CN105709728B - A kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin - Google Patents
A kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of propane dehydrogenation catalyst, including following process：Using aluminum oxide containing Sn as carrier, load active component Pt first, dechlorination processing is carried out to it using the inert gas containing hydroxyl organic matter after drying, roasting, processing time is 0.5h ~ 8h, preferably 1h ~ 4h, treatment temperature is 200 DEG C ~ 300 DEG C, and preferably 240 DEG C ~ 280 DEG C, processing pressure is less than 30kPa（Gauge pressure）, mixed gas air speed is 200h‑1~2000h‑1, the volumetric concentration of hydroxyl organic matter is 10v% ~ 60v%, final load auxiliary agent K in inert gas, then through drying, roasting, obtains described propane dehydrogenation catalyst.This method can avoid destruction of the vapor dechlorination to catalyst structure, improve the activity stability and Propylene Selectivity of catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, a kind of dehydrogenating propane system is related in particular to
The preparation method of propylene catalyst.
Background technology
The development and application of North America shale gas make Gas Prices declining to a great extent relative to crude oil price, while also cause second
The raw material lighting of alkene cracker, the yield for the byproduct propylene that oil is raw material is caused to decline to a great extent.And with oil
The increasingly scarcity of resource, the production of propylene is that raw material turns to the diversified technology path of raw material sources from the simple oil that relies on
Become, be increasingly becoming a kind of trend.By natural gas（Conventional gas, shale gas, coal bed gas, combustible ice etc.）The propane of middle by-product
It is the effective way for solving this problem to carry out dehydrogenation reaction and produce propylene.In recent years, the technology of dehydrogenating propane production propylene
Large development is achieved, has become the third-largest propylene production.
Low-carbon alkanes catalytic dehydrogenation is strong endothermic reaction, is limited by thermodynamical equilibrium, severe reaction conditions, carbon deposit and activity
Metal sintering is always the reason for influenceing catalyst activity and stability.Due to relatively low conversion of propane and harsh reaction bar
The shortening of catalyst life under part, makes PDH methods be restricted in commercial Application.Therefore, exploitation is with high activity, Gao Xuan
The catalyst for preparing propylene with propane dehydrogenation of selecting property and high stability turns into the key of the technology.Patent CN1201715, which is disclosed, to be used for
Low-carbon alkanes（C1~C5）The Pt-Sn-K/Al of dehydrogenation2O3The preparation method of catalyst.Patent CN101066532 discloses one kind and adopted
Sn is incorporated into the method for ZSM-5 molecular sieve skeleton with Hydrothermal Synthesiss, and is used for propane dehydrogenation catalyst carrier, obtained catalysis
Agent runs 100h, conversion of propane 30%, Propylene Selectivity more than 99%.CN1579616 patents provide one kind with macropore, low heap
Than, have double-pore structure γ-Al2O3Bead is carrier, for the catalyst of linear alkanes dehydrogenation, by the modulation of catalyst,
The reactivity worth of dehydrogenating low-carbon alkane can be improved.USP4,914,075 discloses propane and other dehydrogenating low-carbon alkane aluminum oxide are
The Pt base catalyst of carrier, there is high alkane conversion and olefine selective.USP6,103,103 discloses one kind with borosilicate
Hydrochlorate and alkali metal are carrier, and platinum group metal active metal, zinc is the dehydrogenation of auxiliary agent, shows preferable dehydrogenation
Energy.Although catalyst of the prior art can show certain performance under some reaction conditions, catalyst activity,
Stability, selectivity of product and preparation economy etc. tend not to take into account.In traditional technology, in order to improve catalyst
Stability and selectivity, often using the method for high-temperature vapor dechlorination after leaching Pt.But high-temperature vapor dechlorination can cause to carry
Surface area per unit volume product, the destruction of pore structure, PtSn interactions are weakened, the agglomeration of Pt particles is ultimately resulted in, reduces third
Alkane conversion ratio.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of preparation method of propane dehydrogenation catalyst.This method can
Destruction of the vapor dechlorination to catalyst structure is avoided, improves the activity stability and Propylene Selectivity of catalyst.
The preparation method of propane dehydrogenation catalyst of the present invention, including following process：Using aluminum oxide containing Sn as carrier,
Load active component Pt first, dechlorination processing is carried out to it using the inert gas containing hydroxyl organic matter after drying, roasting,
Processing time is 0.5h ~ 8h, preferably 1h ~ 4h, and treatment temperature is 200 DEG C ~ 300 DEG C, and preferably 240 DEG C ~ 280 DEG C, processing is pressed
Power is less than 30kPa（Gauge pressure）, preferably 10kPa ~ 20kPa（Gauge pressure）, mixed gas air speed is 200h-1~2000h-1, it is preferably
500h-1~1000h-1, the volumetric concentration of hydroxyl organic matter is 10v% ~ 60v%, preferably 20v% ~ 40v% in inert gas, finally
Auxiliary agent K is loaded, then through drying, roasting, obtains described propane dehydrogenation catalyst.
In the inventive method, hydroxyl organic matter can be the one or more in methanol, ethanol, propyl alcohol, isopropanol, excellent
Elect methanol, ethanol or the two mixing as.
In the inventive method, inert gas can also contain appropriate N2O gases, N2O volumetric concentration is 0.01v%-
1v%, preferably 0.1v%-0.5v%.N2O addition can significantly improve the speed of dechlorination.
The present invention relates to alumina support containing Sn, can be existing product, can also be ripe by professional and technical personnel in the field
It is prepared by the method known.Above-mentioned alumina support containing Sn can be spherical, bar shaped, microballoon or abnormity, particle equivalent diameter 0.1
~ 5mm, preferably 0.5 ~ 2mm.Carrying alumina surface area per unit volume is 200 ~ 240 m2/ g, pore volume are 0.60 ~ 0.80 cm3/g.It is above-mentioned to contain
Sn in Sn alumina supports can be introduced during aluminum oxide conclusion of the business, can also be introduced by way of load, can be with
Kneading introduces in aluminum oxide forming process.Auxiliary agent Sn predecessors can be cationic tin salt, such as nitric acid tin, butter of tin, vinegar
Sour tin etc., or stannic acid metalloid salt, such as sodium stannate, potassium stannate, preferably butter of tin.
The present invention relates to the active metal component Pt of propane dehydrogenation catalyst to be carried on carrying alumina containing Sn using infusion process
In body, loading process is method well known to those skilled in the art.Such as：First using oxidation of the aqueous solution dipping containing Sn containing Pt
Alumina supporter, preferably dip time 1h ~ 72h, 2h ~ 8h.After dipping dry, drying temperature be 60 DEG C ~ 150 DEG C, drying time be 1h ~
24h, 4h ~ 8h is dried at preferably 80 DEG C ~ 120 DEG C.Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2h ~ 24h, is preferably
4h ~ 8h is calcined at 500 DEG C ~ 700 DEG C.The above-mentioned aqueous solution containing Pt is prepared by the inorganic metal salt containing Pt, wherein described containing Pt's
Inorganic metal salt is preferably chloroplatinic acid.
The present invention relates in the preparation method of propane dehydrogenation catalyst, alkali metal promoter K carrying method is this area skill
Dipping method known to art personnel.K predecessor is soluble salt containing K, can be inorganic salts or organic salt, excellent
Elect potassium nitrate as.Maceration extract can be the aqueous solution, or organic solution.
Weight percentage is counted as 0.1%-1.0% using element the present invention relates to Pt in propane dehydrogenation catalyst, is preferably
0.4%-0.8%；Sn counts weight percentage as 0.5%-10% using element, preferably 1%-3%；K percentage compositions in terms of element wt
For 0.5%-10%, preferably 1%-3%.
In the present invention, low-temperature treatment is carried out to catalyst using the gaseous mixture of gas phase hydroxyl organic matter, utilizes halogen
The nucleophilic displacement of fluorine of hydroxyl organic matter is acted on, the halogen that effectively can be introduced in Removal of catalyst preparation process, simultaneously
Active component caused by avoiding High-temperature water heat treatment is assembled, and can also avoid the destruction to alumina support pore structure, is improved
The activity and stability of propane dehydrogenation catalyst.Method for preparing catalyst of the present invention is simple, mature technology, is advantageous to urge
The industrial production of agent.
Brief description of the drawings
Fig. 1 is the gained catalyst transmission electron microscope picture of embodiment 1.Fig. 2 is the gained catalyst transmission electron microscope picture of comparative example 3.
Embodiment
The technology of the present invention is described further below by the implementation of dehydrogenating propane.
Example 1
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Account for and urge by Pt contents
Agent 0.6wt% is counted, and the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, adds to above-mentioned sample
In, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular heater, in nitrogen
240 DEG C are warming up under atmosphere, is mixed after methanol gasifying with nitrogen, methanol concentration 30v%, is cut into heating furnace, mixed gas
Product air speed is 800h-1, control system pressure is 15kPa（Gauge pressure）, constant temperature 2h, after constant temperature terminates, near room temperature under nitrogen atmosphere.
By the sample impregnation aids K after processing, after drying and roasting, catalyst C-1 is made, the content of each component is in catalyst：Pt
0.6wt%, Sn 3.0wt%, K 1.0wt%.
Appreciation condition：Catalyst quality 3.0g, hydrogen atmosphere reduction, the mass space velocity of propane is 3h-1, reaction pressure
0.1MPa（Gauge pressure）, reaction temperature is 630 DEG C.Evaluating catalyst condition obtained by following examples is same, and evaluation result is shown in Table 1.
Example 2
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.6wt%, the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 2h, 120 DEG C of dry 4h, 8h is calcined in 500 DEG C.Sample obtained by above-mentioned steps is placed in tubular type and added
In hot stove, 260 DEG C are warming up in a nitrogen atmosphere, is mixed after methanol gasifying with nitrogen, methanol concentration 20v%, be cut into heating
In stove, gaseous mixture volume space velocity is 1000h-1, control system pressure is 20kPa（Gauge pressure）, constant temperature 4h, after constant temperature terminates, nitrogen
Near room temperature under atmosphere.By the sample impregnation aids K after processing, after drying and roasting, catalyst C-2 is made, it is each in catalyst
The content of component is：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation result is shown in Table 1.
Example 3
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.6wt%, the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 8h, 100 DEG C of dry 6h, 6h is calcined in 700 DEG C.Sample obtained by above-mentioned steps is placed in tubular type and added
In hot stove, 280 DEG C are warming up in a nitrogen atmosphere, is mixed after methanol gasifying with nitrogen, methanol concentration 40v%, be cut into heating
In stove, gaseous mixture volume space velocity is 500h-1, control system pressure is 15kPa（Gauge pressure）, constant temperature 1h, after constant temperature terminates, nitrogen gas
Near room temperature under atmosphere.By the sample impregnation aids K after processing, after drying and roasting, catalyst C-3 is made, each group in catalyst
Point content be：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation result is shown in Table 1.
Example 4
With example 3, difference mixes after being methanol gasifying with nitrogen, while is passed through N2O, make N2O volumetric concentrations are
0.2v%, is made catalyst C-4, and the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation
It the results are shown in Table 1.
Example 5
With example 3, difference mixes after being methanol gasifying with nitrogen, while is passed through N2O, make N2O volumetric concentrations are
0.4v%, is made catalyst C-5, and the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation
It the results are shown in Table 1.
Example 6
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.4wt%, the chloroplatinic acid for weighing the Pt containing 0.12g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular type heating
In stove, 240 DEG C are warming up in a nitrogen atmosphere, and methanol mixes after gasifying respectively with ethanol with nitrogen, methanol concentration 10v%, second
Determining alcohol 10v%, is cut into heating furnace, and gaseous mixture volume space velocity is 500h-1, control system pressure is 15kPa（Gauge pressure）, it is permanent
Warm 2h, after constant temperature terminates, near room temperature under nitrogen atmosphere.By the sample impregnation aids K after processing, after drying and roasting, it is made
Catalyst C-6, the content of each component is in catalyst：Pt 0.4wt%, Sn 1.0wt%, K 3.0wt%.Evaluation result is shown in Table 1.
Example 7
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.6wt%, the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular type heating
In stove, 240 DEG C are warming up in a nitrogen atmosphere, is mixed after methanol gasifying with nitrogen, methanol concentration 30v%, be cut into heating furnace
In, gaseous mixture volume space velocity is 500h-1, control system pressure is 15kPa（Gauge pressure）, constant temperature 2h, after constant temperature terminates, nitrogen atmosphere
Under near room temperature.By the sample impregnation aids K after processing, after drying and roasting, catalyst C-7 is made, each component in catalyst
Content be：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation result is shown in Table 1.
Example 8
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.6wt%, the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular type heating
In stove, 260 DEG C are warming up in a nitrogen atmosphere, is mixed after methanol gasifying with nitrogen, methanol concentration 30v%, be cut into heating furnace
In, gaseous mixture volume space velocity is 1000h-1, control system pressure is 15kPa（Gauge pressure）, constant temperature 2h, after constant temperature terminates, nitrogen gas
Near room temperature under atmosphere.By the sample impregnation aids K after processing, after drying and roasting, catalyst C-8 is made, each group in catalyst
Point content be：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation result is shown in Table 1.
Comparative example 1
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.6wt%, the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular type heating
In stove, 240 DEG C are warming up in a nitrogen atmosphere, maintain constant temperature, nitrogen volume space velocity is 800h-1, control system pressure is 15kPa
（Gauge pressure）, constant temperature 2h, after constant temperature terminates, near room temperature under nitrogen atmosphere.By the sample impregnation aids K after processing, roasted through drying
After burning, catalyst D-1 is made, the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation knot
Fruit is shown in Table 1.
Comparative example 2
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.6wt%, the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular type heating
In stove, 240 DEG C are warming up in a nitrogen atmosphere, cut vapor, vapor volume space velocity is 800h-1, control system pressure is
15kPa（Gauge pressure）, constant temperature 2h, after constant temperature terminates, near room temperature under nitrogen atmosphere.By the sample impregnation aids K after processing, through dry
After dry roasting, catalyst D-2 is made, the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Comment
Valency the results are shown in Table 1.
Comparative example 3
The alumina support 30g containing a certain amount of Sn is weighed, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.
Accounted for by Pt contents based on catalyst 0.6wt%, the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, is added
Enter into above-mentioned sample, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular type heating
In stove, 550 DEG C are warming up in a nitrogen atmosphere, cut vapor, vapor volume space velocity is 800h-1, control system pressure is
15kPa（Gauge pressure）, constant temperature 2h, after constant temperature terminates, near room temperature under nitrogen atmosphere.By the sample impregnation aids K after processing, through dry
After dry roasting, catalyst D-3 is made, the content of each component is in catalyst：Pt 0.6wt%, Sn 3.0wt%, K 1.0wt%.Comment
Valency the results are shown in Table 1.
Comparative example 4
Weigh the alumina support containing a certain amount of Sn（It is spherical, diameter 1mm, pore volume 0.73cm3/ g, specific surface area 232m2/ g,
Following examples use the carrier）30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Account for and urge by Pt contents
Agent 0.6wt% is counted, and the chloroplatinic acid for weighing the Pt containing 0.18g is dissolved in deionized water, is settled to 27mL, adds to above-mentioned sample
In, aging 4h, 80 DEG C of dry 8h, 4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps is placed in tubular heater, in nitrogen
240 DEG C are warming up under atmosphere, N2O mixes with nitrogen, wherein N2O concentration is 0.3v%, is cut into heating furnace, and gaseous mixture volume is empty
Speed is 800h-1, control system pressure is 15kPa（Gauge pressure）, constant temperature 2h, after constant temperature terminates, near room temperature under nitrogen atmosphere.Will place
Sample impregnation aids K after reason, after drying and roasting, it is made catalyst D-4, the content of each component is in catalyst：Pt
0.6wt%, Sn 3.0wt%, K 1.0wt%.Evaluation result is shown in Table 1.
The reactivity worth of the catalyst of table 1
Claims (14)
- A kind of 1. preparation method of propane dehydrogenation catalyst, it is characterised in that：Including following process：Using aluminum oxide containing Sn as load Body, first load active component Pt, it is carried out at dechlorination using the inert gas containing hydroxyl organic matter after drying, roasting Reason, processing time are 0.5h ~ 8h, and treatment temperature is 200 DEG C ~ 300 DEG C, and processing pressure is less than 30kPa, and mixed gas air speed is 200h-1~2000h-1, the volumetric concentration of hydroxyl organic matter is 10v% ~ 60v%, final load auxiliary agent K in inert gas, then through dry Dry, roasting, obtains propane dehydrogenation catalyst；Wherein, the hydroxyl organic matter is the one or more in methanol, ethanol, propyl alcohol, isopropanol.
- 2. according to the method for claim 1, it is characterised in that：Processing time is 1h ~ 4h, and treatment temperature is 240 DEG C ~ 280 DEG C, processing pressure is 10kPa ~ 20kPa, and mixed gas air speed is 500h-1~1000h-1, the body of hydroxyl organic matter in inert gas Product concentration is 20v% ~ 40v%, final load auxiliary agent K, then through drying, roasting, obtains described propane dehydrogenation catalyst.
- 3. according to the method for claim 1, it is characterised in that：Hydroxyl organic matter is methanol, ethanol or the two mixing.
- 4. according to the method for claim 1, it is characterised in that：Contain appropriate N in inert gas2O gases, N2O volume Concentration is 0.01v%-1v%.
- 5. according to the method for claim 4, it is characterised in that：N in inert gas2O volumetric concentration is 0.1v%-0.5v%.
- 6. according to the method for claim 1, it is characterised in that：Alumina support containing Sn is spherical, bar shaped, microballoon or different Shape, particle equivalent diameter are 0.1 ~ 5mm, and specific surface area is 200 ~ 240 m2/ g, pore volume are 0.60 ~ 0.80 cm3/g。
- 7. according to the method for claim 1, it is characterised in that：Sn in alumina support containing Sn is in aluminum oxide plastic process Middle introducing, either it is introduced into by way of load or kneading introduces in aluminum oxide forming process.
- 8. according to the method for claim 1, it is characterised in that：Sn predecessors are nitric acid tin, butter of tin, tin acetate, tin One or more in sour sodium, potassium stannate.
- 9. according to the method for claim 1, it is characterised in that：Active metal component Pt is carried on oxygen containing Sn using infusion process Change in alumina supporter.
- 10. according to the method for claim 1, it is characterised in that：First using aluminum oxide of the aqueous solution dipping containing Sn containing Pt Carrier, dip time 1h ~ 72h, dry after dipping, roasting, drying temperature is 60 DEG C ~ 150 DEG C, and drying time be 1h ~ 24h, is roasted It is 400 DEG C ~ 800 DEG C to burn temperature, and roasting time 2h ~ 24h, the aqueous solution containing Pt is prepared by chloroplatinic acid.
- 11. according to the method for claim 10, it is characterised in that：Dip time 2h ~ 8h, it is to be done at 80 DEG C ~ 120 DEG C to dry Dry 4h ~ 8h, it is roasted to roasting 4h ~ 8h at 500 DEG C ~ 700 DEG C.
- 12. according to the method for claim 1, it is characterised in that：Alkali metal promoter K carrying method uses art technology Infusion process known to personnel, K predecessor is inorganic salts or organic salt, and maceration extract is the aqueous solution or is organic solution.
- 13. according to the method for claim 1, it is characterised in that：Pt weight percents in terms of element in propane dehydrogenation catalyst Content is 0.1%-1.0%；Sn counts weight percentage as 0.5%-10% using element；K counts percentage composition as 0.5%- using element wt 10%。
- 14. according to the method for claim 13, it is characterised in that：Pt weight percents in terms of element in propane dehydrogenation catalyst Content is 0.4%-0.8%；Sn counts weight percentage as 1%-3% using element；K counts percentage composition as 1%-3% using element wt.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997465A (en) * | 1970-07-17 | 1976-12-14 | General Electric Company | Dehalogenation process |
| US4308172A (en) * | 1980-05-21 | 1981-12-29 | Phillips Petroleum Company | Chemical dehydroxylation of silica |
| EP0486993A1 (en) * | 1990-11-19 | 1992-05-27 | Phillips Petroleum Company | Preparation of a zinc aluminate supported dehydrogenation catalyst |
| CN102441444A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst |
| CN102911000A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Dehydrogenation method for light alkanes |
-
2014
- 2014-12-04 CN CN201410723846.8A patent/CN105709728B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997465A (en) * | 1970-07-17 | 1976-12-14 | General Electric Company | Dehalogenation process |
| US4308172A (en) * | 1980-05-21 | 1981-12-29 | Phillips Petroleum Company | Chemical dehydroxylation of silica |
| EP0486993A1 (en) * | 1990-11-19 | 1992-05-27 | Phillips Petroleum Company | Preparation of a zinc aluminate supported dehydrogenation catalyst |
| CN102441444A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst |
| CN102911000A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Dehydrogenation method for light alkanes |
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