CN1121844A - Catalyst for preparing ethylene by oxidation and dehydrogenation of ethane and process thereof - Google Patents
Catalyst for preparing ethylene by oxidation and dehydrogenation of ethane and process thereof Download PDFInfo
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- CN1121844A CN1121844A CN94116060A CN94116060A CN1121844A CN 1121844 A CN1121844 A CN 1121844A CN 94116060 A CN94116060 A CN 94116060A CN 94116060 A CN94116060 A CN 94116060A CN 1121844 A CN1121844 A CN 1121844A
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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
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- 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 compound oxide type catalyst is used for preparing ethylene by oxidizing dehydrogenation of ethane under the conditions of 300-650 deg.C and 100-1500/hr space velocity of ethane and features high conversion of ethane (20-70%) and ethylene selectivity (50-95%).
Description
The present invention relates to catalyst and process that a class is used for making ethylene from ethane oxidative dehydrogenation.
Contain a certain amount of ethane in natural gas, the associated gas, if its reasonable processing and utilization will be able to be brought remarkable economic efficiency.Especially in recent years, along with the continuous discovery and the exploitation in the big gauging of western China, gas field, it is urgent all the more that the chemical utilization of ethane seems.Producing ethene by ethane is one of its chemical utilization approach.For a long time, industrial production ethene is mainly realized by ethane steam cracking under 600 ℃～1000 ℃ high temperature.Existing technology itself exists some intrinsic limitation.At first, because heat scission reaction is the endothermic reaction, and is subjected to the restriction of molecular balance, therefore, than under the condition, ethane conversion is not high at actual steam/alkane.Secondly, the reaction time of cracking process is very short, and this brings difficulty with regard to the recycling of giving energy.Moreover relatively large low-boiling by-products such as hydrogen, methane etc. that cracking process produced make the separation and the removal process complexity of ethene and expense costliness.In addition, pyroreaction needs the reacting furnace or the reactor of specific alloy, and equipment cost is improved greatly.
Comparatively speaking, the ethane catalytic oxidative dehydrogenation is produced the method for ethene, then is a up-and-coming new technology route.The oxidative dehydrogenation accessory substance is water rather than hydrogen, and product is simple.Reaction is heat release, and it is possible reaching higher ethane conversion at a lower temperature, has so just reduced the energy consumption of process widely and has simplified lock out operation.In addition, the oxidative dehydrogenation process investment of founding the factory is little, and dried gas in oil field that again can the health valency or gas material are produced ethene, thereby has opened up new way for the comprehensive utilization of casing-head gas or natural gas.
The research of catalyst for making ethylene from ethane oxidative dehydrogenation, existing at home and abroad institute carries out, and relates to the catalyst of several individual system.USP4,410,752 have reported that the V-P-M-O type catalyst has certain oxidative dehydrogenation of ethane reactivity worth, wherein M is an auxiliary agent, the multiselect transition metal, no matter it is high that the type catalyst from the conversion ratio of ethane or from generating selectivity of ethylene, does not all include, still can't compete mutually with traditional cracking process.
A.D.Eastman etc. (USP4,368,346) find that the Co-P System Catalyst that is promoted by other element also demonstrates the oxidative dehydrogenation of ethane reactivity worth, but need higher reaction temperature and pressure, are operated the restriction with factor such as economic consideration in actual applications.
At present this reaction system of research is the most active surely belongs to Union Carbide company, and the catalyst research of the said firm has been applied for several pieces of patents, and wherein with USP4,524,236 are the representative result of study, and its catalyst system adopts the composite oxides form of Mo-V-Nb-Sb-X, wherein X can be down at least a in the column element: Li, Sc, Na, Be, Mg, Ca, Sr, Ba, Ti, Zr, Hf, Ta, Cr, Fe, Co, Ni, Ce, La, Zn, Cd, Hg, Al, Tl, Pb, As, Bi, Te, U and W.The above-mentioned catalyst system of the said firm is applied for a patent in China.
The purpose of this invention is to provide a kind of NEW TYPE OF COMPOSITE oxide catalyst, it is used for the making ethylene from ethane oxidative dehydrogenation process.
Detailed description of the present invention:
The present invention is a class oxidative dehydrogenation of ethane composite oxide catalysts, and its catalyst general formula is:
X is at least a alkali metal in the alkali metal family in the periodic table in XaYbZeOd or the XaYbZcOd/ carrier type, is selected from Li, Na, K, Rb, Cs; Y can be in some divalence in the formula, selects in trivalent or the variable valency metal element, can be at least a in these elements, and these elements comprise La, Zr, Cr, Mo, W, Mn, Fe, Co, Ni, Pt, Pd, Cu, Zn, Cd, Al, Pb, Sn, Bi; Z is selected from the periodic table at least a in the alkaline-earth metal family in the formula, is selected from Be, Mg, and Ca, Sr, Ba, wherein catalyst a: b can be 0.0～5.0, a: c can be 0.0～0.5, loaded catalyst, carrier should be selected SiO for use
2, γ-or η-Al
2O
3, TiO
2, ZrO
2The load capacity of active constituent should account for 2%～50% of gross weight.Above-mentioned catalyst a: b is preferably 0.1～3.0, a: b is 0.1～0.3 at last.
Preparation of catalysts can adopt the precipitation method, infusion process, mixed method, and other suitable preparation method.Coprecipitation mode can be with being added drop-wise to alkaline precipitating agent the positive precipitation method that in the relevant catalyst ingredients solution pH value changed from small to big, and also available relevant catalyst ingredients solution is added drop-wise to the anti-precipitation method in the alkaline solution.Precipitating reagent can be with ammoniacal liquor or ammoniacal liquor and (NH
4)
2CO
3Mixture, the XOH solution of the suitable concentration in the also available component, also available solid Z (OH)
2Powder adds precipitation Y component in the Y salting liquid.For the mode of Y in the first precipitated catalyst and Z component, the salting liquid of the precipitation of formation and X component or aqueous slkali XOH are mixed, stir and add thermosetting pasty state, oven dry then.
Infusion process can adopt the soluble-salt with active constituent X and Y, is dipped on the oxide solid of X component, soaks oven dry 6～48 hours.Can adopt soluble-salt in addition, with Z (OH) with X and Y
2Powder is mixed, stirs and adds thermosetting pasty state, oven dry then.
For loaded catalyst, can be made into the mixed salting liquid of solubility of active constituent, this mixed liquid is dipped on the carrier altogether, also the soluble-salt solution substep of active constituent can be dipped on the carrier separately.During dipping, the volume ratio that the solution for preparing suitably is diluted to solution and carrier was uniformly impregnated within on the carrier under room temperature, and stirs rapidly near 1: 1, left standstill a few hours.
The catalyst oven dry is to carry out under 80～120 ℃, dries 16～36 hours, and the catalyst of oven dry activates in 600 ℃～700 ℃ following air or oxygen atmosphere.During activation, at first decomposed down some volatility acid group (as nitrate anion etc.) 1～4 hour, be warming up to 600 ℃～700 ℃ activation 4～16 hours down then at 300 ℃～400 ℃.
Is with unstripped gas ethane by above-mentioned catalyst with the process of making ethylene from ethane oxidative dehydrogenation, oxygen donator (oxygen or air) and inert gas N
2, and the ratio of ethane and oxygen is 4: 1～1: 4, ethane air speed (GHSV) is 100～1500 hours
-1, be 300 ℃～650 ℃ in temperature, pressure is to carry out under 1～3atm.
The ethane air speed is preferably 150～450 hours
-1, optimal reaction temperature is 500 ℃～650 ℃.
Catalyst of the present invention has some unique feature and advantage:
This type catalyst reaction condition comparatively relaxes, only need lower temperature and pressure just can operate, and higher ethane conversion is arranged and generate selectivity of ethylene, its ethane conversion value can reach with the result of U.S. Union Carbvde company approaching, can can reach more than 90% far above the result of Union Carbide company but generate selectivity of ethylene, this is rarely seen in all disclosed reports, help improving utilization ratio of raw materials like this, cut down the consumption of raw materials greatly.The ethane conversion of some catalyst of this type and generation selectivity of ethylene have been higher than the index that has thermal cracking legal system ethene now, and it has the very big potentiality of competing mutually with the traditional hot cracking process.
Reactor feed gas is behind reactor, and except required product ethene, other also has a small amount of methane, combustion by-products CO, CO
2Deng.Also has micro oxygen containing compound in addition, as aldehyde, ketone, acid etc.
Realize mode of the present invention and embodiment:
Composition, preparation process, reaction condition and the obtained corresponding result of the test of the catalyst that the example of enumerating below only is used for illustrating that the present invention uses, but do not limit the present invention by better catalyst form, preparation technology and reaction condition.
Example 1: with 18.7 gram La (NO
3)
36H
2O, 49.7 gram Ca (NO
3)
24H
2O is dissolved in 200 ml distilled waters, stirs the ammonia spirit that splashes into 10% (weight) down fast, precipitation terminal point PH=10.0.Filter cake after filtration distilled water washed twice is used 100 milliliters of distilled water at every turn.With 1.5 gram LiNO
3Be dissolved in 100 ml distilled waters, with filter cake after the above-mentioned washing and LiNO
3Solution is mixed, and heating also evenly is stirred to pasty state, 120 ℃ dry 24 hours down, moved in the muffle furnace calcination then 10 hours, 650 ℃ of furnace temperature.With catalyst breakage, sieve is got 20-60 mesh sieve branch, is on 1 milliliter the flow-type constant temperature fixed bed in the catalyst loading amount, in 620 ℃ of reaction temperatures, and ethane air speed 150 hours
-1Reaction condition under can get ethene once through yield 39.4%, ethane conversion 42.0% generates the result of ethylene selectivity 93.8%.
Example 2: with 41.1 gram La (NO
3)
36H
2O, 56.1 gram Ca (NO
3)
24H
2O is dissolved in 200 ml distilled waters, and operating procedure and condition are with example 1.With 1.6 gram LiNO
3Be dissolved in 100 ml distilled waters, implement Preparation of Catalyst operating procedure and the condition identical with example 1, and identical with the catalyst oxidative dehydrogenation of ethane activity rating condition of example 1.Reaction result is a yield of ethene 33.1%, and ethane conversion 39.3% generates ethylene selectivity 84.2%.
Example 3: with 18.9 gram La (NO
3)
36H
2O, 51.5 gram Ca (NO
3)
24H
2O is dissolved in 200 ml distilled waters, stirs the mixed solution (10: 1) that splashes into the ammoniacal liquor and 1% ammonium carbonate of 10% (weight) down fast, and precipitation process was finished in 15 minutes, precipitation terminal point PH=10.0.Filter cake after filtration distilled water washed twice, 100 milliliters of each distilled water consumptions.With 1.9 gram NaNO
3Be dissolved in 100 ml distilled waters, with above filter cake and NaNO
3Solution is mixed, and heating also evenly is stirred to pasty state, 120 ℃ dry 24 hours down, moved in the muffle furnace calcination then 10 hours, 680 ℃ of furnace temperature.With catalyst breakage, sieve is got 20-60 mesh sieve branch, and appreciation condition is identical with example 1, yield of ethene 30.6%, and ethane conversion 43.5% generates ethylene selectivity 70.4%.
Example 4: with 18.5 gram La (NO
3)
36H
2O is dissolved in 200 ml distilled waters, under agitation adds Ca (OH)
2Powder 18.5 grams, terminal point PH=12.5 filters and obtains filter cake, with 2.2 gram KNO
3Be dissolved in 100 ml distilled waters, with this KNO
3Solution is mixed with the filter cake that obtains, and heating also evenly is stirred to pasty state, 120 ℃ dry 24 hours down, moved in the muffle furnace calcination then 10 hours, 680 ℃ of furnace temperature.With catalyst breakage, sieve is got 20-60 mesh sieve branch, is on 1 milliliter the flow-type constant temperature fixed bed in the catalyst loading amount, in 600 ℃ of reaction temperatures, and ethane air speed 300 hours
-1Condition under estimate, obtain yield of ethene 22.9%, ethane conversion 28.4% generates ethylene selectivity 80.5%.
Example 5: take by weighing 1.9 gram LiNO
3With 23.3 gram La (NO
3)
36H
2O is dissolved in 20 ml distilled waters, pours the MgO powder of 10.8 grams that weigh up into, after stirring, places 16 hours, 120 ℃ of oven dry down, and is interrupted and stirs, and moves to then in the muffle furnace 640 ℃ of following calcinations 10 hours.Sieve is got 20-60 purpose catalyst and is estimated, and the appreciation condition of catalyst is with example 4.Yield of ethene 20.0%, ethane conversion 26.7% generates ethylene selectivity 74.9%.
Example 6: take by weighing 2.3 gram LiNO
3Be dissolved in 20 ml distilled waters, the 8.5 gram BeO powder that example goes into to weigh up after stirring, were placed 10 hours, 120 ℃ of oven dry down, and were interrupted and stirred.Move to then in the muffle furnace 600 ℃ of following calcinations 3 hours.With 29.3 gram La (NO
3)
36H
2O is dissolved in 20 ml distilled waters, and example is gone into the above-mentioned sample that is cooled to room temperature and flooded it.After stirring, placed 10 hours,, and be interrupted and stir 120 ℃ of oven dry down.Sample is moved in the muffle furnace 660 ℃ of following calcinations 10 hours, and sieve is got 20-60 purpose catalyst and is estimated, and the appreciation condition of catalyst is with example 4, yield of ethene 19.3%, and ethane conversion 27.4% generates ethylene selectivity 70.6%.
Example 7: take by weighing 16.7 gram Cu (NO
3)
23H
2O is dissolved in 20 ml distilled waters, pours the 14.0 gram MgO powder that weigh up into, after stirring, places 10 hours, 120 ℃ of oven dry down, and is interrupted and stirs.Move in the muffle furnace 600 ℃ of following calcinations 4 hours.With 2.4 gram LiNO
3Be dissolved in 20 ml distilled waters, pour the above-mentioned sample that is cooled to room temperature into and flood it.After stirring, placed 10 hours,, and be interrupted and stir 120 ℃ of oven dry down.Sample is moved in the muffle furnace 660 ℃ of following calcinations 10 hours.Sieve is got 20-60 purpose catalyst and is estimated 600 ℃ of reaction temperatures, ethane air speed 150 hours
-1, obtaining yield of ethene 24.0%, ethane conversion 30.6% generates ethylene selectivity 78.4%.
Example 8: take by weighing 4.6 gram LiNO
3With 53.9 gram Fe (NO
3)
39H
2) be dissolved in 20 ml distilled waters, the 8.3 gram BeO powder that example goes into to weigh up after stirring, were placed 16 hours, 120 ℃ of oven dry down, and were interrupted and stirred.Move in the muffle furnace 660 ℃ of following calcinations 10 hours.Sieve is got 20-60 purpose catalyst and is estimated, and appreciation condition obtains yield of ethene 27.4% with example 7, and ethane conversion 37.8% generates ethylene selectivity 72.6%.
Example 9: take by weighing 25.0 gram Bi (NO
3)
35H
2O and 30.4 gram Ca (NO
3)
24H
2O is dissolved in 200 milliliters the acid solution (claiming to release preparation by salpeter solution), stirs the mixed solution (10: 1) that splashes into the ammoniacal liquor and 5% ammonium carbonate of 10% (weight) down fast, and precipitation process was finished in 20 minutes, precipitation terminal point PH=10.5.Filter cake after filtration distilled water washed twice, 100 milliliters of each distilled water consumptions.With 2.2 gram NaNO
3Be dissolved in 100 ml distilled waters, with above-mentioned filter cake and NaNO
3Solution is mixed, and heating also evenly is stirred to pasty state, 120 ℃ dry 24 hours down, moved in the muffle furnace calcination then 10 hours, 680 ℃ of furnace temperature.With catalyst breakage, sieve is got 20-60 mesh sieve branch, estimates at 600 ℃ ethane air speed 150 hours
-1Under carry out, obtain yield of ethene 21.2%, ethane conversion 30.9% generates ethylene selectivity 68.6%.
Example 10: take by weighing 13.8 gram Zn (NO
3)
26H
2O and 50.7 gram (CaCl
26H
2O is dissolved in 200 ml distilled waters, splashes into 10% ammoniacal liquor (weight) solution under stirring fast, and precipitation process was finished in 20 minutes, terminal point PH=9.0.Filter cake after filtration distilled water washed twice, 100 milliliters of each distilled water consumptions.With 3.8 gram Cs
2CO
3Be dissolved in 100 ml distilled waters, with above-mentioned filter cake and Cs
2CO
3Solution is mixed, and heating also evenly is stirred to pasty state, 120 ℃ dry 24 hours down, moved in the muffle furnace calcination then 10 hours, 660 ℃ of furnace temperature.With catalyst breakage, sieve is got 20-60 mesh sieve branch, and the evaluating catalyst condition is with example 9.Obtain yield of ethene 52.9%, ethane conversion 58.4% generates ethylene selectivity 90.6%.
Example 11: take by weighing 17.6 gram Ni (NO
3)
26H
2O, 38.8 gram Mg (NO
3)
26H
2O and 35.7 gram Ca (NO
3)
24H
2O is dissolved in 200 ml distilled waters.Splash into 10% LiOH solution of preparation under stirring fast, precipitation process was finished in 30 minutes, and terminal point PH=12.0 filters.With 2.5 gram LiOHH
2O is dissolved in 100 ml distilled waters, and is mixed with above-mentioned filter cake then, evenly is being heated to pasty state under constantly stirring, 120 ℃ dry 24 hours down, moved in the muffle furnace calcination then 10 hours, 660 ℃ of furnace temperature.With catalyst breakage, sieve is got 20-60 mesh sieve branch, and the evaluating catalyst condition is with example 9.Obtain yield of ethene 41.2%, ethane conversion 46.9% generates ethylene selectivity 87.8%.
Example 12: take by weighing 0.3 gram LiNO
3, 2.5 gram Ni (NO
3)
26H
2O and 11.2 gram Ca (NO
3)
24H
2O is dissolved in 20 ml distilled waters.Take by weighing 10 gram 40-60 purpose silica gel beads and put into above-mentioned solution, stir, placed 16 hours, dry under 120 ℃ then, and be interrupted and stir.Moved in the muffle furnace calcination then 10 hours, 660 ℃ of furnace temperature.Evaluating catalyst under 620 ℃, ethane air speed 300 hours
-1Under carry out, obtain yield of ethene 20.2%, ethane conversion 34.8% generates ethylene selectivity 58.1%.
Example 13: take by weighing 0.3 gram LiNO
3, 2.5 gram Ni (NO
3)
26H
2O and 11.2 gram Ca (NO
3)
24H
2O is dissolved in 20 ml distilled waters.Take by weighing 10 gram 40-60 purpose γ-Al
2O
3Put into above-mentioned solution, stir, placed 16 hours, then 240～260 ℃ of bakings down, and interruption is stirred to till the oven dry.Moved in the muffle furnace calcination then 10 hours, 660 ℃ of furnace temperature.The evaluating catalyst condition obtains yield of ethene 29.4% with example 12, and ethane conversion 43.0% generates ethylene selectivity 68.4%.
Example 14: take by weighing 1.0 gram KNO
3, 8.3 gram Fe (NO
3)
39H
2O and 13.2 gram Mg (NO
3)
26H
2O is dissolved in 25 ml distilled waters.Take by weighing 16 gram ZrO
2Powder and above-mentioned solution are mixed, stir the back and place 10 hours.Heating and constantly be stirred to pasty state then, 120 ℃ dry 24 hours down, moved in the muffle furnace calcination then 10 hours, 660 ℃ of furnace temperature.With catalyst breakage, sieve is got 20-60 mesh sieve branch, and appreciation condition obtains yield of ethene 41.9% with example 12, and ethane conversion 58.4% generates ethylene selectivity 71.7%.
Aforesaid various embodiments of the present invention also can adopt the implementer to think that mass unit reaches relevant other unit easily.Key is that correlation and the manufacture craft process between the material meets condition of the present invention.
Claims (3)
1, a kind of catalyst that is used for making ethylene from ethane oxidative dehydrogenation is characterized in that the composite oxide catalysts general formula is: XzYbZcOd or XzYbZcOd/ carrier, and X is selected from Li in (1) formula, Na, K, Rb, at least a among the Cs, (2) Y is selected from La, Zr, Cr, Mo, W, Mn, Fe, Co, Ni, Pt, Pd, Cu, Zn, Cd, Zl, Pb, at least a among the Sn, (3) Z is selected from Be, Mg, at least a among the Ca, (4) catalyst-supporting support SiO
2, γ-or η-Al
2O
3, TiO
2Or ZrO
2, wherein: a: b is 0.0～5.0, and a: b is 0.0～0.5, and the total load amount of the active constituent of supported catalyst accounts for 2%～50% of gross weight.
2, catalyst as claimed in claim 1 is characterized in that a: b is 0.1～3.0, and a: c is 0.1～0.3.
3, a kind of process with making ethylene from ethane oxidative dehydrogenation, it is characterized in that this process be included in make under 300～650 ℃ ethane with oxygen in the presence of with claim 1-2 in arbitrary described catalyst contact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116060A CN1052431C (en) | 1994-09-12 | 1994-09-12 | Catalyst for preparing ethylene by oxidation and dehydrogenation of ethane and process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116060A CN1052431C (en) | 1994-09-12 | 1994-09-12 | Catalyst for preparing ethylene by oxidation and dehydrogenation of ethane and process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1121844A true CN1121844A (en) | 1996-05-08 |
| CN1052431C CN1052431C (en) | 2000-05-17 |
Family
ID=5037773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116060A Expired - Fee Related CN1052431C (en) | 1994-09-12 | 1994-09-12 | Catalyst for preparing ethylene by oxidation and dehydrogenation of ethane and process thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086820A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Light olefin production method |
| CN104487165A (en) * | 2012-07-26 | 2015-04-01 | 沙特基础工业公司 | Alkane dehydrogenation catalyst and process for its preparation |
| CN105408291A (en) * | 2013-03-04 | 2016-03-16 | 诺瓦化学品(国际)股份有限公司 | Complex comprising oxidative dehydrogenation unit |
| CN109843434A (en) * | 2016-10-18 | 2019-06-04 | 诺瓦化学品(国际)股份有限公司 | Use the method for hydro-thermal process and peroxide treatment production Oxydehydrogenation catalyst |
| CN112717920A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | N-butane dehydrogenation catalyst and preparation method thereof |
| CN114632523A (en) * | 2022-04-25 | 2022-06-17 | 西南化工研究设计院有限公司 | Catalyst for preparing olefin by alkane chemical chain dehydrogenation and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956189A (en) * | 1972-02-14 | 1976-05-11 | Chemical Construction Corporation | Catalyst for treating combustion exhaust gas |
| US4331566A (en) * | 1978-05-04 | 1982-05-25 | Phillips Petroleum Company | Catalyst for hydrodealkylation process |
| US4191844A (en) * | 1978-05-04 | 1980-03-04 | Phillips Petroleum Company | Hydrodealkylation process and catalyst |
| US4410752A (en) * | 1980-07-10 | 1983-10-18 | The Standard Oil Company | Process for the oxydehydrogenation of ethane to ethylene |
| US4368346A (en) * | 1980-08-26 | 1983-01-11 | Phillips Petroleum Company | Oxidative dehydrogenation of paraffins with a promoted cobalt catalyst |
| US4524236A (en) * | 1984-06-28 | 1985-06-18 | Union Carbide Corporation | Process for oxydehydrogenation of ethane to ethylene |
| US5079203A (en) * | 1990-05-25 | 1992-01-07 | Board Of Trustees Operating Michigan State University | Polyoxometalate intercalated layered double hydroxides |
| CN1064907A (en) * | 1992-04-07 | 1992-09-30 | 四川省交通厅公路规划勘察设计院 | Wire-mesh cement thin-walled box-girder |
-
1994
- 1994-09-12 CN CN94116060A patent/CN1052431C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086820A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Light olefin production method |
| CN103086820B (en) * | 2011-10-28 | 2015-03-11 | 中国石油化工股份有限公司 | Light olefin production method |
| CN104487165A (en) * | 2012-07-26 | 2015-04-01 | 沙特基础工业公司 | Alkane dehydrogenation catalyst and process for its preparation |
| CN105408291A (en) * | 2013-03-04 | 2016-03-16 | 诺瓦化学品(国际)股份有限公司 | Complex comprising oxidative dehydrogenation unit |
| CN105408291B (en) * | 2013-03-04 | 2018-12-14 | 诺瓦化学品(国际)股份有限公司 | Synthesis including oxidative dehydrogenation unit |
| CN109843434A (en) * | 2016-10-18 | 2019-06-04 | 诺瓦化学品(国际)股份有限公司 | Use the method for hydro-thermal process and peroxide treatment production Oxydehydrogenation catalyst |
| CN109843434B (en) * | 2016-10-18 | 2022-02-11 | 诺瓦化学品(国际)股份有限公司 | Method for producing oxidative dehydrogenation catalysts using hydrothermal treatment and peroxide treatment |
| CN112717920A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | N-butane dehydrogenation catalyst and preparation method thereof |
| CN114632523A (en) * | 2022-04-25 | 2022-06-17 | 西南化工研究设计院有限公司 | Catalyst for preparing olefin by alkane chemical chain dehydrogenation and preparation method thereof |
| CN114632523B (en) * | 2022-04-25 | 2023-08-25 | 西南化工研究设计院有限公司 | Catalyst for preparing olefin by dehydrogenation of alkane chemical chains and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1052431C (en) | 2000-05-17 |
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