CN1045902C - Preparing synthetic gas catalyst by anti-carbon methane partial oxidation and its preparation method - Google Patents
Preparing synthetic gas catalyst by anti-carbon methane partial oxidation and its preparation method Download PDFInfo
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- CN1045902C CN1045902C CN96101766A CN96101766A CN1045902C CN 1045902 C CN1045902 C CN 1045902C CN 96101766 A CN96101766 A CN 96101766A CN 96101766 A CN96101766 A CN 96101766A CN 1045902 C CN1045902 C CN 1045902C
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- synthetic gas
- oxide
- gas catalyst
- partial oxidation
- cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- 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 synthetic gas catalyst prepared by partial oxidation of methane, and a preparation method thereof. The synthetic gas catalyst is composed of nickel oxide, lanthanum oxide, magnesium oxide, and chromium oxide or cobalt oxide; each constituent of the synthetic gas catalyst contains metal constituents by the molar percentage content of 10.0% to 50.0% of nickel, 1.0% to 50.0% of lanthanum, 0.1% to 50.0% of magnesium, and 1.0% to 40.0% of chromium or cobalt. Each gauged constituent is dissolved in distilled water under the condition that citric acid exists; the dissolved solution removes water contents through depressurization and steaming at a temperature of 80 DEG C, and is dried in a vacuum drying box at a temperature of 80 DEG C to 120 DEG C and under the pressure of 1.0KPa; finally, the dried mixture is ignited for 3 to 5 hours at a temperature of 650 DEG C to 900 DEG C in a muffle furnace. The catalyst of the present invention has the advantages of stable catalytic activity, good carbon deposit resistance performance, simple and convenient manufacturing technology, and good repeatability.
Description
The present invention relates to a kind of methane portion oxidation synthesis gas catalyzer and manufacture method thereof.
In the last few years, the research of methane portion oxidation synthesis gas was very active.V.R.Choudhary etc. are at Catalysis Letter[22 (1993) 289-297] reported a kind of Ni-La
2O
3Catalyzer can catalytic methane portion oxidation synthesis gas (CO/H
2) reaction: consist of CH at normal pressure, 833K, unstripped gas
4/ O
2=2/1 (mol ratio), unstripped gas air speed are 5.2 * 10
5Milliliter/hour-reaction conditions of Ke catalyzer under, methane (CH
4) transformation efficiency X
CH4Be 68.8%, carbon monoxide in the product (CO) selectivity S
COBe 88.2% (being done 100%) to transform methane institute carbon containing.Yet the operate continuously that realizes said process on nickel-base catalyst but runs into the problem that catalyst surface is easy to carbon deposit.According to above, ongoing operation is 6 hours under above-mentioned reaction conditions, and coke content reaches the 9.1wt% of catalyst levels on this catalyzer, and its carbon deposit mean rate is 15 milligrams/hour-Ke catalyzer, so cause beds to stop up and active decline, make this reaction process can't continue to carry out.
Purpose of the present invention is intended to develop a kind of efficient anti-carbon deposit, methane portion oxidation synthesis gas catalyzer that operational stability is good.
Catalyzer of the present invention contains NiO, La
2O
3, MgO, and Cr
2O
3Or component such as CoO, each component metal molar percentage composition (mol%) is: Ni:10.0～50.0mol%, preferably 20.0～50.0mol%, especially 30.0～45.0mol%; La:1.0～50.0mol%, preferably 2.0～50.0mol%, especially 4.0～45.0mol%; Mg:0.1～50.0mol%, preferably 10.0～50.0mol%, especially 20.0～45.0mol%; Cr or Co:1.0～40.0mol%, preferably 2.0～30.0mol%, especially 3.0～25.0mol%;
Preparation of catalysts is in the presence of citric acid, with the Ni (NO of metering
3)
26H
2O, La (NO
3)
35H
2O, Mg (NO
3)
26H
2O, and Cr (NO
3)
39H
2O or Co (NO
3)
26H
2O mixes and is dissolved in a certain amount of distilled water, makes solution A; With solution A reduction vaporization under the 353K temperature, remove moisture until becoming mashed prod B; B moved in the vacuum drying oven does 353K～393K, under the pressure of 1.0KPa, dry fluffy body C; Thereafter C is moved in the retort furnace under 923K～1173K, calcination 3～7 hours, then prepared catalyst samples.
Evaluating catalyst carries out on atmospheric fixed bed gas continuous flow reaction unit.Reactant and product composition are analyzed by an on-line gas chromatography thermal conductivity detector.Reaction product mainly contains: CO, H
2, CO
2, and H
2O.Consist of CH at unstripped gas
4/ O
2=2.1/1 (mol ratio), temperature of reaction are 1053K, unstripped gas air speed GHSV=1.0 * 10
5Milliliter/hour-reaction conditions of Ke catalyzer under, methane conversion X
CH4Be 88%, carbon monoxide selective S
COBe 94%.Knot charcoal amount is measured by a PCT-1 differential thermal balance.In lasting 50 hours evaluation experimentals, catalyst activity is stable, and anti-carbon deposit performance is better than having reported so far the level of catalyzer greatly.And catalyzer of the present invention is simple for production, good reproducibility.
The invention will be further described by embodiment below.
Embodiment 1
With 2.62 gram Ni (NO
3)
26H
2O, 0.42 gram La (NO
3)
35H
2O, 2.30 gram Mg (NO
3)
26H
2O, 0.40 gram Cr (NO
3)
39H
2O and 2 gram citric acids are mixed together and are dissolved in the 20.0ml distilled water and make solution A, move in A to the 100ml round-bottomed flask with the decompression well heater heating evaporation under 353K that circles round, and take out most of moisture, must a mashed prod B.With B move under 373K, 1.0KPa, dry in the vacuum drying oven a fluffy body C, thereafter C was moved in the retort furnace under the 1023K temperature calcination 5 hours, promptly get prepared catalyst samples.Evaluating catalyst carries out on atmospheric fixed bed gas continuous flow reaction unit, and each experiment catalyst consumption is 40 milligrams, and at 1053K, unstripped gas consists of CH
4/ O
2=2.1/1 (mol ratio), unstripped gas air speed GHSV=1.0 * 10
5Milliliter/hour-reaction conditions of Ke catalyzer under, methane conversion X
CH4Be 88%, CO selectivity S
COBe 94%; In the ongoing operation that lasts 50 hours, catalyst activity and selectivity are very stable.After ongoing operation in 50 hours, unload catalyzer, detect through PCT-1 type differential thermal balance, its carbon deposit total amount is less than the 0.5wt% of catalyst levels (promptly at this below instrument lowest detection limit).
Embodiment 2
Catalyzer is by 2.47 gram Ni (NO
3)
26H
2O, 4.16 gram La (NO
3)
35H
2O, 0.026 gram Mg (NO
3)
26H
2O and 0.60 gram Cr (NO
3)
39H
2O and 2 gram citric acids are mixed and made into the aqueous solution, make through the drying under reduced pressure of finding time, calcination successively.Calcination temperature is 973K, lasts 6 hours.Concrete preparation method, evaluating catalyst experiment condition are with embodiment 1.The result shows, methane conversion X
CH4Be 87%, CO selectivity S
COBe 93%; In the ongoing operation that lasts 20 hours, catalyst activity and selectivity are very stable.20 hours total carbon depositions are less than the 0.5wt% of catalyst levels (promptly at this below instrument lowest detection limit).
Embodiment 3
With 2.62 gram Ni (NO
3)
26H
2O, 0.42 gram La (NO
3)
35H
2O, 2.30 gram Mg (NO
3)
26H
2O, 0.29 gram Co (NO
3)
36H
2O and 2 gram citric acids are mixed and made into the aqueous solution, make through the drying under reduced pressure of finding time, calcination successively.Calcination temperature is 1073K, lasts 5 hours.Preparation method, evaluating catalyst are with embodiment 1.The result shows, methane conversion X
CH4Be 88.2%, CO selectivity S
COBe 94.4%; In going through 23 hours ongoing operation, catalyst activity and selectivity are very stable.23 hours total carbon depositions are less than the 0.5wt% of catalyst levels (promptly at this below instrument lowest detection limit).
Embodiment 4
With 1.74 gram Ni (NO
3)
26H
2O, 0.28 gram La (NO
3)
35H
2O, 1.54 gram Mg (NO
3)
26H
2O, 1.6 gram Cr (NO
3)
39H
2O and 2 gram citric acids are mixed and made into the aqueous solution, make through the drying under reduced pressure of finding time, calcination successively.Calcination temperature is 1023K, lasts 5 hours.Preparation method, evaluating catalyst are with embodiment 1.The result shows, methane conversion X
CH4Be 88%, CO selectivity S
COBe 94%; In the ongoing operation that lasts 24 hours, catalyst activity and selectivity are very stable.24 hours total carbon depositions are less than the 0.5wt% of catalyst levels (promptly at this below instrument lowest detection limit).
Claims (4)
1. preparing synthetic gas catalyst by anti-carbon methane partial oxidation, contain nickel oxide, lanthanum trioxide, it is characterized in that also containing magnesium oxide, and chromic oxide or cobalt oxide, the metal component molar content of each component is: nickel content is 10.0%～50.0%, lanthanum is 1.0%～50.0%, and magnesium is 0.1%～50.0%, and chromium or cobalt are 1.0%～40.0%.
2. preparing synthetic gas catalyst by anti-carbon methane partial oxidation as claimed in claim 1, it is characterized in that each metal component molar content is in the described catalyzer: nickel 20.0%～50.0%, lanthanum 2.0%～50.0%, magnesium 10.0%～50.0%, chromium or cobalt 2.0%～30.0%.
3. preparing synthetic gas catalyst by anti-carbon methane partial oxidation as claimed in claim 2, it is characterized in that each metal component molar content in the described catalyzer: nickel 30.0%～45.0%, lanthanum 4.0%～45.0%, magnesium 20.0%～45.0%, chromium or cobalt 3.0%～25.0%.
4. the manufacture method of a kind of preparing synthetic gas catalyst by anti-carbon methane partial oxidation of claim 1 is characterized in that Preparation of catalysts is in the presence of citric acid, with the Ni (NO of metering
3)
26H
2O, La (NO
3)
35H
2O, Mg (NO
3)
26H
2O, and Cr (NO
3)
39H
2O or Co (NO
3)
26H
2O mixes and is dissolved in the distilled water, make solution A, with solution A reduction vaporization under 80 ℃ of temperature, remove moisture until becoming mashed prod B, with B move under 80 ℃～120 ℃ pressure, dry in the vacuum drying oven at 1.0KPa fluffy body C, then C is moved in the retort furnace in 650 ℃～900 ℃ following calcinations 3～7 hours, prepared catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96101766A CN1045902C (en) | 1996-02-16 | 1996-02-16 | Preparing synthetic gas catalyst by anti-carbon methane partial oxidation and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96101766A CN1045902C (en) | 1996-02-16 | 1996-02-16 | Preparing synthetic gas catalyst by anti-carbon methane partial oxidation and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1157256A CN1157256A (en) | 1997-08-20 |
| CN1045902C true CN1045902C (en) | 1999-10-27 |
Family
ID=5117263
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96101766A Expired - Fee Related CN1045902C (en) | 1996-02-16 | 1996-02-16 | Preparing synthetic gas catalyst by anti-carbon methane partial oxidation and its preparation method |
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| Country | Link |
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| CN (1) | CN1045902C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513116B (en) * | 2011-11-02 | 2013-06-12 | 太原理工大学 | Preparation method of thermometal methanation catalyst with high-temperature resistance |
| CN102580752B (en) * | 2011-12-24 | 2013-08-07 | 太原理工大学 | Method for preparing nickel-containing methanation catalyst quickly |
| CN104084211B (en) * | 2014-07-10 | 2017-01-11 | 山西潞安矿业(集团)有限责任公司 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102194A (en) * | 1985-04-01 | 1986-08-13 | 中国科学院成都有机化学研究所 | Hydrocarbon vapor reforming catalyst |
| CN85103556A (en) * | 1985-04-29 | 1986-10-29 | 化学工业部西南化工研究院 | Low steam carbon ratio hydrocarbon gas conversion catalyst and manufacturing thereof and purposes |
| CN1030533A (en) * | 1987-06-23 | 1989-01-25 | 英国石油公司 | Catalyst |
| US4902659A (en) * | 1988-07-26 | 1990-02-20 | Council Of Scientific And Industrial Research | Preparation of improved nickel-containing catalyst and process for conversion of alcohols to carboxylic acids therewith |
| EP0452693A1 (en) * | 1990-03-30 | 1991-10-23 | BASF Aktiengesellschaft | Method of preparing 2,2-disubstituted pentane 1,5-diamines |
-
1996
- 1996-02-16 CN CN96101766A patent/CN1045902C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102194A (en) * | 1985-04-01 | 1986-08-13 | 中国科学院成都有机化学研究所 | Hydrocarbon vapor reforming catalyst |
| CN85103556A (en) * | 1985-04-29 | 1986-10-29 | 化学工业部西南化工研究院 | Low steam carbon ratio hydrocarbon gas conversion catalyst and manufacturing thereof and purposes |
| CN1030533A (en) * | 1987-06-23 | 1989-01-25 | 英国石油公司 | Catalyst |
| US4902659A (en) * | 1988-07-26 | 1990-02-20 | Council Of Scientific And Industrial Research | Preparation of improved nickel-containing catalyst and process for conversion of alcohols to carboxylic acids therewith |
| EP0452693A1 (en) * | 1990-03-30 | 1991-10-23 | BASF Aktiengesellschaft | Method of preparing 2,2-disubstituted pentane 1,5-diamines |
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| Publication number | Publication date |
|---|---|
| CN1157256A (en) | 1997-08-20 |
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