CN87101513A - Dehydrogen of saturated hydrocarbon platinum, tin, lithium, sulfur catalyst - Google Patents
Dehydrogen of saturated hydrocarbon platinum, tin, lithium, sulfur catalyst Download PDFInfo
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- CN87101513A CN87101513A CN87101513.7A CN87101513A CN87101513A CN 87101513 A CN87101513 A CN 87101513A CN 87101513 A CN87101513 A CN 87101513A CN 87101513 A CN87101513 A CN 87101513A
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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
Dehydrogen of saturated hydrocarbon is made up of platinum, tin, lithium, sulphur/r-aluminium sesquioxide with platinum, tin, lithium, sulfur catalyst.The diplopore distribution macropore r-Al that the present invention adopts high temperature to become the glue method to make
2O
3Be carrier; Platinum, tin complex are solvent with the aqueous ethanolic solution, the preparation method that platinum, tin, lithium soak altogether; After roasting, carry out the wet method method for pre-sulphuration and introduce the sulphur component with sulfide; And technology such as control moisture content etc. in the reduction process, prepared efficient dehydrogenation catalyst.Compare with the catalyzer of the same type of present industrial employing and to have better stability.Therefore can obtain good economic benefit by improving per pass conversion.
Description
The present invention be a kind of be used for saturated hydrocarbons as
Alkane, the dehydrogenation of alkylaromatic hydrocarbon is applicable to that particularly dehydrogenation of long-chain alkane produces the Catalysts and its preparation method of monoolefine.
Long-chain n-praaffin in the petroleum cuts is produced synthetic detergent raw material alkylbenzene or high fatty alcohol is a new technological line that grows up sixties end through dehydrogenation.The seventies has carried out industrial production.The reaction catalyst system therefor is (as U.S. Pat 3,293,319; US3,998,900; US4,374,046; US4,396,500; English Patent GB1,499,297; And the catalyzer of German patent DE 2,723,246 grades reports) mostly with platinum as active constituent, with arsenic, selenium, germanium, tin, lead, rhenium, iridium, tungsten, nickel, cobalt etc. as second and third component; And be added with basic metal or alkaline-earth metal is an auxiliary agent.Technology such as the US3 the most approaching with the present invention, the technology that 998,900 patents provide is: the carrier of catalyzer adopts the pore distribution concentration of oil column balling-up preparation in intermediate pore size, the γ-Al of high surface area
2O
3, the bead bulk density is 0.3～0.7 grams per milliliter, mean pore size 20～300
0.1～1 milliliter/gram of pore volume, 100～500 meters of surface-area
2/ gram, catalyzer consist of platinum, tin, lithium.Preparation of catalysts is to be steeping fluid with platinum, tin complex acidic aqueous solution.Soak platinum, tin earlier, soak lithium after the processing again, platinum is metallic state after the catalyst reduction, and tin is oxidation state.Before catalyzer uses in reactor the gas mixture with hydrogen sulfide and hydrogen vulcanize.The main drawback of this class catalyzer is a poor stability, and the life-span is shorter.
The objective of the invention is to prepare a kind of dehydrogen of saturated hydrocarbon, especially for long-chain C
10～C
13Normal paraffin dehydrogenation is produced the catalyzer of monoolefine, and catalyzer not only has selectivity and activity preferably, and has advantages of higher stability, thereby can improve prolonged operation under the per pass conversion situation.
Platinum of the present invention, tin, lithium, sulphur/γ-Al
2O
3Catalyzer as active constituent, is modulation agent with tin, lithium, sulphur with platinum, and the carrier of catalyzer adopts high temperature to become the glue preparation, has the wide aperture of diplopore distribution, the γ-Al of low bulk density
2O
3Bead, the weight percent that catalyzer is formed is: platinum 0.2～0.8%; Tin 0.4～1.2%; Lithium (or potassium) 0.1～1.5%; All the other are γ-Al for sulphur 0.05～0.5%
2O
3For improving the performance of catalyzer, the proportioning that should allocate certain activity component and auxiliary agent.Catalyzer platinum of the present invention, tin metal atomic ratio are 1: 1.5～1: 4, and it is best than 1: 3.
One of reason that the catalyst life that industry is at present adopted is short is a catalyst surface carbon distribution under reaction conditions.For improving the stability of catalyzer, support of the catalyst of the present invention is to become the glue legal system to get γ-Al with high temperature
2O
3Bead is after the steam-treated reaming, and Preparation of Catalyst adopts platinum tin complexing location, and platinum, tin, lithium soak technology altogether.
In addition, the sulfuration of catalyzer is to carry out sulfidizing with hydrogen sulfide and hydrogen mixed gas after reduction usually, and its purpose is to suppress the initial stage cracking performance of catalyzer in order to long-term stability.Effect is different therewith, and method of the present invention is to introduce the sulphur component with the wet method prevulcanized before reduction, has promoted activity of such catalysts and stability.Can save simultaneously sulfurized step in the reactor again.Make catalyzer at high temperature have strong adsorptive power like this, help under reaction conditions, suppressing the formation of carbon distribution hydrogen.
The Preparation of catalysts process is
One, the preparation of carrier
High temperature becomes the glue legal system to be equipped with γ-Al
2O
3The process of carrier is with the certain density aluminum chloride aqueous solution and the certain amount of ammonia water generation aluminium hydroxide gel that neutralizes under 60～80 ℃ of temperature, filter then, wash, filter cake is through balling-up in oil ammonia column after the acidifying, wet bulb is through washing, carry out roasting and steam-treated after the drying, under 600～800 ℃ of conditions, carry out the water vapor reaming at last and handle.Its physico-chemical property of gained carrier is bulk density 0.28～0.39 grams per milliliter, 100～160 meters of specific surface areas
2/ gram, total pore volume is greater than 1.0 milliliters/gram, and mean pore size is greater than 200
, 1.25～2.2 millimeters of particle diameter φ, 0.8～1.2 kilogram of average grain pressure.
Two, the preparation of complexing location impregnated catalyst
1. platinum salt and tin protochloride add lithium salts after forming complex compound;
2. above-mentioned mixed solution is dissolved in the alcoholic acid aqueous hydrochloric acid and makes steeping fluid;
3. " 2 " steeping fluid is immersed in the γ-Al that makes
2O
3On the carrier, roasting and steam-treated are carried out in 400～600 ℃ in dry back, and airborne vapour content is 10～35%.
4. the catalyzer after above-mentioned processing vulcanizes with wet method, and vulcanizing agent can be sulfide such as ammonium sulfide, potassium sulphide, sodium sulphite etc., and the sample after the sulfuration is dry in baking oven, finished catalyst.
Dipping solution is with 5～60% ethanolic soln in the above-mentioned catalyst preparation process, and the most handy 30～50% ethanol is made solvent.
Before catalyzer uses in reactor (or outer) reduce under 400～600 ℃ of temperature with moisture hydrogen less than 20ppm, export and keep below the moisture 1000ppm.Catalyzer after the reduction can be used for the dehydrogen of saturated hydrocarbon reaction, as C
3～C
30Alkane or alkyl aromatics dehydrogenation.
Embodiment 1:
Carrier γ-Al
2O
3Preparation
With concentration be/100 milliliters of 4 grams aluminum chloride with contain 6%(weight) ammoniacal liquor add by calculated amount, under 60～80 ℃ of temperature, in neutralization tank, mix control PH 7.5～8.5; Generating aluminium glue filters, washes, filter cake is with the nitric acid acidifying, slurries balling-up under pressure that acidifying is good, bead after wearing out in becoming goalpost is through water rinse, in 120～130 ℃ of oven dryings, gained aluminium hydroxide bead is 600～700 ℃ of roastings in activation furnace, and 0.5～10 water vapor reaming was by volume handled more than 10 hours, sifted out γ-Al of 1.25～2.2 millimeters of φ after the cooling
2O
3Bead gets carrier.
Embodiment 2:
Preparation of catalysts
Get carrier 1000 grams that example 1 makes and place steeping cell.Get 375 milliliters of the chloroplatinic acid aqueous solutions of platiniferous 0.01 grams per milliliter simultaneously; Contain 114 milliliters of 37% concentrated hydrochloric acids; 272 milliliters of the tin protochloride aqueous solution of stanniferous 0.025 grams per milliliter; 96 milliliters of the lithium nitrate aqueous solution that contain lithium 0.05 grams per milliliter.With 40% aqueous ethanolic solution is solvent, and above-mentioned solution is added mixing in the steeping cell successively.Flood even after drying, bead is in stoving oven during with air velocity 1500 then
-1, be warming up to 480～500 ℃, this roasting temperature 4 hours, again under same temperature with the air handling of moisture vapor 30% 4 hours, stop water vapor then and lower the temperature with dry air.With sulphur content is that 0.5% ammonium sulfide solution is made steeping fluid for 400 milliliters, above-mentioned baked catalyzer is carried out prevulcanized handle after-filtration, 120 ℃ of dryings 4 hours.With moisture hydrogen less than 20ppm reductase 12 hour under 480 ℃ of temperature, the catalyzer that gets product (A), its composition (weight %) are platinum 0.375%, tin 0.68%, lithium 0.48%, sulphur 0.2% again.
Embodiment 3:
Get carrier 1000 grams that example 1 makes and place rotary steeping cell, get 375 milliliters of the chloroplatinic acid aqueous solutions of platiniferous 0.01 grams per milliliter simultaneously; Contain 114 milliliters of 37% concentrated hydrochloric acids; 90 milliliters of the tin protochloride aqueous solution of stanniferous 0.05 grams per milliliter; 96 milliliters of the aqueous solution that contain lithium 0.05 grams per milliliter are by example 2 described methods preparations, gained catalyzer (B) (weight %) platiniferous 0.28%, tin 0.45%, lithium 0.48%.
Embodiment 4:
Get carrier 1000 grams that example 1 makes and place the rotary dipping device, get 375 milliliters of the chloroplatinic acid aqueous solutions of platiniferous 0.02 grams per milliliter simultaneously; Contain 114 milliliters of 37% concentrated hydrochloric acids; 200 milliliters of the tin protochloride aqueous solution of stanniferous 0.05 grams per milliliter; Get 300 milliliters of the saltpetre aqueous solution that contain potassium 0.05 grams per milliliter, be prepared gained catalyzer (C) (weight %) platiniferous 0.75%, tin 1.0%, potassium 1.5%, sulphur 0.2% by the method for example 2.
Embodiment 5:
Be on 3 milliliters the fixed-bed flow reactor in the catalyzer loading amount, take to accelerate the stability of aging method evaluation catalyzer, with through the positive structure C of hydrofining sulfur-bearing less than 1ppm
10～C
13The carbon alkane fraction is that raw material is in 2 kilograms per centimeter
2(gauge pressure) is during liquid hourly space velocity 30
-1, hydrogen-hydrocarbon ratio 6: the 1(mol ratio), react under the condition that the reactor wall temperature is 450～452 ℃, by generating the selectivity that oily product compositional analysis calculates the transformation efficiency of normal paraffin and generates monoolefine.Improve temperature to 480 ℃, system pressure 1.0 kilograms per centimeter then
2(gauge pressure), liquid hourly space velocity transferred to 20 o'clock
-1Hydrogen hydrocarbon mol ratio 5: 1,90 hours reaction times, generating oily bromine valency descends gradually by 21～23, its fall is represented the stability of catalyzer, the results are shown in table 1, listing in table 2, have very high activity, selectivity and stability by the visible catalyzer of the present invention of the data of table 1, table 2 near the operation result under the industrial condition.
Table 1 is at Pt-Sn-Li-S/ γ-Al
2O
3Long-chain n-praaffin on the catalyzer
The dehydrogenation reaction performance
| Catalyzer | （A） | （B） |
| Catalyzer is formed heavy %Pt Sn Li S | 0.375 0.68 0.48 0.20 | 0.28 0.45 0.48 0.20 |
| Initial performance: transformation efficiency % selectivity % | 10.2 92 | 10.0 91 |
| Stability, bromine valency: latter stage mid-term at initial stage | 22.3 17.2 14.5 | 22.1 17.0 14.2 |
Annotate: the data in 1 hour initial stage, 45 hours mid-terms, 90 hours latter stages.
Table 2 long-chain n-praaffin continuous operation result
Catalyzer (A) (A)
3 milliliters 1 liter of catalyzer Intake Quantity
During liquid hourly space velocity
-130 28-32
Initial reaction temperature ℃ 453 452
Generate oily bromine valency 8.8-9.0 8.8-9.9
Transformation efficiency % 9.7-10.0 9.7-10.4
Selectivity % 90-92 90-92
The running cumulative time (hour)＞1504＞1504
Temperature when running finishes (℃) 458 458
Catalyst performance situation mid-term in mid-term
The thick alkylbenzene of throughput (ton)/per kilogram catalyzer＞12＞12
Annotate: reaction pressure 2.0 kilograms per centimeter
2(gauge pressure), hydrogen hydrocarbon mol ratio 8: 1.
Embodiment 6:
Vulcanization process is to the influence of catalyzer dehydrogenation
Catalyzer composition and method for making and embodiment 2 are the Pt-Sn-Li/ γ-Al after the roasting together
2O
3Oxide compound is handled without the wet method prevulcanized, but in reactor (or outside) vulcanize with the gas mixture with hydrogen sulfide and hydrogen behind the clean hydrogen reducing, make catalyst A-1, estimate contrast by the reaction conditions of example 5, result such as table 3.
Table 3 vulcanization process is to Pt-Sn-Li/ γ-Al
2O
3The influence of dehydrogenation
Vulcanization process initial performance stability (bromine valency)
Transformation efficiency % selectivity % latter stage mid-term at initial stage
Wet method prevulcanized 10.1 92 22.1 17.3 14.7
Reduction postcure 9.8 91 20.2 14.5 12.8
Embodiment 7:
Catalyst-assembly is 1.0 milliliters in the continuous fixed bed reaction or continuous device, is that raw material (containing normal butane＞99% weight) and technical grade ethylbenzene are raw material (containing ethylbenzene 99.5% weight) with the technical grade normal butane, shown in reaction conditions under operation result list in table 4.According to gas chromatographic analysis data computation transformation efficiency that is connected on the reactive system rear portion and generation purpose product selectivity.
The present invention is used for dehydrogen of saturated hydrocarbon, and particularly dehydrogenation of long-chain alkane is produced platinum, tin, lithium, the sulfur catalyst of monoolefine, owing to adopt special process to handle the diplopore distribution macropore that obtains, and the γ-Al of low bulk density
2O
3Bead is a carrier and with complexing location dipping technology of preparing and wet method prevulcanized treatment technology, thus catalyzer to hydrocarbon dehydrogenation reaction active and selectivity height, compare with the catalyzer of the same type that present industry is adopted, catalyzer has better to be stablized
The dehydrogenation reaction performance of table 4 normal butane and ethylbenzene
Raw material normal butane ethylbenzene
Catalyst A C
Reaction conditions
The pressure kilograms per centimeter
2(table) 0.5 1.0
Temperature ℃ 540 560
During liquid hourly space velocity
-14.0 32.0
Hydrogen hydrocarbon mol ratio 38
Transformation efficiency % 40＞85
*
Selectivity % 87.3 95
*Finger is to equilibrium conversion
The property, under the situation of identical running period, can improve the one-pass yield of reaction, reduce production costs.
Claims (6)
1, a kind of platinum, tin, lithium, sulphur/aluminium oxide catalyst that is used for the dehydrogen of saturated hydrocarbon reaction the invention is characterized in that carrier is that (mean pore size is greater than 200 in diplopore distribution wide aperture
, total pore volume is greater than 1.0 milliliters/gram), the r-Al of low bulk density (bulk density 0.28～0.39 grams per milliliter)
2O
3, the sulphur in the catalyzer adds with the wet method method for pre-sulphuration, and the composition weight percent of catalyzer is: platinum 0.2～0.8%; Tin 0.4～1.2%, lithium (or potassium) 0.1～1.5%; Sulphur 0.05～0.5%, all the other are γ-Al
2O
3
2, according to the described catalyzer of claim 1, it is characterized in that platinum tin metal content atomic ratio is 1: 1.5～1: 4 in the catalyzer, it is best than being 1: 3.
3,, press following particular step according to the described Preparation of catalysts method of claim 1:
One, the preparation of carrier:
γ-Al that high temperature becomes the glue method to make
2O
3Carry out roasting and steam-treated at 600～800 ℃.
Two, Preparation of Catalyst:
(1) platinum salt mixes the back and adds lithium salts with tin protochloride;
(2) above-mentioned mixing solutions is dissolved in the alcoholic acid aqueous hydrochloric acid makes steeping fluid;
(3) γ-Al that " (2) " steeping fluid dipping "-" was handled
2O
3On the carrier, roasting and steam-treated are carried out in 400～600 ℃ in dry back, and the water in air steam content is 10～35%;
(4) " (3) " product is carried out the wet method sulfuration with sulfide, vulcanizing agent can be ammonium sulfide, potassium sulphide, sodium sulphite etc., makes finished catalyst after the samples dried after the sulfuration.
4, according to the described Preparation of catalysts method of claim 4, the concentration that it is characterized in that aqueous ethanolic solution is 5～65%, and preferable concentration is 30～50%(weight).
5, according to the described catalyzer of claim 1, it is characterized in that catalyzer is moisture less than 20ppm to enter the mouth in reactor or outside the reactor before using, export moisture hydrogen and under 400～600 ℃, reduce less than 1000ppm.
6,, it is characterized in that this catalyzer is more suitable for positive structure C according to the described catalyzer that is used for hydrocarbon dehydrogenation reaction of claim 1
10～C
13The dehydrogenation reaction of alkane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101513A CN1013361B (en) | 1987-03-13 | 1987-03-13 | Catalyst containing pt, sn, li, s for dehydrogenation of saturated hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101513A CN1013361B (en) | 1987-03-13 | 1987-03-13 | Catalyst containing pt, sn, li, s for dehydrogenation of saturated hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101513A true CN87101513A (en) | 1988-10-12 |
| CN1013361B CN1013361B (en) | 1991-07-31 |
Family
ID=4813487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87101513A Expired CN1013361B (en) | 1987-03-13 | 1987-03-13 | Catalyst containing pt, sn, li, s for dehydrogenation of saturated hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013361B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358920A (en) * | 1992-12-21 | 1994-10-25 | China Petro-Chemical Corporation | Dehydrogenating catalyst for saturate hydrocarbons |
| CN1040846C (en) * | 1993-05-11 | 1998-11-25 | 中国石油化工总公司 | Method for preparation of superstrong acid of carried oxide system |
| CN1069226C (en) * | 1996-01-24 | 2001-08-08 | 中国科学院大连化学物理研究所 | Preparation of low carbon alkane dehydrogenating catalyst |
| CN1081081C (en) * | 1994-11-29 | 2002-03-20 | 底古萨股份公司 | Dehydrogenationc atalyst for C6-15 Chain Alkane |
| CN1086150C (en) * | 1996-12-24 | 2002-06-12 | 中国科学院兰州化学物理研究所 | Catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and procedure thereof |
| CN103962147A (en) * | 2014-05-13 | 2014-08-06 | 山东金诚重油化工技术研究院 | Heavy fraction oil hydro-refined catalyst as well as preparation method and application thereof |
| CN104105546A (en) * | 2011-11-21 | 2014-10-15 | 信实工业公司 | Catalyst composite for dehydrogenation of hydrocarbons and method of preparation thereof |
| CN105142785A (en) * | 2013-03-15 | 2015-12-09 | 沙特基础工业公司 | Method for manufacture of an alkane dehydrogenation catalyst |
| CN104588042B (en) * | 2013-11-01 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of preparation method of vulcanization type propane dehydrogenation catalyst |
| CN108371950A (en) * | 2017-01-30 | 2018-08-07 | 通用汽车环球科技运作有限责任公司 | Highly stable platinum group metal（PGM）Catalyst system |
| CN108722403A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108722402A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109675567A (en) * | 2019-01-05 | 2019-04-26 | 丹东明珠特种树脂有限公司 | Gasoline hydrodesulfurizationmethod refining catalytic agent carrier, catalyst, preparation method and hydrodesulfurizationprocess process |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
| WO2021068934A1 (en) * | 2019-10-11 | 2021-04-15 | 高化学株式会社 | Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof |
| US11951465B2 (en) | 2017-01-05 | 2024-04-09 | GM Global Technology Operations LLC | Solution-based approach to make porous coatings for sinter-resistant catalysts |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2758478B1 (en) * | 1997-01-21 | 1999-02-26 | Elf Aquitaine | PROCESS FOR THE PRESULFURIZATION OF CATALYSTS |
-
1987
- 1987-03-13 CN CN87101513A patent/CN1013361B/en not_active Expired
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358920A (en) * | 1992-12-21 | 1994-10-25 | China Petro-Chemical Corporation | Dehydrogenating catalyst for saturate hydrocarbons |
| CN1040846C (en) * | 1993-05-11 | 1998-11-25 | 中国石油化工总公司 | Method for preparation of superstrong acid of carried oxide system |
| CN1081081C (en) * | 1994-11-29 | 2002-03-20 | 底古萨股份公司 | Dehydrogenationc atalyst for C6-15 Chain Alkane |
| CN1069226C (en) * | 1996-01-24 | 2001-08-08 | 中国科学院大连化学物理研究所 | Preparation of low carbon alkane dehydrogenating catalyst |
| CN1086150C (en) * | 1996-12-24 | 2002-06-12 | 中国科学院兰州化学物理研究所 | Catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and procedure thereof |
| CN104105546A (en) * | 2011-11-21 | 2014-10-15 | 信实工业公司 | Catalyst composite for dehydrogenation of hydrocarbons and method of preparation thereof |
| US9452421B2 (en) | 2013-03-15 | 2016-09-27 | Saudi Basic Indutries Corporation | Method for manufacture of an alkane dehydrogenation catalyst |
| CN105142785A (en) * | 2013-03-15 | 2015-12-09 | 沙特基础工业公司 | Method for manufacture of an alkane dehydrogenation catalyst |
| CN105142785B (en) * | 2013-03-15 | 2017-10-31 | 沙特基础工业公司 | The manufacture method of alkane dehydrogenating catalyst |
| CN104588042B (en) * | 2013-11-01 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of preparation method of vulcanization type propane dehydrogenation catalyst |
| CN103962147A (en) * | 2014-05-13 | 2014-08-06 | 山东金诚重油化工技术研究院 | Heavy fraction oil hydro-refined catalyst as well as preparation method and application thereof |
| US11951465B2 (en) | 2017-01-05 | 2024-04-09 | GM Global Technology Operations LLC | Solution-based approach to make porous coatings for sinter-resistant catalysts |
| CN108371950A (en) * | 2017-01-30 | 2018-08-07 | 通用汽车环球科技运作有限责任公司 | Highly stable platinum group metal（PGM）Catalyst system |
| CN108722403A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108722402A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108722403B (en) * | 2017-04-20 | 2019-09-27 | 中国石油化工股份有限公司 | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN109675567A (en) * | 2019-01-05 | 2019-04-26 | 丹东明珠特种树脂有限公司 | Gasoline hydrodesulfurizationmethod refining catalytic agent carrier, catalyst, preparation method and hydrodesulfurizationprocess process |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
| WO2021068934A1 (en) * | 2019-10-11 | 2021-04-15 | 高化学株式会社 | Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1013361B (en) | 1991-07-31 |
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