CN100438978C - Catalyst for preparing synthetic gas by partial oxidation of natural gas and preparation method thereof - Google Patents
Catalyst for preparing synthetic gas by partial oxidation of natural gas and preparation method thereof Download PDFInfo
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- CN100438978C CN100438978C CNB2006101023082A CN200610102308A CN100438978C CN 100438978 C CN100438978 C CN 100438978C CN B2006101023082 A CNB2006101023082 A CN B2006101023082A CN 200610102308 A CN200610102308 A CN 200610102308A CN 100438978 C CN100438978 C CN 100438978C
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Abstract
The mass percent of a catalyst which is prepared by oxygenating natural gas partly is: nickel oxide 5-20%, oxide additives 5-25%, silicon carbide 55-90%. The preparation method is: allocating water solution or alcohol solution of soluble nickel salt, allocating metal salt water solution or alcohol solution of oxide additives, mixing the soluble nickel salt solution and metal salt solution according to the component of catalyst, dipping silicon carbide in mixing solution after stirring 1-36 hours, pressurizing 12-24 hours under 1-2MPa, filtering solution, drying under 80-150degreeC, roasting 1-6 hours under 400-900 degree C; repeating the step(2)2-10 times until reaching the mass percent component of catalyst requirement. The invention has characteristics of high activity, high stability and long life time.
Description
Technical field
The invention belongs to a kind of Catalysts and its preparation method, specifically raw catelyst of a kind of preparing synthetic gas by partial oxidation of natural gas and preparation method thereof.
Background technology
Along with the consumption day by day of petroleum resources, with natural gas as an alternative the energy new synthesis route for preparing high added value liquid chemical and other organic chemicals be subjected to the great attention of countries in the world.The China's natural gas resource is very abundant, and with its effective development and utilization, energy resource structure strategical reajustment and sustainable economic development to China have very important realistic meaning.Preparing synthetic gas by partial oxidation of natural gas is the important intermediate link that realizes conversion of natural gas, and the research and development of effective catalyst are its keys.At present, the catalyst that is used for gas by partial oxidation of natural mainly is divided into two classes: noble metal (Rh, Pt) catalyst and nickel catalyst.Because nickel catalyst has similar performance in reactivity with high-temperature stability and noble metal catalyst, and low price, therefore have more application prospect.Chinese patent (Granted publication number: CN 1569330A) announced a kind of Catalysts and its preparation method of preparing synthetic gas by partial oxidation of natural gas.It is characterized in that with Ni being active component, Al
2O
3Be carrier, adopt sol-gel in-situ modification technology, introduce Ni
2+And Li
+And La
3+The promoter metal ion makes.Document (chemistry of fuel journal Vol.34No.4) has also been reported a kind of Catalysts and its preparation method of preparing synthetic gas by natural gas partial oxidation.It is characterized in that adopting the distribution equi-volume impregnating, introduce metal oxide MgO, prepared the Ni/Al of modification
2O
3Catalyst.It is carrier that yet these catalyst all adopt oxide, and their poor thermal conductivity are easy to generate focus in the course of reaction, causes catalyst stability to descend.(patent No.: ZL200310109658.8) disclose a kind of is the Ni catalyst of carrier with SiC high temperature resistant, good heat conductivity to Chinese patent.Its preparation method is by soluble metal nickel salt or soluble metal nickel salt and rare earth metal salt mixture are dissolved in distilled water or the ethanolic solution, then high-specific surface area carbonization silicon is immersed in the above-mentioned solution, slaine is deposited on silicon carbide under certain condition, the oven dry roasting makes.Yet because used carrier is a powder, the carbon distribution that produces in the course of reaction is easy to make catalyst to be bonded to piece, stops up bed, and reaction pressure is increased, even causes reaction to be forced to stop.Simultaneously, the Carboround surface is more weak with the intergranular effect of metallic nickel, exists problems such as active component Ni sintering, easy loss in catalytic reaction, causes catalyst carbon deposition and active decline.
Summary of the invention
The objective of the invention is by utilizing spherical silicon carbide of biological appearance (bioSiC) is carrier, and the surface of bioSiC carried out modification, promptly introduce other component at silicon carbide, improve the interaction between carrier surface and active component, in partial oxidation reaction of methane, bond and stop up bed and active component Ni sintering and losing issue to solve the Ni/SiC catalyst, develop the catalyst of a kind of high activity and stable preparing synthetic gas by partial oxidation of natural gas.
The mass percent of catalyst of the present invention consists of:
Nickel oxide: 5-20%
Oxides additive: 5-25%
Carborundum: 55-90%
Described carborundum is spherical porous bioSiC, is transformed by crops fruits such as millet, rice and soybean.Particle size range is at 1-5mm, and pore diameter range is at 0.001 μ m-200 μ m.
Described oxides additive comprises aluminium oxide, silica, magnesia, calcium oxide, strontium oxide strontia, zirconia, titanium oxide and gallium oxide etc.
The present invention realizes by following manner:
(1) configuration concentration is the aqueous solution or the alcoholic solution of 1-30wt% soluble nickel salt, and configuration concentration is the aqueous metal salt or the alcoholic solution of 1-30wt% oxides additive, and wherein the silica in the oxides additive is the own ester of positive silicic acid;
(2) pressing the catalyst composition mixes solvable nickel salt solution with metal salt solution or ethyl orthosilicate, get mixed solution, stir after 1-36 hour SiC dipping in mixed solution, pressurization is after 12-24 hour under 1-2Mpa, filter out solution, under 80-150 ℃ condition, dry, at 400-900 ℃ of roasting 1-6 hour;
(3) repeat (2) step 2-10 time, form up to the mass percent that reaches the catalyst requirement.
Described soluble nickel salt is nitrate, acetate or sulfate.
Described slaine is nitrate or hydrochloride.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min.Wherein, under 800 ℃, methane conversion is more than 90%, and the selectivity of carbon monoxide and hydrogen is more than 95%.
Feature of the present invention is that the spherical silicon carbide of biological appearance of employing is a carrier, and oxides additive is incorporated in the Ni/bioSiC catalyst, prepares a kind of Ni/bioSiC-M of modification
xO
y
Catalyst (M
xO
yRepresent oxides additive).Catalyst of the present invention is a carrier by adopting spherical bioSiC, and the introducing auxiliary agent is to the surface modification of carrier, promoted the dispersion of active component at carrier surface, and the active force of reinforcement and carrier, the carbon accumulation resisting ability of raising catalyst has solved catalyst activity component sintering, easy losing issue, have active and characteristics such as stability is high, life-span length, simultaneously, used carrier has also solved catalyst bonding in the partial oxidation reaction of methane, stops up the bed problem.
Embodiment one:
Take by weighing the 1g nickel nitrate and be dissolved in the 10ml distilled water, be configured to the nickel nitrate aqueous solution of 10wt%, take by weighing the 1.2g aluminum nitrate again and be dissolved in the 10ml distilled water, the aluminum nitrate aqueous solution of configuration 12wt% then with the two mixing, stirred 5 hours.Taking by weighing the 1g specific area is 15m
2The spherical biological pattern carborundum of/g is immersed in the mixed liquor, the pressure of packing into is filled in 2Mpa and pressurizeed 24 hours down, filter out solution, dry catalyst down at 100 ℃, 400 ℃ of roastings 6 hours in Muffle furnace again, immersion-pressurization repeatedly-roasting process 5 times can obtain nickel oxide loaded amount 10%, auxiliary agent aluminium oxide 15%, the catalyst of the preparing synthetic gas by partial oxidation of natural gas of catalyst carrier 75%.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min, and wherein, under 800 ℃, methane conversion is 95%, and carbon monoxide selective is 99%, and the selectivity of hydrogen is 98%.
Embodiment two:
Take by weighing the 0.15g nickel nitrate and be dissolved in the 10ml absolute ethyl alcohol, be configured to the nickel nitrate alcoholic solution of 1.5wt%, take by weighing the 0.08g aluminum nitrate again and be dissolved in the 5ml distilled water, the aluminum nitrate aqueous solution of configuration 1.6wt% then with the two mixing, stirred 20 hours.Taking by weighing the 1g specific area is 20m
2The spherical biological pattern carborundum of/g is immersed in the mixed liquor, the pressure of packing into is filled in 1Mpa and pressurizeed 12 hours down, filter out solution, dry catalyst down at 120 ℃, 500 ℃ of roastings 6 hours in Muffle furnace again, immersion-pressurization repeatedly-roasting process 7 times can obtain nickel oxide loaded amount 15%, auxiliary agent aluminium oxide 10%, the catalyst of the preparing synthetic gas by partial oxidation of natural gas of catalyst carrier 75%.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min, and wherein, under 800 ℃, methane conversion is 92%, and carbon monoxide selective is 98%, and the selectivity of hydrogen is 98%.
Embodiment three:
Take by weighing the 2g nickel acetate and be dissolved in the 10ml distilled water, be configured to the nickel acetate aqueous solution of 20wt%, take by weighing the 3g magnesium nitrate again and be dissolved in the 10ml absolute ethyl alcohol, the magnesium nitrate alcoholic solution of configuration 30wt% then with the two mixing, stirred 5 hours.Taking by weighing the 3g specific area is 8m
2The spherical biological pattern carborundum of/g is immersed in the mixed liquor, the pressure of packing into is filled in 2Mpa and pressurizeed 15 hours down, filter out solution, dry catalyst down at 150 ℃, 700 ℃ of roastings 3 hours in Muffle furnace again, immersion-pressurization repeatedly-roasting process 5 times can obtain nickel oxide loaded amount 10%, auxiliary agent magnesia 10%, the catalyst of the preparing synthetic gas by partial oxidation of natural gas of catalyst carrier 80%.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min, and wherein, under 800 ℃, methane conversion is 94%, and carbon monoxide selective is 98%, and the selectivity of hydrogen is 97%.
Embodiment four
Take by weighing the 1g nickel acetate and be dissolved in the 20ml distilled water, be configured to the nickel acetate aqueous solution of 5wt%, take by weighing the 0.5g magnesium nitrate again and be dissolved in the 15ml distilled water, the magnesium nitrate aqueous solution of configuration 3wt% then with the two mixing, stirred 20 hours.Taking by weighing the 3g specific area is 25m
2The spherical biological pattern carborundum of/g is immersed in the mixed liquor, the pressure of packing into is filled in 1.5Mpa and pressurizeed 24 hours down, filter out solution, dry catalyst down at 130 ℃, 600 ℃ of roastings 4 hours in Muffle furnace again, immersion-pressurization repeatedly-roasting process 6 times can obtain nickel oxide loaded amount 20%, auxiliary agent magnesia 7%, the catalyst of catalyst carrier 73% preparing synthetic gas by partial oxidation of natural gas.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min, and wherein, under 800 ℃, methane conversion is 93%, and carbon monoxide selective is 97%, and the selectivity of hydrogen is 95%.
Embodiment five:
Take by weighing the 0.5g nickel nitrate and be dissolved in the 2ml absolute ethyl alcohol, be configured to the nickel nitrate alcoholic solution of 25wt%, take by weighing the 2.3g zirconium nitrate again and be dissolved in the 10ml distilled water, the zirconium nitrate aqueous solution of configuration 23wt% then with the two mixing, stirred 24 hours.Taking by weighing the 2g specific area is 10m
2The spherical biological pattern carborundum of/g is immersed in the mixed liquor, the pressure of packing into is filled in 2Mpa and pressurizeed 10 hours down, filter out solution, dry catalyst down at 120 ℃, 900 ℃ of roastings 3 hours in Muffle furnace again, immersion-pressurization repeatedly-roasting process 2 times can obtain nickel oxide loaded amount 5%, auxiliary agent zirconia 20%, the catalyst of the preparing synthetic gas by partial oxidation of natural gas of catalyst carrier 75%.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min, and wherein, under 800 ℃, methane conversion is 91%, and carbon monoxide selective is 96%, and the selectivity of hydrogen is 95%.
Embodiment six
Take by weighing the 1g nickel acetate and be dissolved in the 10ml distilled water, be configured to the nickel acetate aqueous solution of 10wt%, take by weighing the 1.3g zirconium nitrate again and be dissolved in the 10ml absolute ethyl alcohol, the zirconium nitrate alcoholic solution of configuration 13wt% then with the two mixing, stirred 18 hours.Taking by weighing the 2.6g specific area is 17m
2The spherical biological pattern carborundum of/g is immersed in the mixed liquor, the pressure of packing into is filled in 1.7Mpa and pressurizeed 19 hours down, filter out solution, dry catalyst down at 110 ℃, 600 ℃ of roastings 5 hours in Muffle furnace again, immersion-pressurization repeatedly-roasting process 4 times can obtain nickel oxide loaded amount 10%, auxiliary agent zirconia 30%, the catalyst of the preparing synthetic gas by partial oxidation of natural gas of catalyst carrier 60%.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min, and wherein, under 800 ℃, methane conversion is 93%, and carbon monoxide selective is 97%, and the selectivity of hydrogen is 98%.
Embodiment seven
Take by weighing the 1.5g nickel acetate and be dissolved in the 10ml absolute ethyl alcohol, be configured to the nickel acetate alcoholic solution of 15wt%, measure the 2.3ml ethyl orthosilicate again,, stirred 24 hours then with the two mixing.Taking by weighing the 5g specific area is 17m
2The spherical biological pattern carborundum of/g is immersed in the mixed liquor, the pressure of packing into is filled in 1.8Mpa and pressurizeed 20 hours down, filter out solution, dry catalyst down at 140 ℃, 500 ℃ of roastings 3 hours in Muffle furnace again, immersion-pressurization repeatedly-roasting process 4 times can obtain nickel oxide loaded amount 15%, auxiliary agent silica 7%, the catalyst of the preparing synthetic gas by partial oxidation of natural gas of catalyst carrier 78%.
The evaluation experimental of catalyst carries out in the fixed bed quartz tube reactor, and the mol ratio of methane and oxygen is 2: 1, flow 100ml/min, and wherein, under 800 ℃, methane conversion is 92%, and carbon monoxide selective is 96%, and the selectivity of hydrogen is 97%.
Claims (6)
1. the catalyst of a preparing synthetic gas by partial oxidation of natural gas is characterized in that catalyst quality percentage consists of:
Nickel oxide: 5-20%
Oxides additive: 5-25%
Spherical biological pattern carborundum: 55-90%
2, the catalyst of a kind of preparing synthetic gas by partial oxidation of natural gas as claimed in claim 1 is characterized in that described carborundum is spherical porous, and particle size range is at 1-5mm, and pore diameter range is at 0.001 μ m-200 μ m.
3, the catalyst of a kind of preparing synthetic gas by partial oxidation of natural gas as claimed in claim 1 is characterized in that described oxides additive is aluminium oxide, silica, magnesia, calcium oxide, strontium oxide strontia, zirconia, titanium oxide or gallium oxide.
4, as each described a kind of preparing synthetic gas by partial oxidation of natural gas Preparation of catalysts method of claim 1-3, it is characterized in that comprising the steps:
(1) configuration concentration is the aqueous solution or the alcoholic solution of 1-30wt% soluble nickel salt, and configuration concentration is the aqueous metal salt or the alcoholic solution of 1-30wt% oxides additive, and wherein the silica in the oxides additive is the own ester of positive silicic acid;
(2) pressing the catalyst composition mixes solvable nickel salt solution with metal salt solution or ethyl orthosilicate, get mixed solution, stir after 1-36 hour spherical biological pattern SiC dipping in mixed solution, pressurization is after 12-24 hour under 1-2Mpa, filter out solution, under 80-150 ℃ condition, dry, at 400-900 ℃ of roasting 1-6 hour;
(3) repeat (2) step 2-10 time, form up to the mass percent that reaches the catalyst requirement.
5, a kind of preparing synthetic gas by partial oxidation of natural gas Preparation of catalysts method as claimed in claim 4 is characterized in that described soluble nickel salt is nitrate, acetate or sulfate.
6, a kind of preparing synthetic gas by partial oxidation of natural gas Preparation of catalysts method as claimed in claim 4 is characterized in that described slaine is nitrate or hydrochloride.
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| CN100438978C true CN100438978C (en) | 2008-12-03 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102049179B (en) * | 2009-10-30 | 2015-06-10 | 北京三聚环保新材料股份有限公司 | Method for preparing supported iron oxide series desulfurizing agent |
| CN102614903A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院大连化学物理研究所 | Monolithic catalyst and use of the monolithic catalyst in natural gas reforming for synthesis gas preparation |
| CN107537482B (en) * | 2016-06-29 | 2020-12-01 | 中国石油化工股份有限公司 | Porous composite catalyst and method of using same |
| CN109382145B (en) * | 2017-08-02 | 2021-10-22 | 中国石油化工股份有限公司 | Catalyst impregnation equipment and application method thereof |
| CN109382042B (en) * | 2017-08-02 | 2021-08-10 | 中国石油化工股份有限公司 | Impregnation equipment and method for preparing organic tail gas treatment catalytic incineration catalyst by using same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130150A (en) * | 1995-02-28 | 1996-09-04 | 中国科学院大连化学物理研究所 | Producing synthetic gas reaction by methane partial oxidation and its catalyst |
| CN1131638A (en) * | 1995-03-23 | 1996-09-25 | 中国科学院成都有机化学研究所 | Catalyst for preparing synthetic gas by natural gas partial oxidation and its preparation method |
| CN1544311A (en) * | 2003-11-11 | 2004-11-10 | 中国科学院山西煤炭化学研究所 | Catalyzer for preparing synthetic gas from natural gas partial oxidation and its preparation method |
| US6916417B2 (en) * | 2000-11-01 | 2005-07-12 | Warden W. Mayes, Jr. | Catalytic cracking of a residuum feedstock to produce lower molecular weight gaseous products |
| US7105147B2 (en) * | 2000-09-20 | 2006-09-12 | Teïkokuoil Co., Ltd. | Method for partial oxidation of methane using dense, oxygen selective permeation ceramic membrane |
-
2006
- 2006-12-20 CN CNB2006101023082A patent/CN100438978C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130150A (en) * | 1995-02-28 | 1996-09-04 | 中国科学院大连化学物理研究所 | Producing synthetic gas reaction by methane partial oxidation and its catalyst |
| CN1131638A (en) * | 1995-03-23 | 1996-09-25 | 中国科学院成都有机化学研究所 | Catalyst for preparing synthetic gas by natural gas partial oxidation and its preparation method |
| US7105147B2 (en) * | 2000-09-20 | 2006-09-12 | Teïkokuoil Co., Ltd. | Method for partial oxidation of methane using dense, oxygen selective permeation ceramic membrane |
| US6916417B2 (en) * | 2000-11-01 | 2005-07-12 | Warden W. Mayes, Jr. | Catalytic cracking of a residuum feedstock to produce lower molecular weight gaseous products |
| CN1544311A (en) * | 2003-11-11 | 2004-11-10 | 中国科学院山西煤炭化学研究所 | Catalyzer for preparing synthetic gas from natural gas partial oxidation and its preparation method |
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