
2, Al
2O
3, in silica-rich zeolite molecular sieve or the alkaline earth oxide on the carrier of one or more mixtures, simultaneously for improving its catalyst performance, interpolation alkali metal ion or iron component are made auxiliary agent in above-mentioned catalyst, each components by weight is in the catalyst: (100) carrier: (1-25) Ni: (0-20) alkali metal ion: (0-20) Fe, wherein the content of alkali metal ion or iron is not O simultaneously.The components by weight of its optimum range is: (100) carrier: (5-16) Ni: (4-12) alkali metal ion: (0-8) Fe.Alkali metal ion is Li, and Na, the ion of K or Cs, silica-rich zeolite molecular sieve are Silicalite type or ZSM type molecular sieve, and alkaline earth oxide is MgO, CaO or BaO.Metallic element is to exist with oxide in the catalyst.
Described Ni catalyst carries out being CH by the course of reaction of low-carbon alkanes and carbon dioxide reaction preparing synthetic gas
4-C
5H
12Single or mix low-carbon alkanes directly with carbon dioxide reaction production synthesis gas.
Catalyst preparation process of the present invention is undertaken by following step:
One. non-supported catalyst:
1. with Ni
2O
3Mix, or with said mixture and binding agent clay for example, SiO by a certain percentage with iron oxide and/or alkali metal oxide
2Or Al
2O
3The even aftershaping of mechanical mixture, the content of binding agent can be 0～80% of catalyst weight;
2. the salt of the also available Ni of containing and Fe and/or alkali metal ion element or alkali mixes by a certain percentage or above-mentioned salt and binding agent machinery rod are closed even aftershaping, the content of binding agent can be 0～80% of catalyst weight;
With the catalyst after 1 or 2 moulding in 300～800 ℃ of following calcination process 1～10 hour, can obtain catalyst of the present invention.
Two. supported catalyst:
1. with carrier SiO
2, Al
2O
3, silica-rich zeolite molecular sieve or alkaline earth oxide with and compound carrier, through mechanical compression molding or add the binding agent moulding; Or carrier earlier mixed the back reshaping with the salt of part active component, described binding agent can be SiO
2, Al
2O
3Or clay, the addition of binding agent be carrier heavy 0～40%.
With contain the saline solution of active component Ni and contain the additive alkali metal ion or and the above-mentioned carrier of salt solution impregnation of Fe, active component and auxiliary element are supported on the carrier, salting liquid is with nitrate or hydrochloric acid solution.Above-mentioned moulding and dipping process all routinely technology carry out.
3. the carrier of dipping active component carried out calcination process 1～10 hour in the 300-800 degree after 80～120 degree oven dry, and catalyst gets product.
The new process of low-carbon alkanes such as methane of the present invention and carbon dioxide reaction preparing synthetic gas, can adopt molecular proportion is alkane and the carbon dioxide mix raw material charging (the most practical molecular proportion of industry is 0.5-2.0) of 0.1-20, pass through fixed bed reactors, get final product high low-carbon alkanes conversion ratio, highly selective is produced synthesis gas; Also can adopt the two-way system to add low-carbon alkanes and carbon dioxide respectively, by fixed bed reactors, high produced in yields synthesis gas can obtain different H according to different catalyst and different process conditions
2The synthesis gas of/CO molecular proportion.
Above-mentioned 500～900 ℃ of reaction temperatures, reaction pressure 0.01～4.0MPa, the reaction velocity 100～10000h of being reflected at
-1Reaction condition under carry out.
Below by example content of the present invention is described in detail:
Embodiment 1 SiO
2The preparation of supported catalyst A
With SiO
2The mechanical compression molding of 500 grams through 540 degree roastings 5 hours, vacuumizes dipping Ni (NO
3)
3And KNO
3Mixed solution, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst A, wherein the composition weight ratio of each component is: (100) carrier: (10) K: (8): Ni.
The preparation of embodiment 2 MgO supported catalyst B
With MgO500 gram and 20 gram Ni (NO
3)
3After the mechanical mixture,,, vacuumize dipping Ni (NO through 540 degree roastings 5 hours by adding the moulding of 100g clay bond
3)
3, Fe (NO
3)
3, KNO
3Mixed solution, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst B.Wherein the composition weight ratio of each component is: (100) carrier: (5) K: (20) Ni: (4) Fe.
The preparation of the molecular sieve supported type catalyst of embodiment 3 silica-rich zeolites C
With the mechanical compression molding of Silicalite-2 zeolite molecular sieve 500 grams, respectively through 410,500,540 each roasting of degree vacuumized dipping Ni (NO after 1 hour
3)
3, Fe (NO
3)
3Mixed solution, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst C.Wherein the composition weight ratio of each component is: (100) carrier: (6) Fe: (8) Ni.
The preparation of the molecular sieve supported type catalyst of embodiment 4 silica-rich zeolites D
ZSM-5 zeolite molecular sieve 500 grams and 20 gram Ni (NO
3)
3After the mechanical mixture, add 100 gram SiO
2The binding agent moulding, respectively through 410,500,540 each roasting of degree vacuumize a certain amount of Ni (NO of dipping after 1 hour again
3)
3, Fe (NO
3)
3, KNO
3Mixed solution, through 120 degree oven dry 8 hours, 540 degree roastings 10 hours, the catalyst of gained is called catalyst D, wherein the composition weight ratio of each component is: (100) carrier: (12) K: (12) Ni: (6) Fe.
The preparation of embodiment 5 non-supported Ni-Fe-Cs or Li catalyst E
With a certain proportion of Ni (NO
3)
3, Fe (NO
3)
3, CsNO
3After mechanical mixture was even, mechanical compression molding through 540 degree roastings 10 hours, promptly got catalyst E
1Wherein the composition weight ratio of each metal component is: (8) Cs: (9) Ni: (4) Fe.Toward Ni (NO
3)
3In the mixed aqueous solution, add a certain amount of LiOH aqueous solution, the precipitation of gained is washed for several times with deionized water, oven dry and mechanical compression molding in 540 degree roastings 10 hours, promptly get catalyst E more then
2, wherein the composition weight ratio of each metal component is: (6) Li: (16) Ni.
Embodiment 6 methane and carbon dioxide reaction preparing synthetic gas experiment 1
The made catalyst of 20 milliliters of above-mentioned example 1～examples of filling 5 on continuous flow fixed bed reactor, at 0.05～2.0MPa, 700～850 ℃, 500～2500h
-1, CH
4/ CO
2Under the condition of=0.5-10, carry out the methane and the carbon dioxide reaction preparing synthetic gas performance evaluation of catalyst, catalytic reaction the results are shown in Table 1, wherein CH
4Conversion ratio can reach 95.2%, CO
2Conversion ratio reaches 76.2%.
Embodiment 7 ethane and carbon dioxide reaction preparing synthetic gas experiment 2
Above-mentioned example 1～example 5 made catalyst are contained on the continuous flow fixed bed reactor for 20 milliliters, under the reaction condition identical with above-mentioned example 6, carry out the ethane and the carbon dioxide reaction performance evaluation of catalyst, catalytic reaction the results are shown in Table 2.C wherein
2H
6Conversion ratio can reach 91.8%, CO
2Conversion ratio reaches 72.6%.
Embodiment 8 propane and carbon dioxide reaction preparing synthetic gas experiment 3
Above-mentioned example 1～example 5 made catalyst are contained on the continuous flow fixed bed reactor for 20 milliliters, at 0.05～0.1MPa, 600～870 ℃, 800～5000h
-1, CH
4/ CO
2Under=0.5～4.0 the reaction condition, carry out the propane and the carbon dioxide reaction performance evaluation of catalyst, catalytic reaction the results are shown in Table 3, wherein C
3H
8Conversion ratio reaches 89.6%, CO
2Conversion ratio reaches 70.7%.
Embodiment 9 low-carbon alkanes gaseous mixtures and carbon dioxide reaction preparing synthetic gas experiment 4
The catalyst of above-mentioned example 1～example 5 systems is contained on the continuous flow fixed bed reactor for 20 milliliters, under the reaction condition identical with above-mentioned example 6, carry out the methane of catalyst, ethane and propane mixing low-carbon alkanes and carbon dioxide reaction performance evaluation, catalytic reaction the results are shown in Table 4.Wherein the total conversion of low-carbon alkanes can reach 93.6%, CO
2Conversion ratio reaches 76.9%.
Low-carbon alkanes and carbon dioxide reaction preparing synthetic gas experiment 5 in embodiment 10 catalytic cracked dry gas
Adopt the reaction condition identical with above-mentioned example 6, above-mentioned example 1～example 5 made catalyst (20 milliliters) are directly carried out methane in the catalytic cracked dry gas, the catalytic perfomance evaluation of ethane and propane and carbon dioxide reaction preparing synthetic gas, catalytic reaction the results are shown in Table 5, wherein the total conversion of low-carbon alkanes can reach 92.1%, CO
2Conversion ratio reaches 75.1%.The reactant low-carbon alkanes is a large amount of methane contained in natural gas or the casing-head gas, the mixing low-carbon alkanes of ethane and propane or the methane in the catalytic cracked dry gas and ethane mixing low-carbon alkanes.
Can be used for methane by above-mentioned example catalyst of the present invention, low-carbon alkanes such as ethane and propane and carbon dioxide are directly produced synthesis gas as raw material, at reaction pressure 0.05-5.0MPa, under reaction temperature 600-900 ℃ the condition, but the low-carbon alkanes high conversion is converted into synthesis gas (conversion per pass of alkane is greater than 92%, and the conversion ratio of carbon dioxide reaches 72%).Alleviate China's chemical industry to the hydrogen contradiction that supply falls short of demand, and the technology of this new reaction process and simple to operate, be easy to industry and apply.
The reaction result of table 1 methane and carbon dioxide reaction preparing synthetic gas
| Catalyst | Catalyst A | Catalyst C | Catalyst D |
| Reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) methane/carbon dioxide (molecule) is than methane conversion (%) carbon dioxide conversion (%) | 820 0.2 2000 2.0 88.4 78.1 | 820 0.15 2000 0.5 96.6 71.0 | 810 0.1 2500 1.0 95.2 76.2 |
The reaction result of table 2 ethane and carbon dioxide reaction preparing synthetic gas
| Catalyst | Catalyst B | Catalyst C | Catalyst D |
| Reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) ethane/carbon dioxide (molecule) is than ethane conversion (%) carbon dioxide conversion (%) | 820 0.25 1500 4.0 79.6 82.4 | 820 0.2 2000 0.5 92.7 69.1 | 820 0.1 2500 1.0 91.8 72.6 |
The reaction result of table 3 propane and carbon dioxide reaction preparing synthetic gas
The reaction result of table 4 methane, ethane and propane and carbon dioxide reaction preparing synthetic gas
*
| Catalyst | Catalyst A | Catalyst C | Catalyst D |
| Reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) propane/carbon dioxide (molecule) is than conversion of propane (%) carbon dioxide conversion (%) | 820 0.1 1000 3.0 84.5 84.3 | 820 0.5 2000 0.4 94.0 68.4 | 820 0.1 3000 1.0 89.6 70.7 |
| Catalyst | Catalyst E | Catalyst C | Catalyst D |
| Reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) methane/carbon dioxide (molecule) is than methane conversion (%) carbon dioxide conversion (%) | 830 0.15 1000 2.0 85.7 78.5 | 830 0.2 2000 0.5 91.5 70.2 | 820 0.08 3000 1.0 93.6 76.9 |
* each alkane in the reactor feed gas is than methane: ethane: propane=1: 1: 1
Mixed alkanes and CO in table 5 catalytic cracked dry gas
2Reaction preparing synthetic gas result
*
| Catalyst | Catalyst E | Catalyst C | Catalyst D |
| Reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) methane/carbon dioxide (molecule) is than methane conversion (%) carbon dioxide conversion (%) | 830 0.3 3000 2.0 88.3 77.4 | 830 0.2 2500 0.5 95.2 72.3 | 820 0.1 2000 1.0 92.1 75.1 |
* each alkane in the reactor feed gas is than methane: ethane: propane=30: 20: 1
Claims (8)
1. Ni catalyst that is used for by low-carbon alkanes and carbon dioxide reaction preparing synthetic gas, it is characterized in that this activity of such catalysts component is the Ni element, add Fe or/and alkali metal ion as catalyst promoter, each components by weight in the catalyst: (1-25) Ni: (0-20) alkali metal ion: (0-20) Fe, and the content of alkali metal ion or iron is not zero simultaneously.
2. by the described catalyst of claim 1, it is characterized in that this catalyst is a supported catalyst, being supported on by carrier is SiO
2, Al
2O
3, on the carrier that one or more mixtures are made in alkaline earth oxide or the silica-rich zeolite molecular sieve, each components by weight in the catalyst: (100) carrier: (1-25) Ni: (0-20) alkali metal ion: (0-20) Fe.
3. by the described catalyst of claim 2, it is characterized in that each components by weight in the catalyst: (100) carrier: (4-12) alkali metal ion: (4-16) Ni: (0-8) Fe.
4. according to claim 2 or 3 described catalyst, it is characterized in that alkaline earth oxide is MgO, CaO or BaO silica-rich zeolite molecular sieve are Silicalte type or ZSM type molecular sieve.
5. one kind is utilized the described Ni catalyst of claim 1 to carry out course of reaction by low-carbon alkanes and carbon dioxide reaction preparing synthetic gas, it is characterized in that: CH
4-C
5H
12Single or mix low-carbon alkanes directly with carbon dioxide reaction production synthesis gas.
6. according to the described course of reaction of claim 5, it is characterized in that reaction condition is:
Reaction temperature: 500-900 ℃,
Reaction pressure: 0.01-4.0MPa,
Reaction velocity: 100-10000h
-1,
Low-carbon alkanes/carbon dioxide molecule ratio: 0.1-20.
7. according to claim 5 or 6 described courses of reaction, it is characterized in that reaction condition is:
Reaction temperature: 600-870 ℃,
Reaction pressure: 0.05-1.0MPa,
Reaction velocity: 800-5000h
-1,
Low-carbon alkanes/carbon dioxide molecule ratio: 0.5-4.0.
8. by the described course of reaction of claim 5, it is characterized in that the reactant low-carbon alkanes is a large amount of methane contained in natural gas or the casing-head gas, the mixing low-carbon alkanes of ethane and propane or the methane in the catalytic cracked dry gas and ethane mixing low-carbon alkanes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115391A CN1087656C (en) | 1996-06-19 | 1996-06-19 | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115391A CN1087656C (en) | 1996-06-19 | 1996-06-19 | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use |
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|---|---|
| CN1168298A CN1168298A (en) | 1997-12-24 |
| CN1087656C true CN1087656C (en) | 2002-07-17 |
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|---|---|---|---|
| CN96115391A Expired - Fee Related CN1087656C (en) | 1996-06-19 | 1996-06-19 | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use |
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Cited By (1)
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|---|---|---|---|---|
| CN101391936B (en) * | 2007-09-20 | 2013-03-13 | 罗门哈斯公司 | Catalytic process for producing ethylene and carbon monoxide mixtures from ethane |
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| CN103752315B (en) * | 2014-01-15 | 2016-08-10 | 易高环保能源研究院有限公司 | A kind of metal phase carrier load type catalyst and its production and use |
| CN104475111B (en) * | 2014-11-24 | 2016-10-12 | 太原理工大学 | A kind of catalyst of coal and reaction of carbon monoxide methane and preparation method thereof |
| CN104815688B (en) * | 2015-04-23 | 2017-05-24 | 中国科学院大连化学物理研究所 | Iron-based molecular sieve catalyst and preparation method and application thereof |
| CN104998654B (en) * | 2015-06-25 | 2018-05-01 | 中国石油天然气集团公司 | The method of nickel-base catalyst and preparation method thereof and methane catalytic decomposition production hydrogen |
| CN106512999B (en) * | 2016-08-31 | 2019-11-15 | 华东师范大学 | A kind of methane dry gas reforming catalyst and preparation method thereof |
| CN112403475B (en) * | 2020-11-06 | 2023-05-23 | 上海簇睿低碳能源技术有限公司 | Preparation method of catalyst for preparing synthesis gas by reforming carbon dioxide |
| CN112569896B (en) * | 2020-12-07 | 2023-08-25 | 华东理工大学 | Calcium oxide-based bimetal composite material, preparation method and application |
| CN115445622A (en) * | 2021-06-08 | 2022-12-09 | 华东理工大学 | Porous adsorption and catalysis dual-function material, preparation method and application |
| CN115888725B (en) * | 2022-09-20 | 2024-04-16 | 山西大学 | C (C)2+Catalyst for conversion reaction of alkane and carbon dioxide to synthesis gas and preparation thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0335668A2 (en) * | 1988-03-28 | 1989-10-04 | Exxon Research And Engineering Company | Method and catalyst for synthesis gas preparation |
| EP0673877A1 (en) * | 1994-03-25 | 1995-09-27 | Exxon Research And Engineering Company | Synthesis gas preparation |
| EP0700866A1 (en) * | 1994-09-06 | 1996-03-13 | Exxon Research And Engineering Company | Fluidized bed synthesis gas production process |
-
1996
- 1996-06-19 CN CN96115391A patent/CN1087656C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0335668A2 (en) * | 1988-03-28 | 1989-10-04 | Exxon Research And Engineering Company | Method and catalyst for synthesis gas preparation |
| EP0673877A1 (en) * | 1994-03-25 | 1995-09-27 | Exxon Research And Engineering Company | Synthesis gas preparation |
| EP0700866A1 (en) * | 1994-09-06 | 1996-03-13 | Exxon Research And Engineering Company | Fluidized bed synthesis gas production process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391936B (en) * | 2007-09-20 | 2013-03-13 | 罗门哈斯公司 | Catalytic process for producing ethylene and carbon monoxide mixtures from ethane |
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| CN1168298A (en) | 1997-12-24 |
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