CN109647391A - Method for preparing propylene by dehydrogenating propane - Google Patents
Method for preparing propylene by dehydrogenating propane Download PDFInfo
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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Abstract
The present invention relates to a kind of method for preparing propylene by dehydrogenating propane, mainly solve the problems, such as that the dehydrogenation activity of prior art preparation is lower.The present invention by using preparing propylene by dehydrogenating propane method, reaction raw materials are propane, in reaction condition are as follows: vapor and propane volume ratio are (10~1): 1, reaction temperature is 400 DEG C~600 DEG C, reaction pressure is 0~1MPa, and propane mass space velocity is 3.0~8.0h‑1When, reaction raw materials are contacted with catalyst, and reaction obtains propylene；Based on parts by weight, catalyst includes following components: 0.1~5 part of Pt or its oxide；0.1~5 part of Sn or its oxide；90~99 parts of composite oxides M1-M2-Al-O carriers, M1 is selected from the mixture of IIA and IIIB element, M2 is selected from at least one of lanthanide series, can preferably solve the problems, such as this, can be used for the industrial production of preparing propylene by dehydrogenating propane.
Description
Technical field
The present invention relates to a kind of methods for preparing propylene by dehydrogenating propane.
Background technique
Low-carbon alkene, such as propylene, are very important Organic Chemicals, they and isobutene, ethylene are recognized together
For the basis for being modern petrochemical, to produce polymer, gasoline, detergent and other chemical raw materials etc..Prepare propylene
Conventional method is to use ethylene coproduction and light oil (naphtha, light diesel fuel) cracking technology, but petroleum reserves is limited, and propylene is limited by
Target product, it is difficult to it is extensive to increase, so countries in the world are dedicated to the variation route that exploitation prepares propylene.Wherein with petrochemical industry by-product
Or the propane in natural gas etc. is raw material, prepares corresponding cyclopropene method by direct dehydrogenation technique and is greatly paid attention to.In recent years
Carry out the mankind to continue to increase worldwide petrochemical raw material and petroleum chemicals demand, propylene, isobutene demand as petrochemical industry basic material
Sustainable growth, traditional conventional method have been unable to meet its increased requirement, occur global in short supply.And with petroleum resources day
Beneficial deficient isobutene production is raw material to the conversion of the technology path of diversification of feedstock from the simple petroleum that relies on, especially with low-carbon
Alkane is the technology path of waste propylene, isobutene, is prepared using abundance, cheap dehydrogenating low-carbon alkane low
Carbon olefin is one of most promising method.It is being run currently, having more than 20 set dehydrogenating low-carbon alkane devices in the world, it is main de-
Hydrogen technology have the Oleflex technique of UOP, the Catofin technique of Lummus, the STAR technique of Uhde, the PDH technique of Linde,
The FBD technique etc. of Snamprogetti-Yarsintez cooperative development.
It is one kind of manufacturing olefin by low-carbon alkane dehydrogenation catalysis reaction with the catalyst that noble metal platinum element is main active component
Important catalyst.In view of Thermodynamics, catalysis reaction carries out under high temperature, lower pressure, and catalyst is during the reaction
Since the sintering of carbon deposit and active component is easy quickly to lose activity, thus frequent progress is needed to regenerate.Develop high activity, Gao Xuan
The catalyst of selecting property and high stability becomes the key of the technology.Catalyst disclosed in Chinese patent (CN200910209534.4)
K-Ce-Pt-Sn/γ-Al2O3After reacting 6h, the conversion ratio of propane is 38%, and the selectivity of propylene is 98%, and coke content compared with
It is few.Vu etc. is in " Catalysis Today " (catalysis today) 2011,164 (1): " Propane delivered on 214-220
dehydrogenation over Pt-Sn/Rare-earth-doped Al2O3:Influence of La,Ce,or Y on
The formation and stability of Pt-Sn alloys " (rare earth doped Al2O3Supporting Pt-Sn catalyst
On dehydrogenating propane reaction: the influence of La, Ce, Y and the formation and stability of Pt-Sn alloy) article discovery carrier in La, Ce and
The dispersion degree of Pt can be improved in the addition of Y, and catalyst carbon deposit is less, the PtSn and PtSn formed in them2Alloy has very high
Stability, so that PtSn/La-Al and PtSn/Ce-Al show preferable catalytic performance and stability, the conversion ratio after 3h point
It Yue Wei not be about 30% and 20%, selectivity about 95%.
Propane dehydrogenation catalyst has been achieved with greater advance at present, but there are also the spaces promoted for catalyst activity.This hair
The bright performance for using M1-M2-Al-O to improve catalyst for carrier loaded Pt-Sn catalyst has preferable application prospect, at present
There has been no relevant reports.
Summary of the invention
The first technical problem to be solved by the present invention is that propane dehydrogenation catalyst activity is lower in the prior art, provides one
The method that kind is used for preparing propylene by dehydrogenating propane.This method has the characteristics that propane dehydrogenation catalyst high activity.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of for preparing propylene by dehydrogenating propane
Method, reaction raw materials are propane, and in the presence of propane dehydrogenation catalyst, reaction raw materials and catalyst haptoreaction obtain third
Alkene, reaction condition are as follows: vapor and propane volume ratio are (10~1): 1, reaction temperature is 400 DEG C~600 DEG C, reaction pressure
For 0~1MPa, propane mass space velocity is 3.0~8.0h-1When；Wherein propane dehydrogenation catalyst is in terms of catalyst weight number, packet
Include following components: 0.1~5 part of Pt or its oxide；0.1~5 part of Sn or its oxide；90~99 parts of composite oxides M1-M2-
Al-O carrier, M1 is selected from the mixture of IIA and IIIB element, M2 is selected from at least one of lanthanide series.
In above-mentioned technical proposal, in terms of the catalyst weight number of preparing propylene by dehydrogenating propane, the number of Pt or its oxide
It is 0.1~2.5 part, the number of Sn or its oxide is 0.1~2.5 part；
In above-mentioned technical proposal, preferred technical solution is IIIB member in M1 in composite oxides M1-M2-Al-O carrier
Element is selected from Sc or Y, and preferred technical solution is Y.
In above-mentioned technical proposal, in composite oxides M1-M2-Al-O carrier in M1 IIA element be selected from Be, Mg, Ca, Sr,
At least one of Ba.
Preferred technical solution is that IIA element is selected from least one of Mg, Ca, Sr in M1 in carrier.
Preferred technical solution is that IIA element is selected from Mg and Ca in M1 in carrier.
In above-mentioned technical proposal, preferred technical solution is composite oxides M1-M2-Al-O carrier, M1 be selected from IIA and
Y, Mg and Ca in IIIB element.
M2 is selected from least one of La or Ce in composite oxides M1-M2-Al-O carrier.
Preferred technical solution is that M2 is selected from La and Ce in composite oxides M1-M2-Al-O carrier.
In above-mentioned technical proposal, IIA the and IIIB element and M2 of M1 selection in composite oxides M1-M2-Al-O carrier
Lanthanide series is used in conjunction with, and has synergy in dehydrogenating propane activity.
In above-mentioned technical proposal, with molar ratio computing in composite oxides M1-M2-Al-O carrier, Al: M1 is (1~1.99):
1, preferably (1.5-1.8): the molar ratio of IIA and IIIB in 1, M1 are (0.25~4): 1；Al: M2 is (1~199): 1, it is excellent
It is selected as (3~9): 1.
The preparation method of catalyst for preparing propylene with propane dehydrogenation, comprising the following steps:
A) soluble-salt of M1, M2 and Al of content needed for weighing are dissolved in suitable deionized water, are uniformly mixed, are being held
Slowly ammonium hydroxide is instilled under continuous stirring, adjusting pH value is 7~10；By product aging, suction filtration, drying, roast up to M1-M2-Al-
O carrier；
B) soluble-salt of the desired amount of Sn is dissolved in suitable hydrochloric acid solution, the carrier of a step is added under stiring
In, it is uniformly mixed, ultrasonic assistant soakage, it is dry, roast to obtain catalyst precarsor I；
C) soluble-salt of the desired amount of Pt is dissolved in suitable water, the catalyst precarsor of b step is added under stiring
I is uniformly mixed, ultrasonic assistant soakage, dry, roasts to obtain propane dehydrogenation catalyst.
In above-mentioned technical proposal, the dipping temperature of dipping process is 10~80 DEG C, and dip time is 1~24 hour, dry
Temperature is 80 DEG C~150 DEG C, and drying time is 6~24 hours, and maturing temperature is 450 DEG C~650 DEG C, and calcining time is 6~24
Hour.The soluble-salt of M1, M2 or its oxide can be selected from one of chloride, nitrate or acetate；The solubility of Pt
Salt is preferably chloroplatinic acid；The soluble-salt of tin is selected from one kind of stannous chloride or tin tetrachloride.
The method that the present invention produces propylene, specifically includes the following steps: one, pretreatment: preparing propylene by dehydrogenating propane is catalyzed
Agent loads in the reactor, is passed through nitrogen after heating in reactor, heats up under conditions of nitrogen flow is 10mL/min, temperature
Rise to is 450 DEG C~580 DEG C, preferably 510 DEG C~570 DEG C.It is changed to be passed through hydrogen, in the condition that hydrogen flowing quantity is 30mL/min
Lower holding 2h；Two, dehydrogenation reaction: will enter reaction zone after propane gas and vapor pre-add hot mixing, it is de- to carry out propane catalysis
Hydrogen reaction；Propane air speed is 3.0~8.0h-1, preferably 3.5~6.5h-1；Vapor and propane volume ratio (8~1): 1, preferably
For (6~2): 1；The reading of control pressure power table is 0~1MPa, preferably 0.01MPa~0.5MPa；Three, it detects: after reaction
After gas passes through drainer, the gas after dehydrogenating propane reaction is continuously monitored on-line using gas chromatograph, to survey
Calculate the selectivity of the conversion ratio of propane and propylene on catalyst in entire reaction process.
For propane dehydrogenation catalyst, many side reactions will also occur for the acid site of carrier surface, such as the cracking, different of alkane
Structure, cracking, isomerization, polymerization reaction of alkene etc., single Al2O3 are unfavorable for the selectivity and stability of catalysis reaction.
It the use of method selection composite oxides M1-M2-Al-O provided by the invention is carrier, M1 is selected from IIA and IIIB member
Mixture, the M2 of element are selected from at least one of lanthanide series.The catalyst of preparation is reacted for dehydrogenating propane, propane initial conversion
Rate is higher than 96% up to 43% or more, propane selectivity；Achieve preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
The aluminium chloride for weighing 39.97g beryllium chloride, 151.68g yttrium chloride, the lanthanum chloride of 73.58g and 226.68g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Be0.5Y0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorination
Stannous is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then 90
DEG C dry 16 hours, up to catalyst precarsor, it is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is as follows: 0.5 gram of catalyst is fitted into (catalyst bed in isothermal fixed bed reactors
Height 17mm), reaction normal pressure, 560 DEG C of temperature；Vapor and propane volume ratio are 2: 1；Propane mass space velocity is 4.0h-1.It is tied
Fruit is shown in Table 1.
[embodiment 2]
The aluminum nitrate for weighing 128.2g magnesium nitrate, 191.50g yttrium nitrate, the lanthanum nitrate of 97.47g and 637.71g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Mg0.5Y0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorination
Stannous is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then 90
DEG C dry 16 hours, up to catalyst precarsor, it is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 3]
The eston for weighing 88.09g calcium acetate, 191.50g yttrium nitrate, the lanthanum acetate of 94.81g and 275.54g can
Soluble is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, will
Product aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle furnaces
Middle roasting 20 hours to get Ca0.5Y0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g
Stannous chloride is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then
16 hours are dried at 90 DEG C up to catalyst precarsor, is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, and stirring is lower to be added
Enter in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be obtain
Propane dehydrogenation catalyst.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 4]
The eston for weighing 107.36g strontium acetate, 191.50g yttrium nitrate, the lanthanum acetate of 97.47g and 275.54g can
Soluble is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, will
Product aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle furnaces
Middle roasting 20 hours to get Sr0.5Y0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g
Stannous chloride is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then
16 hours are dried at 90 DEG C up to catalyst precarsor, is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, and stirring is lower to be added
Enter in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be obtain
Propane dehydrogenation catalyst.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 5]
The aluminium chloride for weighing 122.13g barium chloride, 151.68g yttrium chloride, the lanthanum chloride of 73.58g and 226.68g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Ba0.5Y0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorination
Stannous is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then 90
DEG C dry 16 hours, up to catalyst precarsor, it is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 6]
The aluminum nitrate for weighing 51.28g magnesium nitrate, 306.41g yttrium nitrate, the lanthanum nitrate of 97.47g and 637.71g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Mg0.2Y0.8La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorination
Stannous is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then 90
DEG C dry 16 hours, up to catalyst precarsor, it is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 7]
The aluminum nitrate for weighing 205.13g magnesium nitrate, 76.60g yttrium nitrate, the lanthanum nitrate of 97.47g and 637.71g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Mg0.8Y0.2La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorination
Stannous is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then 90
DEG C dry 16 hours, up to catalyst precarsor, it is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 8]
Weigh the aluminum nitrate soluble-salt of 66.6g beryllium nitrate, 115.49 scandium nitrates, the lanthanum nitrate of 97.47g and 637.71g
It is dissolved in the deionized water of 1L, is uniformly mixed, under continuous stirring slowly instills ammonium hydroxide, adjusting pH value is 8.5, and product is old
Change 2 hours, obtain filter cake with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle kiln roastings
20 hours to get Be0.5Sc0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorination
Stannous is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then 90
DEG C dry 16 hours, up to catalyst precarsor, it is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 9]
The aluminum nitrate for weighing 128.21g magnesium nitrate, 115.49 scandium nitrates, the lanthanum nitrate of 97.47g and 637.71g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Mg0.5Sc0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorine
Change stannous to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then exist
I is denoted as up to catalyst precarsor within 90 DEG C of dryings 16 hours.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 10]
The aluminum nitrate for weighing 118.08g calcium nitrate, 115.49 scandium nitrates, the lanthanum nitrate of 97.47g and 637.71g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Ca0.5Sc0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorine
Change stannous to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then exist
I is denoted as up to catalyst precarsor within 90 DEG C of dryings 16 hours.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 11]
The aluminum nitrate for weighing 105.82g strontium nitrate, 115.49 scandium nitrates, the lanthanum nitrate of 97.47g and 637.71g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Sr0.5Sc0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorine
Change stannous to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then exist
I is denoted as up to catalyst precarsor within 90 DEG C of dryings 16 hours.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 12]
The aluminum nitrate for weighing 130.67g barium nitrate, 115.49 scandium nitrates, the lanthanum nitrate of 97.47g and 637.71g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Ba0.5Sc0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorine
Change stannous to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then exist
I is denoted as up to catalyst precarsor within 90 DEG C of dryings 16 hours.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 13]
The aluminum nitrate for weighing 128.2g magnesium nitrate, 191.50 yttrium nitrates, the ammonium ceric nitrate of 164.48g and 637.71g is solvable
Property salt be dissolved in the deionized water of 1L, be uniformly mixed, slowly ammonium hydroxide is instilled under continuous stirring, adjust pH value be 8.5, will produce
Object aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle furnaces
Roasting 20 hours to get Mg0.5Y0.5Ce0.3Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorine
Change stannous to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then exist
I is denoted as up to catalyst precarsor within 90 DEG C of dryings 16 hours.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 14]
Weigh 128.2g magnesium nitrate, 191.50 yttrium nitrates, the lanthanum nitrate of 48.74g, 82.23g ammonium ceric nitrate and
The aluminum nitrate soluble-salt of 637.71g is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly dripped ammonium hydroxide
Enter, adjusting pH value is 8.5, by product aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake at 90 DEG C dry 16
Hour after, 580 DEG C Muffle kiln roasting 20 hours to get Mg0.5Y0.5La0.15Ce0.15Al1.7OxCarrier.Weigh 9.84g carrier
It is put into beaker, then weighs 0.190g stannous chloride and be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, mix
Uniformly, it impregnates 12 hours for 30 DEG C, dries 16 hours at 90 DEG C then up to catalyst precarsor, be denoted as I.Weigh the chlorine platinum of 0.159g
Acid is dissolved in 10mL water, is added with stirring in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, in 580 DEG C of horses
Not obtain propane dehydrogenation catalyst within kiln roasting 20 hours.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 15]
The aluminum nitrate for weighing 128.2g magnesium nitrate, 191.50 yttrium nitrates, the lanthanum nitrate of 162.46g and 562.70g is soluble
Salt is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, by product
Aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, is roasted in 580 DEG C of Muffle furnaces
20 hours are burnt to get Mg0.5Y0.5La0.5Al1.5OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorination
Stannous is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then 90
DEG C dry 16 hours, up to catalyst precarsor, it is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 16]
Weigh the aluminum nitrate soluble-salt of 128.2g magnesium nitrate, 191.50 yttrium nitrates, the lanthanum nitrate of 64.98g and 675.23g
It is dissolved in the deionized water of 1L, is uniformly mixed, under continuous stirring slowly instills ammonium hydroxide, adjusting pH value is 8.5, and product is old
Change 2 hours, obtain filter cake with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle kiln roastings
20 hours to get Mg0.5Y0.5La0.2Al1.8OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g protochloride
Tin is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C impregnate 12 hours, then at 90 DEG C
Up to catalyst precarsor, it is denoted as I within dry 16 hours.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring in I,
Be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours i.e. obtain propane take off
Hydrogen catalyst.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 17]
Weigh the lanthanum nitrate and 637.71g of 64.10g magnesium nitrate, the calcium nitrate of 59.04g, 191.50 yttrium nitrates, 97.47g
Aluminum nitrate soluble-salt be dissolved in the deionized water of 1L, be uniformly mixed, slowly ammonium hydroxide is instilled under continuous stirring, adjust pH
Value is 8.5, by product aging 2 hours, obtains filter cake with 4L water filtering and washing, by filter cake after 90 DEG C are 16 hours dry,
580 DEG C Muffle kiln roasting 20 hours to get Mg0.25Ca0.25Y0.5La0.3Al1.7O4Carrier.It weighs 9.84g carrier and is put into beaker
In, it then weighs 0.190g stannous chloride and is dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30
DEG C dipping 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor, be denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in
In 10mL water, be added with stirring in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, in 580 DEG C of Muffle furnaces
Obtain propane dehydrogenation catalyst within roasting 20 hours.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 18]
Weigh the lanthanum nitrate and 637.71g of 64.10g magnesium nitrate, the calcium nitrate of 59.04g, 115.49g scandium nitrate, 97.47g
Aluminum nitrate soluble-salt be dissolved in the deionized water of 1L, be uniformly mixed, slowly ammonium hydroxide is instilled under continuous stirring, adjust pH
Value is 8.5, by product aging 2 hours, obtains filter cake with 4L water filtering and washing, by filter cake after 90 DEG C are 16 hours dry,
580 DEG C Muffle kiln roasting 20 hours to get Mg0.25Ca0.25Sc0.5La0.3Al1.7OxCarrier.It weighs 9.84g carrier and is put into beaker
In, it then weighs 0.190g stannous chloride and is dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30
DEG C dipping 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor, be denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in
In 10mL water, be added with stirring in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, in 580 DEG C of Muffle furnaces
Obtain propane dehydrogenation catalyst within roasting 20 hours.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 19]
Weigh the lanthanum nitrate and 637.71g of 64.10g magnesium nitrate, the calcium nitrate of 59.04g, 191.50g yttrium nitrate, 97.47g
Aluminum nitrate soluble-salt be dissolved in the deionized water of 1L, be uniformly mixed, slowly ammonium hydroxide is instilled under continuous stirring, adjust pH
Value is 8.5, by product aging 2 hours, obtains filter cake with 4L water filtering and washing, by filter cake after 90 DEG C are 16 hours dry,
580 DEG C Muffle kiln roasting 20 hours to get Mg0.25Ca0.25Y0.5Ce0.15La0.15Al1.7OxCarrier.9.84g carrier is weighed to be put into
In beaker, then weighs 0.190g stannous chloride and be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, mixing is equal
Even, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.Weigh the chloroplatinic acid of 0.159g
Be dissolved in 10mL water, be added with stirring in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, in 580 DEG C of Muffles
Obtain propane dehydrogenation catalyst within kiln roasting 20 hours.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[embodiment 20]
Weigh 25.64g magnesium nitrate, the calcium nitrate of 23.61g, 306.41g yttrium nitrate, 82.23g ammonium ceric nitrate, 48.74g
The aluminum nitrate soluble-salt of lanthanum nitrate and 637.71g are dissolved in the deionized water of 1L, are uniformly mixed, and slowly will under continuous stirring
Ammonium hydroxide instills, and adjusting pH value is 8.5, by product aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake at 90 DEG C
After dry 16 hours, 580 DEG C Muffle kiln roasting 20 hours to get Mg0.1Ca0.1Y0.8Ce0.15La0.15Al1.7OxCarrier.Claim
Amount 9.84g carrier is put into beaker, is then weighed 0.190g stannous chloride and is dissolved in the hydrochloric acid solution of 10mL, is added with stirring
Carrier is stated, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C of dryings 16 are small
When, propane dehydrogenation catalyst is obtained within Muffle kiln roasting 20 hours at 580 DEG C.Evaluating catalyst condition is the same as embodiment 1.It is tied
Fruit is shown in Table 1.
[embodiment 21]
Weigh 102.56g magnesium nitrate, the calcium nitrate of 94.46g, 76.60g yttrium nitrate, 82.23g ammonium ceric nitrate, 97.47g
The aluminum nitrate soluble-salt of lanthanum nitrate and 637.71g are dissolved in the deionized water of 1L, are uniformly mixed, and slowly will under continuous stirring
Ammonium hydroxide instills, and adjusting pH value is 8.5, by product aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake at 90 DEG C
After dry 16 hours, 580 DEG C Muffle kiln roasting 20 hours to get Mg0.4Ca0.4Y0.2Ce0.15La0.15Al1.7OxCarrier.Claim
Amount 9.84g carrier is put into beaker, is then weighed 0.190g stannous chloride and is dissolved in the hydrochloric acid solution of 10mL, is added with stirring
Carrier is stated, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C of dryings 16 are small
When, propane dehydrogenation catalyst is obtained within Muffle kiln roasting 20 hours at 580 DEG C.Evaluating catalyst condition is the same as embodiment 1.It is tied
Fruit is shown in Table 1.
[embodiment 22]
Use the catalyst of example 14, evaluation condition are as follows: normal pressure, 450 DEG C of temperature；Vapor and propane volume ratio are 2: 1；
Propane mass space velocity is 4.0h-1.The result is shown in tables 1.
[embodiment 23]
Use the catalyst of example 14, evaluation condition are as follows: normal pressure, 510 DEG C of temperature；Vapor and propane volume ratio are 2: 1；
Propane mass space velocity is 4.0h-1.The result is shown in tables 1.
[embodiment 24]
Use the catalyst of example 14, evaluation condition are as follows: normal pressure, 580 DEG C of temperature；Vapor and propane volume ratio are 2: 1；
Propane mass space velocity is 4.0h-1.The result is shown in tables 1.
[comparative example 1]
The aluminum nitrate soluble-salt of the lanthanum nitrate and 637.71g that weigh 97.47g is dissolved in the deionized water of 1L, and mixing is equal
It is even, slowly ammonium hydroxide is instilled under continuous stirring, adjusting pH value is 8.5, by product aging 2 hours, with 4L water filtering and washing
Obtain filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C Muffle kiln roasting 20 hours to get La0.3Al1.7O3It carries
Body.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g stannous chloride and be dissolved in the hydrochloric acid solution of 10mL, under stirring
Above-mentioned carrier is added, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as
I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C dry
Dry 16 hours, propane dehydrogenation catalyst was obtained within Muffle kiln roasting 20 hours at 580 DEG C.The same embodiment of evaluating catalyst condition
1.The result is shown in tables 1.
[comparative example 2]
Weigh the deionized water that 128.2g magnesium nitrate, 191.50 yttrium nitrates and 750.26g aluminum nitrate soluble-salt are dissolved in 1L
In, it is uniformly mixed, under continuous stirring slowly instills ammonium hydroxide, adjusting pH value is 8.5, and product aging 2 hours are taken out with 4L water
Filter washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Mg0.5Y0.5Al2OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs the hydrochloric acid that 0.190g stannous chloride is dissolved in 10mL
In solution, it is added with stirring above-mentioned carrier, is uniformly mixed, 30 DEG C impregnate 12 hours, then urge to obtain the final product within dry 16 hours at 90 DEG C
Agent precursor, is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring in I, is uniformly mixed, 30 DEG C of dippings
12 hours, 90 DEG C drying 16 hours, obtain propane dehydrogenation catalyst within Muffle kiln roasting 20 hours at 580 DEG C.Catalyst is commented
Valence condition is the same as embodiment 1.The result is shown in tables 1.
[comparative example 3]
The aluminum nitrate for weighing 256.40g magnesium nitrate, the lanthanum nitrate of 48.74g, the ammonium ceric nitrate of 82.23g and 637.71g can
Soluble is dissolved in the deionized water of 1L, is uniformly mixed, is under continuous stirring slowly instilled ammonium hydroxide, and adjusting pH value is 8.5, will
Product aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle furnaces
Middle roasting 20 hours to get MgLa0.15Ce0.15Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g
Stannous chloride is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then
16 hours are dried at 90 DEG C up to catalyst precarsor, is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, and stirring is lower to be added
Enter in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be obtain
Propane dehydrogenation catalyst.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[comparative example 4]
The aluminum nitrate for weighing 383.0 yttrium nitrates, the lanthanum nitrate of 48.74g, the ammonium ceric nitrate of 82.23g and 637.71g is solvable
Property salt be dissolved in the deionized water of 1L, be uniformly mixed, slowly ammonium hydroxide is instilled under continuous stirring, adjust pH value be 8.5, will produce
Object aging 2 hours, filter cake is obtained with 4L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle furnaces
Roasting 20 hours to get YLa0.15Ce0.15Al1.7OxCarrier.It weighs 9.84g carrier to be put into beaker, then weighs 0.190g chlorine
Change stannous to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then exist
I is denoted as up to catalyst precarsor within 90 DEG C of dryings 16 hours.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is added with stirring I
In, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain propane
Dehydrogenation.Evaluating catalyst condition is the same as embodiment 1.The result is shown in tables 1.
[comparative example 5]
The aluminum nitrate soluble-salt for weighing 637.71g is dissolved in the deionized water of 1L, is uniformly mixed, is delayed under continuous stirring
Slowly ammonium hydroxide is instilled, adjusting pH value is 8.5, by product aging 2 hours, obtains filter cake with 4L water filtering and washing, filter cake is existed
90 DEG C after drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours, obtain carrier Al2O3.It is poured into containing 256.41 nitre
Sour magnesium, 97.47g lanthanum nitrate 500ml mixed solution in 30 DEG C impregnate 12 hours, it is then 16 hours dry at 90 DEG C,
580 DEG C Muffle kiln roasting 20 hours to get MgLa0.3Ox/Al1.7Ox, weighed 9.84g and be put into beaker, then weighed
0.190g stannous chloride is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C of dippings 12 are small
When, it dries 16 hours at 90 DEG C then up to catalyst precarsor, is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is stirred
Mix in lower addition I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours
Obtain propane dehydrogenation catalyst.Evaluating catalyst condition the results are shown in Table 1 with embodiment 1.
[comparative example 6]
The aluminum nitrate soluble-salt for weighing 637.71g is dissolved in the deionized water of 1L, is uniformly mixed, is delayed under continuous stirring
Slowly ammonium hydroxide is instilled, adjusting pH value is 8.5, by product aging 2 hours, obtains filter cake with 4L water filtering and washing, filter cake is existed
90 DEG C after drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours, obtain carrier Al2O3.It is poured into containing 128.2g nitre
Sour magnesium, 191.50 yttrium nitrates, the lanthanum nitrate of 48.74g, 82.23g ammonium ceric nitrate 500ml mixed solution in 30 DEG C dipping
It is 12 hours, then 16 hours dry at 90 DEG C, 580 DEG C Muffle kiln roasting 20 hours to get Mg0.5Y0.5La0.15Ce0.15Ox/
Al1.7Ox, weighed 9.84g and be put into beaker, then weighed 0.190g stannous chloride and be dissolved in the hydrochloric acid solution of 10mL, stir
Mix it is lower above-mentioned carrier is added, be uniformly mixed, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor,
It is denoted as I.Weigh 0.159g chloroplatinic acid be dissolved in 10mL water, be added with stirring in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90
DEG C dry 16 hours, propane dehydrogenation catalyst was obtained within Muffle kiln roasting 20 hours at 580 DEG C.Evaluating catalyst condition is the same as real
Example 1 is applied, the results are shown in Table 1.
[comparative example 7]
The aluminum nitrate soluble-salt for weighing 637.71g is dissolved in the deionized water of 1L, is uniformly mixed, is delayed under continuous stirring
Slowly ammonium hydroxide is instilled, adjusting pH value is 8.5, by product aging 2 hours, obtains filter cake with 4L water filtering and washing, filter cake is existed
90 DEG C after drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours, obtain carrier Al2O3.It is poured into containing 383.0g nitre
Sour yttrium, 97.47g lanthanum nitrate 500ml mixed solution in 30 DEG C impregnate 12 hours, it is then 16 hours dry at 90 DEG C,
580 DEG C Muffle kiln roasting 20 hours to get YLa0.3Ox/Al1.7Ox, weighed 9.84g and be put into beaker, then weighed
0.190g stannous chloride is dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned carrier, is uniformly mixed, and 30 DEG C of dippings 12 are small
When, it dries 16 hours at 90 DEG C then up to catalyst precarsor, is denoted as I.The chloroplatinic acid for weighing 0.159g is dissolved in 10mL water, is stirred
Mix in lower addition I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours
Obtain propane dehydrogenation catalyst.Evaluating catalyst condition the results are shown in Table 1 with embodiment 1.
Catalyst for preparing propylene with propane dehydrogenation is formed, is fixed as Pt:0.6 parts, Sn:1.0 parts, remaining is that carrier is 98.4
Part.Above example and comparative example carrier are standby according to 1mol numeral system, and table 1 lists the composition and molfraction and corresponding of carrier
Catalyst performance.
Table 1
Claims (10)
1. a kind of method for preparing propylene by dehydrogenating propane, which is characterized in that reaction raw materials are propane, in propane dehydrogenation catalyst
In the presence of, reaction raw materials and catalyst haptoreaction obtain propylene, reaction condition are as follows: vapor and propane volume ratio are
(10~1): 1, reaction temperature is 400 DEG C~600 DEG C, and reaction pressure is 0~1MPa, and alkane mass space velocity is 3.0~8.0h-1
When；Wherein propane dehydrogenation catalyst is in terms of catalyst weight number, including following components: 0.1~5 part of Pt or its oxide；0.1
~5 parts of Sn or its oxide；90~99 parts of composite oxides M1-M2-Al-O carriers, M1 are selected from the mixing of IIA and IIIB element
Object, M2 are selected from at least one of lanthanide series.
2. being used for the method for preparing propylene by dehydrogenating propane according to claim 1, it is characterised in that with preparing propylene by dehydrogenating propane
The number of catalyst weight number meter, Pt or its oxide is 0.1~2.5 part, and the number of Sn or its oxide is 0.1~2.5
Part.
3. being used for the method for preparing propylene by dehydrogenating propane according to claim 1, it is characterised in that composite oxides M1-M2-Al-
IIIB element in O carrier in M1 is selected from Sc or Y.
4. being used for the method for preparing propylene by dehydrogenating propane according to claim 1, it is characterised in that composite oxides M1-M2-Al-
IIA element is selected from least one of Be, Mg, Ca, Sr, Ba in M1 in O carrier.
5. being used for the method for preparing propylene by dehydrogenating propane according to claim 1, it is characterised in that composite oxides M1-M2-Al-
M2 is selected from least one of La or Ce in O carrier.
6. being used for the method for preparing propylene by dehydrogenating propane according to claim 1, which is characterized in that with molar ratio computing, Al:M1 is
(1~1.99): the molar ratio of IIA and IIIB in 1, M1 are (0.25~4): 1.
7. being used for the method for preparing propylene by dehydrogenating propane according to claim 1, which is characterized in that with molar ratio computing, Al:M2 is
(1~199): 1.
8. the method according to claim 1 for preparing propylene by dehydrogenating propane, which is characterized in that the dehydrogenating propane system
The preparation method of propylene catalyst, comprising the following steps:
A) soluble-salt of M1, M2 and Al of content needed for weighing are dissolved in suitable deionized water, are uniformly mixed, are persistently being stirred
Mix it is lower slowly ammonium hydroxide is instilled, adjust pH value be 7~10；By product aging, suction filtration, drying, roast up to M1-M2-Al-O load
Body；
B) soluble-salt of the desired amount of Sn is dissolved in suitable hydrochloric acid solution, is added in the carrier of a step under stiring, mixed
It closes uniformly, ultrasonic assistant soakage is dry, roasts to obtain catalyst precarsor I；
C) soluble-salt of the desired amount of Pt is dissolved in suitable water, the catalyst precarsor I of b step is added under stiring, mixed
It closes uniformly, ultrasonic assistant soakage is dry, roasts to obtain propane dehydrogenation catalyst.
9. the preparation method of the catalyst according to claim 8 for preparing propylene by dehydrogenating propane method, it is characterised in that
Dipping temperature in step b) and step c) is 10~80 DEG C, and drying temperature is 80 DEG C~150 DEG C, maturing temperature is 450 DEG C~
650℃。
10. the preparation method of the catalyst according to claim 8 for preparing propylene by dehydrogenating propane method, it is characterised in that
Dip time in step b) and step c) is 1~24 hour, and drying time is 6~24 hours, calcining time is 6~24 small
When.
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| CN104084198A (en) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst |
| CN105363443A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Catalyst used for preparing low-carbon olefin through low-carbon alkane dehydrogenation and using method thereof |
| CN106607100A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Carrier of catalyst for light alkane dehydrogenation preparation of light olefin and use thereof |
| CN105396586A (en) * | 2015-11-05 | 2016-03-16 | 中国海洋石油总公司 | Quaternary platinum-based light-alkane dehydrogenation catalyst and preparation method thereof |
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