CN1110248A - Catalyst for converting methane into synthetic gas and its process - Google Patents
Catalyst for converting methane into synthetic gas and its process Download PDFInfo
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- CN1110248A CN1110248A CN94103728A CN94103728A CN1110248A CN 1110248 A CN1110248 A CN 1110248A CN 94103728 A CN94103728 A CN 94103728A CN 94103728 A CN94103728 A CN 94103728A CN 1110248 A CN1110248 A CN 1110248A
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a catalyst capable of converting methane into synthetic gas. It includes at least one of metal elements of VIII group, at least one metal element capable of converting methane into synthetic gas, at least one alkaline and alkaline earth metal element and aluminium oxide or has aluminium globules with proper specific surface area and aperture, and the process converting methane into synthetic gas includes the procedure of making the methane contact with gas containing molecular oxygen and the invented catalyst at 300-800 deg.C.
Description
The present invention relates to methane oxidation is become the catalyzer and the process of synthetic gas.
At present, the vapour reforming of industrial employing methane is produced synthetic gas:
T（k）??800??1000
△H（kCal/mol）
[1]53.21 6.33
△G（kCal/mol）??53.87??-6.47
This process has some more serious defectives: (one) owing to reaction (1) absorb heat in a large number consume energy serious; (2) reaction (1) is subjected to the equilibrated restriction and need carries out under high temperature condition with pressure; (3) the synthetic gas H of Sheng Chenging
2Content is higher, is not suitable for doing the raw material of reaction such as synthol.
And come preparing synthetic gas by methane portion oxidation:
T（k）??298??500??700??1000
△H（kCal/mol
-1） -8.53 -7.00 -5.7 -5.37
△G（kCal/mol
-1） -20.58 -29.34 -36.6 -52.52
From reaction and thermodynamic data thereof, may avoid existing problem in the above-mentioned steam reforming reaction fully.Therefore over the past two years, people began this reaction is studied.
English Patent (application number 9018781.6) has been introduced to use and has been supported d district metal or d district metal oxide catalyst under 650～900 ℃, the condition of 10～600KPa, and methane portion oxidation is become synthetic gas.
Recently, Patrick D.F.Vernon etc. has reported about what methane oxidation is become synthetic gas and has supported noble metal catalyst and rare earth and noble metal composite oxide Ln
2M
2O
7(Ln is a rare earth element, and M is a precious metal element) catalyzer at 650～1050K, under 1～20atm condition, becomes synthetic gas with methane portion oxidation.These catalyzer can be obtained good reaction result (methane conversion reaches 90～95%, and the selectivity of hydrogen and carbon monoxide is all greater than 95%) down at high temperature (1050K).
The object of the invention just provides a kind of catalyzer, can with selectivity methane conversion be become synthetic gas with very high transformation efficiency under relatively low temperature.
The objective of the invention is to be achieved through the following technical solutions.
Catalyzer provided by the present invention has following two kinds of experience expressions: a kind of is expression with the catalyzer of coprecipitation method preparation: AaBbCcDdOx, another kind are the expressions with the supported catalyst of immersion process for preparing: the AaBbCcOx/ carrier.In above-mentioned catalyzer, A is the element of at least a Ni of being selected from, Pd, Pt, Ir, Rh, Ru, Co, B is at least a element that is selected from rare earth and Cu, Ag, Zn, Cd, V, Cr, Mo, W, Mn, C is the element of at least a Li of being selected from, Na, K, Rb, Be, Mg, Ca, Sr, Ba, D is at least a element that is selected from Si, Al, Ti, Zr, and catalyst-supporting support can be silicon bead, aluminium bead, sial ball or the molecular sieve with suitable specific surface area and aperture.
Wherein: the atomic ratio of b/a, c/a, d/a independent variation separately in 0～20 scope, and the loading of active principle is 0.01～50%(weight in the supported catalyst).
Above-mentioned catalyst A element Ni preferably, the B element is Cu preferably, and the C element is Ca preferably, and the D element is Al preferably.
Wherein: b/a 0.04-0.4 preferably, c/a is 0-0.4 preferably, and d/a is 0.5-10 preferably.The loading of active principle is preferably 1-30%(weight most in the supported catalyst), carrier is the aluminium bead preferably.
Catalyzer among the present invention can adopt general co-precipitation, the methods such as slurry or pickling process of mixing prepare.With co-precipitation, mix the catalyst precursor that slurry or pickling process make, 80～150 ℃ dry down, then 400～1000 ℃ of following roastings, concrete maturing temperature is different because of the difference of the raw material forming and select for use.
Methane conversion is become the process of synthetic gas by above-mentioned catalyzer, be with methane with to mix with the gas of molecule-containing keto before catalyzer contacts, the scope of methane/oxygen (mol ratio) is 1.9-2.5, and the gas hourly space velocity of reactor feed gas is controlled at 500-5000,000hr
-1(under the standard state) contacts with catalyzer then, reacts, and the temperature during reaction is 100-1000 ℃, and pressure is the 0.01-10 MPa.
Above-mentioned reaction methane/oxygen optimum is 2.0.
Optimum temps during reaction is controlled at 300-800 ℃.
Optimum pressure during reaction is 0.1 MPa.
The gas hourly space velocity of reactor feed gas is suitably 10,000-500,000hr
-1
Raw material methane can be pure methane, also can be the methane that contains a small amount of gaseous paraffin hydrocarbons.
The gas of molecule-containing keto can be pure oxygen, also can be the gas mixture of air or air and oxygen.
Compare with present methane steam reforming preparing synthetic gas, the present invention has the following advantages: (1) reacts micro-heat release, consumed energy no longer, CO/H in the synthetic gas that (2) make
2Near 0.5, be more suitable for being synthesizing methanol and fischer-tropsch synthetic raw material, low 600-700 ℃ of (3) temperature of reaction, (4) reaction efficiency height, the selectivity of methane conversion and carbon monoxide and hydrogen all can be higher than 95%.
Following comparative examples is further illustrated catalyzer of the present invention.
Embodiment 1:
Take by weighing Ni(NO
3)
26H
2O 0.998 gram, Ca(NO
3)
23H
3O 0.166 gram, Al(NO
3)
39H
2O 3.001 grams, Ca(NO
3)
24H
2O 0.041 restrains and they is dissolved in the 20ml water, under agitation slowly adds 10%(NH then
4)
2CO
3Solution is until being completed into gel; With the gel detergent that obtains, in 110 ℃ of following dry 16hr, 750 ℃ of roasting 4hr promptly make catalyzer in the air afterwards.
Get 0.2ml 20～40 purpose catalyzer and put into the quartz tube reactor that internal diameter is 8mm, following at 500 ℃ with containing 10%H
2N
2-H
2Gas mixture (flow 40ml/min) is handled 1hr and is reacted then, and gained the results are shown in Table 1:
Table 1
T(℃) XCH
4(%) XO
2(%) SCO(%) SH
2(%)
500??84.3??100??86.1??90.2
550??89.1??100??90.5??95.4
600??94.2??100??94.2??98.1
650??96.0??100??95.4??99.0
700??98.1??100??97.1??100
Reaction conditions: GHSV=3 * 10
4Hr
-1, CH
4: O
2: N
2=2: 1: 0
Embodiment 2:
Employed catalyzer and pretreatment condition all are same as embodiment 1 in this example, change the intake velocity of reactor feed gas, and the reaction result of gained is as shown in table 2:
Table 2
GHSV(hr
-1) XCH
4(%) XO
2(%) SCO(%) SH
2(%)
5,000??98.5??100??98.0??100
10,000??98.1??100??97.2??100
20,000??99.0??100??97.2??100
30,000??98.1??100??97.1??100
40,000??97.1??100??96.5??99.0
60,000??90.2??100??92.1??96.5
300,000??83.4??100??87.2??84.7
Reaction conditions: T=700 ℃, CH
4: O
2: N
2=2: 1: 0
Embodiment 3:
Employed catalyzer and pretreatment condition all are same as embodiment 1 in this example, change the composition of reactor feed gas, and the reaction result of gained is as shown in table 3:
Table 3
CH
4:O
2:N
2XCH
4XO
2SCO SH
2
2:1:0??98.2??100??97.0??100
2:1:2??98.2??100??97.1??100
2:1:4??99.0??100??97.0??100
Reaction conditions: T=700 ℃, GHSV=3 * 10
4Hr
-1
Embodiment 4:
Take by weighing Ni(NO
3)
26H
2O 0.931 gram, Zn(NO
3)
26H
2O 0.076 gram, Ca(NO
3)
24H
20.283 gram, Al(NO
3)
39H
2O 3.001 gram is dissolved in them in the 20ml water, slowly adds 10%(NH when stirring this mixing solutions
4)
2CO
3Solution is completed into gel until mixed solution.With gel detergent, 110 ℃ of following dry 16hr, 750 ℃ of roasting 4hr in the air, 500 ℃ of following reduction 1hr(10%H
2-N
2, GHSV=10,000h
-1) catalyzer gets product.
Get in the reactor of 0.2ml catalyzer in example 1 and react, change the temperature of reaction gained and the results are shown in Table 4.
Table 4
T(℃) GHSV-(hr
-1) XCH
4XO
2SCO SH
2
600??30,000??78.2??100??90.1??90.3
700??30,000??84.6??100??93.2??92.1
750??30,000??89.2??100??94.6??95.0
750??60,000??91.0??100??95.2??93.8
Reaction conditions: CH
4: O
2: N
2=2: 1: 0
Embodiment 5:
Take by weighing Al(NO
3)
39H
2O 3.60 grams, and be dissolved in the 15ml water, adding 10%(NH down stirred
4)
2CO
3Be about 8 to pH, with the at room temperature aging 24hr of gel that obtains, washing.Take by weighing Ni(NO
3)
26H
2O 1.98 grams, La(NO
3)
36H
2O 0.356 restrains, and mixes with the gel that makes previously, after the grinding evenly, and 110 ℃ of following dry 16hr, 750 ℃ of roasting 4hr in the air.Get 20～40 purpose catalyzer 0.2ml, at the O of 40ml/min
2Air-flow and 500 ℃ of following 1hr that handle react resulting result in the reactor in embodiment 1, see Table 5.
Table 5
T(℃) XCH
4XO
2SCO SH
2
750??96.0??100??97.0??99.0
700??90.4??100??91.2??94.8
550??78.2??100??82.4??89.5
Reaction conditions: CH
4: O
2: N
2=2: 1: 0, GHSV=3 * 10
4Hr
-1
Embodiment 6:
Take by weighing 20～40 purpose Al
2O
3(specific surface 168m
2/ g) 1.608 restrain, be dissolved with 1.222 gram Ni(NO with 1.6ml
3)
26H
2O, 0.201 gram Cu(NO
3)
23H
2O, 0.051 gram Ca(NO
3)
24H
2The aqueous solution of O floods it, in the drying of 110 ℃ of following 16hr and air 750 ℃, after the roasting of 4hr, makes catalyzer.
Get the reactor that the 0.2ml catalyzer places example 1, use the O of 40ml/min earlier
2Handle 1hr down at 500 ℃, carry out the methane oxidation reaction then, reaction result such as table 6 expression.
Table 6
T(℃) XCH
4(%) XO
2(%) SCO(%) SH
2(%)
750??90.8??100??95.2??99.0
700??93.6??100??94.0??98.0
600??90.2??100??90.1??94.6
500??82.1??100??85.7??90.1
Reaction conditions: GHSV=3 * 10
4Hr
-1, CH
4: O
2: N
2=2: 1: 0
Embodiment 7:
Take by weighing 1.397 gram Ni(NO
3)
26H
2O, 0.232 gram Cu(NO
3)
23H
2O, 4.20 gram Al(NO
3)
39H
2O is dissolved in the 30ml water and is made into mixing solutions, stirs this mixed solution and adds 10%(NH
4)
2CO
3Solution is until being completed into gel.Detergent gel and at 110 ℃ of following dry 16hr, 750 ℃ of following roasting 4hr.
Get the reactor that the above-mentioned catalyzer of 0.2ml places example 1, at first at 500 ℃ of O that use 40ml/min down
2Handle 1hr, react then, the results are shown in Table 7.
Table 7
T(℃) GHSV(hr
-1) XCH
4(%) XO
2(%) SCO(%) SH
2(%)
700 3×10
496.8 100 96.0 100
600 3×10
491.7 100 93.2 98.0
500 3×10
484.5 100 87.0 90.8
700 6×10
492.1 100 93.8 95.6
700 3×10
584.0 100 88.0 87.2
Reaction conditions: CH
4: O
2: N
2=2: 1: 0
Embodiment 8:
Take by weighing 20～40 purpose silicon bead (specific surface 196m
2/ g) 1.582 restrain, contain 1.339 gram Ni(NO with 1.6ml
3)
26H
2O, 0.225 gram Cu(NO
3)
23H
2Behind the aqueous solution dipping of O, dry 16hr under 110 ℃, 750 ℃ of roasting 4hr promptly make catalyzer.
Get the reactor that the 0.2ml catalyzer places embodiment 1, the methane oxidation reaction result of gained sees Table 8.
Table 8
T(℃) XCH
4(%) XO
2(%) SCO(%) SH
2(%)
750??92.1??100??92.7??95.0
700??88.6??100??89.6??91.4
600??80.1??100??83.7??86.2
500??75.4??100??80.1??80.9
Reaction conditions: GHSV=3 * 10
4Hr
-1, CH
4: O
2: N
2=2: 1: 0
Embodiment 9:
Catalyzer (1) (2) adopts the method for preparing catalyst among the embodiment 1 to prepare, catalyzer (3) (4) adopts the method for preparing catalyst among the embodiment 6 to prepare, carry out methane oxidation reaction according to the response procedures among the embodiment 1, resultingly the results are shown in Table 9.
Table 9
Numbering catalyzer XCH
4(%) XO
2(%) SCO (%) SH
2(%)
1 CoYb
0.2Mg
0.05Al
4Ox 92.1 100 92.7 95.0
2 CoNd
0.33Al
3.33Ox 88.6 100 89.6 91.4
3 1%Pt-0.38%Dy
2O
3/Al
2O
380.1 100 83.7 86.2
4 1%Ru-0.70%Eu
2O
3/Al
2O
375.4 100 80.1 80.9
Reaction conditions: catalyst levels 0.2ml, T=700 ℃, GHSV=3 * 10
4Hr
-1, CH
4: O
2: N
2=2: 1: 0
Claims (7)
1, a kind of catalyzer that is used for the methane conversion preparing synthetic gas is characterized in that the catalyzer expression with coprecipitation method preparation is AaBbCcDdOx, or is the AaBbCcOx/ carrier with the supported catalyst expression of immersion process for preparing.
(1) A is the element of at least a Ni of being selected from, Co, Ru, Rh, Pt, Pd, Ir.
(2) B is at least a element that is selected from rare earth, Cu, Ag, Zn, Cd, V, Cr, Mo, W, Mn.
(3) C is the element of at least a Li of being selected from, Na, K, Rb, Be, Mg, Ca, Sr, Ba.
(4) D is at least a element that is selected from Si, Al, Ti, Zr.
(5) catalyst-supporting support is silicon bead, aluminium bead, sial ball, molecular sieve.Wherein, the atomic ratio of b/a, c/a, d/a independent variation separately in 0～20 scope.The loading of active principle is 0.01～50wt% in the supported catalyst.
2, catalyzer as claimed in claim 1 is characterized in that elements A wherein is Ni, and element B is Cu, and Elements C is Ca, and element D is Al.
3, catalyzer as claimed in claim 1 is characterized in that catalyst-supporting support wherein is Al
2O
3Bead.
4, catalyzer as claimed in claim 1 or 2 is characterized in that b/a is 0.04～0.4, and c/a is 0～0.4, and d/a is 0.5～10.
5, catalyzer as claimed in claim 1 or 2 is characterized in that supported catalyst active principle loading wherein is 1～30%(weight).
6, catalyzer as claimed in claim 4 is characterized in that supported catalyst active principle loading is a 1-30%(weight).
7, a kind of is the process of synthetic gas with methane conversion, it is characterized in that this process is included in the gas mixture that the methane and the gas of molecule-containing keto are made into and contacts with the catalyzer that makes with arbitrary described method among the claim 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103728A CN1047103C (en) | 1994-04-05 | 1994-04-05 | Catalyst for converting methane into synthetic gas and its process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103728A CN1047103C (en) | 1994-04-05 | 1994-04-05 | Catalyst for converting methane into synthetic gas and its process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1110248A true CN1110248A (en) | 1995-10-18 |
| CN1047103C CN1047103C (en) | 1999-12-08 |
Family
ID=5031245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94103728A Expired - Fee Related CN1047103C (en) | 1994-04-05 | 1994-04-05 | Catalyst for converting methane into synthetic gas and its process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1047103C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087657C (en) * | 1996-12-30 | 2002-07-17 | 中国科学院成都有机化学研究所 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
| CN1110362C (en) * | 1996-11-17 | 2003-06-04 | 中国石化齐鲁石油化工公司 | Energy-saving type hydrocarbons water vapour conversion catalyst and preparation method thereof |
| WO2008040175A1 (en) * | 2006-09-20 | 2008-04-10 | China Petroleum & Chemical Corporation | A nickel catalyst for selective hydrogenation |
| CN1982205B (en) * | 2005-06-24 | 2013-03-13 | 南卡罗来纳州大学 | Use of complex metal oxides in the autothermal generation of hydrogen |
| CN103785395A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for preparation of synthetic gas through partial oxidation of methane, and preparation method and application thereof |
| CN104549265A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing ethylidene diacetate and application of catalyst |
| CN109718781A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of silicon tetrachloride adds hydrogen to prepare trichlorosilane catalyst and preparation method thereof |
| CN109876852A (en) * | 2019-03-27 | 2019-06-14 | 太原理工大学 | A kind of PtO@MFI encapsulating structure catalyst and its preparation method and application for methane portion oxidation synthesis gas |
| CN111936232A (en) * | 2018-04-11 | 2020-11-13 | 国立大学法人北海道大学 | Partial oxidation catalyst for light hydrocarbon and process for producing carbon monoxide using the same |
| CN113058613A (en) * | 2021-03-18 | 2021-07-02 | 浙江师范大学 | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of low-load Ni-Mo-based catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU483999A1 (en) * | 1972-06-27 | 1975-09-15 | Институт Химии Ан Уз Сср | Catalyst for natural gas conversion |
| SU1747144A1 (en) * | 1990-04-28 | 1992-07-15 | Государственный Научно-Исследовательский Энергетический Институт Им.Г.М.Кржижановского | Catalyst for carbon dioxide conversion of methane |
| SU1734820A1 (en) * | 1990-05-21 | 1992-05-23 | Институт катализа СО АН СССР | Method of obtaining catalyst for methane conversion by steam |
-
1994
- 1994-04-05 CN CN94103728A patent/CN1047103C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110362C (en) * | 1996-11-17 | 2003-06-04 | 中国石化齐鲁石油化工公司 | Energy-saving type hydrocarbons water vapour conversion catalyst and preparation method thereof |
| CN1087657C (en) * | 1996-12-30 | 2002-07-17 | 中国科学院成都有机化学研究所 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
| CN1982205B (en) * | 2005-06-24 | 2013-03-13 | 南卡罗来纳州大学 | Use of complex metal oxides in the autothermal generation of hydrogen |
| WO2008040175A1 (en) * | 2006-09-20 | 2008-04-10 | China Petroleum & Chemical Corporation | A nickel catalyst for selective hydrogenation |
| US8236726B2 (en) | 2006-09-20 | 2012-08-07 | China Petroleum & Chemical Corporation | Nickel catalyst for selective hydrogenation |
| CN103785395B (en) * | 2012-11-01 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of methane portion oxidation synthesis gas Catalysts and its preparation method and application |
| CN103785395A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for preparation of synthetic gas through partial oxidation of methane, and preparation method and application thereof |
| CN104549265B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst for synthesizing ethylidene diacetate and application of catalyst |
| CN104549265A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing ethylidene diacetate and application of catalyst |
| CN109718781A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of silicon tetrachloride adds hydrogen to prepare trichlorosilane catalyst and preparation method thereof |
| CN109718781B (en) * | 2017-10-27 | 2021-12-31 | 中国石油化工股份有限公司 | Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof |
| CN111936232A (en) * | 2018-04-11 | 2020-11-13 | 国立大学法人北海道大学 | Partial oxidation catalyst for light hydrocarbon and process for producing carbon monoxide using the same |
| CN111936232B (en) * | 2018-04-11 | 2023-05-30 | 国立大学法人北海道大学 | Light hydrocarbon partial oxidation catalyst and method for producing carbon monoxide using same |
| CN109876852A (en) * | 2019-03-27 | 2019-06-14 | 太原理工大学 | A kind of PtO@MFI encapsulating structure catalyst and its preparation method and application for methane portion oxidation synthesis gas |
| CN113058613A (en) * | 2021-03-18 | 2021-07-02 | 浙江师范大学 | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof |
| CN113058613B (en) * | 2021-03-18 | 2022-08-26 | 浙江师范大学 | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of low-load Ni-Mo-based catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1047103C (en) | 1999-12-08 |
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