CN106607023B - For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof - Google Patents
For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof Download PDFInfo
- Publication number
- CN106607023B CN106607023B CN201510690485.6A CN201510690485A CN106607023B CN 106607023 B CN106607023 B CN 106607023B CN 201510690485 A CN201510690485 A CN 201510690485A CN 106607023 B CN106607023 B CN 106607023B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dehydrogenation
- hours
- iso
- butane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The catalyst and preparation method thereof that the present invention relates to a kind of for preparing isobutene through dehydrogenation of iso-butane mainly solves the problems, such as that the dehydrogenation activity of prior art preparation is lower, stability is poor.Catalyst prepared by the present invention in preparing isobutene through dehydrogenation of iso-butane, 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 the AB with spinel structure2O4, A is selected from least one of divalent metal, and B is selected from least one of metal Tricationic；E) 80~99 parts of carrier Al2O3Technical solution, preferably solve the problems, such as this, can be used for preparing isobutene through dehydrogenation of iso-butane Catalyst production in.
Description
Technical field
The catalyst and preparation method thereof that the present invention relates to a kind of for preparing isobutene through dehydrogenation of iso-butane.
Background technique
Isobutene is a kind of important industrial chemicals, is mainly used to produce polyisobutene, butyl rubber and methyl tertbutyl
Ether (MTBE), MTBE are a kind of high-octane liquid, are often used as dopes for gasoline, market demand
It is larger, to drive the development and utilization of MTBE upstream product.Supply falls short of demand for China's isobutene yield at present, and source is mainly stone
The by-product C 4 fraction of the by-product C 4 fraction of cerebrol preparing ethylene by steam cracking device, refinery's fluid catalytic cracking (FCC) device.China
Iso-butane is outer for being alkylated, and is used as domestic fuel mostly, and utility value is lower.Using iso-butane as raw material dehydrogenation preparing isobutene not
It is only capable of improving the utility value of iso-butane, and the shortage problem of domestic isobutene can be alleviated.Dehydrogenation of isobutane is one strong
The endothermic reaction is only possible to obtain comparatively ideal olefin yields at relatively high reaction temperatures.However excessively high reaction
Temperature often brings a series of side reactions, to reduce the selectivity of alkene, makes the quick carbon distribution of catalyst surface, inactivation, makes
It is deteriorated at catalyst performance, the problems such as selectivity is lower, therefore, it is necessary to the excellent dehydrogenation of processability, improves alkane
Conversion ratio and olefine selective.
Currently, industrialized dehydrogenation of isobutane technology have the Oleflex technique of UOP, the Catofin technique of Lummus,
The FBD technique etc. that the STAR technique of Uhde, the PDH technique of Linde, Snamprogetti-Yarsintez develop cooperatively, wherein
Industrialized unit it is most be Oleflex technology and Catofin technology, the catalyst of the two application is that Pt system and Cr system urge respectively
Agent, wherein Pt series catalysts become research hotspot because it has the characteristics that high activity, low pollution, low wear rate.In recent years,
There are more document report and patent application in terms of in relation to dehydrogenation of isobutane Pt series catalysts, Wang Jidong etc. is at " modern chemical industry "
Delivered on 2011,31 supplementary issue 1,205-209 " potassium is to Pt-Sn/Al2O3The shadow of catalyst surface acidity and dehydrogenation of isobutane performance
Ring " article discovery discovery be added K the strong L acid amount of catalyst surface can be effectively reduced, it is suppressed that isomery and cracking etc. side reactions, isobutyl
Alkene is selectively significantly increased, and suitable K amount is 0.4-0.8wt%, and the conversion ratio of catalyst is 35% or so at this time, selectivity
It is 95%.Zhang etc. is sent out on " Fuel Processing Technology " (fuel processing technology) 2012,96:220-227
" the Effect of Zinc Addition on Catalytic Properties of PtSnK/ γ-Al of table2O3Catalyst
(addition of Zn is to dehydrogenation of isobutane PtSnK/ γ-Al by for Isobutane Dehydrogenation "2O3Catalyst
The influence of energy) addition of Zn auxiliary agent is had studied to PtSnK/ γ-Al2O3The influence of dehydrogenation of isobutane performance finds suitable Zn not
But the dispersion degree that Pt can be improved can also reduce carbon deposit.Zn enhances the effect of Sn component and carrier, prevents going back for Sn
It is former.When the additive amount of Zn is 0.4wt%, iso-butane conversion ratio and stability are more excellent, initial conversion 37%, selectivity
97%, conversion ratio is still improved space.Kobayashi etc. " Applied Catalysis A:General " (applied catalysis A:
It is comprehensive) " the Effect of iron oxide on isobutane dehydrogenation that delivers of 2012,417:306-312
over Pt/Fe2O3-Al2O3(Fe oxide is to Pt/Fe by catalyst "2O3-Al2O3The shadow that dehydrogenation of isobutane reacts on catalyst
Ring) have studied composite oxide carrier Fe2O3-Al2O3The dehydrogenation of isobutane performance of supporting Pt-Sn, research are found: working as Fe2O3Matter
When amount score is 7%, catalyst inactivation is eased, and catalyst activity is preferable, and initial conversion turns after reacting 5h up to 50%
Rate > 40%, selectivity are 95%.Mainly due to the addition of Fe so that in catalyst strong acidic site reduce, catalyst carbon deposit compared with
Few, Fe and Pt can form alloy in catalyst, so that the electron density of Pt increases.
Catalyst for preparing isobutene through dehydrogenation of iso-butane has been achieved with greater advance at present, but that there are still conversion ratios is not high, or
The lower problem of olefine selective, stability are also required to further strengthen in the higher situation of conversion ratio.The present invention uses AB2O4Point
Spar and alkali metal element are auxiliary agent, and catalyst surface characteristic can be changed by being added in catalyst, to improve the performance of catalyst, because
This is with preferable application prospect, and there has been no relevant reports at present.
Summary of the invention
The first technical problem to be solved by the present invention is that dehydrogenation of isobutane catalyst activity is lower in the prior art, stablizes
Property difference problem, provide a kind of new for dehydrogenation of isobutane catalyst.The second technical problem to be solved by the present invention is to provide
A kind of corresponding method for preparing catalyst one of with solution technical problem.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of be used for dehydrogenation of isobutane system
The catalyst of isobutene, 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 the AB with spinel structure2O4, A is selected from least one of divalent metal, B choosing
From at least one of metal Tricationic；
E) 80~99 parts of carrier Al2O3。
In above-mentioned technical proposal, based on parts by weight, the preferred scope of Pt or its oxide number is 0.1~2.5 part；Alkali
The preferred scope of metal or its oxide number is 0.5~2 part；The preferred scope of Sn or its oxide number is 0.1~2.5
Part；AB2O4The preferred scope of spinelle number is that 1~5, A is selected from least one of divalent metal, and B is selected from metal three
At least one of valence cation；A is preferably at least one of Mg or Zn, and B is preferably at least one of Al or Fe；With molar ratio
Meter, preferably constituting as Mg:Zn in A for spinel components is (0.25~4): Al:Fe is (0.25~4) in 1, B: 1；Al2O3For
γ, δ and θ type Al2O3One or both of.With Pt:Sn in molar ratio computing catalyst for (0.01~5): 1.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of be used for dehydrogenation of isobutane system
Isobutene catalyst and preparation method thereof, comprising the following steps:
A) Al of content needed for weighing2O3It pours into suitable deionized water and stirs, the A's and B 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 ammonium hydroxide under continuous stirring until pH is 7~10；By product aging, filtering and washing obtains filter cake, through drying,
It roasts up to AB2O4And Al2O3Complex carrier；
B) soluble-salt of the desired amount of Sn is dissolved in suitable hydrochloric acid solution, is added what a step obtained under stiring
In composite carrier, it is uniformly mixed, through dipping, drying, roasts to obtain catalyst precarsor I；
C) soluble-salt of the desired amount of Pt, alkali and alkaline earth metal ions are dissolved in suitable water, b is added under stiring
The catalyst precarsor I of step, be uniformly mixed, through dipping, drying, roast preparing isobutene through dehydrogenation of iso-butane 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.It is 450 DEG C~650 DEG C roastings 6~24 that roasting process, which is in temperature,
Hour.
In above-mentioned technical proposal, the soluble-salt of alkali metal, A and B can be selected from one in chloride, nitrate or acetate
Kind；The preferred chloroplatinic acid of the soluble-salt of Pt；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, to dehydrogenation of isobutane
For preparing isobutene system appraisal, summary process is as follows:
Isobutane feedstock gas is adjusted into flow by mass flowmenter, is mixed into pre-add hot-zone, subsequently into
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, the internal diameter of reactor
For the stainless steel sleeve pipe of Ф 9mm-Ф 6mm, it is about 400mm.Gas after reaction into gas-chromatography by dividing after drainer
Analyse its composition.Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors: 0.5 gram or so of catalyst, which is packed into internal diameter, is
In the isothermal reactor of Ф 9mm-Ф 6mm (catalyst bed layer height about 17mm), iso-butane and hydrogen volume ratio are 10:1~1:
1, reaction temperature is 400 DEG C~600 DEG C, and reaction pressure is 0~1MPa, and iso-butane mass space velocity is 3.0~8.0h-1, reaction original
Material obtains isobutene with the catalyst haptoreaction.
In isobutane dehydrogenation process, simple Pt-Sn/Al2O3Catalyst surface acidity is stronger, the easy carbon distribution of catalyst surface
And accelerate deactivation rate.To slow down catalyst inactivation speed, catalyst performance can be improved by the way that other auxiliary agents are added, while
Reaction temperature can be reduced and mitigate catalyst surface carbon distribution.Compared with prior art, the present invention has the advantages that significant and high-lighting
Effect, the addition of alkali metal element can reduce its catalyst surface acidity, AB2O4The addition of spinelle can improve Pt element and carry
Dispersion on body, or promote the formation of more active sites Pt, to improve Pt series catalysts carbon accumulation resisting ability, and enhance Sn group
Divide the effect with carrier, to improve catalyst performance.Catalyst of the invention is used for by isobutyl using above-mentioned evaluation condition
In alkane dehydrogenation reaction, Activity evaluation shows catalyst alkane conversion with higher, can compared under low reaction temperatures
Reach 54% or more, while selectivity with higher up to iso-butane conversion ratio, selective isobutene is greater than 93%, and passes through 20
Secondary rear catalyst conversion ratio of making charcoal still has 52%, is selectively still greater than 93%, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Weigh after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weigh 1.637g aluminum nitrate with
0.649g zinc 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, 580 DEG C of Muffle kiln roastings 20 hours to get
ZnAl2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, 90 DEG C
16 hours dry, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst is denoted as A within Muffle kiln roasting 20 hours.Evaluating catalyst item
Part is as follows: 0.5 gram of catalyst is fitted into above-mentioned isothermal fixed bed reactors (catalyst bed layer height 17mm), normal pressure is reacted,
550 DEG C of temperature；Iso-butane and hydrogen volume ratio are 2.5:1；Iso-butane mass space velocity is 4.6h-1.The result is shown in tables 2.
[embodiment 2]
Weigh after 9.75g alumina support pours into 200mL deionized water and stir 1 hour, weigh 0.041g aluminum nitrate with
0.017g zinc 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, 580 DEG C of Muffle kiln roastings 20 hours to get
ZnAl2O4-Al2O3Carrier.It weighs 0.295g tin tetrachloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 10 DEG C impregnate 24 hours, 90 DEG C
16 hours dry, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst is denoted as B within Muffle kiln roasting 20 hours.Examination condition is the same as real
Example 1 is applied, the results are shown in Table 2.
[embodiment 3]
Weigh after 8.76g alumina support pours into 200mL deionized water and stir 1 hour, weigh 4.093g aluminum nitrate with
1.623g zinc 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, 580 DEG C of Muffle kiln roastings 20 hours to get
ZnAl2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 80 DEG C impregnate 1 hour, and 90 DEG C dry
Dry 16 hours, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst was denoted as C within Muffle kiln roasting 20 hours.Examination condition is the same as implementation
Example 1, the results are shown in Table 2.
[embodiment 4]
Weigh after 9.26g alumina support pours into 200mL deionized water and stir 1 hour, weigh 2.046g aluminum nitrate with
0.811g zinc 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 80 DEG C after dry 24 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
ZnAl2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, 80 DEG C
24 hours dry, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst is denoted as D within Muffle kiln roasting 20 hours.Examination condition is the same as real
Example 1 is applied, the results are shown in Table 2.
[embodiment 5]
Weigh after 9.66g alumina support pours into 200mL deionized water and stir 1 hour, weigh 0.410g aluminum nitrate with
0.162g zinc 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 150 DEG C after dry 6 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
ZnAl2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, 150 DEG C
6 hours dry, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst is denoted as E within Muffle kiln roasting 20 hours.Examination condition is the same as implementation
Example 1, the results are shown in Table 2.
[embodiment 6]
Weigh after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weigh 0.897 iron chloride with
0.226 zinc 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 90 DEG C after dry 16 hours, 580 DEG C of Muffle kiln roastings 20 hours to get
ZnFe2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.153 potassium chloride are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, 90 DEG C
It is 16 hours dry, at 580 DEG C F is denoted as to get to dehydrogenation of isobutane catalyst within Muffle kiln roasting 20 hours.Examination condition is the same as real
Example 1 is applied, the results are shown in Table 2.
[embodiment 7]
Weigh after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weigh 2.110g aluminum nitrate with
0.721g magnesium 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, 580 DEG C of Muffle kiln roastings 20 hours to get
MgAl2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, 90 DEG C
16 hours dry, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst is denoted as G within Muffle kiln roasting 20 hours.Examination condition is the same as real
Example 1 is applied, the results are shown in Table 2.
[embodiment 8]
Weigh after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weigh 1.616g ferric nitrate with
0.513g magnesium 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, 580 DEG C of Muffle kiln roastings 20 hours to get
MgFe2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.207 potassium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, 90 DEG C
16 hours dry, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst is denoted as H within Muffle kiln roasting 20 hours.Examination condition is the same as real
Example 1 is applied, the results are shown in Table 2.
[embodiment 9]
Weigh after 9.57g alumina support pours into 200mL deionized water and stir 1 hour, weigh 1.412g chromic nitrate with
0.513g nickel 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 1 hour, taken out with 1L 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
NiCr2O4-Al2O3Carrier.It weighs 0.029g tin tetrachloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.027g's
Chloroplatinic acid and 0.100g lithium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C dry
Dry 16 hours, at 450 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst was denoted as I within Muffle kiln roasting 24 hours.Examination condition is the same as implementation
Example 1, the results are shown in Table 2.
[embodiment 10]
Weigh after 8.10g alumina support pours into 200mL deionized water and stir 2 hours, weigh 1.142g chromic nitrate with
0.440g cadmium 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 2 hours, ammonium hydroxide is slowly dropped under lasting stirring until pH is 10.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, 650 DEG C of Muffle kiln roastings 6 hours to get
NiGa2O4-Al2O3Carrier.It weighs 0.951g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 1.327g's
Chloroplatinic acid and 1.848g sodium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C dry
Dry 16 hours, at 650 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst was denoted as J within Muffle kiln roasting 6 hours.The same embodiment of examination condition
1, it the results are shown in Table 2.
[embodiment 11]
It weighs after 8.90g alumina support pours into 200mL deionized water and stir 0.5 hour, weighing 1.275g gallium nitrate
It is dissolved in 50mL deionized water with 0.444g nickel nitrate, is then uniformly mixed the two respectively, pour into the mixing of aluminium oxide and water
In liquid, after continuing stirring 0.5 hour, ammonium hydroxide is slowly dropped under lasting stirring until pH is 7.By product aging 3 hours, with 5L 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
CdCr2O4-Al2O3Carrier.It weighs 0.475g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.664g's
Chloroplatinic acid and 0.345g rubidium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C dry
Dry 16 hours, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst was denoted as K within Muffle kiln roasting 20 hours.Examination condition is the same as implementation
Example 1, the results are shown in Table 2.
[embodiment 12]
Weigh after 9.39g alumina support pours into 200mL deionized water and stir 1 hour, weigh 1.058g gallium nitrate with
0.391g cadmium 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, 580 DEG C of Muffle kiln roastings 20 hours to get
CdGa2O4-Al2O3Carrier.It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in above-mentioned carrier,
It 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.Weigh 0.159g's
Chloroplatinic acid and 0.073 cesium nitrate are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, 90 DEG C
16 hours dry, at 580 DEG C, i.e. obtaining dehydrogenation of isobutane catalyst is denoted as L within Muffle kiln roasting 20 hours.Examination condition is the same as real
Example 1 is applied, the results are shown in Table 2.
[embodiment 13]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.121g zinc nitrate,
0.416 magnesium nitrate and 0.305g aluminum nitrate, 1.312g ferric nitrate are dissolved in respectively in 50mL deionized water, are then mixed the two equal
It is even, it pours into the mixed liquor of aluminium oxide and water, after continuing stirring 1 hour, is slowly dropped into ammonium hydroxide until pH is under lasting stirring
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, at 580 DEG C
Muffle kiln roasting 20 hours to get Zn0.2Mg0.8Al0.4Fe1.6O4-Al2O3Carrier.It weighs 0.190g stannous chloride and is dissolved in 10mL
Hydrochloric acid solution in, be added with stirring in above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 small
When up to catalyst precarsor, be denoted as I.It weighs the chloroplatinic acid of 0.159g and 0.207 potassium nitrate is dissolved in 10mL water, 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
Dehydrogenation of isobutane catalyst is denoted as M.Examination condition the results are shown in Table 2 with embodiment 1.
[embodiment 14]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.509g zinc nitrate,
0.110 magnesium nitrate and 1.284g aluminum nitrate, 0.346g ferric nitrate are dissolved in respectively in 50mL deionized water, are then mixed the two equal
It is even, it pours into the mixed liquor of aluminium oxide and water, after continuing stirring 1 hour, is slowly dropped into ammonium hydroxide until pH is under lasting stirring
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, at 580 DEG C
Muffle kiln roasting 20 hours to get Zn0.8Mg0.2Al1.6Fe0.4O4-Al2O3Carrier.It weighs 0.190g stannous chloride and is dissolved in 10mL
Hydrochloric acid solution in, be added with stirring in above-mentioned carrier, be uniformly mixed, 30 DEG C impregnate 12 hours, then 90 DEG C dry 16 small
When up to catalyst precarsor, be denoted as I.It weighs the chloroplatinic acid of 0.159g and 0.207 potassium nitrate is dissolved in 10mL water, 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
Dehydrogenation of isobutane catalyst is denoted as N.Examination condition the results are shown in Table 2 with embodiment 1.
[embodiment 15]
It weighs after 9.36g alumina support pours into 200mL deionized water and stir 1 hour, weighing 0.310g zinc nitrate,
0.268 magnesium nitrate and 0.784g aluminum nitrate, 0.844g ferric nitrate are dissolved in respectively in 50mL deionized water, are then mixed the two equal
It is even, it pours into the mixed liquor of aluminium oxide and water, after continuing stirring 1 hour, is slowly dropped into ammonium hydroxide until pH is under lasting stirring
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, at 580 DEG C
Muffle kiln roasting 20 hours to get Zn0.5Mg0.5AlFeO4-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.It weighs the chloroplatinic acid of 0.159g and 0.207 potassium nitrate is dissolved in 10mL water, be 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 isobutyl
Alkane dehydrogenation is denoted as O.Examination condition the results are shown in Table 2 with embodiment 1.
[comparative example 1]
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.Weigh the chlorine of 0.159g
The potassium nitrate of platinic acid and 0.207g are dissolved in 10mL water, are added with stirring in I, are uniformly mixed, and 30 DEG C impregnate 12 hours, and 90 DEG C dry
Dry 16 hours, dehydrogenation of isobutane catalyst was obtained within Muffle kiln roasting 20 hours at 580 DEG C, is denoted as P.Examination condition is the same as implementation
Example 1, the results are shown in Table 2.
[comparative example 2]
It weighs 0.190g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring in 9.84g 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.Weigh the chlorine of 0.159g
Platinic 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, at 580 DEG C
It obtains dehydrogenation of isobutane catalyst within Muffle kiln roasting 20 hours, is denoted as Q.Examination condition the results are shown in Table 2 with embodiment 1.
[comparative example 3]
Preparation and catalyst A form identical catalyst, and 0.4g ZnAl is added in 9.36g alumina support2O4Powder stirs
It mixes uniformly to get ZnAl2O4-Al2O3Carrier.It weighs 0.19g stannous chloride to be dissolved in the hydrochloric acid solution of 10mL, be added with stirring
It in the above-mentioned carrier of 10g, 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 potassium nitrate of the chloroplatinic acid and 0.207g that weigh 0.159g is dissolved in 10mL water, is added with stirring in I, is 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 dehydrogenation of isobutane catalyst and be denoted as
R.Examination condition the results are shown in Table 2 with embodiment 1.
Table 1
Table 2
[embodiment 16~23]
The catalyst that embodiment 1 is prepared is used for dehydrogenation of isobutane under the conditions of differential responses, evaluation result is shown in Table
3。
Table 3
[comparative example 4]
Catalyst regeneration stability contrast
It is de- that 0.5g catalyst A, 0.5g catalyst P, 0.5g catalyst Q and 0.5g catalyst R progress iso-butane is weighed respectively
Hydrogen evaluation, the results are shown in Table 4 after reacting 1h.
Table 4
Claims (7)
1. a kind of catalyst for preparing isobutene through dehydrogenation of iso-butane, 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 the AB with spinel structure2O4, wherein A is selected from Mg and Zn, and B is selected from Al and Fe；With molar ratio
Meter, the composition Mg:Zn of A is (0.25~4): it is (0.25~4) that 1, B group, which becomes Al:Fe: 1；
E) 80~99 parts of carrier Al2O3。
2. being used for the catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterised in that with dehydrogenation of isobutane
The number of catalyst weight number meter, Pt or its oxide is 0.1~2.5 part.
3. being used for the catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterised in that with dehydrogenation of isobutane
The number of catalyst weight number meter, alkali metal or its oxide is 0.5~2 part.
4. being used for the catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterised in that with dehydrogenation of isobutane
The number of catalyst weight number meter, Sn or its oxide is 0.1~2.5 part.
5. being used for the catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterised in that spinelle AB2O4, with
Dehydrogenation of isobutane catalyst weight number meter, number are 1~5.
6. the preparation method of the catalyst of the described in any item preparing isobutene through dehydrogenation of iso-butane of Claims 1 to 5, including following step
It is rapid:
A) Al of content needed for weighing2O3It pours into suitable deionized water and stirs, the soluble-salt of the A and B 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 ammonium hydroxide under continuous stirring until pH is 7~10；By product aging, filtering and washing obtains filter cake, through drying, roasting
Up to AB2O4And Al2O3Complex carrier；
B) soluble-salt of the desired amount of Sn is dissolved in suitable hydrochloric acid solution, addition a step obtains compound under stiring
In type carrier, it is uniformly mixed, through dipping, drying, roasts to obtain catalyst precarsor I；
C) soluble-salt of the desired amount of Pt, alkali and alkaline earth metal ions are dissolved in suitable water, b step is added under stiring
Catalyst precarsor I, be uniformly mixed, through dipping, drying, roast preparing isobutene through dehydrogenation of iso-butane catalyst.
7. any one of Claims 1 to 5 catalyst is used for preparing isobutene through dehydrogenation of iso-butane, reaction condition are as follows: iso-butane
It is (10~1) with hydrogen volume ratio: 1, reaction temperature is 400 DEG C~600 DEG C, and reaction pressure is 0~1MPa, and iso-butane quality is empty
Speed is 3.0~8.0h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510690485.6A CN106607023B (en) | 2015-10-22 | 2015-10-22 | For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510690485.6A CN106607023B (en) | 2015-10-22 | 2015-10-22 | For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106607023A CN106607023A (en) | 2017-05-03 |
| CN106607023B true CN106607023B (en) | 2019-11-08 |
Family
ID=58611737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510690485.6A Active CN106607023B (en) | 2015-10-22 | 2015-10-22 | For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106607023B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647433B (en) * | 2017-10-12 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of isobutane |
| CN112403489A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Core-shell type catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
| CN112547089A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst carrier and preparation method and application 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 |
| CN115518651B (en) * | 2021-06-24 | 2023-10-31 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by alkane dehydrogenation and preparation method and application thereof |
| CN115155613B (en) * | 2022-08-04 | 2023-12-05 | 西南化工研究设计院有限公司 | Preparation method and application of novel environment-friendly propane dehydrogenation catalyst |
| CN115646509B (en) * | 2022-10-21 | 2024-04-05 | 西南化工研究设计院有限公司 | Catalyst for preparing olefin by alkane dehydrogenation and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003013728A3 (en) * | 2001-08-08 | 2003-04-24 | Johnson Matthey Plc | Low surface acidity platinum-group metal catalysts for hydrogenation- and dehydrogenation reactions |
| CN104525194A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
-
2015
- 2015-10-22 CN CN201510690485.6A patent/CN106607023B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003013728A3 (en) * | 2001-08-08 | 2003-04-24 | Johnson Matthey Plc | Low surface acidity platinum-group metal catalysts for hydrogenation- and dehydrogenation reactions |
| CN104525194A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis of a structured material based on compact spheres coated with Zn or Mg spinel;Sonia Bocanegra et al.;《Procedia Materials Science》;20150702;第9卷;第69-78页 * |
| 钾盐对Pt-Sn/γ-Al2O3 催化异丁烷脱氢性能的影响;周广林等;《石油学报（石油化工）》;20150831;第31卷(第4期);第869-874页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106607023A (en) | 2017-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106607023B (en) | For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof | |
| CN105582918B (en) | Catalyst for dehydrogenation of low-carbon paraffin and application thereof | |
| CN105582929B (en) | Catalyst for dehydrogenation of low-carbon paraffin, preparation method and its usage | |
| CN105582919B (en) | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof | |
| CN103894201B (en) | Catalyst for dehydrogenation of low-carbon paraffin, preparation method and its usage | |
| CN105312046B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for improving its activity and stability | |
| CN101992095B (en) | Catalyst for preparing styrene through dehydrogenation by using rough ethylbenzene and preparation method thereof | |
| CN105582923A (en) | Catalyst used for producing olefin through light alkane dehydrogenation | |
| CN104549321B (en) | Catalyst for dehydrogenation of low-carbon paraffin and application thereof | |
| CN107537509A (en) | Catalyst of dehydrogenating low-carbon alkane and application thereof | |
| CN106607026B (en) | Catalyst for preparing isobutene by dehydrogenating isobutane and preparation method thereof | |
| CN101993336B (en) | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition | |
| CN105582922B (en) | Catalyst for dehydrogenating low-carbon alkane | |
| CN106607021B (en) | Catalyst for preparing isobutene by dehydrogenating isobutane | |
| CN105582920B (en) | Catalyst for dehydrogenation of low-carbon paraffin and its application | |
| CN102091628B (en) | Method for preparing low-carbon mixed alcohol catalyst by synthesis gas | |
| CN101623642B (en) | Ethylbenzene dehydrogenation catalyst with low water ratio | |
| CN106607025A (en) | Isobutane dehydrogenation catalyst and preparation method thereof | |
| CN105582921B (en) | Catalyst for dehydrogenation of low-carbon paraffin and its application method | |
| CN106607022B (en) | Catalyst for dehydrogenation of isobutane | |
| CN102040464B (en) | Method for preparing styrene from crude ethylbenzene by dehydrogenation | |
| CN105582925A (en) | Light alkane dehydrogenation catalyst | |
| CN102000587B (en) | Catalyst for methyl ethylbenzene dehydrogenation to prepare alpha methyl styrene | |
| CN105582924B (en) | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation | |
| CN100391605C (en) | Dehydrogenating catalyst for preparing alkyl alkenyl arene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |