CN105582922B - Catalyst for dehydrogenating low-carbon alkane - Google Patents
Catalyst for dehydrogenating low-carbon alkane Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane, mainly solve the problems, such as that the dehydrogenation activity of prior art preparation is lower, stability is poor.The present invention is by using a kind of catalyst for dehydrogenating low-carbon alkane, based on parts by weight, including following components: a) 0.1~5 part of Pt or its oxide；B) 0.1~5 part of Sn of 0.1~5 part of alkali metal or its oxide c) or its oxide；D) 0.1~10 part of Ce-Ln-O solid solution, Ln are lanthanide series；E) 80~99 parts of Al2O3The technical solution of carrier, preferably solves the problems, such as this, can be used for dehydrogenating low-carbon alkane and prepares low-carbon alkene industrial production.
Description
Technical field
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane.
Background technique
Low-carbon alkene, such as propylene and isobutene, are very important Organic Chemicals, they and ethylene are recognized together
For the basis for being modern petrochemical, to produce polymer, gasoline, detergent and other chemical raw materials etc..Messenger in recent years
Class continues to increase worldwide petrochemical raw material and petroleum chemicals demand, continues as the propylene of petrochemical industry basic material, isobutene demand
Increase, occurs global in short supply.Prepare propylene and isobutene conventional method be using ethylene coproduction and light oil (naphtha,
Light diesel fuel) cracking technology, but petroleum reserves is limited, and propylene and isobutene are 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 and isobutene.Wherein in petrochemical industry by-product or natural gas etc. propane and
Iso-butane is raw material, prepares corresponding propylene by direct dehydrogenation technique and isobutene method is greatly paid attention to, abundance, valence
It is one of most promising method that the cheap dehydrogenating low-carbon alkane of lattice, which prepares low-carbon alkene,.Currently, having more than 20 sets third in the world
Alkane or dehydrogenation of isobutane device are being run, and main De-hydrogen Technology has the Oleflex technique of UOP, the Catofin work of Lummus
Skill, the STAR technique of Uhde, the PDH technique of Linde, FBD technique of Snamprogetti-Yarsintez cooperative development etc..
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, wherein improving catalyst performance using rare earth element is used for alkane
Dehydrogenation is in recent years by very big attention.Catalyst K-Ce- disclosed in Chinese patent (CN200910209534.4)
Pt-Sn/γ-Al2O3After reacting 6h, the conversion ratio of propane is 38%, and the selectivity of propylene is 98%, and coke content is less, should
Research is without providing stability data.Vu etc. is in " Catalysis Today " (catalysis today) 2011,164 (1): on 214-220
" the Propane dehydrogenation over Pt-Sn/Rare-earth-doped Al delivered2O3:Influence of
La, Ce, or Y on the formation and stability of Pt-Sn alloys " (rare earth doped Al2O3It is negative
Carry the dehydrogenating propane reaction on Pt-Sn catalyst: the influence of La, Ce, Y and the formation and stability of Pt-Sn alloy) article discovery
The dispersion degree of Pt can be improved in the addition of La, Ce and Y in carrier, and catalyst carbon deposit is less, the PtSn and PtSn formed in them2
Alloy has very high stability, so that PtSn/La-Al and PtSn/Ce-Al show preferable catalytic performance and stability, 3h
Conversion ratio afterwards respectively may be about about 30% and 20%, selectivity about 95%.
Catalyst for dehydrogenation of low-carbon paraffin has been achieved with greater advance at present, but catalyst activity is there are also the space promoted,
More importantly stability is also required to further strengthen.The present invention uses Ce-Ln-O solid solution and alkali metal for auxiliary agent, and addition is urged
Change catalyst surface characteristic in agent, to improve the performance of catalyst, therefore there is preferable application prospect, at present there has been no
Relevant report.
Summary of the invention
The first technical problem to be solved by the present invention is that catalyst for dehydrogenation of low-carbon paraffin activity is lower, steady in the prior art
The problem of qualitative difference provides a kind of new for catalyst for dehydrogenation of low-carbon paraffin.The second technical problem to be solved by the present invention is
There is provided one of one kind and solution technical problem corresponding method for preparing catalyst.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of be used for dehydrogenating low-carbon alkane
Catalyst, based on parts by weight, including following components:
A) 0.1~5 part of Pt or its oxide；
B) 0.1~5 part of alkali metal or its oxide；
C) 0.1~5 part of Sn or its oxide；
D) 0.1~10 part of Ce-Ln-O solid solution, Ln are lanthanide series；
E) 80~99 parts of Al2O3Carrier.
In above-mentioned technical proposal, it is used for catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that with low-carbon alkanes catalyst weight
Number meter contains 0.1~2.5 part of Sn or its oxide；Based on parts by weight, the number of alkali metal or its oxide is 0.5~2
Part；Based on parts by weight, the preferred scope of Pt element number is 0.1~2.5 part；It is with Pt:Sn in molar ratio computing catalyst
(0.01~5): 1；Rare earth element Ln is preferably La element, in terms of low-carbon alkanes catalyst weight number, Ce-Ln-O solid solution part
Number is 1~5, and with molar ratio computing, Ce:Ln is (1~99): 1, preferably 3~9；Al used2O3For γ, δ and θ type Al2O3In
It is one or two kinds of.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of be used for dehydrogenating low-carbon alkane
The preparation method of catalyst, comprising the following steps:
A) above-mentioned carrier Al is weighed2O3It pours into suitable deionized water and stirs, the Ce's and Ln of content needed for weighing is solvable
Property salt is dissolved in respectively in suitable deionized water, is then uniformly mixed the two, is poured into the mixed liquor of carrier and water, continues to stir
It mixes, is slowly dropped into pH adjusting agent under continuous stirring until pH is 7~10；By product aging, suction filtration, drying, roast up to Ce-
Ln-O solid solution and Al2O3Complex 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, impregnates, 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, and is impregnated, dry, roasts to obtain catalyst for dehydrogenation of low-carbon paraffin.
In above-mentioned technical proposal, mixing time is 0.5~2 hour, and the dipping temperature of dipping process is 10~80 DEG C, dipping
Time is 1~24 hour, and drying temperature is 80 DEG C~150 DEG C, and drying time is 6~24 hours.Roasting process is to be in temperature
450 DEG C~650 DEG C roast 6~24 hours.The soluble-salt of Ce and Ln can be selected from one in chloride, nitrate or acetate
Kind；The soluble-salt of Pt is preferably chloroplatinic acid；The soluble-salt of tin is selected from one kind of stannous chloride or tin tetrachloride.
Catalyst obtained carries out activity rating in isotherm formula fixed bed reactors according to the above method, de- to low-carbon alkanes
For hydrogen producing light olefins system appraisal, summary process is as follows:
By low-carbon alkanes unstrpped gas by mass flowmenter adjust flow, mixed into pre-add hot-zone, then into
Enter reaction zone, the pre-add hot-zone of reactor and reaction zone are all made of electric-heating-wire-heating, make up to predetermined temperature, reactor it is interior
Diameter is the stainless steel sleeve pipe of Ф 9mm-Ф 6mm, is about 400mm.After gas after reaction passes through drainer, into gas-chromatography
Analyze its composition.Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors: 0.5 gram or so of catalyst is packed into internal diameter
(catalyst bed layer height about 17mm), propane or iso-butane and hydrogen volume ratio are in isothermal reactor for Ф 9mm-Ф 6mm
10:1~1:1, reaction temperature are 400 DEG C~600 DEG C, and reaction pressure is 0~1MPa, and alkane mass space velocity is 3.0~8.0h-1,
Reaction raw materials and the catalyst haptoreaction obtain propylene or isobutene.
During dehydrogenating low-carbon alkane, single Pt catalyst anti-sintering property is poor, and addition auxiliary agent and selection are suitable
The anti-sintering property of Pt catalyst can be improved in carrier.The solid solution of rare earth metal is added, can be enhanced in catalyst metal with
Interaction between metal, metal and carrier improves dispersion of the Pt element on carrier, to improve Pt series catalysts anti-carbon
Ability.In addition, alkali metal can reduce surface acidity, product desorption rate is improved, it is advantageous to selectivity.It is helped simultaneously using two kinds
Agent may be implemented the comprehensive of catalyst performance and be promoted.The catalyst prepared using method provided by the invention is for dehydrogenation of isobutane
Reaction, iso-butane conversion ratio are selectively higher than 93% up to 54% or more, iso-butane；By 20 coke-burning regenerations, iso-butane conversion
Rate is maintained at 53% or more, and iso-butane is selectively higher than 93%, and catalyst performance is preferably and stable, achieves preferable technology effect
Fruit.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.773g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.115g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.8La0.2O2-δ-Al2O3Carrier, La can make CeO here2Oxygen vacancy is generated, δ is the non-stoichiometry value (similarly hereinafter) of oxygen.Claim
Amount 0.190g stannous chloride is dissolved in the hydrochloric acid solution of 10mL, is added with stirring in above-mentioned carrier, is uniformly mixed, 30 DEG C of dippings 12
Hour, it dries 16 hours at 90 DEG C then up to catalyst precarsor, is denoted as I.Weigh the chloroplatinic acid of 0.159g and 0.259 nitric acid
Potassium 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 i.e. obtaining catalyst for dehydrogenation of low-carbon paraffin is denoted as A within kiln roasting 20 hours.Evaluating catalyst condition is as follows: 0.5 gram is catalyzed
Agent is fitted into above-mentioned isothermal fixed bed reactors (catalyst bed layer height 17mm), reaction normal pressure, and 550 DEG C of temperature；Iso-butane and
Hydrogen volume ratio is 2.5:1；Alkane mass space velocity is 4.6h-1.The result is shown in tables 2.
[embodiment 2]
It weighs after 9.73g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.026g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.004g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 7.0.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, is uniformly mixed, 10 DEG C impregnate 24 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 and 0.259 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 10 DEG C of dippings 24 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as B within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 3]
It weighs after 8.74g alumina support pours into 200mL deionized water and stir 1 hour, weighing 2.576g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.382g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 10.0.By product aging 2 hours, 2L is used
Water filtering and 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
Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, is uniformly mixed, 80 DEG C impregnate 1 hour, dry 16 hours at 90 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.259 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 80 DEG C of dippings 1 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as C within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 4]
Weigh after 9.24g alumina support pours into 200mL deionized water and stir 1 hour, weigh 0.875g cerium chloride with
0.144g lanthanum chloride is dissolved in respectively in 50mL deionized water, is then uniformly mixed the two, pours into the mixed liquor of aluminium oxide and water
In, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, taken out with 2L water
Filter washing obtains filter cake, by filter cake at 80 DEG C after dry 24 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 24 hours at 80 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.259 potassium chloride are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 80 DEG C drying 24 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as D within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 5]
It weighs after 9.64g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.258g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.038g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 150 DEG C after dry 6 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.295g tin tetrachloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, is uniformly mixed, 30 DEG C impregnate 12 hours, dry 6 hours at 150 DEG C then up to catalyst precarsor, are denoted as I.It weighs
The chloroplatinic acid of 0.159g and 0.259 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 150 DEG C drying 6 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as E within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 6]
Weigh after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, weigh 0.955 ammonium ceric nitrate with
0.011 lanthanum nitrate is dissolved in respectively in 50mL deionized water, is then uniformly mixed the two, pours into the mixed liquor of aluminium oxide and water
In, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, taken out with 2L water
Filter washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 450 DEG C of Muffle kiln roastings 24 hours to get
Ce0.99La0.01O2-δ-Al2O3-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring
It in above-mentioned carrier, 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 and 0.259 potassium nitrate is dissolved in 10mL water, be added with stirring in I, be uniformly mixed, 30 DEG C of dippings
12 hours, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 450 DEG C and be denoted as F within Muffle kiln roasting 24 hours.
Examination condition the results are shown in Table 2 with embodiment 1.
[embodiment 7]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.484g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.287g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.5La0.5O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, 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 and 0.259 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as G within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 8]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.724g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.143g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.75La0.25O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned
It in carrier, 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 and 0.259 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as H within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 9]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.869g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.057g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.9La0.1O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, 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 and 0.259 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as I within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 10]
It weighs after 9.67g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.773g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.115g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.019g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, 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 0.027g and 0.100 lithium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as J within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 11]
It weighs after 8.20g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.773g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.115g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.951g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, 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 1.327g and 1.848 sodium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as K within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 12]
It weighs after 9.00g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.773g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.115g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 650 DEG C of Muffle kiln roastings 6 hours to get
Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.475g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, 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 0.664g and 0.345 rubidium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 650 DEG C and be denoted as L within Muffle kiln roasting 6 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 13]
It weighs after 9.49g alumina support pours into 200mL deionized water and stir 0.5 hour, weighing 0.773g cerous nitrate
Ammonium and 0.115g lanthanum nitrate are dissolved in respectively in 50mL deionized water, are then uniformly mixed the two, pour into the mixed of aluminium oxide and water
It closes in liquid, after continuing stirring 0.5 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 1 hour, use
1L water filtering and washing obtains filter cake, by filter cake at 90 DEG C after dry 16 hours, 580 DEG C Muffle kiln roasting 20 hours, i.e.,
Obtain Ce0.8La0.2O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring above-mentioned
It in carrier, 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 and 0.073 cesium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as M within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 14]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.771g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.119g praseodymium nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.8Pr0.2O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, is added with stirring above-mentioned load
It in body, 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 and 0.259 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C of dippings 12 are small
When, 90 DEG C drying 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin at 580 DEG C and be denoted as N within Muffle kiln roasting 20 hours.Examination
Condition the results are shown in Table 2 with embodiment 1.
[embodiment 15]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, 0.772 ammonium ceric nitrate of weighing,
0.0286g lanthanum nitrate and 0.0895 praseodymium nitrate are dissolved in respectively in 50mL deionized water, are then uniformly mixed the two, pour into oxidation
In the mixed liquor of aluminium and water, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging
2 hours, filter cake is obtained with 2L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle kiln roastings 20
Hour is to get Ce0.8La0.05Pr0.15O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, stir
Mix it is lower be added in above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 hours up to catalyst before
Body is denoted as I.It weighs the chloroplatinic acid of 0.159g and 0.259 potassium nitrate is dissolved in 10mL water, be added with stirring in I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain dehydrogenating low-carbon alkane
Catalyst is denoted as O.Examination condition the results are shown in Table 2 with embodiment 1.
[embodiment 16]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, 0.772 ammonium ceric nitrate of weighing,
0.0858g lanthanum nitrate and 0.0299 praseodymium nitrate are dissolved in respectively in 50mL deionized water, are then uniformly mixed the two, pour into oxidation
In the mixed liquor of aluminium and water, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging
2 hours, filter cake is obtained with 2L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle kiln roastings 20
Hour is to get Ce0.8La0.15Pr0.05O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, stir
Mix it is lower be added in above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 hours up to catalyst before
Body is denoted as I.It weighs the chloroplatinic acid of 0.159g and 0.259 potassium nitrate is dissolved in 10mL water, be added with stirring in I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain dehydrogenating low-carbon alkane
Catalyst is denoted as P.Examination condition the results are shown in Table 2 with embodiment 1.
[embodiment 17]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, 0.772 ammonium ceric nitrate of weighing,
0.0572g lanthanum nitrate and 0.0597 praseodymium nitrate are dissolved in respectively in 50mL deionized water, are then uniformly mixed the two, pour into oxidation
In the mixed liquor of aluminium and water, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging
2 hours, filter cake is obtained with 2L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, in 580 DEG C of Muffle kiln roastings 20
Hour is to get Ce0.8La0.1Pr0.1O2-δ-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, stir
It is lower to be added in above-mentioned carrier, 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.It weighs the chloroplatinic acid of 0.159g and 0.259 potassium nitrate is dissolved in 10mL water, be added with stirring in I, be uniformly mixed, 30
DEG C dipping 12 hours, 90 DEG C drying 16 hours, 580 DEG C Muffle kiln roasting 20 hours be to obtain catalyst for dehydrogenation of low-carbon paraffin
It is denoted as Q.Examination condition the results are shown in Table 2 with embodiment 1.
[comparative example 1]
It weighs after 9.44g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.773g ammonium ceric nitrate
It is dissolved in 50mL deionized water with 0.115g lanthanum nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 1 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 8.5.By product aging 2 hours, with 2L water
Filtering and 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
Ce0.8La0.2O2-δ-Al2O3Carrier, La can make CeO here2Oxygen vacancy is generated, δ is the non-stoichiometry value (similarly hereinafter) of oxygen.Claim
Amount 0.190g stannous chloride is dissolved in the hydrochloric acid solution of 10mL, is added with stirring in above-mentioned carrier, is uniformly mixed, 30 DEG C of dippings 12
Hour, 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,
Be added with stirring in I, be uniformly mixed, 30 DEG C impregnate 12 hours, 90 DEG C drying 16 hours, it is small in 580 DEG C of Muffle kiln roastings 20
When obtain catalyst for dehydrogenation of low-carbon paraffin and be denoted as R.
[comparative example 2]
It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in 9.76g alumina support, mix
Close uniformly, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 hours up to catalyst precarsor, be denoted as I.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
It obtains catalyst for dehydrogenation of low-carbon paraffin within kiln roasting 20 hours, is denoted as S.Examination condition the results are shown in Table 2 with embodiment 1.
[comparative example 3]
D component is changed to the comparison of Ce-Zr-O solid solution.Weighing 9.39g alumina support, which pours into 200mL deionized water, to be stirred
After mixing 1 hour, weighs 1.081g ammonium ceric nitrate and 0.212g zirconium nitrate is dissolved in respectively in 50mL deionized water, then mix the two
It closes uniformly, pours into the mixed liquor of aluminium oxide and water, after continuing stirring 1 hour, be slowly dropped into ammonium hydroxide until pH under lasting stirring
It is 8.5.By product aging 2 hours, filter cake is obtained with 2L water filtering and washing, by filter cake after 90 DEG C 16 hours dry, 580
DEG C Muffle kiln roasting 20 hours to get Ce0.8Zr0.2O2-Al2O3Carrier,.Weigh the salt that 0.190g stannous chloride is dissolved in 10mL
It in acid solution, is added with stirring in above-mentioned carrier, is uniformly mixed, 30 DEG C impregnate 12 hours, and 16 hours are then dried at 90 DEG C i.e.
Catalyst precarsor is obtained, I is denoted as.The potassium nitrate of the chloroplatinic acid, 0.259g that weigh 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 low-carbon
Alkane dehydrogenating catalyst is denoted as T.
Table 1
Table 2
[embodiment 14~22]
The catalyst that embodiment 1 is prepared is used for dehydrogenating low-carbon alkane, reaction raw materials are propane, and reaction raw materials are one
Propylene is obtained with catalyst haptoreaction under fixed condition；Reaction condition and evaluation result are shown in Table 3.
Table 3
[comparative example 2]
Catalyst regeneration stability contrast
0.5g catalyst A, 0.5g catalyst n is weighed respectively and 0.5g catalyst O carries out dehydrogenation of isobutane evaluation, catalyst
Reaction result after 1 hour is shown in Table 4.
Table 4
Claims (9)
1. one kind is used for catalyst for dehydrogenation of low-carbon paraffin, in terms of catalyst weight number, including following components:
A) 0.1~5 part of Pt or its oxide；
B) 0.1~5 part of alkali metal or its oxide；
C) 0.1~5 part of Sn or its oxide；
D) 0.1~10 part of Ce-Ln-O solid solution, Ln are La and Pr；With molar ratio computing, Ce:Ln is (1~99): 1；
E) 80~99 parts of Al2O3Carrier.
2. catalyst according to claim 1, it is characterised in that in terms of low-carbon alkanes catalyst weight number, Pt or its oxygen
The number of compound is 0.1~2.5 part.
3. catalyst according to claim 1, it is characterised in that in terms of low-carbon alkanes catalyst weight number, alkali metal or
The number of its oxide is 0.5~2 part.
4. catalyst according to claim 1, it is characterised in that in terms of low-carbon alkanes catalyst weight number, Sn or its oxygen
The number of compound is 0.1~2.5 part.
5. catalyst according to claim 1, it is characterised in that with Pt:Sn in molar ratio computing catalyst for (0.01~5):
1。
6. catalyst according to claim 1, it is characterised in that in terms of low-carbon alkanes catalyst weight number, Ce-Ln-O
Solid solution number is 1~5.
7. catalyst according to claim 1, it is characterised in that Al2O3For γ, δ and θ type Al2O3One or both of.
8. the preparation method of the described in any item catalyst for dehydrogenation of low-carbon paraffin of claim 1~7, comprising the following steps:
A) above-mentioned carrier Al is weighed2O3It pours into suitable deionized water and stirs, the soluble-salt of the Ce and Ln of content needed for weighing
It is dissolved in suitable deionized water, is then uniformly mixed the two respectively, pour into the mixed liquor of carrier and water, continue to stir,
It is slowly dropped into pH adjusting agent under continuous stirring until pH is 7~10；By product aging, suction filtration, drying, roast up to Ce-Ln-
O solid solution and Al2O3Complex carrier；
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, impregnates, it is dry, roast to obtain catalyst precarsor I；
C) soluble-salt of the desired amount of Pt and alkali metal are dissolved in suitable water, the catalyst of b step is added under stiring
Precursor I is uniformly mixed, and is impregnated, dry, roasts to obtain catalyst for dehydrogenation of low-carbon paraffin.
9. the application of any one of claim 1~7 catalyst for dehydrogenation of low-carbon paraffin, reaction raw materials are propane or iso-butane,
Reaction condition are as follows: low-carbon alkanes and hydrogen volume ratio are 10:1~1:1, and reaction temperature is 400 DEG C~600 DEG C, reaction pressure 0
~1MPa, alkane mass space velocity are 3.0~8.0h-1, reaction raw materials and the catalyst haptoreaction obtain propylene or isobutene.
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| CN109651047B (en) * | 2017-10-12 | 2022-04-05 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN111054383B (en) * | 2018-10-16 | 2023-01-24 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation reaction of organic liquid hydrogen storage material and preparation method thereof |
| CN113877577B (en) * | 2020-07-02 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for improving alkane conversion rate |
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