CN105582924B - Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation - Google Patents
Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, mainly solves the problems, such as that dehydrogenation activity prepared by prior art is relatively low, stability is poor.The present invention is by using a kind of catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, in terms of parts by weight, including following components：A) 0.1~5 part of Pt or its oxide；B) 0.1~5 part of Sn or its oxide；C) 0.1~5 part of alkali metal or its oxide；D) 0.1~5 part of alkaline-earth metal or its oxide；E) 0.1~10 part of Ce Zr O solid solution；F) 80~99 parts of Al2O3Technical scheme, preferably solve the problem, available in manufacturing olefin by low-carbon alkane dehydrogenation industrial production.
Description
Technical field
The present invention relates to a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation.
Background technology
Low-carbon alkene be widely used in plastics, synthetic rubber, medicine, gasoline additive, ion exchange resin, detergent,
The production of spices and various chemical intermediates, it is important Organic Chemicals, is mainly urged with steam cracking and refinery factory fluidisation
The form for changing cracking process by-product/coproduction obtains.With the development of chemical industry, the demand growth to low-carbon alkene is opened quickly
Hair is by the low carbon alkane preparing low-carbon olefins process of added value for making full use of low-carbon alkanes resource, opening up new alkene source
It is significant, only it has been difficult to meet the needs of China's chemical industry is fast-developing by the above method at present.Propane/iso-butane
De-hydrogen Technology has become important propylene/isobutene after coproduction or by-product after steam cracking and fluid catalytic cracking process
Source.Present industrialized propane/dehydrogenation of isobutane technique includes the Oleflex techniques of Uop Inc., Phillips companies
Star techniques, the Catofin techniques of Air Product＆Chemical companies, the FDB-4 of Snamprogetti SPA companies
With the technique such as the Linde of Linde companies.The country is still without the process units of dehydrogenating low-carbon alkane producing light olefins.
Dehydrogenating low-carbon alkane is a strong endothermic reaction, is only possible to relatively be managed at relatively high reaction temperatures
The olefin yields thought.But too high reaction temperature often brings a series of side reactions, so as to reduce the selectivity of alkene, make
The problems such as quick carbon distribution of catalyst surface, inactivation, cause catalyst performance to be deteriorated, and selectivity is relatively low, therefore, it is necessary to processability
Excellent dehydrogenation, improve alkane conversion and olefine selective.Current industrialized catalyst has Pt systems and Cr systems to urge
Agent, wherein Pt series catalysts because its have the characteristics that high activity, low stain, low wear rate and turn into study hotspot.In recent years,
About having more document report and patent application, Chinese patent in terms of dehydrating alkanes Pt series catalysts
(CN200910209534.4) catalyst K-Ce-Pt-Sn/ γ-Al disclosed in2O3Within 6 hours reaction time, propane conversion
Rate is more than 38%, and Propylene Selectivity is more than 98%, and coke content is less, and the catalyst activity also has the space lifted, does not give
Go out catalyst stability data.Wang Jidong etc. exists《Modern chemical industry》Delivered on 2011,31 supplementary issue 1,205-209 " potassium is to Pt-
Sn/Al2O3The influence of catalyst surface acidity and dehydrogenation of isobutane performance " article finds that catalyst can effectively be reduced by adding K
The strong L acid amount in surface, it is suppressed that side reaction, the selective isobutene such as isomery and cracking are significantly increased, and suitable K amounts are 0.4-
0.8wt%, now the conversion ratio of catalyst is 35% or so, and selectivity is 95%.Zhang etc. exists《Fuel Processing
Technology》" the Effect of magnesium delivered on (fuel process technology) 2011,92,1632-1638
addition on catalytic performance of PtSnK/γ-Al2O3catalyst for isobutane
(Mg addition is to the PtSnK/ γ-Al for dehydrogenation of isobutane by dehydrogenation "2O3The influence of catalytic performance) article hair
Now appropriate Mg can increase Pt decentralization and can reduce carbon deposit, and Mg can not only strengthen Sn components and Al2O3Phase interaction
With, and may insure that Sn exists with oxidation states, so as to increase reactivity and stability, but during Mg excess, Sn is with 0 valency
In the presence of and Pt decentralization reduce all to react it is unfavorable.Find that effect is preferable when Mg is 0.4wt% in experiment, it is different after reaction 6h
The conversion ratio of butane dehydrogenation is 29%, and selectivity is up to 94%.
Catalyst for dehydrogenation of low-carbon paraffin has been achieved with greater advance at present, but it is not high to still suffer from conversion ratio, or conversion ratio
The problem of olefine selective is relatively low in the case of higher, stability are also required to further strengthen.The present invention uses Ce-Zr-O solid solution
It is auxiliary agent with alkali metal and alkaline earth metal, catalyst surface characteristic can be changed by adding in catalyst, to improve catalyst
Performance, therefore there is preferable application prospect, there has been no relevant report at present.
The content of the invention
One of technical problems to be solved by the invention are that catalyst for dehydrogenation of low-carbon paraffin activity is relatively low, steady in the prior art
A kind of the problem of qualitative poor, there is provided new catalyst for manufacturing olefin by low-carbon alkane dehydrogenation.The invention solves technology ask
The two of topic, it is to provide a kind of with solving one of technical problem corresponding method for preparing catalyst.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for dehydrogenating low-carbon alkane
The catalyst of alkene processed, in terms of parts by weight, including following components：
A) 0.1~5 part of Pt or its oxide；
B) 0.1~5 part of Sn or its oxide；
C) 0.1~5 part of alkali metal or its oxide；
D) 0.1~5 part of alkaline-earth metal or its oxide；
E) 0.1~10 part of Ce-Zr-O solid solution；
F) 80~99 parts of Al2O3。
In above-mentioned technical proposal, in terms of parts by weight, the number of Pt or its oxide is 0.1~2.5 part；Sn or its oxidation
The number of thing is 0.1~2.5 part；With Pt in molar ratio computing catalyst:Sn is (0.01~5)：1.Alkali metal or its oxide
Number is 0.1~2 part；The number of alkaline-earth metal or its oxide is 0.1~2 part, and alkaline-earth metal is preferably Mg and Ca；Ce-Zr-
O solid solution is Ce0.8Zr0.2O2, its number is 1~5 part；Al2O3For γ, δ and θ type Al2O3One or both of.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for dehydrogenating low-carbon alkane
Catalyst and preparation method thereof, comprise the following steps：
A) Al of content needed for weighing2O3Pour into appropriate deionized water and stir, the Ce's and Zr of content needed for weighing can
Soluble is dissolved in appropriate deionized water respectively, is then well mixed the two, pours into the mixed liquor of carrier and water, continues
Stirring, ammoniacal liquor is slowly dropped under continuous stirring until pH is 7~10；By product aging, filtering and washing obtains filter cake, through dry
It is dry, be calcined and produce Ce-Zr-O solid solution and Al2O3Complex carrier；
B) the desired amount of Sn soluble-salt is dissolved in appropriate hydrochloric acid solution, adds what a steps obtained under agitation
In composite carrier, it is well mixed, through impregnating, drying, being calcined to obtain catalyst precarsor I；
C) the desired amount of Pt, alkali and alkaline earth metal ions soluble-salt are dissolved in appropriate water, add b under agitation
The catalyst precarsor I of step, be well mixed, through impregnate, dry, be calcined manufacturing olefin by low-carbon alkane dehydrogenation catalyst.
In above-mentioned technical proposal, alkali metal, alkaline-earth metal, Ce and Zr soluble-salt are selected from chloride, nitrate or vinegar
One kind in hydrochlorate；The Pt preferred chloroplatinic acid of soluble-salt；The soluble-salt of tin is selected from one kind of stannous chloride or butter of tin.
Obtained catalyst carries out activity rating in isotherm formula fixed bed reactors as stated above, and low-carbon alkanes are taken off
For hydrogen producing light olefins system appraisal, summary process is as follows：
Low-carbon alkanes unstrpped gas is adjusted into flow by mass flowmenter, mixed into pre-add hot-zone, Ran Houjin
Enter reaction zone, the pre-add hot-zone of reactor and reaction zone use electric-heating-wire-heating, make up to predetermined temperature, reactor it is interior
Footpath is Ф 9mm-Ф 6mm stainless steel sleeve pipe, is about 400mm.After reacted gas is by 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 loaded 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 is 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 obtain propylene or isobutene with the catalyst haptoreaction.
During dehydrogenating low-carbon alkane, simple Pt-Sn/Al2O3Catalyst surface acidity is stronger, and catalyst surface is easily long-pending
Carbon and accelerate deactivation rate.To slow down catalyst inactivation speed, catalyst performance can be improved by adding other auxiliary agents, simultaneously
Also reaction temperature can be reduced and mitigate catalyst surface carbon distribution.Compared with prior art, the present invention has the advantages of notable and protrusion
Property effect, alkali metal can reduce its catalyst surface acidity；Ce-Zr-O solid solution surface acidities are very weak, are not suitable for independent
Dehydrogenation reaction carrier is done, but its addition can improve Pt elements and disperse on carrier, so as to improve Pt series catalysts anti-carbons
Ability, and enhance the effect of Sn components and carrier；Alkaline-earth metal further enhances the effect of these two aspects, so as to improve
Catalyst performance.The catalyst of the present invention is used in dehydrogenating low-carbon alkane reaction using above-mentioned appreciation condition, its activity rating
As a result showing, the catalyst has higher alkane conversion, reaches 55% up to iso-butane conversion ratio compared with low reaction temperatures,
There is higher selectivity simultaneously, selective isobutene is more than 94%, and still has by 20 rear catalyst conversion ratios of making charcoal
53%, selectivity achieves preferable technique effect still greater than 94%.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
Weigh after 9.31g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.159g chloroplatinic acid, 0.207 potassium nitrate and 0.527g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as A.Evaluating catalyst condition is as follows：0.5 gram of catalyst is fitted into (catalyst in above-mentioned isothermal fixed bed reactors
Bed height 17mm), react normal pressure, 550 DEG C of temperature；Iso-butane and hydrogen volume ratio are 2.5：1；Alkane mass space velocity is
4.6h-1.It the results are shown in Table 2.
【Embodiment 2】
Weigh after 9.35g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.159g chloroplatinic acid, 0.207 potassium nitrate and 0.105g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as B.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 3】
Weigh after 8.86g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.159g chloroplatinic acid, 0.207 potassium nitrate and 5.275g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as C.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 4】
Weigh after 9.16g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.159g chloroplatinic acid, 0.207 potassium nitrate and 2.110g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as D.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 5】
Weigh after 9.31g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The beryllium nitrate of 0.159g chloroplatinic acid, 0.207 potassium nitrate and 0.738g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as E.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 6】
Weigh after 9.31g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
0.159g chloroplatinic acid, 0.207 potassium nitrate and 0.295 calcium nitrate are dissolved in 10mL water, are stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as F.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 7】
Weigh after 9.31g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The strontium nitrate of 0.159g chloroplatinic acid, 0.207 potassium nitrate and 0.121g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as G.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 8】
Weigh after 9.31g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The barium nitrate of 0.159g chloroplatinic acid, 0.207 potassium nitrate and 0.095g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as H.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 9】
Weigh after 9.45g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.030g butters of tin to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.027g chloroplatinic acid, 0.207 potassium nitrate and 0.527g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as I.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 10】
Weigh after 8.47g alumina supports pour into 200mL deionized waters and stir 1 hour, weigh 0.735g cerium chlorides with
0.160g zirconium chlorides are dissolved in 50mL deionized waters respectively, are then well mixed the two, pour into the mixed liquor of aluminum oxide and water
In, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.951g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium chloride of 1.327g chloroplatinic acid, 0.153 potassium chloride and 0.196g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as J.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 11】
Weigh after 8.97g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.475g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.664g chloroplatinic acid, 0.207 potassium nitrate and 0.527g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as K.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 12】
Weigh after 9.77g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 0.027g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.005g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 80 DEG C are dried 24 hours, in 450 DEG C of Muffle kiln roastings 24 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 10 DEG C impregnate 24 hours, are then dried 24 hours at 80 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.159g chloroplatinic acid, 0.1g lithium nitrate and 0.527g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 10 DEG C impregnate 24 hours, 80 DEG C of drying 24 hours, and in 450 DEG C of Muffle kiln roastings, 24 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as L.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 13】
Weigh after 8.29g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 2.702g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.529g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 150 DEG C are dried 6 hours, in 650 DEG C of Muffle kiln roastings 6 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 80 DEG C impregnate 1 hour, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh 0.159g
Chloroplatinic acid, 1.848 sodium nitrate and 0.527g magnesium nitrate be dissolved in 10mL water, stir it is lower add in I, be well mixed, 80
DEG C dipping 1 hour, 150 DEG C of drying 6 hours, obtains catalyst for dehydrogenation of low-carbon paraffin for 6 hours in 650 DEG C of Muffle kiln roastings and remembers
For M.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 14】
Weigh after 9.49g alumina supports pour into 200mL deionized waters and stir 0.5 hour, weighing 0.270g cerous nitrates
Ammonium and 0.053g zirconium nitrates are dissolved in 50mL deionized waters respectively, are then well mixed the two, pour into the mixed of aluminum oxide and water
Close in liquid, after continuing stirring 0.5 hour, ammoniacal liquor is slowly dropped under lasting stirring until pH is 7.By product aging 1 hour, 1L is used
Water filtering and washing obtains filter cake, by filter cake after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.159g chloroplatinic acid, 0.345 rubidium nitrate and 0.527g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as N.Examination condition the results are shown in Table 2 with embodiment 1.
【Embodiment 15】
Weigh after 9.21g alumina supports pour into 200mL deionized waters and stir 2 hours, weighing 1.351g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.265g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 2 hours, ammoniacal liquor is slowly dropped under lasting stirring until pH is 10.By product aging 3 hours, with 5L water
Filtering and washing obtains filter cake, by filter cake after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
The magnesium nitrate of 0.159g chloroplatinic acid, 0.117 cesium nitrate and 0.527g is dissolved in 10mL water, is stirred in lower addition I, mixing is equal
Even, 30 DEG C impregnate 12 hours, 90 DEG C of drying 16 hours, and in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain dehydrogenating low-carbon alkane
Catalyst is designated as O.Examination condition the results are shown in Table 2 with embodiment 1.
【Comparative example 1】
Weigh after 9.36g alumina supports pour into 200mL deionized waters and stir 1 hour, weighing 1.081g ammonium ceric nitrates
It is dissolved in 50mL deionized waters with 0.212g zirconium nitrates, is then well mixed the two respectively, pours into the mixing of aluminum oxide and water
In liquid, after continuing stirring 1 hour, ammoniacal liquor 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 after 90 DEG C are dried 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours, produces
Ce0.8Zr0.2O2-Al2O3Carrier.Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, stir the lower above-mentioned carrier of addition
In, it is well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh
0.159g chloroplatinic acid and 0.527g magnesium nitrate are dissolved in 10mL water, are stirred in lower addition I, are well mixed, 30 DEG C of dippings 12
Hour, 90 DEG C of drying 16 hours, in 580 DEG C of Muffle kiln roastings, 20 hours are to obtain catalyst for dehydrogenation of low-carbon paraffin to be designated as P.Examine
Condition is commented to the results are shown in Table 2 with embodiment 1.
【Comparative example 2】
Weigh 0.190g stannous chlorides to be dissolved in 10mL hydrochloric acid solution, under stirring plus in 9.71g alumina support, mix
Close uniformly, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalyst precarsor, are designated as I.Weigh 0.159g chlorine
The magnesium nitrate of platinic acid, 0.207 potassium nitrate and 0.527g is dissolved in 10mL water, is stirred in lower addition I, is well mixed, 30 DEG C of leachings
Stain 12 hours, 90 DEG C of dryings 16 hours, obtain catalyst for dehydrogenation of low-carbon paraffin within 20 hours in 580 DEG C of Muffle kiln roastings and be designated as
Q.Examination condition the results are shown in Table 2 with embodiment 1.
【Comparative example 3】
Weigh 26.241g ammonium ceric nitrates and 5.146g zirconium nitrates are dissolved in 50mL deionized waters respectively, then mix the two
Close uniformly, pour into the mixed liquor of aluminum oxide and water, after continuing stirring 1 hour, ammoniacal liquor is slowly dropped into until pH under lasting stirring
For 8.5.By product aging 2 hours, filter cake is obtained with 2L water filtering and washings, by filter cake after 90 DEG C are dried 16 hours, 580
DEG C Muffle kiln roasting 20 hours, produces Ce0.8Zr0.2O2Carrier.Weigh the hydrochloric acid solution that 0.190g stannous chlorides are dissolved in 10mL
In, stir in the lower above-mentioned carrier of addition, be well mixed, 30 DEG C impregnate 12 hours, are then dried 16 hours at 90 DEG C and produce catalysis
Agent precursor, is designated as I.The magnesium nitrate for weighing 0.159g chloroplatinic acid, 0.207 potassium nitrate and 0.527g is dissolved in 10mL water, is stirred
Mix in lower addition I, be well mixed, 30 DEG C impregnated 12 hours, 90 DEG C of dryings 16 hours, in 580 DEG C of Muffle kiln roastings 20 hours
Obtain catalyst for dehydrogenation of low-carbon paraffin and be designated as R.Examination condition the results are shown in Table 2 with embodiment 1.
Table 1
Table 2
【Embodiment 16~24】
The catalyst that embodiment 1 is prepared is used for dehydrogenating low-carbon alkane, and reaction raw materials are propane, and reaction raw materials are one
Under fixed condition propylene is obtained with catalyst haptoreaction；Reaction condition and evaluation result are shown in Table 3.
Table 3
【Comparative example 4】
Catalyst regenerating stability contrasts
0.5g catalyst A, 0.5g catalyst P is weighed respectively and carries out dehydrogenation of isobutane evaluation, reacts the results are shown in Table after 1h
4。
Table 4
Claims (10)
1. a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, 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 Sn or its oxide；
C) 0.1~5 part of alkali metal or its oxide；
D) 0.1~5 part of alkaline-earth metal or its oxide；
E) 0.1~10 part of Ce-Zr-O solid solution；
F) 80~99 parts of Al2O3；
The catalyst is prepared by the method comprised the following steps：
A) Al of content needed for weighing2O3Pour into appropriate deionized water and stir, the Ce and Zr of content needed for weighing solubility
Salt is dissolved in appropriate deionized water respectively, is then well mixed the two, pours into the mixed liquor of carrier and water, continues to stir
Mix, be slowly dropped into ammoniacal liquor under continuous stirring until pH is 7~10；By product aging, filtering and washing obtains filter cake, through drying,
It is calcined and produces Ce-Zr-O solid solution and Al2O3Complex carrier；
B) the desired amount of Sn soluble-salt is dissolved in appropriate hydrochloric acid solution, addition a steps obtain compound under agitation
In type carrier, it is well mixed, through impregnating, drying, being calcined to obtain catalyst precarsor I；
C) the desired amount of Pt, alkali and alkaline earth metal ions soluble-salt are dissolved in appropriate water, add b step under agitation
Catalyst precarsor I, be well mixed, through impregnate, dry, be calcined manufacturing olefin by low-carbon alkane dehydrogenation catalyst.
2. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that urge with low-carbon alkanes
The number of agent parts by weight meter, Pt or its oxide is 0.1~2.5 part.
3. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that urge with low-carbon alkanes
The number of agent parts by weight meter, Sn or its oxide is 0.1~2.5 part.
4. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that urge with low-carbon alkanes
The number of agent parts by weight meter, alkali metal or its oxide is 0.1~2 part.
5. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that urge with low-carbon alkanes
The number of agent parts by weight meter, alkaline-earth metal or its oxide is 0.1~2 part.
6. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 5, it is characterised in that Ce-Zr-O solid solution
For Ce0.8Zr0.2O2, in terms of low-carbon alkanes catalyst weight number, its number is 1~5 part.
7. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that Al2O3For γ, δ and θ
Type Al2O3One or both of.
8. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that urge with molar ratio computing
Pt in agent:Sn is (0.01~5)：1.
9. the preparation method of the catalyst for manufacturing olefin by low-carbon alkane dehydrogenation described in any one of claim 1~8 comprises the following steps：
A) Al of content needed for weighing2O3Pour into appropriate deionized water and stir, the Ce and Zr of content needed for weighing solubility
Salt is dissolved in appropriate deionized water respectively, is then well mixed the two, pours into the mixed liquor of carrier and water, continues to stir
Mix, be slowly dropped into ammoniacal liquor under continuous stirring until pH is 7~10；By product aging, filtering and washing obtains filter cake, through drying,
It is calcined and produces Ce-Zr-O solid solution and Al2O3Complex carrier；
B) the desired amount of Sn soluble-salt is dissolved in appropriate hydrochloric acid solution, addition a steps obtain compound under agitation
In type carrier, it is well mixed, through impregnating, drying, being calcined to obtain catalyst precarsor I；
C) the desired amount of Pt, alkali and alkaline earth metal ions soluble-salt are dissolved in appropriate water, add b step under agitation
Catalyst precarsor I, be well mixed, through impregnate, dry, be calcined manufacturing olefin by low-carbon alkane dehydrogenation catalyst.
10. any one of claim 1~8 catalyst is reacted for manufacturing olefin by low-carbon alkane dehydrogenation, reaction raw materials third
Alkane or iso-butane, reaction condition are：Low-carbon alkanes and hydrogen volume ratio are 10：1~1：1, reaction temperature is 400 DEG C~600 DEG C,
Reaction pressure is 0~1MPa, and alkane mass space velocity is 3.0~8.0h-1, reaction raw materials and the catalyst haptoreaction obtain third
Alkene or isobutene.
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| CN103418376A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Anti-sintering catalyst for preparing low-carbon olefin by low-carbon alkane dehydrogenation and preparation method thereof |
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| CN103418376A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Anti-sintering catalyst for preparing low-carbon olefin by low-carbon alkane dehydrogenation and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| "Effect of magnesium addition on catalytic performance of PtSnK/γ-Al2O3 catalyst for isobutane dehydrogenation";Yiwei Zhang et al.;《Fuel Processing Technology》;20110504;第92卷(第8期);第1633页 * |
| "The roles of CeyZr1-yO2 in propane dehydrogenation： Enhancing catalytic stability and decreasing coke combustion temperature";Bao Khanh Vu et al.;《Applied Catalysis A：General》;20120727;第443卷;第60-61页，第63-65页 * |
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