CN101450310A - Synthetic gas preparation catalyst through reforming natural gas and carbon dioxide - Google Patents
Synthetic gas preparation catalyst through reforming natural gas and carbon dioxide Download PDFInfo
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- CN101450310A CN101450310A CNA2007101719375A CN200710171937A CN101450310A CN 101450310 A CN101450310 A CN 101450310A CN A2007101719375 A CNA2007101719375 A CN A2007101719375A CN 200710171937 A CN200710171937 A CN 200710171937A CN 101450310 A CN101450310 A CN 101450310A
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Abstract
The invention relates to a catalyst for preparing synthetic gas by reforming natural gas-carbon dioxide. The catalyst comprises the following compositions by weight percentage: 5 to 20 percent of active ingredient nickel and 75 to 90 percent of carrier, wherein the carrier is gamma-Al2O3, SiO2, molecular sieves, MgO or ZrO2 with the diameter between 1 and 10 millimeters, and has a spherical structure, a cylindrical structure, an annular structure, a clover structure or a Raschig ring structure, and the catalyst is prepared by a constant volume impregnation method. The catalyst prepared by the method can make the conversion rate of natural gas and the selectivity of CO and H2 reach more than 95 percent, and the activity of the catalyst is stable for a long time.
Description
Technical field
The invention belongs to the catalyst chemical field, be specifically related to a kind of catalyst of reforming natural gas and carbon dioxide preparing synthetic gas.
Background technology
Along with the raising of people's environmental consciousness, the utilization of greenhouse gases and control more and more receive publicity, and reforming natural gas and carbon dioxide can be converted into carbon dioxide greenhouse gas synthesis gas (mist of carbon monoxide and hydrogen) effectively.Synthesis gas is a kind of very important unstrpped gas, and directly synthesis of low-carbon alcohol, dimethyl ether and funds-Tuo synthesize prepare liquid fuel etc. for it.Synthesis gas and be the basic material of industrial and agricultural development through the methyl alcohol of synthesis gas preparation, synthetic ammonia, hydrogen etc.
The reforming natural gas and carbon dioxide catalyst mainly is divided into two classes, one class is a noble metal catalyst, one class is a nickel-base catalyst, find that after deliberation the latter has more application prospect, because supported ni catalyst has with noble metal catalysts such as Rh, Pt on reactivity and high-temperature stability similar performance is arranged, and low price (oil and gas chemical industry, the 26th volume, the 3rd phase, 145 pages).But this kind catalyst activity component Ni in course of reaction owing to easily run off and sintering aspect etc. reason, its catalytic activity can descend (applied chemistry, the 14th rolls up, the 3rd phase, 19 pages).So further study the aspects such as preparation method of nickel-base catalyst, it is significant to reforming natural gas and carbon dioxide preparing synthetic gas suitability for industrialized production to improve its performance.
The nickel-base catalyst of Chinese patent 02129936.6 disclosed a kind of natural gas preparing synthetic gas, this activity of such catalysts component is a nickel, carrier is the Al of powdery
2O
3Or SiO
2, nickel and Al
2O
3Or SiO
2Mass ratio be 1～25%.This grained catalyst is applicable in the quartz tube reactor of laboratory that the specific surface that exists in the still unresolved industrializeding catalyst forming process, pore volume stop up degradation problem under the catalyst performance that causes.
Summary of the invention
Technical problem to be solved
Technical problem to be solved by this invention provides a kind of Catalysts and its preparation method of reforming natural gas and carbon dioxide preparing synthetic gas, to solve existing powder catalyst after overmolding, the problem that the catalyst performance that beaded catalyst specific area, pore volume obstruction cause changes, thus overcome industrial shortcoming of amplifying difficulty.
Technical scheme
First aspect of the present invention provides a kind of catalyst of reforming natural gas and carbon dioxide preparing synthetic gas, its component and content comprise: percentage by weight is 5%～20% nickel, percentage by weight is 75%～90% carrier, wherein, this activity of such catalysts component is a nickel, and carrier is γ-Al of diameter 1～10mm
2O
3, SiO
2, molecular sieve, MgO or ZrO
2, carrier structure is spherical, cylindric, ring-type, clover or Raschig ring; Specific surface area of catalyst is 10～300m
2/ g, pore volume is not less than 0.3cm
3/ g.
One of preferred version of the catalyst of above-mentioned reforming natural gas and carbon dioxide preparing synthetic gas is, described carrier diameter is 1～5mm, and carrier is γ-Al
2O
3Or SiO
2, carrier structure is spherical or ring-type.
Two of the preferred version of the catalyst of above-mentioned reforming natural gas and carbon dioxide preparing synthetic gas is, it is 1%～5% co-catalyst that described catalyst also contains weight percentage.
Three of the preferred version of the catalyst of above-mentioned reforming natural gas and carbon dioxide preparing synthetic gas is that described co-catalyst is selected from one or more in alkali metal, alkaline-earth metal, the rare-earth oxide.
Four of the preferred version of the catalyst of above-mentioned reforming natural gas and carbon dioxide preparing synthetic gas is that described co-catalyst is selected from rare-earth oxide.
Second aspect of the present invention provides a kind of above-mentioned Preparation of catalysts method, in turn includes the following steps: nickel nitrate is dissolved with the aqueous solution by the content of nickel in catalyst, add 1%～5% co-catalyst; Dipping in the former particulate vector is gone in the nickel salt solution drainage that will contain co-catalyst, dry, roasting obtains catalyst then; Wherein, carrier is γ-Al of diameter 1～10mm
2O
3, SiO
2, molecular sieve, MgO or ZrO
2
One of preferred version of above-mentioned Preparation of catalysts method is that described co-catalyst is selected from one or more in alkali metal, alkaline-earth metal, the rare-earth oxide.
Two of the preferred version of above-mentioned Preparation of catalysts method is that described co-catalyst is selected from rare-earth oxide.
Three of the preferred version of above-mentioned Preparation of catalysts method is, described dip time is 0.1～1 hour, and baking temperature is 80～100 ℃, and in constant pressure and dry 2～6 hours, sintering temperature was 650～850 ℃, roasting 6～12 hours.
The 4th aspect of the present invention provides a kind of preparation method of synthesis gas, comprise utilizing the described catalyst of claim 1, and be raw material, wherein CO with natural gas and carbon dioxide
2/ CH
4Percent by volume is 1～1.4,700～900 ℃ of reaction temperatures, and reaction pressure 0.1～0.5MPa, unstripped gas air speed 4000～7000h
-1Condition under carry out catalytic reaction.
The 5th aspect of the present invention provides a kind of catalyst of reforming natural gas and carbon dioxide preparing synthetic gas, described catalyst prepares by the following method, nickel nitrate is dissolved with the aqueous solution by the content of nickel in catalyst, add 1%～5% co-catalyst; Dipping in the former particulate vector is gone in the nickel salt solution drainage that will contain co-catalyst, dry, roasting obtains catalyst then; Wherein, carrier is γ-Al of diameter 1～10mm
2O
3, SiO
2, molecular sieve, MgO or ZrO
2
One of preferred version of above-mentioned Preparation of catalysts method is that described co-catalyst is selected from one or more in alkali metal, alkaline-earth metal, the rare-earth oxide.
Two of the preferred version of above-mentioned Preparation of catalysts method is that described co-catalyst is selected from rare-earth oxide.
Three of the preferred version of above-mentioned Preparation of catalysts method is, described dip time is 0.1～1 hour, and baking temperature is 80～100 ℃, and in constant pressure and dry 2～6 hours, sintering temperature was 650～850 ℃, roasting 6～12 hours.
Beneficial effect
Provided by the invention is active component with nickel, former particle Al
2O
3Catalyst for carrier, have the following advantages: the carrier of when the preparation catalyst, having selected suitable specific area, pore volume, finish the Preparation of catalysts process, after dipping, drying, the roasting, significant change does not take place in specific surface area of catalyst, pore volume, and through its function admirable after the performance evaluation of catalyst.Thus, Preparation of Catalyst does not need can realize the industry amplification through forming process that whole process of preparation is simple, cost is low, catalyst activity height, CH
4And CO
2Conversion ratio can reach 95% respectively, more than 95%, synthesis gas selectivity height, CO and H
2Selectivity can reach 95% and 95% respectively, and good stability.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, as the catalyst handbook, or the condition of advising according to manufacturer.
Embodiment 1
Spherical γ-the Al that in container, adds 2000g diameter 1mm
2O
3Carrier adds 1020gNi (NO in beaker
3)
26H
2O, 30gLa (NO
3)
3, be stirred to dissolving under the 3200g water, normal temperature.To container, make it solution drainage at Al
2O
3Mix on the carrier, flooded 0.2 hour, make solution absorption fully.With catalyst under 90 ℃, normal pressure dry 6 hours, through 700 ℃ of roastings 10 hours, catalyst got product again.
Get the reactor that the 300g catalyst places diameter 57mm, feed the CH of 1:1
4And CO
2Reaction gas, its air speed are 5000h
-1, 850 ℃, successive reaction 100h under the 0.1MPa pressure.Reaction result is listed in table 1.
The conversion ratio of table 1 natural gas and carbon dioxide and selectivity are with the variation in reaction time
| Time (h) | CH4 conversion ratio % | CO 2Conversion ratio % | CO selectivity % | H 2Selectivity % |
| 2 | 96.3 | 97.8 | 96.5 | 96.2 |
| 20 | 95.9 | 96.9 | 96.3 | 95.8 |
| 40 | 96.2 | 96.9 | 96.2 | 95.9 |
| 60 | 95.7 | 96.8 | 96.1 | 95.7 |
| 80 | 95.8 | 96.7 | 96.4 | 95.5 |
| 100 | 95.5 | 96.3 | 96.2 | 95.4 |
Embodiment 2
Spherical γ-the Al that in container, adds 2000g diameter 5mm
2O
3Carrier adds 1900gNi (NO in beaker
3)
26H
2O, 30gLa (NO
3)
3, be stirred to dissolving under the 3200g water, normal temperature.To container, make it solution drainage at Al
2O
3Mix on the carrier, flooded 1 hour, make solution absorption fully.With catalyst under 100 ℃, normal pressure dry 3 hours, through 800 ℃ of roastings 7 hours, catalyst got product again.
Get the reactor that the 300g catalyst places diameter 57mm, feed the CH of 1:1
4And CO
2Reaction gas, its air speed are 5000h
-1, 850 ℃, successive reaction 100h under the 0.1MPa pressure.Reaction result is listed in table 2.
The conversion ratio of table 2 natural gas and carbon dioxide and selectivity are with the variation in reaction time
| Time (h) | CH 4Conversion ratio % | CO 2Conversion ratio % | CO selectivity % | H 2Selectivity % |
| 2 | 97.2 | 97.8 | 96.9 | 96.7 |
| 20 | 96.8 | 97.3 | 96.7 | 96.1 |
| 40 | 96.6 | 96.9 | 96.4 | 96.0 |
| 60 | 96.1 | 96.9 | 96.3 | 96.0 |
| 80 | 96.3 | 96.8 | 96.4 | 95.9 |
| 100 | 95.5 | 96.7 | 96.2 | 95.3 |
Embodiment 3
In container, add the molecular sieve carrier of the clover shape of 2000g φ 1.5 * 2～3.6mm, in beaker, add 1020gNi (NO
3)
26H
2O, 30gLa (NO
3)
3, be stirred to dissolving under the 3200g water, normal temperature.To container, it is mixed on molecular sieve carrier the solution drainage, flooded 0.2 hour, make solution absorption fully.Catalyst was descended dry 6 hours at 90 ℃, and again through 700 ℃ of roastings 10 hours, catalyst gets product.
Get the reactor that the 300g catalyst places diameter 57mm, feed the CH of 1:1
4And CO
2Reaction gas, its air speed are 5000h
-1, 850 ℃, successive reaction 100h under the 0.1MPa pressure.Reaction result is listed in table 4.
The conversion ratio of table 3 natural gas and carbon dioxide and selectivity are with the variation in reaction time
| Time (h) | CH 4Conversion ratio % | CO 2Conversion ratio % | CO selectivity % | H 2Selectivity % |
| 2 | 95.8 | 96.2 | 95.9 | 95.7 |
| 20 | 95.3 | 96.3 | 95.1 | 95.9 |
| 40 | 95.5 | 95.9 | 95.4 | 95.7 |
| 60 | 94.9 | 95.3 | 95.0 | 95.4 |
| 80 | 95.2 | 95.5 | 95.3 | 95.5 |
| 100 | 94.8 | 95.3 | 95.2 | 95.6 |
Embodiment 4
The spherical SiO that in container, adds 2000g diameter 5mm
2Carrier adds 1900gNi (NO in beaker
3)
26H
2O, 30gLa (NO
3)
3, be stirred to dissolving under the 3200g water, normal temperature.To container, make it solution drainage at SiO
2Mix on the carrier, flooded 1 hour, make solution absorption fully.With catalyst under 100 ℃, normal pressure dry 3 hours, through 800 ℃ of roastings 7 hours, catalyst got product again.
Get the reactor that the 300g catalyst places diameter 57mm, feed the CH of 1:1
4And CO
2Reaction gas, its air speed are 5000h
-1, 850 ℃, successive reaction 100h under the 0.1MPa pressure.Reaction result is listed in table 4.
The conversion ratio of table 4 natural gas and carbon dioxide and selectivity are with the variation in reaction time
| Time (h) | CH 4Conversion ratio % | CO 2Conversion ratio % | CO selectivity % | H 2Selectivity % |
| 2 | 96.2 | 96.4 | 95.9 | 95.8 |
| 20 | 95.5 | 95.9 | 95.3 | 95.5 |
| 40 | 94.9 | 95.2 | 95.1 | 95.3 |
| 60 | 94.6 | 94.9 | 94.8 | 95.1 |
| 80 | 95.2 | 95.7 | 95.3 | 95.8 |
| 100 | 94.9 | 95.3 | 95.1 | 95.2 |
Embodiment 5
Get the reactor that the 300g catalyst places diameter 57mm, change the catalyst reaction process conditions, after reaction unit moved 50h continuously, the reaction result of different catalysts was listed in table 3.
The contrast of table 5 catalyst different technology conditions data
Claims (10)
1. the catalyst of a reforming natural gas and carbon dioxide preparing synthetic gas, its component and content comprise: percentage by weight is 5%～20% nickel, and percentage by weight is 75%～90% carrier, wherein, this activity of such catalysts component is a nickel, and carrier is γ-Al of diameter 1～10mm
2O
3, SiO
2, molecular sieve, MgO or ZrO
2, carrier structure is spherical, cylindric, ring-type, clover or Raschig ring; Specific surface area of catalyst is 10～300m
2/ g, pore volume is not less than 0.3cm
3/ g.
2. the catalyst of reforming natural gas and carbon dioxide preparing synthetic gas as claimed in claim 1 is characterized in that, described carrier diameter is 1～5mm, and carrier is γ-Al
2O
3Or SiO
2, carrier structure is spherical or ring-type.
3. the catalyst of reforming natural gas and carbon dioxide preparing synthetic gas as claimed in claim 1 is characterized in that, it is 1%～5% co-catalyst that described catalyst also contains weight percentage.
4. the catalyst of reforming natural gas and carbon dioxide preparing synthetic gas as claimed in claim 3 is characterized in that, described co-catalyst is selected from one or more in alkali metal, alkaline-earth metal, the rare-earth oxide.
5. the catalyst of reforming natural gas and carbon dioxide preparing synthetic gas as claimed in claim 4 is characterized in that, described co-catalyst is selected from rare-earth oxide.
6. the described Preparation of catalysts method of claim 1 in turn includes the following steps: nickel nitrate is dissolved with the aqueous solution by the content of nickel in catalyst, add 1%～5% co-catalyst; Dipping in the former particulate vector is gone in the nickel salt solution drainage that will contain co-catalyst, dry, roasting obtains catalyst then; Wherein, carrier is γ-Al of diameter 1～10mm
2O
3, SiO
2, molecular sieve, MgO or ZrO
2
7. Preparation of catalysts method as claimed in claim 6 is characterized in that described co-catalyst is selected from one or more in alkali metal, alkaline-earth metal, the rare-earth oxide.
8. as claim 6,7 described Preparation of catalysts methods, it is characterized in that described co-catalyst is selected from rare-earth oxide.
9. Preparation of catalysts method as claimed in claim 6 is characterized in that, described dip time is 0.1～1 hour, and baking temperature is 80～100 ℃, and in constant pressure and dry 2～6 hours, sintering temperature was 650～850 ℃, roasting 6～12 hours.
10. the preparation method of a synthesis gas comprises and utilizes the described catalyst of claim 1, is raw material, wherein CO with natural gas and carbon dioxide
2/ CH
4Percent by volume is 1～1.4,700～900 ℃ of reaction temperatures, and reaction pressure 0.1～0.5MPa, unstripped gas air speed 4000～7000h
-1Condition under carry out catalytic reaction.
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|---|---|---|---|
| CNA2007101719375A CN101450310A (en) | 2007-12-07 | 2007-12-07 | Synthetic gas preparation catalyst through reforming natural gas and carbon dioxide |
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|---|---|---|---|
| CNA2007101719375A CN101450310A (en) | 2007-12-07 | 2007-12-07 | Synthetic gas preparation catalyst through reforming natural gas and carbon dioxide |
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| CN101450310A true CN101450310A (en) | 2009-06-10 |
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ID=40732901
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513115A (en) * | 2011-10-28 | 2012-06-27 | 中国科学院过程工程研究所 | Perovskite supported nickel base methanation catalyst and preparation method thereof |
| CN102950030A (en) * | 2012-10-16 | 2013-03-06 | 大连瑞克科技有限公司 | High-temperature-resistant catalyst carrier and preparation method thereof |
| CN105944733A (en) * | 2016-05-12 | 2016-09-21 | 中国科学院福建物质结构研究所 | Hierarchical pore supported nickel-based catalyst modified with rare earth as well as preparation method and application of catalyst |
| CN106000405A (en) * | 2016-05-12 | 2016-10-12 | 中国科学院福建物质结构研究所 | Hierarchical porous supported nickel-based catalyst, preparation method and application |
| CN108622855A (en) * | 2017-03-15 | 2018-10-09 | 单岩崑 | A kind of method that natural gas catalysis oxidation prepares synthesis gas |
| CN111569893A (en) * | 2020-06-03 | 2020-08-25 | 西南化工研究设计院有限公司 | Low-cost natural gas conversion catalyst and preparation method thereof |
| US11104575B2 (en) | 2016-05-12 | 2021-08-31 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Science | Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas |
-
2007
- 2007-12-07 CN CNA2007101719375A patent/CN101450310A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513115A (en) * | 2011-10-28 | 2012-06-27 | 中国科学院过程工程研究所 | Perovskite supported nickel base methanation catalyst and preparation method thereof |
| CN102513115B (en) * | 2011-10-28 | 2015-08-19 | 中国科学院过程工程研究所 | Methanation catalyst of a kind of perovskite supported nickel base and preparation method thereof |
| CN102950030A (en) * | 2012-10-16 | 2013-03-06 | 大连瑞克科技有限公司 | High-temperature-resistant catalyst carrier and preparation method thereof |
| CN105944733A (en) * | 2016-05-12 | 2016-09-21 | 中国科学院福建物质结构研究所 | Hierarchical pore supported nickel-based catalyst modified with rare earth as well as preparation method and application of catalyst |
| CN106000405A (en) * | 2016-05-12 | 2016-10-12 | 中国科学院福建物质结构研究所 | Hierarchical porous supported nickel-based catalyst, preparation method and application |
| CN105944733B (en) * | 2016-05-12 | 2019-04-16 | 中国科学院福建物质结构研究所 | A kind of rare earth modified multi-stage porous loading type nickel-based catalyst, preparation method and application |
| CN106000405B (en) * | 2016-05-12 | 2019-04-16 | 中国科学院福建物质结构研究所 | A kind of multi-stage porous loading type nickel-based catalyst, preparation method and application |
| US11104575B2 (en) | 2016-05-12 | 2021-08-31 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Science | Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas |
| CN108622855A (en) * | 2017-03-15 | 2018-10-09 | 单岩崑 | A kind of method that natural gas catalysis oxidation prepares synthesis gas |
| CN111569893A (en) * | 2020-06-03 | 2020-08-25 | 西南化工研究设计院有限公司 | Low-cost natural gas conversion catalyst and preparation method thereof |
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Application publication date: 20090610 |