CN1125681C - Catalyst for preparing C2 hydrocarbon from transition metal and methane through oxidization and coupling by cocatalysis with S and W elements and its preparing process - Google Patents
Catalyst for preparing C2 hydrocarbon from transition metal and methane through oxidization and coupling by cocatalysis with S and W elements and its preparing process Download PDFInfo
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- CN1125681C CN1125681C CN01142307A CN01142307A CN1125681C CN 1125681 C CN1125681 C CN 1125681C CN 01142307 A CN01142307 A CN 01142307A CN 01142307 A CN01142307 A CN 01142307A CN 1125681 C CN1125681 C CN 1125681C
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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
Abstract
The present invention discloses a catalyst for preparing C2 hydrocarbon from transition metal and methane through oxidation and coupling by cocatalysis of mercapto and tungsten elements and a preparation method thereof. The catalyst uses transition metal of Zr and Mn as main components, uses S and W elements as a cocatalyst, uses alkali metal ions as a modifier, and is loaded on SiO2 carriers. The catalyst is used for the methane oxidation and coupling reaction, high methane conversion rate and C2 hydrocarbon (which mainly contains ethylene and ethane) selectivity are obtained under the conditions of a lower temperature and no diluent gas, the C2 hydrocarbon yield reaches higher than 25%, and the maximum C2 hydrocarbon yield can reach 26.83%. The catalyst is favorable to the direct utilization of natural gas in industry and the development of the chemical industry of the natural gas.
Description
Technical field
The present invention relates to methane is directly transformed system C
2The Catalysts and its preparation method of hydrocarbon (mainly comprising ethene and ethane), particularly a kind of transition metal and methane oxidative coupling system C that helps catalysis with sulphur, W elements
2Hydrocarbon catalyst and preparation method thereof.
Background technology
Along with the exhaustion day by day of petroleum resources, seeking new alternative energy source and industrial chemicals becomes the problem that national governments all pay attention to.Existing explored petroleum reserves only can be kept 30 years, and equally as the base stock of chemical industry, natural gas is not but well utilized; Be not converted into the more chemical products of high value.
Recent two decades comes, and the methane oxidative coupling catalyst of having studied reaches kind more than 2000, relates in the periodic table element nearly all except that zero group, if merely with C
2The yield of hydrocarbon is an evaluation index, and these catalyst all do not obtain result preferably.In recent years, there is the researcher to attempt improving the course of reaction of oxidative coupling of methane from the angle of reactor and reaction process, and rare ethene that reaction obtains directly is used to synthesize epoxyethane, propionic aldehyde, ethylbenzene and wet goods downstream product, but angle from Technological Economy, owing to have problems such as separation difficulty, still can not compare on the economy with petrochemical industry.Therefore, the improvement catalyst remains an important directions in the oxidative coupling of methane research.
Oxidative coupling of methane realizes that industrialized key is C
2The raising of hydrocarbon yield, its core are to develop methane oxidative coupling catalyst efficiently.The C of the methane oxidative coupling catalyst of having developed at present,
2Hydrocarbon once through yield great majority the analysis showed that the oxidative coupling of methane process below 25%, are guaranteeing C
2On the basic basis of invariable of hydrocarbon-selective, improve methane conversion and help to improve C
2The hydrocarbon yield.The high conversion of methane can reduce the power consumption of course of reaction, improves the utilization rate of methane, helps promoting the economy of course of reaction.
More in the methane oxidative coupling catalyst is alkali and alkaline-earth metal catalyst, the C of this class catalyst
2Hydrocarbon-selective is generally higher, reach 70～80% usually, but methane conversion is lower, so C
2The hydrocarbon yield is no more than 23%.Some transition-metal catalysts of Recent study have shown good catalytic performance in oxidative coupling of methane, as the Na with precipitation method preparation such as Yoon
4P
2O
7-ZrOCl
2Catalyst and Na
+-ZrO
2-Cl
-/ SiO
2Catalyst has good catalytic performance in reaction, wherein the former C
2Selectivity reaches 79%, CH
4Conversion ratio reaches 28% (C
2Yield ≈ 22% reaches as high as 30%), shortcoming is a less stable, behind reaction 2～3hr, activity of such catalysts obviously descends.Two kinds is respectively the Na of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences's exploitation in addition
+-Mn-W/SiO
2The Mn-S/SiO of catalyst and Zhejiang University's exploitation
2Catalyst, the both has oxidative coupling of methane activity preferably, the highest C
2Yield reaches 24.1% and 22.3% respectively, it should be noted simultaneously, and the former has added inert gas in course of reaction and dilutes, and increases the separating difficulty of product, and economy is relatively poor; The latter's stability is not high, easily inactivation.
Summary of the invention
The object of the invention provides a kind of transition metal and methane oxidative coupling system C that helps catalysis with sulphur, W elements
2Hydrocarbon catalyst and preparation method thereof is to solve the problem that exists in the background technology.
Methane oxidation coupling system C provided by the invention
2Hydrocarbon catalyst is to be major constituent with Mn and two kinds of transition metal of Zr, as cocatalyst, is modification with alkali metal ion with S, W element, loads on SiO
2On the carrier, the catalyst of invention contains:
1) at least a alkaline or alkaline-earth salts of 10～35 (mol) %;
2) oxysalt of 0.5～12 (mol) % element sulphur;
3) oxysalt of 1.0～2.5 (mol) % W elements;
4) the solubility oxysalt of 0.5～13 (mol) % zr element;
5) soluble-salt of 1.0～4.0 (mol) % manganese element;
6) surplus silica.
Wherein used alkaline or alkaline-earth salts is Na
+, K
+, Li
+, Mg
2+And Ca
2+In one or more, wherein with Na
+Effect best; Employed element sulphur oxysalt can be sodium sulphate or potassium sulfate or sodium sulfite, and is best with sodium sulphate; Used W elements oxysalt can be sodium tungstate or potassium tungstate, is best with sodium tungstate; The soluble-salt of used manganese can be manganese chloride or manganese acetate; The soluble-salt of used zirconium is zirconium oxychloride preferably.
Methane oxidation coupling system C provided by the invention
2The preparation method of hydrocarbon catalyst in turn includes the following steps:
1) get the silica gel solution that concentration is 20～35% silica, regulating its pH value is 5～9, and preferred pH value is 6～8, and temperature is 10～100 ℃, and preferred temperature is 20～50 ℃;
2) the oxysalt aqueous solution that will contain the alkaline or alkaline-earth salts of requirement and sulfur-bearing, tungsten adds in the silica gel solution, prepares gel, and the pH value of solution value of gel process is 8～12, and preferred pH value is 9～10;
3) with step 2) gel of gained is under 60～180 ℃ of temperature, dry 2～12 hours, preferred baking temperature was 100～150 ℃, high-temperature roasting in air then, last cool to room temperature, wherein two-step method is adopted in high-temperature roasting, and first step sintering temperature is 400～650 ℃, and preferred sintering temperature is 500～600 ℃, roasting time is 2～4 hours, the second one-step baking temperature is 800～1100 ℃, and preferred sintering temperature is 850～950 ℃, and roasting time is 5～8 hours;
4) manganese of aequum and the soluble-salt of zirconium are dissolved with suitable quantity of water, with equivalent impregnation method impregnation steps 3) calcining matter that obtains, the pH value of solution value of dipping process is 8～12, preferred pH value is 9～10;
5) macerate that step 4) is obtained is under 60～180 ℃ of temperature, dry 2～12 hours, preferred baking temperature is 100～150 ℃, high-temperature roasting in air then, and two-step method is adopted in roasting, first step sintering temperature is 400～650 ℃, preferred sintering temperature is 500～600 ℃, and roasting time is 2～4 hours, and the second one-step baking temperature is 800～1100 ℃, preferred sintering temperature is 850～950 ℃, and roasting time is 5～8 hours.
Catalyst of the present invention is implemented by following experimental program:
Atmospheric fixed bed quartz reactor is adopted in experiment.With content is that methane more than 99% and content are the oxygen mix more than 99%, and the mol ratio of methane and oxygen is controlled at 2～4.The gaseous mixture of methane and oxygen reacts by the beds that is equipped with method for preparing.Reaction temperature is 750～850 ℃, is the best with 770～800 ℃; Be reflected under the normal pressure and carry out; The reaction gas air speed that converts by standard temperature and pressure (STP) is 0.5 * 10
4～2.5 * 10
4Hour
-1, be preferably 0.7 * 10
4～1.5 * 10
4Hour
-1
The present invention compares the beneficial effect that has and is with background technology: the present invention can effectively improve the activation of methane by the strong oxidizing property of Mn and Zr, promotes the conversion of methane, reduces the temperature of reaction, adds sulphur, tungsten and alkali metal salt simultaneously and guarantees C
2The selectivity of hydrocarbon improves C
2The yield of hydrocarbon.And need not add inert gas in the reactor feed gas, help the industrialization of oxidative coupling of methane.
The specific embodiment
By the following examples the present invention is described in further detail:
Embodiment 1
This catalyst contains 16.45mol%Na, 5.73mol%S, 1.45mol%W, 6.75mol%Zr and 2.27mol%Mn.Choose the silica gel solution that contains 8 gram silica, regulating the pH value is 9, and temperature is 30 ℃, stirs to add down to contain 0.06 gram sodium carbonate, 1.10 gram sodium sulphate, 0.65 gram sodium tungstate; With the gained gel 130 ℃ of dryings 3 hours, 550 ℃ of roastings 3 hours, 875 ℃ of roastings 5 hours; Is equivalent impregnation gel calcining matter under 10 conditions with the mixed solutions that contain 2.90 gram zirconium oxychlorides and 0.56 gram manganese acetate in the pH value, again 130 ℃ of dryings 3 hours, and 550 ℃ of roastings 3 hours, 875 ℃ of roastings 5 hours.
The catalyst of preparation is applied to oxidative coupling of methane.20～40 order 0.5ml catalyst of screening gained are packed in the quartz reactor of internal diameter 6mm, methane and oxygen mol are passed through beds continuously than the mist that is 3, reaction gas air speed (STP) is 8000 hours
-1, be reflected under 770 ℃ of temperature and the normal pressure and carry out.Carry out online detection reaction product by two 102G gas-chromatographies.The result is as shown in table 1.
Table 1
| Reaction temperature | The reaction gas air speed | The alcoxyl ratio | Methane conversion | C 2Selectivity | C 2Yield | Ethylenic alkoxy rate |
| ℃ | Hour -1 | ?mol.mol -1 | ％ | ％ | ％ | Mol.mol -1 |
| 770 | 8000 | ?3∶1 | 36.54 | 73.07 | 26.70 | 4.0 |
Embodiment 2
Preparation process is identical with embodiment 1 with method.This catalyst contains 14.54mlo%K, 3.33mol%S, 1.99mol%W, 6.50mol%Zr and 2.68mol%Mn.S adopts sodium sulfite, W to adopt sodium tungstate, Zr to adopt zirconium oxychloride, Mn to adopt manganese acetate.Getting granularity is that 20～40 purpose catalyst 0.5ml carry out oxidative coupling of methane, and reaction condition and result are as shown in table 2.
Table 2
| Reaction temperature | The reaction gas air speed | The alcoxyl ratio | Methane conversion | C 2Selectivity | C 2Yield | Ethylenic alkoxy rate |
| ℃ | Hour -1 | ?mol.mol -1 | ％ | ％ | ％ | Mol.mol -1 |
| 800 | 7000 | ?3∶1 | 30.67 | 83.26 | 25.54 | 3.4 |
Embodiment 3
Preparation process is identical with embodiment 1 with method.This catalyst contains 18.91mlo%K, 2.65mol%S, 1.99mol%W, 5.05mol%Zr and 3.67mol%Mn.S adopts potassium sulfate, W to adopt potassium tungstate, Zr to adopt zirconium oxychloride, Mn to adopt manganese acetate.Getting granularity is that 20～40 purpose catalyst 0.5ml carry out oxidative coupling of methane, and reaction condition and result are as shown in table 3.
Table 3
| Reaction temperature | The reaction gas air speed | The alcoxyl ratio | Methane conversion | C 2Selectivity | C 2Yield | Ethylenic alkoxy rate |
| ℃ | Hour -1 | mol.mol -1 | ?％ | ％ | ％ | ?Mol.mol -1 |
| 770 | ?7000 | 3∶1 | ?36.91 | 73.36 | 27.08 | ?4.0 |
| 800 | ?9000 | 3∶1 | ?35.67 | 70.26 | 25.06 | ?3.7 |
| 830 | ?11000 | 3∶1 | ?33.44 | 66.24 | 22.15 | ?2.3 |
Embodiment 4
Preparation process is identical with embodiment 1 with method.This catalyst contains 22.88mlo%Na, 8.13mol%S, 1.93mol%W, 11.85mol%Zr and 3.44mol%Mn.S adopts sodium sulphate, W to adopt sodium tungstate, Zr to adopt zirconium oxychloride, Mn to adopt manganese acetate.Getting granularity is that 20～40 purpose catalyst 0.5ml carry out oxidative coupling of methane, and reaction condition and result are as shown in table 4.
Table 4
| Reaction temperature | The reaction gas air speed | The alcoxyl ratio | Methane conversion | C 2Selectivity | C 2Yield | Ethylenic alkoxy rate |
| ℃ | Hour -1 | mol.mol -1 | ％ | ％ | ％ | mol.mol -1 |
| 830 | ?8000 | 3∶1 | 34.24 | 74.90 | 25.65 | 3.4 |
Claims (8)
1. one kind is helped the transition metal and methane oxidative coupling system C2 hydrocarbon catalyst of catalysis with sulphur, W elements, it is characterized in that this catalyst contains;
1) at least a alkaline or alkaline-earth salts of 10～35 (mol) %;
2) oxysalt of 0.5～12 (mol) % element sulphur;
3) oxysalt of 1.0～2.5 (mol) % W elements;
4) the solubility oxysalt of 0.5～13 (mol) % zr element;
5) soluble-salt of 1.0～4.0 (mol) % manganese element;
6) surplus silica.
2. by the described transition metal and methane oxidative coupling system C that helps catalysis with sulphur, W elements of claim 1
2Hydrocarbon catalyst is characterized in that said alkaline or alkaline-earth salts is Na
+, K
+, Li
+, Mg
2+, Ca
2+In one or more, the element sulphur oxysalt is sodium sulphate or potassium sulfate or sodium sulfite; The W elements oxysalt is sodium tungstate or potassium tungstate; The soluble-salt of manganese is manganese chloride or manganese acetate; The soluble-salt of used zirconium is a zirconium oxychloride.
3. one kind is used for the described transition metal and methane oxidative coupling system C that helps catalysis with sulphur, W elements of claim 1
2The preparation method of hydrocarbon catalyst is characterized in that it in turn includes the following steps:
1) get the silica gel solution that concentration is 20～35% silica, regulating its pH value is 5～9, and temperature is 10～100 ℃;
2) the oxysalt aqueous solution that will contain the alkaline or alkaline-earth salts of requirement and sulfur-bearing, tungsten adds in the silica gel solution, prepares gel, and the pH value of solution value of gel process is 8～12;
3) with step 2) gel of gained is under 60～180 ℃ of temperature, dry 2～12 hours, high-temperature roasting in air then, last cool to room temperature, wherein two-step method is adopted in high-temperature roasting, and first step sintering temperature is 400～650 ℃, and roasting time is 2～4 hours, the second one-step baking temperature is 800～1100 ℃, and roasting time is 5～8 hours;
4) manganese of aequum and the soluble-salt of zirconium are dissolved with suitable quantity of water, with equivalent impregnation method impregnation steps 3) calcining matter that obtains, the pH value of solution value of dipping process is 8～12;
5) macerate that step 4) is obtained is under 60～180 ℃ of temperature, dry 2～12 hours, high-temperature roasting in air then, two-step method is adopted in roasting, first step sintering temperature is 400～650 ℃, roasting time is 2～4 hours, and the second one-step baking temperature is 800～1100 ℃, and roasting time is 5～8 hours.
4. by the described methane oxidation coupling system C of claim 3
2The preparation method of hydrocarbon catalyst, the pH value that it is characterized in that said step 1) silica sol solution is 6～8, temperature is 20～50 ℃.
5. by the described methane oxidation coupling system C of claim 3
2The preparation method of hydrocarbon catalyst is characterized in that said step 2) the pH value of solution value of gel process is 9～10.
6. by the described methane oxidation coupling system C of claim 3
2The preparation method of hydrocarbon catalyst, the temperature that it is characterized in that said step 3) desiccant gel is 100～150 ℃, and first step sintering temperature is 500～600 ℃, and the second one-step baking temperature is 850～950 ℃.
7. by the described methane oxidation coupling system C of claim 3
2The preparation method of hydrocarbon catalyst, the pH value of solution value that it is characterized in that said step 4) dipping process is 9～10.
8. by the described methane oxidation coupling system C of claim 3
2The preparation method of hydrocarbon catalyst is characterized in that the temperature of the dry macerate of said step 5) is 100～150 ℃, and first step sintering temperature is 500～600 ℃, and the second one-step baking temperature is 850～950 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01142307A CN1125681C (en) | 2001-11-22 | 2001-11-22 | Catalyst for preparing C2 hydrocarbon from transition metal and methane through oxidization and coupling by cocatalysis with S and W elements and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01142307A CN1125681C (en) | 2001-11-22 | 2001-11-22 | Catalyst for preparing C2 hydrocarbon from transition metal and methane through oxidization and coupling by cocatalysis with S and W elements and its preparing process |
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|---|---|
| CN1356172A CN1356172A (en) | 2002-07-03 |
| CN1125681C true CN1125681C (en) | 2003-10-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8846120B2 (en) | 2009-06-17 | 2014-09-30 | Koninklijke Douwe Egberts B.V. | System, a method and a capsule for preparing a pre-determined quantity of beverage |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325164C (en) * | 2004-08-20 | 2007-07-11 | 东南大学 | Manganese series methane oxidation coupling catalyst using multicomponent promoter and its preparation method |
| US8921256B2 (en) * | 2011-05-24 | 2014-12-30 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
| WO2018078567A1 (en) * | 2016-10-31 | 2018-05-03 | Sabic Global Technologies B.V. | Catalysts for soft oxidation coupling of methane to ethylene and ethane |
| AU2022232792A1 (en) * | 2021-03-08 | 2023-09-07 | Mitsubishi Heavy Industries, Ltd. | Olefin production device and olefin production method |
| WO2023197339A1 (en) * | 2022-04-16 | 2023-10-19 | 浙江大学 | Composite oxide containing tungsten and alkali metal elements, as well as preparation method therefor and use thereof |
-
2001
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8846120B2 (en) | 2009-06-17 | 2014-09-30 | Koninklijke Douwe Egberts B.V. | System, a method and a capsule for preparing a pre-determined quantity of beverage |
| US9371174B2 (en) | 2009-06-17 | 2016-06-21 | Koninklijke Douwe Egberts B.V. | Capsule for preparing a pre-determined quantity of beverage |
| US9409705B2 (en) | 2009-06-17 | 2016-08-09 | Koninklijke Douwe Egberts B.V. | System, a method and a capsule for preparing a pre-determined quantity of beverage |
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| CN1356172A (en) | 2002-07-03 |
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