CN101623633A - Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof - Google Patents
Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing olefin by dehydrogenating low-carbon alkane, and a preparation method and an application thereof, which belong to the technical field of the preparation of basic organic chemical raw materials. The catalyst is prepared by a dipping method of using an aluminium silicophosphate molecular sieve as a carrier, VIII group or VIB group elements as active constituents and IVA group elements as an auxiliary agent. In the process for preparing olefin by dehydrogenating low-carbon alkane, the catalyst is firstly reduced by hydrogen gas, then participates in a reaction, and is finally regenerated. Compared with the existing catalyst for preparing olefin by dehydrogenating low-carbon alkane, the catalyst has a pore shape selecting function and moderate acidity, thereby the selectivity of the low-carbon alkane can reach more than 90 percent in the process for preparing olefin by dehydrogenating low-carbon alkane. The preparation method of the catalyst is simple; the regeneration process flow of the reaction has a large choice, a fixed bed, a fluidized bed or a moving bed can be used as a reactor, and the catalyst can be regenerated in the reactor or outside the reactor.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application that is used for manufacturing olefin by low-carbon alkane dehydrogenation, belong to basic organic chemical industry's raw material preparing technical field.
Background technology
Propylene is a kind of important Organic Chemicals, is widely used in the preparation of products such as macromolecular materials such as polypropylene, polyacrylonitrile and butanols, octanol, expoxy propane, isopropyl alcohol, acrylic acid.Different with other chemicals, the present production of propylene is generally based on naphtha steam cracking system ethylene process and catalytic cracking process coproduction or by-product, China has surpassed ethene to propylene growth of requirement speed since the nineties, and original propylene source can not satisfy the demands.At a large amount of low-carbon alkanes of technical process such as catalytic cracking, naphtha steam cracking, MTO/MTP meeting by-product, therefore how low-carbon alkanes is converted into the focus that the required propylene in market becomes research.Low-carbon alkene is ripe relatively to the Study on Transformation of propylene, and present difficult point is how low-carbon alkanes elder generation height need optionally be converted into low-carbon alkene, has also obtained some progress.Dehydrogenating low-carbon alkane especially dehydrogenating propane technology has become tertiary propylene source after coproduction continue preparing ethylene by steam cracking, the refinery catalytic cracking unit's refining by-product.Dehydrogenating low-carbon alkane technology can be divided into oxidative dehydrogenation and non-oxide dehydrogenation is two types of direct dehydrogenations.The purpose selectivity of product is low under oxidative dehydrogenation process thermal discharge height, the high conversion, and operating process has danger, and therefore non-oxide direct dehydrogenation process receives increasing concern.The related process of being developed at present comprises Oleflex technology, the Air Product﹠amp of Uop Inc.; Linde technology of the FBD-4 of the Catofin technology of Chemical company, the Star technology of Phillips company, Snamprogetti SPA company and German Linde company etc.; The had an appointment technology of ten cover industrialized manufacturing olefin by low-carbon alkane dehydrogenation, especially propylene, domestic still do not have an industrialized process units.
With the platinum element is that the catalyst of main active component is a class important in the catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, utilize advanced technology to add various auxiliary agents, and use aluminium oxide or alumino-silicate etc. to do preparing carriers to form, its production method is also open in relevant patent, as U.S.Pat.5,132,484; 3,488,402; 2,374,404 and WO/2005/040075 described in.Above-mentioned catalyst uses one or more auxiliary agents further to modify, reach the catalysis behavior of control dehydrogenation reaction process, as shown in US Pat.2814599 and US Pat.3679773-A, the auxiliary agent of frequent use is the IIIA from the periodic table of elements, IVA selects among VIB and the VIII.Alkali metal and alkaline-earth metal, Na for example, Ca, K etc. also often be used as second auxiliary agent be used in and the acidity in the carrier, as US Pat.5,146,034 and 3,899, shown in 544.In recent years, ZSM-5 is used as carrier to replace aluminium oxide, as U.S.Pat.5416052; 5146034; 0110630A1; 3,442,794 and 4,489,216 and CN200610086006.0 shown in.The main cause that molecular sieve, particularly ZSM-5 are used is its no etching problem, and the high conversion of propane that itself just has, and because of its big surface area can reduce carbon deposit, as U.S.Pat., 507,931; 3,551,353; 3,932,554; 4,400,576; 4,935,578 and 5,132, described in 479.
Though low-carbon alkanes catalytic dehydrogenation system alkene technology has obtained remarkable progress, it is not high that the shortcoming of above-mentioned technology is under the high conversion olefine selective, and in the propane catalytic dehydrogenation processes, when conversion of propane was 30%, the propylene selectivity only was about 40%.SAPO-34 is a kind of aperture aluminium silicophosphate molecular sieve, and its aperture is selected shape effect, moderate acidity, high hydrothermal stability and made its important catalyst that becomes methanol-to-olefins, is studied widely.In recent years, it is found that this catalyst also can carry out hydro carbons and transform mutually,, and the selectivity of low-carbon alkene is increased substantially, but this molecular sieve yet there are no report as the carrier of low-carbon alkanes catalytic dehydrogenation system alkene because it selects shape effect and suitable acidity.
Summary of the invention
First purpose of the present invention provides a kind of catalyst that is used for low-carbon alkanes catalytic dehydrogenation system alkene that can significantly improve olefine selective.
Another object of the present invention provides a kind of Preparation of catalysts method that is used for manufacturing olefin by low-carbon alkane dehydrogenation.
Another purpose of the present invention provides the application process of described catalyst in manufacturing olefin by low-carbon alkane dehydrogenation.
Technical scheme of the present invention is as follows:
A kind of catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that: this catalyst is carrier with the aluminium silicophosphate molecular sieve, with VIII family or group vib element is active component, with IVA family element is auxiliary agent, the percentage by weight that described active component accounts for catalyst is 0.001～20%, and the percentage by weight that auxiliary agent accounts for catalyst is 0.001～20%; Described low-carbon alkanes comprises propane, butane and pentane.
In the technique scheme, described aluminium silicophosphate molecular sieve adopts SAPO-34 or SAPO-5 molecular sieve, Al wherein
2O
3With SiO
2Mol ratio be 1～6; The mol ratio of P and Si is 0～0.1.Described VIII element employing Pt, Pd of family or Ni, its percentage by weight that accounts for catalyst is between 0.001～10%.Described group vib element adopts Cr, Mo or W, its its account for catalyst percentage by weight be between 0.001～20%.Described IVA element employing Ge, Sn of family or Pb, its percentage by weight that accounts for catalyst is between 0.001～20%.
A kind of method for preparing catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation provided by the invention is characterized in that this method carries out as follows:
1) aluminium silicophosphate molecular sieve is at first added in the soluble salt solution of auxiliary agent, assistant concentration is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
2) aluminium silicophosphate molecular sieve behind the step 1) dipping is carried out drying and roasting, baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, and roasting time is 1～10 hour;
3) with step 2) aluminium silicophosphate molecular sieve after the roasting puts in the salting liquid of active component again, and the concentration of active component is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
4) aluminium silicophosphate molecular sieve behind the step 3) dipping is carried out drying and roasting and promptly make corresponding catalyst, wherein baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, roasting time is 1～10 hour, obtains described catalyst.
Another kind provided by the invention is used for the method for preparing catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that this method carries out as follows:
1) aluminium silicophosphate molecular sieve is added in the mixed solution of auxiliary agent and active component soluble salt, assistant concentration is 0.01～3 mol, and the concentration of active component is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
2) aluminium silicophosphate molecular sieve behind the step 1) dipping is carried out drying and roasting, baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, and roasting time is 1～10 hour; Obtain described catalyst.
The application of catalyst of the present invention in manufacturing olefin by low-carbon alkane dehydrogenation is characterized in that related processing step is as follows:
1) catalyst reduction: at first with catalyst reduction activation in hydrogen atmosphere, reduction temperature is 300～700 ℃, and the recovery time is 1～20 hour;
2) catalytic dehydrogenating reaction: with the low-carbon alkanes is raw material, or is that raw material carries out catalytic dehydrogenating reaction in reactor with low-carbon alkanes and hydrogen, and reactor is fixed bed, fluid bed or moving bed, and reaction temperature is 300～700 ℃, and weight space velocity is 0.1～100hr
-1, reaction pressure is 0.01～4MPa, the mol ratio of hydrogen and low-carbon alkanes is 0.001～10 in the raw material;
3) catalyst regeneration: reacted catalyst need carry out coke-burning regeneration, adopt in-situ regeneration or device to regenerate outward, regeneration temperature is 400～700 ℃, and regeneration pressure is 0.05～0.5Mpa, recovery time is 1-20 hour, and regeneration atmosphere is oxygen, air, steam or carbon dioxide.
The present invention compared with prior art has the following advantages and the high-lighting effect:
(1) compare with existing low-carbon alkanes catalytic dehydrogenation system alkene catalyst, catalyst provided by the present invention has aperture and selects shape effect, moderate acidity, and the selectivity of light olefin that makes the manufacturing olefin by low-carbon alkane dehydrogenation process is up to more than 90%.
(2) method for preparing catalyst is simple; Reaction regeneration technological process choice is big, and reactor can be adopted as fixed bed, fluid bed or moving bed, and catalyst regeneration can adopt in-situ regeneration or device to regenerate outward.
The specific embodiment
The present invention relates to Catalysts and its preparation method and application that a kind of dehydrogenating low-carbon alkane prepares alkene, described low-carbon alkanes comprises propane, butane and pentane.Described catalyst with aluminium silicophosphate molecular sieve as carrier, VIII family or group vib element are as active component, IVA family element is as auxiliary agent, under preferred reaction condition, carry out low-carbon alkanes catalyst dehydrogenation system alkene, described reactor adopts fixed bed, moving-burden bed reactor, or fluidized-bed reactor.
A kind of catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation provided by the invention is carrier with the aluminium silicophosphate molecular sieve, with VIII family or group vib element is active component, with IVA family element is auxiliary agent, the percentage by weight that described active component accounts for catalyst is 0.001～20%, and the percentage by weight that auxiliary agent accounts for catalyst is 0.001～20%; Described low-carbon alkanes comprises propane, butane and pentane.Described aluminium silicophosphate molecular sieve adopts SAPO-34 or SAPO-5 molecular sieve, Al wherein
2O
3With SiO
2Mol ratio be 1～6; The mol ratio of P and Si is 0～0.1.Described VIII element employing Pt, Pd of family or Ni, its percentage by weight is between 0.001～10%.Described group vib element adopts Cr, Mo or W, and it accounts for catalyst weight percentage is between 0.001～20%.Described IVA element employing Ge, Sn of family or Pb, its percentage by weight is between 0.001～20%.
A kind of method for preparing catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation provided by the invention, its concrete processing step is performed as follows:
1) aluminium silicophosphate molecular sieve is at first added in the soluble salt solution of auxiliary agent, assistant concentration is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
2) aluminium silicophosphate molecular sieve behind the step 1) dipping is carried out drying and roasting, baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, and roasting time is 1～10 hour;
3) with step 2) aluminium silicophosphate molecular sieve after the roasting puts in the salting liquid of active component again, and the concentration of active component is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
4) aluminium silicophosphate molecular sieve behind the step 3) dipping is carried out drying and roasting and promptly make corresponding catalyst, wherein baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, roasting time is 1～10 hour, obtains described catalyst.
Another kind provided by the invention is used for the method for preparing catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, and its concrete processing step is performed as follows:
1) aluminium silicophosphate molecular sieve is added in the mixed solution of auxiliary agent and active component soluble salt, assistant concentration is 0.01～3 mol, and the concentration of active component is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
2) aluminium silicophosphate molecular sieve behind the step 1) dipping is carried out drying and roasting, baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, and roasting time is 1～10 hour; Obtain described catalyst.
The application of catalyst of the present invention in manufacturing olefin by low-carbon alkane dehydrogenation, its related processing step is as follows:
1) catalyst reduction: at first with catalyst reduction activation in hydrogen atmosphere, reduction temperature is 300～700 ℃, and the recovery time is 1～20 hour;
2) catalytic dehydrogenating reaction: with the low-carbon alkanes is raw material, or is that raw material carries out catalytic dehydrogenating reaction in reactor with low-carbon alkanes and hydrogen, and reactor is fixed bed, fluid bed or moving bed, and reaction temperature is 300～700 ℃, and weight space velocity is 0.1～100hr
-1, reaction pressure is 0.01～4MPa, the mol ratio of hydrogen and low-carbon alkanes is 0.001～10 in the raw material;
3) catalyst regeneration: reacted catalyst need carry out coke-burning regeneration, adopt in-situ regeneration or device to regenerate outward, regeneration temperature is 400～700 ℃, and regeneration pressure is 0.05～0.5Mpa, recovery time is 1-20 hour, and regeneration atmosphere is oxygen, air, steam or carbon dioxide.
Below in conjunction with specific embodiment the content that arrives involved in the present invention is described, but following specific embodiment is not construed as limiting the invention, protection domain of the present invention is as the criterion with the claim of application.
Embodiment 1
The present embodiment explanation is of the present invention to be the preparation of the propane dehydrogenation catalyst of carrier with SAPO-34.
At first the SAPO-34 molecular sieve is at the SnCl of 0.16M
2.2H
2Flood 10hr in the O solution in 80 ℃, the load capacity of Sn reaches 0.001～20% (mass percent) in the catalyst, then dry 6hr under 120 ℃.Dried sample next in Muffle furnace under air atmosphere roasting 4hr, sintering temperature is 550 ℃.Sn/SAPO-34 powder after the roasting and the H of 0.03M
2PtCl
66H
2O solution floods 4hr down at 80 ℃, and the content that makes Pt in the final catalyst is 0.001～10%.Then at 120 ℃ of following dry 6hr, 550 ℃ of following roasting 4hr in Muffle furnace again.Before reaction evaluating, all catalyst samples are all used steam dechlorination 8hr down at 500 ℃; Then with hydrogen reduction 12hr under 550 ℃.Content by Pt and Sn in the change catalyst makes A1～A5 catalyst respectively.
According to the method described above, adopt the former powder of the ZSM-5 Pt-Sn/ZSM-5 catalyst C that has been preparing carriers.
SAPO-34 is a carrier, and Cr is that the catalyst for preparing propylene with propane dehydrogenation preparation method of modified component is as described below.At first the SAPO-34 molecular sieve is at the Cr of 0.2M (NO
3)
39H
2Flood 4hr in 80 ℃ in the O solution, make that the load capacity of Cr reaches 10% and 20% (quality percentage composition) in the catalyst, then at 120 ℃ of following dry 6hr, catalyst B 1Cr (the 10wt%)/SAPO-34 and B2Cr (the 20wt%)/SAPO-34 that in Muffle furnace, under air atmosphere, promptly make of these samples then in 550 ℃ of roasting 9hr.
The label of table 1 catalyst
Embodiment 2
The present embodiment explanation is of the present invention to be the preparation of the propane dehydrogenation catalyst of carrier with SAPO-5.
According to the method described in the embodiment 1, at first the SAPO-5 molecular sieve is at the SnCl of 0.16M
2.2H
2Flood 4hr in the O solution in 90 ℃, the load capacity of tin reaches 0.5-2% (mass percent) in the catalyst, then dry 10hr under 120 ℃.These samples next in Muffle furnace under air atmosphere roasting 4hr, sintering temperature is 400 ℃.Sn/SAPO-5 powder after the roasting and the H of 0.01M
2PtCl
66H
2O solution floods 4hr down at 90 ℃, and the content that makes Pt in the final catalyst is 0.001-1%.Then at 120 ℃ of following dry 6hr, again in Muffle furnace in 550 ℃ of following roasting 4hr, the catalyst D1 and the D2 of system form and are respectively (Pt (0.5wt%) Sn (1.2wt%)/SAPO-5) and (Pt (0.001wt%) Sn (0.001wt%)/SAPO-5).Before reaction evaluating, all catalyst samples are all used steam dechlorination 8h down at 500 ℃; Then with hydrogen reduction 12hr under 550 ℃.
Embodiment 3
Dehydrogenation the advantage in dehydrogenating propane reaction of SAPO-34 as carrier adopted in the present embodiment explanation.
The catalyst A 2 and the C that take by weighing 0.2g respectively carry out little anti-experiment, and mass space velocity is 5.6hr
-1, the mol ratio of hydrogen and charging propane (purity 99.5%) is 0.25; Reaction temperature is 600 ℃, and the experimental result behind charging 4hr is as shown in table 2.
Table 2 catalyst carrier is to the influence of preparing propylene by dehydrogenating propane process
Embodiment 4
The present embodiment explanation adopts SAPO-5 as catalyst carrier, and Pt is an active component, and Sn is the response characteristic of catalyst in propane catalytic dehydrogenation system propylene process that auxiliary agent makes.
The catalyst D1, the D2 that take by weighing 0.2g respectively carry out little anti-experiment, and mass space velocity is respectively 5.6hr
-1And 0.1hr
-1The mol ratio of hydrogen and charging propane (purity 99.5%) is 0.25; Reaction temperature is 600 ℃, and the experimental result behind charging 4hr is as shown in table 3.
Table 3 catalyst carrier is to the influence of preparing propylene by dehydrogenating propane process
Embodiment 5
The present embodiment explanation adopts SAPO-34 as catalyst carrier, and Cr is the response characteristic of active component in propane catalyst dehydrogenation producing propylene process.
The catalyst B 1 and the B2 that take by weighing 0.2g carry out little anti-experiment, and mass space velocity is for being respectively 5.6hr
-1And 100hr
-1, the mol ratio of hydrogen and charging propane (purity 99.5%) is 0.01; Reaction temperature is 600 ℃, and the experimental result behind charging 4hr is as shown in table 4.
Table 4Cr modified catalyst is at the response characteristic of preparing propylene by dehydrogenating propane process
Embodiment 6
The present embodiment explanation adopts SAPO-34 as catalyst carrier, the influence that active component Pt and auxiliary agent Sn content are active to catalyst reaction and product distributes.
The catalyst that takes by weighing 0.2g carries out little anti-experiment, and mass space velocity is 5.6hr
-1, the mol ratio of hydrogen and charging propane (purity 99.5%) is 0.5; Reaction temperature is 600 ℃; Experimental result behind charging 4hr is as shown in table 5.
Table 5 catalyst activity component and auxiliary agent content are to the influence of preparing propylene by dehydrogenating propane process
Embodiment 7
The present embodiment explanation adopts SAPO-34 as catalyst carrier, adopts the method for soaking altogether to prepare catalyst for manufacturing olefin by low-carbon alkane dehydrogenation.Prepare nickel nitrate and the lead nitrate solution of 0.3M at first respectively, then SAPO-34 be impregnated in the mixed liquor of above-mentioned two kinds of solution, dipping temperature is 30 ℃, and dip time is 1hr.Catalyst behind the dipping is dry 1hr under 150 ℃; Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation Ni of the present invention (0.5wt%) Pb (the 1wt%)/SAPO-34 that in Muffle furnace, can make then in 650 ℃ of roasting 10hr.Prepare catalyst for manufacturing olefin by low-carbon alkane dehydrogenation Pd (0.5wt%) Ge (1wt%)/SAPO-34 according to the method described above again.
Catalyst n i (0.5wt%) Pb (the 1wt%)/SAPO-34 and Pd (0.5wt%) Ge (the 1wt%)/SAPO-34 that take by weighing 0.2g respectively carry out little anti-experiment, and mass space velocity is 5.6hr
-1, the mol ratio of hydrogen and charging propane (purity 99.5%) is 1; Reaction temperature is 600 ℃, and the experimental result behind charging 2hr is as shown in table 6.
Table 6 modified metal is to the influence of preparing propylene by dehydrogenating propane process
Embodiment 8
It is catalyst that Pt (0.3wt%) Sn (0.8wt%)/SAPO-34 is adopted in the present embodiment explanation, and reaction temperature is to the influence of dehydrogenating propane process.The catalyst that takes by weighing 0.2g carries out little anti-experiment, and mass space velocity is 5.6hr
-1, the mol ratio of hydrogen and charging propane (purity 99.5%) is that 0.25 experimental result behind charging 2hr and 10hr is as shown in table 7.
Table 7 reaction temperature optionally influences preparing propylene by dehydrogenating propane process propylene
Embodiment 9
Present embodiment description weight air speed is to the influence of dehydrogenating propane process.The catalyst that takes by weighing 0.2g carries out little anti-experiment, and reaction temperature is 600 ℃, and the mol ratio of hydrogen and charging propane (purity 99.5%) is 0.25, and the experimental result after 2hr is carried out in reaction is as shown in table 8.
Table 8 weight space velocity optionally influences preparing propylene by dehydrogenating propane process propylene
Embodiment 10
Present embodiment explanation reaction pressure is to the influence of dehydrogenating propane process.The catalyst that takes by weighing 0.2g carries out little anti-experiment, and reaction temperature is 600 ℃, and the mol ratio of hydrogen and charging propane (purity 99.5%) is 0.25, and the experimental result after 2hr is carried out in reaction is as shown in table 9.
Table 9 reaction pressure optionally influences preparing propylene by dehydrogenating propane process propylene
Embodiment 11
It is the response characteristic of catalyst in normal butane catalytic dehydrogenation system olefin hydrocarbon that Pt (0.3wt%) Sn (0.8wt%)/SAPO-34 is adopted in the present embodiment explanation.
The catalyst that takes by weighing 0.2g carries out little anti-experiment, and reaction temperature is 585 ℃, and mass space velocity is 2.8hr-1, and the mol ratio of hydrogen and charging normal butane (purity 99.5%) is 5, and the experimental result behind charging 2hr is as shown in table 10.
Table 10 normal butane catalytic dehydrogenating reaction characteristic (TOS=2hr
-1)
Embodiment 12
It is the response characteristic of catalyst in pentane catalytic dehydrogenation system olefin hydrocarbon that Pt (0.3wt%) Sn (0.8wt%)/SAPO-34 is adopted in the present embodiment explanation.
The catalyst that takes by weighing 0.2g carries out little anti-experiment, and reaction temperature is 585 ℃, and mass space velocity is 2.8hr-1, and the mol ratio of hydrogen and charging pentane (purity 99.5%) is 0.25.Experimental result behind charging 2hr is as shown in table 11.
Table 11 pentane catalytic dehydrogenating reaction characteristic (TOS=2hr
-1)
Embodiment 13
The influence of catalyst regeneration condition to catalyst activity adopted in the present embodiment explanation
The catalyst that takes by weighing 0.2g carries out little anti-experiment, and reaction temperature is 585 ℃, and mass space velocity is 2.8hr-1, and the mol ratio of hydrogen and charging propane (purity 99.5%) is 0.25.Behind charging 30hr, temperature is raised under the catalyst regeneration condition, in oxygen, air, steam, carbon dioxide atmosphere, carry out catalyst regeneration respectively, carry out the catalyst activity evaluation after the regeneration, evaluation result is as shown in table 12.
Table 12 catalyst regeneration condition effect
The foregoing description is the part preferred embodiment, and protection domain of the present invention is as the criterion with the claim of application.Those skilled in the art can be the technology of catalyst with Preparation of catalysts and with it by the low-carbon alkanes catalytic dehydrogenation system propylene of using for reference the present invention's proposition, and links such as appropriate change raw material, technological parameter realize.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and content.
Claims (8)
1. catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that: this catalyst is carrier with the aluminium silicophosphate molecular sieve, with VIII family or group vib element is active component, with IVA family element is auxiliary agent, the percentage by weight that described active component accounts for catalyst is 0.001～20%, and the percentage by weight that auxiliary agent accounts for catalyst is 0.001～20%; Described low-carbon alkanes comprises propane, butane and pentane.
2. a kind of catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 1 is characterized in that: described aluminium silicophosphate molecular sieve adopts SAPO-34 or SAPO-5 molecular sieve, Al wherein
2O
3With SiO
2Mol ratio be 1～6; The mol ratio of P and Si is 0～0.1.
3. a kind of catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 1 is characterized in that: described VIII element employing Pt, Pd of family or Ni, its percentage by weight that accounts for catalyst is 0.001～10%.
4. a kind of catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 1 is characterized in that: described group vib element adopts Cr, Mo or W, and its percentage by weight that accounts for catalyst is 0.001～20%.
5. a kind of catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 1 is characterized in that: described IVA element employing Ge, Sn of family or Pb, its percentage by weight that accounts for catalyst is 0.001～20%.
6. method for preparing catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 1 is characterized in that this method carries out as follows:
1) aluminium silicophosphate molecular sieve is at first added in the soluble salt solution of auxiliary agent, assistant concentration is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
2) aluminium silicophosphate molecular sieve behind the step 1) dipping is carried out drying and roasting, baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, and roasting time is 1～10 hour;
3) with step 2) aluminium silicophosphate molecular sieve after the roasting puts in the salting liquid of active component again, and the concentration of active component is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
4) aluminium silicophosphate molecular sieve behind the step 3) dipping is carried out drying and roasting and promptly make corresponding catalyst, wherein baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, roasting time is 1～10 hour, obtains described catalyst.
7. method for preparing catalyst that is used for manufacturing olefin by low-carbon alkane dehydrogenation as claimed in claim 1 is characterized in that this method carries out as follows:
1) aluminium silicophosphate molecular sieve is added in the mixed solution of soluble salt of auxiliary agent and active component, assistant concentration is 0.01～3 mol, and the concentration of active component is 0.01～3 mol, and dipping temperature is 20～90 ℃, and dip time is 0.1～10 hour;
2) aluminium silicophosphate molecular sieve behind the step 1) dipping is carried out drying and roasting, baking temperature is 90～150 ℃, and be 1～10 hour drying time, and sintering temperature is 400～700 ℃, and roasting time is 1～10 hour; Promptly obtain described catalyst.
8. the application of catalyst in manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1 is characterized in that related processing step is as follows:
1) catalyst reduction: at first with catalyst reduction activation in hydrogen atmosphere, reduction temperature is 300～700 ℃, and the recovery time is 1～20 hour;
2) catalytic dehydrogenating reaction: with the low-carbon alkanes is raw material, or is that raw material carries out catalytic dehydrogenating reaction in reactor with low-carbon alkanes and hydrogen, and reactor is fixed bed, fluid bed or moving bed, and reaction temperature is 300～700 ℃, and weight space velocity is 0.1～100hr
-1, reaction pressure is 0.01～4MPa, the mol ratio of hydrogen and low-carbon alkanes is 0.001～10 in the raw material;
3) catalyst regeneration: reacted catalyst need carry out coke-burning regeneration, adopt in-situ regeneration or device to regenerate outward, regeneration temperature is 400～700 ℃, and regeneration pressure is 0.05～0.5Mpa, recovery time is 1-20 hour, and regeneration atmosphere is oxygen, air, steam or carbon dioxide.
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