CN102989455A - Low carbon alkane dehydrogenation olefin production catalyst and preparation method thereof - Google Patents

Low carbon alkane dehydrogenation olefin production catalyst and preparation method thereof Download PDF

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CN102989455A
CN102989455A CN2011102741300A CN201110274130A CN102989455A CN 102989455 A CN102989455 A CN 102989455A CN 2011102741300 A CN2011102741300 A CN 2011102741300A CN 201110274130 A CN201110274130 A CN 201110274130A CN 102989455 A CN102989455 A CN 102989455A
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沈宜泓
田志坚
王晓化
徐竹生
阎立军
解晓伟
迟克彬
曲炜
罗琛
王磊
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Dalian Institute of Chemical Physics of CAS
Petrochina Co Ltd
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Dalian Institute of Chemical Physics of CAS
Petrochina Co Ltd
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Abstract

The present invention provides a low carbon alkane dehydrogenation olefin production catalyst and a preparation method thereof. According to the catalyst, a carrier is loaded with 0.01-5% by mass of a platinum group transition metal element, 0.01-10% by mass of a gold element, 0.01-10% by mass of a Group VIA metal element, and 0.01-10% by mass of an alkali metal element; or 0.2-15% by mass of a halogen element and 0.01-3% by mass of a sulfur element are added to be adopted as a modification component; the Group VIA metal element, the platinum group transition metal element, the gold element, the alkali metal element, the halogen element and the sulfur element are sequentially and respectively impregnated onto a carrier such as silica, a molecular sieve, magnesium-aluminum spinel or alumina, and a steam treatment is performed after the Group VIA metal element, the platinum group transition metal element and the gold element are impregnated and loaded on the carrier, wherein the Group VIA metal element, the platinum group transition metal element, the gold element, the alkali metal element, the halogen element and the sulfur element are adopted as catalyst components; and the catalyst has characteristics of high alkane conversion rate, high monoene selectivity and good stability.

Description

A kind of for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof
Technical field
The present invention relates to a kind of for manufacturing olefin by low-carbon alkane dehydrogenation catalysts and preparation method thereof.This catalyst is used for C 2-8The dehydrogenation reaction of alkane is preferred for C 3-6The dehydrogenation reaction of alkane more preferably is used for the dehydrogenation reaction of propane, iso-butane, normal butane.
Background technology
At present two major oil companies of China all have the oil plant of ten-million-ton scale, and a large amount of ethane, propane and the carbon four of the attached product of the catalytic pyrolysis of these ten-million-ton scale oil plants is to carbon six alkane.Therefore, how rationally utilizing these resources, improve to greatest extent the economy of industrial process, is the important scientific research task that current urgent need solves.And manufacturing olefin by low-carbon alkane dehydrogenation is a feasible process route.Be about to ethane, propane and carbon four to the alkane catalytic dehydrogenation of carbon six and produce alkene and hydrogen.Progressively substitute thermal process reactor with catalytic process comprehensively, improve the olefin production process economy.
Obtaining alkene behind the dehydrating alkanes is an important catalysis industrial process, and its dehydrogenation product is the important industrial chemicals of making a lot of chemicals (such as plastics, rubber, gasoline, washing agent etc.).For example, the propylene that is obtained by dehydrogenating propane is the important source material of synthetic polypropylene, acrylonitrile and expoxy propane, and the isobutene that dehydrogenation of isobutane obtains can synthesizing polyisobutylene, lucite, methyl tertiary butyl ether(MTBE) (MTBE) etc.But take propylene as example, merely from cracking technology obtain propylene can not satisfying the market to the demand of propylene, the production technology that exploitation enlarges the propylene source becomes focus in recent years.Therefore select suitable catalyst, the low-carbon alkanes catalytic dehydrogenation alkene processed that carries out hydro condition under the temperature relatively low than thermal cracking processes has important economic implications.
Alkane dehydrogenating catalyst, wherein an important class is that to include platinum group be main active component, adds all kinds auxiliary agent, the high performance catalyst that utilizes advanced technology to make.Such as USP 4,353,815 is Pt-Re-Mn/Al 2O 3Catalyst is used for dehydrogenation of isobutane; USP 4,420, and 649 is Pt-Ru-Re/Al 2O 3Catalyst is used for dehydrogenation of isobutane; EP 98,622 is Pt-Sn-Cs/Al 2O 3Catalyst is used for dehydrogenation of isobutane; USP 4,914, and 075 is Pt-Sn-Cs/Al 2O 3Catalyst is used for dehydrogenating propane; EP 562,906 is Pt-Sn-K/Al 2O 3Catalyst, moving-burden bed reactor is used for dehydrogenation of isobutane (C 2-C 20).USP 4,506, and 032 is Pt-Sn-K-Cl/Al 2O 3Catalyst contains Sn alumina carrier H 2PtCl 6Aqueous solution dipping, then drying, dechlorination, roasting flood KNO 3, dry, roasting, and in the time of 525 ℃ with air through water-bath with certain density HCl solution by catalyst, make catalyst a certain amount of Cl element of feeling deeply ashamed after the roasting, the catalyst that makes is used for ethane and dehydrogenation of isobutane.USP 4,595, and 673 is Pt-Sn-K-Li-Cl/Al 2O 3Catalyst contains Sn alumina carrier H 2PtCl 6And LiNO 3Total immersion, then drying, roasting flood KNO 3, dry, roasting makes again, and this catalyst is used for dehydrogenation of long-chain alkane.
The major advantage of precious metals pt catalyst is active high, and is better selective.But catalyst is comparatively responsive to impurity, and inactivation is very fast, and regeneration is frequent, expends mass energy, has also brought huge pressure to environment.
Summary of the invention
The purpose of this invention is to provide a kind of for manufacturing olefin by low-carbon alkane dehydrogenation catalysts and preparation method thereof.This catalyst is used for C 2-8The dehydrogenation reaction of alkane is preferred for C 3-6The dehydrogenation reaction of alkane more preferably is used for the dehydrogenation reaction of propane, iso-butane, normal butane.The catalyst of the type has higher selective and longer catalyst service life than known catalyst system to above-mentioned reaction.
Catalyst provided by the invention is take platinum family transition metal and gold element as active component, and adds VIA family metallic element and alkali metal as auxiliary agent, and preferred halogen and the element sulphur of further adding is as modified component.The carrier of catalyst is selected from silica, molecular sieve, magnesium aluminate spinel, aluminium oxide.
Above-mentioned platinum family transition metal as active component is one or more in platinum, palladium, iridium, ruthenium, rhodium, osmium or the rhenium, wherein take platinum as best.The weight content of better platinum family transition metal is 0.01～5%, preferred 0.01～2%.Optimum content as the gold element of active component is 0.01～10%, preferred 0.01～4%.Auxiliary agent VIA family metallic element is one or more elements among Si, Ge, Sn or the Pb, and wherein take the Sn element as best, better VIA family metallic element weight content is 0.01～10%, preferred 0.2～3%.Alkali metal is one or more elements among Li, Na, K, Rb, Cs or the Fr, and wherein take Li or K as best, the better weight content of alkali metal is 0.01～10%, preferred 0.1～5%.Halogen is F, Cl, Br or I, and take Cl as best, the halogen weight content is preferably 0.2～15%.Element sulphur weight content preferred 0.01～3%.
The preparation method of catalyst provided by the present invention is that the solubility soln using dipping technique as catalyst components is supported on the carrier, it is characterized in that dipping process press the order carry out:
The adjuvant component that 1) will contain VIA family metallic element is impregnated on the carrier, and drying and roasting make the carrier that carries VIA family metallic element.Its drying and roasting routinely technology are carried out;
2) be used as again active component the platinum group transition metal solution and contain the solution impregnation 1 of gold element), drying and roasting make the carrier that carries VIA family metallic element and platinum family transition elements and gold element; Wherein platinum group transition metal solution with contain gold element solution can hybrid infusion, also can flood respectively, when flooding respectively, can flood first platinum group transition metal solution, also can flood first and contain gold element solution; Its drying and roasting routinely technology are carried out;
3) 2) on the carrier that makes, dipping contains the solution of alkali metal ion, make and supported alkali metal ion on the carrier, again drying and roasting, its dry and roasting process also routinely technology carry out;
4) with halogen-containing first cellulose solution, dipping 3) carrier that makes, carry out drying and roasting more according to a conventional method;
5) use at last Na 2S or (NH 4) 2S sulfur-containing compound solution impregnating carrier 4), make after drying catalyst.
Dipping solution in the above-mentioned preparation process, the available nitrate that contains each metal component, ammonium salt, chloride or containing metal acid solution; Halogen can be sour accordingly with it, but best halogen maceration extract is hydrochloric acid.Drying under 50～150 ℃, was carried out 1～10 hour usually, and roasting process carried out 1～10 hour under 400～800 ℃.
In the preparation method of catalyst of the present invention, it is characterized in that the carrier 1 that carrier impregnation auxiliary agent and active component make) and 2) after, for improving the activity of catalyst, also use water vapour and process, the steam treatment time is 1～8 hour, and treatment temperature is 500～700 ℃.
Catalyst of the present invention is being used for low-carbon alkanes (preferred C 2-8Alkane, more preferably C 3-6Alkane, further preferably propane, normal butane, iso-butane) before the dehydrogenation reaction, need reduce with hydrogen, make platinum family transition elements and gold element as active component be reduced into metallic state.Reduction temperature is 300～600 ℃, and the time is 1～5 hour, namely can be used for catalytic reaction through the catalyst after the reduction.The condition of its catalytic reaction is:
Reaction temperature: 500～700 ℃; Reaction pressure: normal pressure～1MPa; Liquid air speed: 0.1～10h -1Give to illustrate further for technology of the present invention below by embodiment.
The prepared catalyst of the present invention has preferably reaction selectivity and activity, have simultaneously preferably stability, and the preparation method is simple.The present invention can be significantly improved the yield of alkene and the service life of extending catalyst as the dehydrogenation of low-carbon alkanes.
The specific embodiment
The following examples are used for the present invention is specifically described, but scope of the present invention is not limited.If no special instructions, all percentage compositions are weight percentage among following Comparative Examples and the embodiment.
Method described in the following embodiment if no special instructions, is conventional method.
Embodiment 1.
Catalyst A consists of 0.375%Pt, 0.5%Au, and 0.5%Sn, 1.4%K, 1.0%Cl and 0.2%S are supported on γ-Al 2O 3On.The preparation method is as follows:
(1) 0.5%Sn/Al 2O 3Preparation
A certain amount of carrier places the dipping bottle, will prepare the SnCl that is equivalent to 0.5%Sn content 2Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 550 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
(2) 0.375%Pt～0.5%Au～0.5%Sn/Al 2O 3Preparation
With 0.5%Sn/Al 2O 3Place the dipping bottle, will configure the H that is equivalent to 0.375%Pt content 2PtCl 6HAuCl with 0.5%Au content 4Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 500 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
(3) 0.375%Pt～0.5%Au～0.5%Sn～1.4%K～1.0%Cl/Al 2O 3Preparation
The KNO that will be equivalent to 1.4%K content 3Solution is dipped in Pt-Au-Sn/Al 2O 3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.Then, will contain Cl amount is that 1.0% hydrochloric acid solution is dipped in Pt-Au-Sn-K/Al 2O 3On, after the drying, 525 ℃ of roastings of blowing air one hour.
(4) wet type sulfuration
(NH is adopted in sulfuration 4) 2S makes vulcanizing agent, and the sulfuration amount is 0.2%, with (the NH after the metering 4) 2S solution is dipped on the catalyst, and then room temperature dipping 24 hours inclines and flood remaining liquid, and taking-up is dried, and respectively dries by the fire 4 hours at 60 ℃ and 120 ℃.Through elementary analysis as can be known, its actual load capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyst is as shown in table 1:
Table 1. dehydrogenation of isobutane reactivity worth
Figure BDA0000091521970000051
Figure BDA0000091521970000061
Reaction condition: 625 ℃ of reaction temperatures, LHSV=9h -1, H 2/ C 4(mol/mol)=1, reaction pressure 1atm.
Embodiment 2.
Catalyst B consists of 0.5%Pt, 0.5%Au, and 0.5%Sn, 1.4%Li, 1.0%Cl and 0.2%S are supported on γ-Al 2O 3On.The preparation method is as follows:
(1) 0.5%Sn/Al 2O 3Preparation
A certain amount of carrier places the dipping bottle, will prepare the SnCl that is equivalent to 0.5%Sn content 2Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 550 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
(2) 0.5%Pt～0.5%Au～0.5%Sn/Al 2O 3Preparation
With 0.5%Sn/Al 2O 3Place the dipping bottle, will configure the H that is equivalent to 0.5%Pt content 2PtCl 6Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 500 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
With Pt-Sn/Al obtained above 2O 3Place the dipping bottle, with the HAuCl that is equivalent to 0.5%Au content that configures 4Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 500 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
(3) 0.5%Pt～0.5%Au～0.5%Sn～1.4%Li～1.0%Cl/Al 2O 3Preparation
The LiNO that will be equivalent to 1.4%Li content 3Solution is dipped in Pt-Au-Sn/Al 2O 3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.Then, will contain Cl amount is that 1.0% hydrochloric acid solution is dipped in Pt-Au-Sn-Li/Al 2O 3On, after the drying, 525 ℃ of roastings of blowing air one hour.
(4) wet type sulfuration
(NH is adopted in sulfuration 4) 2S makes vulcanizing agent, and the sulfuration amount is 0.2%, with (the NH after the metering 4) 2S solution is dipped on the catalyst, and then room temperature dipping 24 hours inclines and flood remaining liquid, and taking-up is dried, and respectively dries by the fire 4 hours at 60 ℃ and 120 ℃.Through elementary analysis as can be known, its actual load capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyst is as shown in table 2:
Table 2. normal butane dehydrogenation reaction performance
Figure BDA0000091521970000071
Figure BDA0000091521970000081
Reaction condition: 610 ℃ of reaction temperatures, LHSV=6h -1, H 2/ C 4(mol/mol)=1, reaction pressure 1atm.
Embodiment 3.
Catalyst C consists of 0.375%Ru, 0.5%Au, and 0.5%Sn, 1.4%K, 1.0%Cl and 0.2%S are supported on the ZSM-5 molecular sieve.The preparation method is with embodiment 1, with H 2PtCl 6Change RuCl into 3Hydrochloric acid solution, carrier is transformed to ZSM-5.Through elementary analysis as can be known, its actual load capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyst is as shown in table 3:
Table 3. dehydrogenating propane reactivity worth
Figure BDA0000091521970000082
Reaction condition: 620 ℃ of reaction temperatures, LHSV=3h -1, H 2/ C 3(mol/mol)=1, reaction pressure 1atm.
The catalysqt deactivation of this composition is very fast.
Embodiment 4
Catalyst D consists of 0.375%Pd, 0.5%Au, and 0.5%Sn, 0.7%K, 0.7%Li, 1.0%Cl and 0.2%S are supported on the magnesium aluminate spinel.The preparation method is with embodiment 1, just H 2PtCl 6Change PdCl into 2Hydrochloric acid solution, with the LiNO of targeted loads amount 3And KNO 3The total immersion stain, carrier changes magnesium aluminate spinel into.Through elementary analysis as can be known, its actual load capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyst is as shown in table 4:
Table 4. normal butane dehydrogenation reaction performance
Reaction condition: 610 ℃ of reaction temperatures, LHSV=6h -1, H 2/ C 4(mol/mol)=1, reaction pressure 1atm.
Embodiment 5.
Catalyst E consists of 0.375%Pt, 0.375%Au, and 0.8%Sn, 1.4%K, 1.0%Cl and 0.2%S are supported on θ-Al 2O 3On.The preparation method is as follows:
(1) 0.8%Sn/Al 2O 3Preparation
A certain amount of carrier places the dipping bottle, will prepare the SnCl that is equivalent to 0.8%Sn content 2Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 550 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
(2) 0.375%Pt～0.375%Au～0.8%Sn/Al 2O 3Preparation
With 0.8%Sn/Al 2O 3Place the dipping bottle, will configure the HAuCl that is equivalent to 0.375%Au content 4Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 500 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
With Au-Sn/Al obtained above 2O 3Place the dipping bottle, with the H that is equivalent to 0.375%Pt content that configures 2PtCl 6Hydrochloric acid solution (quite alumina carrier weight 2%) maceration extract put into fast carrier, kept 4 hours, and constantly shake, make dipping evenly, then incline and flood remaining liquid, taking-up is dried, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then in tube furnace, pass into air (SV=5000h -1), in 500 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control by 70 ℃, use steam treatment 4 hours.
(3) 0.375%Pt～0.375%Au～0.8%Sn～1.4%K～1.0%Cl/Al 2O 3Preparation
The KNO that will be equivalent to 1.4%K content 3Solution is dipped in Pt-Au-Sn/Al 2O 3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.Then, will contain Cl amount is that 1.0% hydrochloric acid solution is dipped in Pt-Au-Sn-K/Al 2O 3On, after the drying, 525 ℃ of roastings of blowing air one hour.
(4) wet type sulfuration
(NH is adopted in sulfuration 4) 2S makes vulcanizing agent, and the sulfuration amount is 0.2%, with (the NH after the metering 4) 2S solution is dipped on the catalyst, and then room temperature dipping 24 hours inclines and flood remaining liquid, and taking-up is dried, and respectively dries by the fire 4 hours at 60 ℃ and 120 ℃.Through elementary analysis as can be known, its actual load capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyst is as shown in table 5:
Table 5. dehydrogenation of isobutane reactivity worth
Figure BDA0000091521970000111
Reaction condition: 625 ℃ of reaction temperatures, LHSV=9h -1, H 2/ C 4(mol/mol)=1, reaction pressure 1atm.
This catalyst has preferably stability and higher selective isobutene.This catalyst is carried out the single pass life experiment, and the result is as shown in table 6.
Table 6. catalyst is to butane/dehydrogenation of isobutane reaction experiment result
Figure BDA0000091521970000121
Reaction condition: 590 ℃ of reaction temperatures, LHSV=3h -1, H 2/ C 4(mol/mol)=2, reaction pressure 0.5atm (gauge pressure).
Embodiment 6.
Catalyst F consists of 0.5%Pt, 0.5%Au, and 0.5%Ge, 1.4%K, 1.0%Cl and 0.2%S are supported on γ-Al 2O 3On.The preparation method is with embodiment 1, and it is 0.5% that the solution of Pt is transferred to the final load amount, with SnCl 2Hydrochloric acid solution replace to GeO 2Hydrochloric acid solution, and the preparation 0.5%Ge/Al 2O 3The time with 600 ℃ of roastings.Through elementary analysis as can be known, its actual load capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyst is as shown in table 7:
Table 7. dehydrogenating propane reactivity worth
Figure BDA0000091521970000122
Figure BDA0000091521970000131
Reaction condition: 620 ℃ of reaction temperatures, LHSV=3h -1, H 2/ C 3(mol/mol)=1, reaction pressure 1atm.
Comparative Examples 1.
The chief component of catalyst G is identical with catalyst A, but does not soak HAuCl 4, the reactivity worth of its dehydrogenation of isobutane reaction is more as shown in table 8:
The dehydrogenation of isobutane reactivity worth of table 8. catalyst G and A
Figure BDA0000091521970000132
Reaction condition: 625 ℃ of reaction temperatures, LHSV=9h -1, H 2/ C 4(mol/mol)=1, reaction pressure 1atm.
Comparative Examples 2.
The chief component of catalyst H is identical with catalyst B, but is making Sn/Al 2O 3After, do not adopt high-temperature water vapor to process the dechlorination process, the reactivity worth of its normal butane dehydrogenation reaction is more as shown in table 9:
The normal butane dehydrogenation reaction performance of table 9. catalyst H and B
Figure BDA0000091521970000133
Reaction condition: 610 ℃ of reaction temperatures, LHSV=6h -1, H 2/ C 4(mol/mol)=1, reaction pressure 1atm.
Comparative Examples 3.
The chief component of catalyst I is identical with catalyst E, but does not soak HCl, and the reactivity worth of its dehydrogenation of isobutane reaction is more as shown in table 10:
The dehydrogenation of isobutane reactivity worth of table 10. catalyst I and E
Figure BDA0000091521970000151
Reaction condition: 625 ℃ of reaction temperatures, LHSV=9h -1, H 2/ C 4(mol/mol)=1, reaction pressure 1atm.
Can find out that from above Comparative Examples it is active preferably to adopt catalyst that method provided by the invention prepares to have for the dehydrogenation reaction of low-carbon alkanes, higher is selective, and good stability, has the prospect of commercial Application.

Claims (9)

1. one kind is used for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, and low-carbon alkanes is C 2-8Alkane is characterized in that: load has platinum family transition metal, 0.01～10% gold element, 0.01～10% VIA family metallic element and 0.01～10% the alkali metal of carrier quality 0.01～5% on the carrier; Or the element sulphur that adds 0.2～15% halogen and 0.01～3% is as modified component.
2. as claimed in claim 1 for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that: described platinum family transition metal is one or more in platinum, palladium, iridium, ruthenium, rhodium, osmium or the rhenium, VIA family metallic element is one or more among Si, Ge, Sn, the Pb, and alkali metal is one or more among Li, Na, K, Rb, Cs or the Fr.
3. as claimed in claim 1 for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that: the quality percentage composition of platinum family transition metal is 0.01～2%, and the quality percentage composition of gold element is 0.01～4%.
4. as claimed in claim 1 for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that: carrier is selected from silica, molecular sieve, magnesium aluminate spinel, aluminium oxide.
5. preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation claimed in claim 1 is characterized in that: to support on the carrier be to be undertaken by following order to each component dipping in the catalyst:
The adjuvant component that 1) will contain VIA family metallic element is impregnated on the carrier drying and roasting;
2) with platinum group transition metal solution and gold element solution impregnation 1) the gained carrier, again drying and roasting, wherein platinum group transition metal solution with contain gold element solution hybrid infusion or respectively the dipping, when flooding respectively, flood first platinum group transition metal solution, or dipping contains gold element solution first;
3) use again the solution impregnation 2 of alkali metal containing element) the gained carrier, drying and roasting;
4) then with the solution impregnation 3 that contains the halogen family element) gained carrier, again drying and roasting;
5) use at last Na 2S or (NH 4) 2S sulfur-containing compound solution impregnating carrier 4), make after drying catalyst.
6. the preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 5 is characterized in that: each dipping solution nitrate, ammonium salt, chloride or containing metal acid solution that contains each metal component.
7. the preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 5 is characterized in that: halogen with halide as maceration extract.
8. the preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 5, it is characterized in that: dry run was carried out under 50～150 ℃ 1～10 hour, and roasting process carried out under 400～800 ℃ 1～10 hour.
9. the preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 5, it is characterized in that: after catalytic component VIA family metallic element, platinum family transition metal and gold element dipping, drying and the roasting, also need through steam treatment 1～8 hour, treatment temperature is 500～700 ℃.
CN2011102741300A 2011-09-15 2011-09-15 Low carbon alkane dehydrogenation olefin production catalyst and preparation method thereof Pending CN102989455A (en)

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CN105268459A (en) * 2014-07-21 2016-01-27 中国石油化工股份有限公司 Sulfur-containing low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN105582924A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Catalyst used for producing olefin through light alkane dehydrogenation
CN105921148A (en) * 2016-05-09 2016-09-07 青岛神飞化工科技有限公司 Catalyst for preparing olefins from saturated alkanes through dehydrogenation and preparing method and application thereof
CN108325523A (en) * 2018-02-02 2018-07-27 华东理工大学 A kind of propane dehydrogenation catalyst and preparation method thereof
CN110072612A (en) * 2016-12-13 2019-07-30 Smh有限公司 Hydroconversion process
CN112934230A (en) * 2019-11-26 2021-06-11 中国石油天然气股份有限公司 Low-Pt long paraffin dehydrogenation catalyst, and preparation method and application thereof

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105268459A (en) * 2014-07-21 2016-01-27 中国石油化工股份有限公司 Sulfur-containing low-carbon alkane dehydrogenation catalyst and preparation method thereof
CN105268459B (en) * 2014-07-21 2018-02-23 中国石油化工股份有限公司 A kind of catalyst for dehydrogenation of low-carbon paraffin of sulfur-bearing and preparation method thereof
CN105582924A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Catalyst used for producing olefin through light alkane dehydrogenation
CN105582924B (en) * 2014-10-24 2018-04-06 中国石油化工股份有限公司 Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation
CN105921148A (en) * 2016-05-09 2016-09-07 青岛神飞化工科技有限公司 Catalyst for preparing olefins from saturated alkanes through dehydrogenation and preparing method and application thereof
CN110072612A (en) * 2016-12-13 2019-07-30 Smh有限公司 Hydroconversion process
CN108325523A (en) * 2018-02-02 2018-07-27 华东理工大学 A kind of propane dehydrogenation catalyst and preparation method thereof
CN108325523B (en) * 2018-02-02 2021-01-08 华东理工大学 Propane dehydrogenation catalyst and preparation method thereof
CN112934230A (en) * 2019-11-26 2021-06-11 中国石油天然气股份有限公司 Low-Pt long paraffin dehydrogenation catalyst, and preparation method and application thereof
CN112934230B (en) * 2019-11-26 2023-10-27 中国石油天然气股份有限公司 Low Pt type long-chain alkane dehydrogenation catalyst, and preparation method and application thereof

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