CN107213919A - A kind of alumina support and its preparation method and application - Google Patents
A kind of alumina support and its preparation method and application Download PDFInfo
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- CN107213919A CN107213919A CN201610165171.9A CN201610165171A CN107213919A CN 107213919 A CN107213919 A CN 107213919A CN 201610165171 A CN201610165171 A CN 201610165171A CN 107213919 A CN107213919 A CN 107213919A
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- alkali metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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Abstract
The present invention relates to catalyst field, specifically disclose a kind of alumina support and its application, contain aluminum oxide, auxiliary agent and modifying agent in the alumina support, the auxiliary agent is group iva element and alkali metal, the modifying agent is halogen, the group iva element is that, selected from least one of germanium, tin and lead, the alkali metal is selected from least one of lithium and potassium.Present invention also offers a kind of preparation method of alumina support, this method includes：Under the solution state containing halogen, aluminum contained compound, element compound containing group iva and alkali metal-containing compound are contacted and be co-precipitated；Then obtained solid is dried and is calcined successively.The method for preparing alumina support of the invention is simple, cost is relatively low and is suitable for industrial production, the intensity of catalyst that the alumina support of the present invention is prepared is high, and can improve when for dehydrogenation reaction the yield and selectivity of product and the conversion ratio of raw material.
Description
Technical field
The present invention relates to catalyst field, in particular it relates to a kind of alumina support and preparation method thereof and
Using.
Background technology
In recent years, due to the appearance of every environmental protection policy, unleaded gas is promoted the use of, MTBE, ETBE
The demand of contour octane number additive is increased rapidly in the whole world, and isobutene is used as production methyl tertiary butyl ether(MTBE)
Raw material, demand also increases severely therewith.In addition the exploitation of isobutene downstream product so that conventional petroleum
The isobutene of catalytic pyrolysis production increases far from current demand, therefore the source of expansion isobutene is met
Plus the yield of isobutene, the task of top priority as current oil development of chemical industry.China, catalytic cracking gasoline
Iso-butane is mainly used for burning up as cheap fuel in gas, causes the significant wastage of resource.Therefore, will
Substantial amounts of cheap iso-butane carries out dehydrogenation reaction and the high isobutene of added value is made, with important warp
Ji, society and environmental benefit.
However, the catalyst used in dehydrogenation reaction process has vital work to dehydrogenation reaction
With, and the physical parameter of the carrier of catalyst and the performance of catalyst have very big relation, therefore how to make
On the one hand the important task of standby more efficient dehydrogenation also falls in that how to develop significantly more efficient carrier
On.
At present, there are large quantities of researchers to be directed to the improvement of catalyst carrier both at home and abroad, for example for
Specific surface area, pore volume, aperture of catalyst carrier containing aluminum oxide etc. are improved to be catalyzed
The higher catalyst such as activity, selectivity.Although however, prior art is respectively adopted in alumina raw material
It is middle to add the method such as alkaline earth metal compound or fluoride to improve alumina support, but with middle Gao Xuan
The heavy industrialization application of selecting property dehydrogenation, the requirement to alumina support performance is also constantly being carried
Height, the carrier for how developing the dehydrogenation that the catalytic activity of catalyst is further improved will
As primary study direction.
It is different that such as Publication No. CN101862669A patent application discloses a kind of dehydrogenation of isobutane system
Butylene catalyst and preparation method thereof, and specifically disclose using meso-porous alumina molecule stanniferous in skeleton
Sieve the catalyst as carrier, but the preparation method of stanniferous skeleton disclosed in the prior art it is complicated and into
This height, and when the catalyst containing the stanniferous skeleton is used for into catalyzing iso-butane alkane dehydrogenation reaction, iso-butane
Conversion ratio, the selectivity of isobutene and yield can not be obtained under the preparation condition of the high cost especially to be had
The raising of power.
In addition, the physico-chemical property of catalyst the process efficiency of preparing isobutene through dehydrogenation of iso-butane can also be produced to
Important influence is closed, such as dehydrogenation of isobutane disclosed in CN102000593A produces isobutene catalyst
Although ensure that higher iso-butane conversion ratio and isobutene yield, its disclosed dehydrogenation of isobutane
The intensity for producing isobutene catalyst is not high, thus greatly have impact on preparing isobutene through dehydrogenation of iso-butane
Economic benefit so that the catalyst that must be used within the shorter cycle during Replacement procedure.
The content of the invention
The purpose of the present invention is to overcome the defect of prior art there is provided a kind of alumina support and its preparation side
Method and application, are used for dehydrogenation reaction, particularly by the catalyst prepared by the alumina support of the present invention
Can be bright while the yield for ensureing isobutene is higher during reaction for preparing isobutene through dehydrogenation of iso-butane
The aobvious intensity for improving catalyst prepared by alumina support, so that by preparing isobutene through dehydrogenation of iso-butane
Economic benefit is significantly improved, and the method for preparing alumina support of the present invention is simple, cost compared with
It is low and be suitable for industrial production.
To achieve these goals, on the one hand, the present invention provides a kind of alumina support, the carrying alumina
In body contain aluminum oxide, auxiliary agent and modifying agent, the auxiliary agent be group iva element and alkali metal,
The modifying agent be halogen, wherein, the group iva element be in germanium, tin and lead extremely
Few one kind, the alkali metal is selected from least one of lithium and potassium.
On the other hand, the present invention also provides a kind of preparation method of alumina support, and this method includes：
Under solution state containing halogen, by aluminum contained compound, element compound containing group iva and containing alkali
Metallic compound is contacted and is co-precipitated；Then obtained solid is dried and is calcined successively；Its
In, group iva element in the element compound containing group iva be in germanium, tin and lead extremely
Few one kind；Alkali metal in the alkali metal-containing compound is selected from least one of lithium and potassium.
The third aspect, the present invention also provides a kind of carrier of the invention and the preparation oxidation using the present invention
Application of the alumina support that the method for alumina supporter is obtained in dehydrogenation is prepared.
The outer surface for the carrier that the method for preparing alumina support provided using the present invention is obtained and oxidation
Auxiliary agent and modifying agent are respectively provided with aluminium skeleton, using the alumina support of the invention provided or using this hair
When the carrier that the method for preparing alumina support of bright offer is obtained prepares dehydrogenation, ensureing isobutyl
The intensity of the catalyst of alumina support preparation is significantly improved while the yield of alkene is higher, so that by
The economic benefit of preparing isobutene through dehydrogenation of iso-butane is significantly improved, and the preparation method of the present invention also has
Have that simple, cost is relatively low and is suitable for industrial advantage, especially, will use institute of the present invention
The dehydrogenation that the carrier stated is prepared is used to make during the reaction of preparing isobutene through dehydrogenation of iso-butane
Isobutene yield it is higher, according to an embodiment of the invention effect can be seen that its yield can be with
More than 34.7% is reached, even up to 36.7% can be reached；And the selectivity of isobutene can reach
To more than 96.1%, 97.2% even up to can be reached.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of alumina support, in the alumina support containing aluminum oxide,
Auxiliary agent and modifying agent, the auxiliary agent are group iva element and alkali metal, and the modifying agent is halogen family
Element, wherein, the group iva element is selected from least one of germanium, tin and lead, the alkali gold
It is selected from least one of lithium and potassium to belong to element.
By the dehydrogenation of the above-mentioned alumina support with excellent intensity provided containing the present invention
Enable to the yield of isobutene higher during reaction for preparing isobutene through dehydrogenation of iso-butane.
According to alumina support of the present invention, preferably in terms of the total amount of the carrier, the aluminum oxide
The content of auxiliary agent in carrier can be 0.1-10wt%.
According to alumina support of the present invention, wherein, it is described preferably in terms of the total amount of the carrier
The content of modifying agent in alumina support can be 0.1-15wt%.
According to alumina support of the present invention, the group iva element in preferably described alumina support
Weight ratio with alkali metal can be 1：1-2.
According to one kind of the present invention preferred embodiment, the group iva in the alumina support
Element is tin, and the alkali metal is potassium.
According to another preferred embodiment of the present invention, the iv A in the alumina support
Race's element is tin and lead, and the alkali metal is potassium.
In above-mentioned another preferably embodiment, in the carrier, preferably described alumina support
In tin and lead mass ratio be 1：0.2-0.6.
Carrier with aforementioned component of the present invention can be prepared using various methods, as long as ensureing energy after preparing
Enough aforementioned bearer requirements for meeting the present invention.
On the other hand, present invention also offers a kind of preparation method of alumina support, this method includes：
Under the solution state containing halogen, by aluminum contained compound, element compound containing group iva and contain
Alkali metal compound is contacted and is co-precipitated；Then the solid obtained after co-precipitation is dried successively
And roasting；Wherein, the group iva element in the element compound containing group iva is selected from germanium, tin
At least one of with lead；Alkali metal in the alkali metal-containing compound is in lithium and potassium
It is at least one.
According to the method for the present invention for preparing alumina support, halogen in preferably described solution
The consumption of consumption and the element compound containing group iva and alkali metal-containing compound is so that with institute
The total amount for stating the group iva element in the total amount meter of carrier, alumina support and alkali metal is
0.1-10wt%；Halogen in alumina support is 0.1-15wt%.
Preferably, it is described containing group iva member according to the method for the present invention for preparing alumina support
The consumption of plain compound and alkali metal-containing compound is so that the group iva in the alumina support is first
The weight ratio of element and alkali metal can be 1：1-2.
Under preferable case, the method for alumina support is prepared of the present invention, the A containing iv
Group iva element in group element compound can be tin；Alkali metal in the alkali metal-containing compound
Element can be potassium.
According to another preferred embodiment of the present invention, aluminum oxide is prepared of the present invention
In the method for carrier, group iva element in preferably described element compound containing group iva is tin and lead,
And the alkali metal in the alkali metal-containing compound is potassium.
In the case of more preferably, in the above-mentioned another preferred embodiment of the present invention, described
In carrier, the consumption of the element compound containing group iva causes the matter of tin and lead in alumina support
Amount is than being 1：0.2-0.6.
In method of the present invention, the species to the solution containing halogen is not special
Limit, as long as enabling to contain halogen, in the method described in the present invention, halogen in solution
Race's element can be carried by least one of element compound containing group iva, alkali metal-containing compound
For.Also there is no particular limitation for species of the present invention to the halogen, still, in order to reduce production
Cost, the present invention preferably halogen is chlorine element.In the present invention, the solution state can be with
For aqueous solution state.
According to the method for the present invention for preparing alumina support, preferably described aluminum contained compound includes choosing
From at least one of aluminum sulfate, aluminium chloride and aluminum nitrate and meta-aluminate.
In method of the present invention, the species to the alkali metal-containing compound is not limited particularly
It is fixed, alkali metal in the present invention preferably alkali metal-containing compound can by alkali metal nitre
Hydrochlorate is provided, and the present invention preferably alkali metal-containing compound is potassium nitrate.
According to the method for the present invention for preparing alumina support, preferably described aluminum contained compound is sulfuric acid
Aluminium and meta-aluminate.In method of the present invention, the species to the meta-aluminate is not special
Limit, the present invention preferably meta-aluminate can be sodium metaaluminate.
, it is necessary to which what is illustrated is in method of the present invention：Present invention preferably employs double aluminium legal systems
Standby alumina support, therefore, when preparing the alumina support using double aluminium methods, in order to save production
Cost and raising production efficiency, the consumption mol ratio of preferably described aluminum sulfate and sodium metaaluminate is 1：6.
Prepare the method for alumina support of the present invention, it is preferably described by aluminum contained compound, contain
The method that group iva element compound and alkali metal-containing compound are contacted and be co-precipitated is：First distinguish
Aluminum contained compound, element compound containing group iva and alkali metal-containing compound are each dissolved in appropriate
In solvent, formed respectively lysate (there is no particular limitation to the concentration of the lysate by the present invention, as long as
Above-mentioned each compound is enabled to be completely dissolved, those skilled in the art can enter according to conventional meanses
Row selection), then again the solution is mixed to be contacted and be co-precipitated.It is of the invention preferably above-mentioned molten
Solution liquid carries out mixing contact and is co-precipitated by the way of current stabilization pump is by dropwise addition, and method of the invention is to institute
Stating the speed of dropwise addition, there is no particular limitation, as long as enabling to above-mentioned each lysate within the identical time
The completion of dropping and aluminum sulfate and the amount of sodium metaaluminate that are added dropwise in synchronization meet 1：6 mol ratio is
Can.
The method of alumina support is prepared of the present invention, to the element compound containing group iva
There is no particular limitation for species, is aoxidized as long as can be prepared by using the element compound containing group iva
Cause that group iva element can be contained in resulting alumina support during alumina supporter.According to this hair
Preferred embodiment, the element compound containing group iva can be containing group iva member to bright one kind
In chloride, the sulfate of the element containing group iva and the nitrate of the element containing group iva of element at least
It is a kind of.
The method of alumina support is prepared of the present invention, to described by aluminum contained compound, containing
The condition that IVA group element compounds and alkali metal-containing compound are contacted and be co-precipitated is not limited particularly
It is fixed, still, in order that the intensity for obtaining the catalyst for containing alumina support of the present invention is higher, and
The isobutene of more high yield is resulted in the reaction for preparing isobutene through dehydrogenation of iso-butane, the present invention is excellent
The condition for contacting and being co-precipitated is selected to include：Time is 6-15h.
The method of alumina support is prepared of the present invention, the preferably described bar for contacting and being co-precipitated
Part includes：Temperature is 40-80 DEG C.
The method of alumina support is prepared of the present invention, the preferably described bar for contacting and being co-precipitated
Part includes：PH value is 8-10.
The method of alumina support is prepared of the present invention, to described by consolidating for being obtained after co-precipitation
There is no particular limitation for the condition that body is dried and is calcined successively.In order that must contain of the present invention
The intensity of the catalyst of alumina support is higher, and the energy in the reaction for preparing isobutene through dehydrogenation of iso-butane
Enough isobutenes for obtaining more high yield, the temperature of the present invention preferably drying is 60-120 DEG C, more preferably
Dry temperature is 80-120 DEG C.
In order that it is different for dehydrogenation of isobutane system to obtain the catalyst containing alumina support of the present invention
The isobutene of more high yield is resulted in during the reaction of butylene, the temperature of the present invention preferably roasting is
400-750 DEG C, the temperature of more preferably described roasting is 450-650 DEG C.
The method of alumina support is prepared of the present invention, can also include drying and roast to passing through
The activated alumina obtained after burning is molded, and the present invention is not limited particularly the method for the shaping
It is fixed, in order that obtaining the catalyst containing alumina support of the present invention is used for dehydrogenation of isobutane isobutyl
Result in the isobutene of more high yield during the reaction of alkene, the method for the present invention preferably shaping can be with
For：Activated alumina obtained by after roasting is mixed with thickener such as sesbania powder, and adds peptizing agent
Such as 2wt% nitric acid is molded, and shaping carrier is conserved into 5-7h at room temperature, and is entered again successively
Row is dried and is calcined, so as to obtain shaping carrier.In method of the present invention, preferably described shaping
Allow the alumina support shape for spherical, trifolium-shaped, bunge bedstraw herb type, butterfly etc..
The third aspect, oxygen is prepared present invention also offers a kind of carrier of the invention and using the present invention
Application of the alumina support that the method for change alumina supporter is obtained in dehydrogenation is prepared.
In the present invention, those skilled in the art can be used of the present invention using various conventional methods
Alumina support to prepare dehydrogenation, in order that must containing alumina support of the present invention
The intensity of catalyst is higher, and results in the reaction for preparing isobutene through dehydrogenation of iso-butane higher
The isobutene of yield and selectivity, the present invention can preferably be adopted to be obtained for dehydrogenation of isobutane with the following method
The catalyst of the reaction of preparing isobutene：
Appropriate alumina support of the present invention is taken with containing such as chloroplatinic acid, stannic chloride, potassium chloride
Deng mixed liquor contact to be impregnated, time of dipping can be 10-15h, then at reduced pressure conditions
The solvent in dipping gained mixture is removed, then the solids of gained is dried and is calcined successively.
In the present invention, there is no particular limitation for the method that the solids of gained is dried and is calcined successively, this
Invention can preferably be dried overnight at 100 DEG C, then be calcined to be used at 600 DEG C
In the catalyst of the reaction of preparing isobutene through dehydrogenation of iso-butane.
The present invention will be described in detail by way of examples below.In following examples, not special
In the case of explanation, used various reagents are all from commercially available.
Embodiment 1
The present embodiment prepares alumina support of the present invention using method of the present invention.
By 491.4g sodium metaaluminates, the hydrazine aluminum sulfates of 666g tri-, 4.48g stannic chlorides, 5.29g potassium nitrate
Each self-forming lysate is dissolved with appropriate amount of deionized water respectively, is then 60 DEG C in temperature, pH value is 8
Under conditions of resulting saturated solution is added to 10h is contacted and be co-precipitated in 1L deionized water.
Then the solid obtained by co-precipitation is dried overnight at 100 DEG C, is then calcined and obtains at 600 DEG C
Activated alumina.
Take 300g activated aluminas to be mixed with appropriate sesbania powder, add 2wt% nitric acid as peptizing agent,
The extruded moulding on clover orifice plate.The bar of extrusion is conserved into 6h, Ran Hou under room temperature (25 DEG C)
It is dried overnight, and is calcined at 600 DEG C, the active aluminum oxide carrier 1-A being molded at 100 DEG C.
After tested, the tin containing 0.43wt% is (ultraviolet by using L5S in the alumina support 1-A
Spectrophotometer is tested, similarly hereinafter), 0.43wt% potassium (enters by using FP640 flame photometers
Row test, similarly hereinafter), 0.25wt% chlorine (being tested by using PXS-450 ionometers, similarly hereinafter).
Embodiment 2
The present embodiment prepares alumina support of the present invention using method of the present invention.
By 491.4g sodium metaaluminates, the hydrazine aluminum sulfates of 666g tri-, 8.96g stannic chlorides, 5.29g potassium nitrate
Each self-forming lysate is dissolved with appropriate amount of deionized water respectively, is then 50 DEG C in temperature, pH value is 9
Under conditions of resulting saturated solution is added to 12h is contacted and be co-precipitated in 1L deionized water.
Then the solid obtained by co-precipitation is dried overnight at 60 DEG C, is then calcined and is lived at 750 DEG C
Property aluminum oxide.
Take 300g activated aluminas to be mixed with appropriate sesbania powder, add 2wt% nitric acid as peptizing agent,
The extruded moulding on clover orifice plate.The bar of extrusion is conserved into 5h, Ran Hou under room temperature (25 DEG C)
It is dried overnight, and is calcined at 700 DEG C, the active aluminum oxide carrier 2-A being molded at 60 DEG C.
After tested, the tin containing 0.88wt% in the alumina support 2-A, 0.41wt% potassium,
0.27wt% chlorine.
Embodiment 3
The present embodiment prepares alumina support of the present invention using method of the present invention.
By 491.4g sodium metaaluminates, the hydrazine aluminum sulfates of 666g tri-, 2.24g stannic chlorides, 5.29g potassium nitrate
Each self-forming lysate is dissolved with appropriate amount of deionized water respectively, is then 70 DEG C in temperature, pH value is 8
Under conditions of resulting saturated solution is added to 8h is contacted and be co-precipitated in 1L deionized water.So
The solid obtained by co-precipitation is dried overnight at 120 DEG C afterwards, is then calcined and is lived at 500 DEG C
Property aluminum oxide.
Take 300g activated aluminas to be mixed with appropriate sesbania powder, add 2wt% nitric acid as peptizing agent,
The extruded moulding on clover orifice plate.The bar of extrusion is conserved into 7h, Ran Hou under room temperature (25 DEG C)
It is dried overnight, and is calcined at 450 DEG C, the active aluminum oxide carrier 3-A being molded at 110 DEG C.
After tested, the tin containing 0.21wt% in the alumina support 3-A, 0.42wt% potassium,
0.14wt% chlorine.
Embodiment 4
The present embodiment prepares alumina support of the present invention using method of the present invention.
By 491.4g sodium metaaluminates, the hydrazine aluminum sulfates of 666g tri-, 3.20g stannic chlorides, 0.75g lead chlorides,
5.29g potassium nitrate dissolves each self-forming lysate with appropriate amount of deionized water respectively, is then 80 DEG C in temperature,
PH value is that resulting saturated solution is added in 1L deionized water into contact and coprecipitated under conditions of 9
Shallow lake 15h.Then the solid obtained by co-precipitation is dried overnight at 80 DEG C, then roasted at 650 DEG C
Burning obtains activated alumina.
Take 300g activated aluminas to be mixed with appropriate sesbania powder, add 2wt% nitric acid as peptizing agent,
The extruded moulding on clover orifice plate.The bar of extrusion is conserved into 7h, Ran Hou under room temperature (25 DEG C)
It is dried overnight, and is calcined at 550 DEG C, the active aluminum oxide carrier 4-A being molded at 100 DEG C.
After tested, the tin containing 0.31wt% in the alumina support 4-A, 0.12wt% lead,
0.43wt% potassium, 0.48wt% chlorine.
Embodiment 5
The present embodiment prepares alumina support using method same as Example 4, except that：
The consumption of stannic chloride and lead chloride is respectively 2.21g and 1.35g in the present embodiment.
Remaining method is in the same manner as in Example 4, the active aluminum oxide carrier 5-A being molded.
After tested, the tin containing 0.21wt% in the alumina support 5-A, 0.21wt% lead,
0.43wt% potassium, 0.20wt% chlorine.
Embodiment 6
The present embodiment prepares alumina support using method same as Example 4, except that：
Stannic chloride consumption is 3.20g in the present embodiment, and without using lead chloride.
Remaining method is in the same manner as in Example 4, the active aluminum oxide carrier 6-A being molded.
After tested, the tin containing 0.31wt% in the alumina support 6-A, 0.43wt% potassium,
0.18wt% chlorine.
Embodiment 7
The present embodiment prepares alumina support using method same as Example 4, except that：
Stannic chloride consumption is 4.53g in the present embodiment, and without using lead chloride.
Remaining method is in the same manner as in Example 4, the active aluminum oxide carrier 7-A being molded.
After tested, the tin containing 0.43wt% in the alumina support 7-A, 0.43wt% potassium,
0.18wt% chlorine.
Embodiment 8
The present embodiment prepares alumina support using method same as Example 1, except that：
Nitric acid potassium application rate is 10.58g in the present embodiment.
Remaining method is in the same manner as in Example 1, the active aluminum oxide carrier 8-A being molded.
After tested, the tin containing 0.44wt% in the alumina support 8-A, 0.84wt% potassium,
0.24wt% chlorine.
Embodiment 9
The present embodiment prepares alumina support using method same as Example 1, except that：
Nitric acid potassium application rate is 2.65g in the present embodiment.
Remaining method is in the same manner as in Example 1, the active aluminum oxide carrier 9-A being molded.
After tested, the tin containing 0.44wt% in the alumina support 9-A, 0.22wt% potassium,
0.27wt% chlorine.
Comparative example 1
The method disclosed in embodiment 4 using CN101862669A prepares mesoporous oxygen stanniferous in carrier
Change aluminum molecular screen carrier 1-D.
After tested, the tin containing 1.02wt%, no potassium element, 0.87wt% in the alumina support 1-D
Chlorine.
Test case 1-10
200g alumina support as shown in table 2 below is taken to be added to by 2.65g chloroplatinic acids, 1.10g chlorine
In the maceration extract for changing tin, 1.91g potassium chloride and 376g water composition, removal of solvent under reduced pressure after dipping 12h,
Gained solids is dried at 100 DEG C overnight and at 600 DEG C successively and is calcined to be used
In the catalyst 1-B to 9-B and 10-D of the reaction of preparing isobutene through dehydrogenation of iso-butane, each test case
The name of the catalyst respectively obtained and its result of the tear strength represented with wear rate are specific such as the institute of table 2
Show, wherein, tear strength is tested using rotary collision method, is in particular：1kg catalyst is filled
Enter to rotate in container, (rotating speed is catalyst in the rotary course of ball shape rotary instrument (volume is 5L)
1000 turns/min) scroll-up/down and be worn, by 10h, take out sample, fine powder sifted out, with unit
Fine powder amount produced by quality (1kg) catalyst sample, i.e. wear rate (wear rate=fine powder amount/catalysis
Agent original weight amount × 100%) is come the data of the tear strength that represents catalyst.
Above-mentioned catalyst 1-B to 9-B and 10-D is used for the reaction that dehydrogenation of isobutane prepares isobutene,
As shown in table 1, reaction result is as shown in table 2 for the appreciation condition of the reaction.
Test case 11
Using the catalysis in the embodiment 1 that CN102000593A is determined with above-mentioned test case identical method
The tear strength of agent particle, as a result its wear rate is 15.3%.
Table 1
| Volume space velocity | Reaction pressure | Reaction temperature | Hydrogen hydrocarbon mol ratio |
| 1500h-1 | 0.1MPa | 600℃ | 2：1 |
Table 2
It is can be seen that from the result in above-described embodiment, comparative example, test case and table 2 using this hair
Just contain auxiliary agent and modifying agent in the alumina support that bright method is prepared, and contain the present invention
The wear rate of the dehydrogenation of the above-mentioned alumina support provided is low, namely intensity is high, and apparently higher than
The intensity of catalyst in comparative example.Moreover, the above-mentioned catalyst of the present invention is used for into dehydrogenation of isobutane system
During the reaction of standby isobutene, the conversion ratio of iso-butane, the selectivity of isobutene and isobutene are enabled to
The carrier height that yield is substantially relatively obtained using the method for prior art.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible combinations.
Claims (13)
1. a kind of alumina support, it is characterised in that contain aluminum oxide, auxiliary agent in the alumina support
And modifying agent, the auxiliary agent is group iva element and alkali metal, and the modifying agent is halogen,
Wherein, the group iva element is selected from least one of germanium, tin and lead, the alkali metal
For selected from least one of lithium and potassium.
2. carrier according to claim 1, wherein, in terms of the total amount of the carrier, the oxygen
The content for changing the auxiliary agent in alumina supporter is 0.1-10wt%；The content of modifying agent in the alumina support
For 0.1-15wt%.
3. carrier according to claim 1 or 2, wherein, the iv A in the alumina support
The weight ratio of race's element and alkali metal is 1：1-2.
4. carrier according to claim 1 or 2, wherein, the group iva element is tin；
The alkali metal is potassium.
5. carrier according to claim 1 or 2, wherein, the group iva element be tin and
Lead；The alkali metal is potassium.
6. carrier according to claim 5, wherein, in the carrier, the carrying alumina
The mass ratio of tin and lead in body is 1：0.2-0.6.
7. a kind of preparation method of alumina support, it is characterised in that this method includes：Containing halogen
Under the solution state of race's element, by aluminum contained compound, element compound containing group iva and alkali metal containing
Compound is contacted and is co-precipitated；Then obtained solid is dried and is calcined successively；Wherein, institute
It is selected from least one of germanium, tin and lead to state the group iva element in element compound containing group iva；
Alkali metal in the alkali metal-containing compound is selected from least one of lithium and potassium.
8. method according to claim 7, wherein, in the solution consumption of halogen with
And the consumption of the element compound containing group iva and alkali metal-containing compound is so that with the carrier
Total amount meter, the total amount of group iva element and alkali metal in alumina support is 0.1-10wt%；
Halogen in alumina support is 0.1-15wt%；
Preferably, the consumption of the element compound containing group iva and alkali metal-containing compound is so that institute
The weight ratio for stating the group iva element in alumina support and alkali metal is 1：1-2.
9. the method according to claim 7 or 8, wherein, the element compounds containing group iva
Group iva element in thing is tin；Alkali metal in the alkali metal-containing compound is potassium.
10. the method according to claim 7 or 8, wherein, the element compounds containing group iva
Group iva element in thing is that the alkali metal in tin and lead, the alkali metal-containing compound is potassium；
It is preferred that in the carrier, the consumption of the element compound containing group iva causes the alumina support
In tin and lead mass ratio be 1：0.2-0.6.
11. the method according to claim 7 or 8, wherein, the aluminum contained compound includes being selected from
At least one of aluminum sulfate, aluminium chloride and aluminum nitrate and meta-aluminate；It is preferred that the aluminum contained compound is
Aluminum sulfate and meta-aluminate.
12. method according to claim 7, wherein, the condition for contacting and being co-precipitated includes：
Time is 6-15h, and temperature is 40-80 DEG C, and pH value is 8-10.
13. any one in the carrier or claim 7-12 in claim 1-6 described in any one
Application of the carrier that described method is prepared in dehydrogenation is prepared.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862669A (en) * | 2010-06-23 | 2010-10-20 | 东南大学 | Catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
| CN103785384A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of catalyst for low carbon alkane dehydrogenation to prepare alkene |
| CN104549249A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for alkene preparation through dehydrogenation and preparation method of catalyst |
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2016
- 2016-03-22 CN CN201610165171.9A patent/CN107213919B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862669A (en) * | 2010-06-23 | 2010-10-20 | 东南大学 | Catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
| CN103785384A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of catalyst for low carbon alkane dehydrogenation to prepare alkene |
| CN104549249A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for alkene preparation through dehydrogenation and preparation method of catalyst |
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