CN106807441A - A kind of catalyst and its preparation and application that propylene is prepared for propane direct dehydrogenation - Google Patents
A kind of catalyst and its preparation and application that propylene is prepared for propane direct dehydrogenation Download PDFInfo
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Abstract
The invention provides a kind of catalyst that propylene is prepared for propane direct dehydrogenation, including carrier, the active component that is carried on the carrier and auxiliary agent；Wherein, the carrier is nano flake MFI structure molecular sieve, and the auxiliary agent includes at least one at least one and alkali earth metal in group iib metallic element.Present invention also offers the preparation method of the catalyst, comprise the following steps：During nano flake MFI structure molecular sieve impregnated in into the aqueous solution of platinum group metal compounds, group iib metallic compound and alkaline earth metal compound, then through drying and being calcined, combination of molecular sieve is obtained, obtain catalyst prod.Present invention also offers application of the catalyst in propane direct dehydrogenation prepares propylene reaction.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of catalyst and its system that propylene is prepared for preparing propane direct dehydrogenation
Standby and application.
Background technology
Propylene is widely used in production polypropylene, acrylonitrile, expoxy propane, isopropanol as a kind of important Organic Chemicals
With the chemical products such as acrylic acid.Propylene is mainly derived from the accessory substance of the coproduction of petroleum cracking ethene and petroleum catalytic cracking refining.
Since the nineties in last century, because original propylene source can not meet demand, dehydrogenating propane technology has turned into and steam cracking system
The propylene source of the 3rd after ethene coproduction, refinery catalytic cracking unit's refining by-product.Develop high activity, high selectivity and
The dehydrogenation of high stability is still the core in propylene De-hydrogen Technology.
At present, the catalyst of dehydrogenating propane is mainly with γ-Al2O3It is carrier, by loading platinum family metal element active component, and
Various metal promoters are added to be prepared from.Alumina support acidity is larger, causes the easy coking of catalyst, it is necessary to frequent regeneration.
In recent years, the molecular screen material with special pore passage structure and Shape-selective is increasingly used for dehydrogenating low-carbon alkane field.Molecular sieve
Micropore canals with larger specific surface area and uniqueness, are conducive to improving active component such as dispersion of the platinum element in catalyst surface
With the diffusion of reacting gas, suppress the formation of carbon distribution, be conducive to improving the stability of catalyst reaction.
South Korea Ryoo in 2009 report the nano flake MFI structure molecular sieve synthesized by asymmetric bi-quaternary ammonium salt, its b axle
The length of direction straight channels is only 2nm or so, drastically increases the diffusion of molecular sieve.
The content of the invention
In order to overcome the deficiencies in the prior art, urging for propylene is prepared for propane direct dehydrogenation it is an object of the invention to provide a kind of
Agent and preparation method thereof.The catalyst has specific surface area higher, good catalysis activity and selectivity, and longer
Service life, propylene quickly, efficiently at low cost can be prepared by propane direct dehydrogenation.
Present invention also offers application of the catalyst in propane direct dehydrogenation prepares propylene reaction.
On the one hand, the invention provides a kind of catalyst that propylene is prepared for propane direct dehydrogenation, including carrier, it is carried on institute
State the active component and auxiliary agent on carrier；Wherein, the carrier is nano flake MFI structure molecular sieve, and the auxiliary agent is included
At least one at least one and alkali earth metal in group iib metallic element.
In the present invention, term " MFI structure " be skilled artisans appreciate that known MFI structure.In the present invention
In the X-ray diffraction analysis XRD spectrum of nano flake MFI structure molecular sieve, go out for 7.8 °, 8.7 ° and 22.5-25 ° in 2 θ
Existing characteristic diffraction peak；And in scanning electron microscope analysis SEM spectrum, it is shown as nano flake structure.
According to the present invention, the weight meter based on the catalyst, the content of the carrier is preferably 80-99wt%, more preferably
92-99.7wt%.The content of the active component is preferably 0.01-5.0wt%, more preferably 0.1-1.0 with its contained elemental metal
Wt%.The content of the auxiliary agent is preferably 0.02-15.0wt%, more preferably 0.2-10.0wt% with its contained elemental metal.Its
In, the content preferred 0.01-10.0wt%, most preferably more preferably 0.1-5.0wt%, 0.1-2.0 of the group iib metallic element
Wt%.The content of the alkali earth metal is preferably 0.01-5.0wt%, more preferably 0.1-2.0wt%.
According to the present invention, the thickness of thin layer of the molecular sieve is preferably 5-50nm, such as 10-30nm.
The platinum group is preferably selected from least one in platinum, palladium, osmium, iridium, ruthenium and rhodium, more preferably platinum and/or palladium.
The group iib metallic element is preferably zinc and/or cadmium, more preferably zinc.The alkali earth metal is preferably magnesium and/or calcium.
On the other hand, the invention provides the preparation method of the catalyst, comprise the following steps：By nano flake MFI structure
Molecular sieve impregnated in the aqueous solution of platinum group metal compounds, group iib metallic compound and alkaline earth metal compound, then through dry
Dry and roasting, obtains combination of molecular sieve, obtains catalyst prod.
The present invention through step dipping can the quick good molecular sieve catalyst of processability, be applied to it is convenient and swift during industry, into
This is controllable.
According to the present invention, based on molecular sieve meter, the consumption of the group iib metallic compound is with group iib elemental metal
Preferably 0.01-12.0wt%, more preferably 0.1-6.0wt%.The consumption of the platinum group metal compounds is preferably 0.01-7wt%,
More preferably 0.1-2wt%.The platinum group metal compounds are preferably chloroplatinic acid.The consumption of the alkaline earth metal compound is with alkaline earth gold
Category element meter is preferably 0.01-6wt%, more preferably 0.1-3wt%.The alkaline earth metal compound is preferably calcium nitrate, magnesium nitrate
With at least one in barium nitrate.
Preferred embodiment of the invention, the time of the dipping is 8-16h, preferably 10-14h.The dry temperature
It is 80-150 DEG C, preferably 100-130 DEG C.The temperature of the roasting is 400-700 DEG C, preferably 450-600 DEG C.The roasting when
Between be 2-14h, preferably 4-12h.
Present invention also offers the preparation method of the molecular sieve, comprise the following steps：By template, silicon source, silicon source, alkali gold
Category hydroxide and sour mixing soluble in water, obtain gel；Gel is carried out into crystallization at a certain temperature, is reacted
Product；Product is dried and is calcined, nano flake MFI structure molecular sieve is obtained.
According to the present invention, the template is preferably the asymmetric bi-quaternary ammonium salt C of dication surfactantn-p-mX2, its molecular formula
Such as formula (a)：
In formula (a), n values are 10,12,14,16,18,20 or 22；M values are 1,2,3,4,5,6,7
Or 8；P values are 6 or 8, preferably 6；X is halogen, preferably bromine.
In a preferred embodiment of the invention, the silicon source includes at least one in Ludox, white carbon and waterglass.Institute
State silicon source and include at least one in aluminum sulfate, aluminum nitrate, boehmite and aluminium isopropoxide.
The acid is inorganic acid and organic acid, preferably inorganic acid, more preferably sulfuric acid.The alkali metal hydroxide is preferably hydrogen
Sodium oxide molybdena and/or potassium hydroxide.
According to the present invention, counted by 4000mol of water, the template is preferably 5-20mol in terms of corresponding halogens, more excellent
Select 8-15mol；The silicon source is preferably 50-600mol, more preferably 100-400mol in terms of element silicon；Source of aluminium is with aluminium unit
Element meter is preferably 1-3mol, more preferably 1.5-2.5mol；The acid is preferably 30-50mol, more preferably 35-45mol；And
The alkali metal hydroxide is preferably 20-80mol, more preferably 40-60mol in terms of alkali metal.
In a preferred embodiment of the invention, by the aluminium element in source of aluminium based on 1mol, the template is with corresponding halogen
Element is calculated as 2-10mol, and the silicon source is calculated as 50-300mol with element silicon.
According to the present invention, the temperature of the crystallization is preferably 120-180 DEG C, more preferably 140-160 DEG C.The crystallization
Time be preferably 80-180h, more preferably 100-150h.
According to the present invention, the dry temperature is preferably 80-150 DEG C, more preferably 100-130 DEG C.The temperature of the roasting is preferred
It is 400-700 DEG C, more preferably 500-600 DEG C.The time of the roasting is preferably 4-10h, more preferably 5-8h.
On the other hand, the application present invention also offers the catalyst in propane direct dehydrogenation prepares propylene reaction.It is described to answer
In the presence of the catalyst, dehydrogenation reaction is carried out under uniform temperature, pressure and feedstock quality air speed with including by propane.It is excellent
Selection of land, the temperature is 400-800 DEG C, preferably 500-700 DEG C；The feedstock quality air speed is 2.0-5.0h-1, preferably
2.5-4.5h-1.With hydrogen as diluent gas, the hydrogen is preferably (1-5) with the volume ratio of propane:1, more preferably (2-4):1,
The catalyst uses hydrogen reducing in the reactor.The step of reduction and condition use catalyst commonly used in the art again
Raw step and condition.
The catalyst that the present invention is provided is applied to propane direct dehydrogenation reaction and prepares propylene, be obtained in that the third of more than 50%
Alkane conversion ratio, and more than 98% Propylene Selectivity.After successive reaction 100h, the fall of conversion of propane is no more than
10%, the fall of Propylene Selectivity is no more than 5%.
The nano flake MFI structure molecular sieve prepared according to the method for the invention, its straight channels are extremely short, relative to list
Unit cell thickness is bigger, and with bigger surface area, effectively increases the diffusion of MFI structure molecular sieve.It is prepared into it
The catalyst for arriving, can effectively suppress the carbon distribution of catalyst, hence it is evident that improve the stability of catalyst.
The beneficial effects of the present invention are：
1st, the catalyst for preparing has good preparing propylene by dehydrogenating propane activity and Propylene Selectivity；
2nd, the catalyst for preparing has specific surface area higher；
3rd, coking is little during the course of the reaction for catalyst, and the single pass life of catalyst is long, with stability higher；
4th, method for preparing catalyst is simple, and cost is controllable.
Brief description of the drawings
Fig. 1 is the x-ray diffraction pattern of nano flake MFI structure molecular sieve prepared by embodiment 1.Wherein, abscissa is angle
2 θ (unit °), ordinate is the intensity (unit a.u.) of diffraction maximum.From XRD spectra as can be seen that there is sample MFI to tie
The characteristic diffraction peak of structure molecular sieve.Illustrating the nano flake MFI structure molecular sieve of the synthesis of embodiment 1 has good crystallinity,
XRD spectra with document report is consistent.
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of nano flake MFI structure molecular sieve prepared by embodiment 1.It can be seen that embodiment 1
The sample of synthesis is formed by thin laminas, and the thickness of thin layer is 5-50nm.
Fig. 3 is the conversion of propane that the catalyst for preparing embodiment 1 reacts for dehydrogenating propane and Propylene Selectivity anaplasia at any time
The curve map of change.It can be seen that after successive reaction 100h, conversion of propane stills remain in 38% or so, and Propylene Selectivity is still
It is maintained at 93% or so.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, it will be appreciated by those skilled in the art that
The following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted actual conditions person in embodiment,
The condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, being to pass through
City available from conventional products.
Embodiment 1
Prepare nano flake MFI structure molecular sieve：By NaOH, aluminum sulfate, waterglass, template C22-6-6Br2、H2SO4
With distilled water with 30Na2O:1Al2O3:100SiO2:8C22-6-6Br2:18H2SO4:4000H2Mol ratio (wherein " the Na of O2O's "
Amount refers to NaOH with Na2The amount of O meters) stirring mixing, molecular sieve gel is obtained.Gel is placed in equipped with polytetrafluoro internal layer
In autoclave, in 140-160 DEG C of crystallization 120h.After the completion of crystallization, by product distillation water washing, at 120 DEG C
Drying, then 6h is calcined at 550 DEG C, that is, nano flake MFI structure molecular sieve is obtained.
Prepare catalyst：0.082g chloroplatinic acids, 0.1753g magnesium nitrates and 0.2730g zinc nitrates are dissolved in 50mL water and are prepared
Mixed solution, above-mentioned nano flake MFI structure molecular sieve 6g is put into and wherein impregnates 12h, in 120 DEG C of dryings, then at 500 DEG C
Lower roasting 12h, obtains Pt-Zn-Mg/MFI structure molecular screens.
Through elementary analysis, the catalyst for preparing includes Pt 0.5wt%, Zn 1.0wt%, Mg 0.48wt%.
The catalyst is reacted for dehydrogenating propane：Reaction condition includes：At ambient pressure, 600 DEG C of reaction temperature, propane quality
Air speed 3h-1, C3H8:H2=3:1 (volume).Propane initial conversion 41% is obtained after reaction 1h；After successive reaction 100h, third
Alkane conversion ratio drops to 38%, and Propylene Selectivity maintains more than 93%.
Embodiment 2
Prepare nano flake MFI structure molecular sieve：By NaOH, aluminum sulfate, white carbon, template C18-6-6Br2、H2SO4
With distilled water with 28Na2O:1Al2O3:300SiO2:8C18-6-6Br2:18H2SO4:4000H2The mol ratio stirring mixing of O, is obtained and divides
Son sieve gel.Gel is placed in the autoclave equipped with polytetrafluoro internal layer, in 140-160 DEG C of crystallization 120h.Crystallization
After the completion of, by product distillation water washing, in 120 DEG C of drying, then 12h is calcined at 550 DEG C, that is, nano flake MFI is obtained
Structure molecular screen.
Prepare catalyst：0.080g chloroplatinic acids, 0.1351g calcium nitrate and 0.2730g zinc nitrates are dissolved in 50mL water and are prepared
Mixed solution, above-mentioned nano flake MFI structure molecular sieve 6g is put into and wherein impregnates 12h, in 120 DEG C of dryings, then at 500 DEG C
Lower roasting 12h, obtains Pt-Zn-Ca/MFI structure molecular screens.
Through elementary analysis, the catalyst for preparing includes Pt 0.5wt%, Zn 1.0wt%, Ca 0.55wt%.
Gained catalyst is reacted for dehydrogenating propane：Reaction condition includes：At ambient pressure, 600 DEG C of reaction temperature, propane matter
Amount air speed 3h-1, C3H8:H2=3:1 (volume).Propane initial conversion 40% is obtained after reaction 1h, after successive reaction 100h,
Conversion of propane drops to 38%, and Propylene Selectivity maintains more than 95%.
Embodiment 3
Prepare nano flake MFI structure molecular sieve：By NaOH, aluminum sulfate, Ludox, template C16-6-3Br2、H2SO4
With distilled water with 26Na2O:1Al2O3:500SiO2:8C16-6-3Br2:18H2SO4:4000H2The mol ratio stirring mixing of O, is obtained and divides
Son sieve gel.Gel is placed in the autoclave equipped with polytetrafluoro internal layer, in 140-160 DEG C of crystallization 120h.Crystallization
After the completion of, by product distillation water washing, in 120 DEG C of drying, then 6h is calcined at 550 DEG C, that is, nano flake MFI is obtained
Structure molecular screen.
Prepare catalyst：0.080g chloroplatinic acids, 0.0812g strontium nitrates and 0.1251g zinc chloride are dissolved in 50mL water and are prepared
Mixed solution, above-mentioned nano flake MFI structure molecular sieve 6g is put into wherein, 12h is impregnated, in 120 DEG C of dryings, then at 550 DEG C
Lower roasting 10h, obtains Pt-Zn-Sr/MFI structure molecular screens.
Through elementary analysis, the catalyst for preparing includes Pt0.5wt%, Zn 1.0wt%, Sr0.56wt%.
Gained catalyst is reacted for dehydrogenating propane：Reaction condition includes：At ambient pressure, 600 DEG C of reaction temperature, propane matter
Amount air speed 3h-1, C3H8:H2=3:1 (volume).Propane initial conversion 39% is obtained after reaction 1h, after successive reaction 100h,
Conversion of propane drops to 35%, and Propylene Selectivity maintains more than 94%.
Comparative example 1
Prepare catalyst：MFI structure molecular sieve prepared in accordance with the present invention is replaced to be prepared as carrier using gama-alumina
Pt-Zn-Mg/Al2O3Catalyst, it includes Pt 0.5wt%, Zn 1.0wt%, Mg 0.8wt%.
Gained catalyst is reacted for dehydrogenating propane：600 DEG C of reaction temperature, propane mass space velocity 3h-1, C3H8:H2=3:1 (body
Product).Propane initial conversion 38% is obtained after reaction 1h, after successive reaction 40h, conversion of propane drops to less than 30%,
Propylene Selectivity is less than 90%.
Comparative example 2
Prepare catalyst：MFI structure molecular sieve prepared in accordance with the present invention is replaced to be prepared as carrier using gama-alumina
Pt-Zn-Sr/Al2O3Catalyst, it includes Pt 0.5wt%, Zn 1.1wt%, Sr 0.58wt%.
Gained catalyst is reacted for dehydrogenating propane：600 DEG C of reaction temperature, propane mass space velocity 3h-1, C3H8:H2=3:1 (body
Product).Propane initial conversion 38% is obtained after reaction 1h, after successive reaction 40h, conversion of propane drops to less than 30%,
Propylene Selectivity is less than 80%.
According to embodiment and comparative example, the catalyst that the present invention is provided is applied to propane direct dehydrogenation and prepares propylene, be obtained in that
Conversion of propane higher and Propylene Selectivity, and after long-term successive reaction, still can keep activity higher.As implemented
In example 1, propane initial conversion is 41%, and 8% is only declined after successive reaction 100h, and Propylene Selectivity is maintained all the time
More than 93%.And in comparative example 1, propane initial conversion is 38%, 27%, and third is just declined after successive reaction 40h
Alkene selectivity is all the time less than 90%.It follows that the catalyst that the present invention is provided has good stability during the course of the reaction,
Reaction single pass life is long, using industrially with good economic benefit.
It should be noted that embodiment described above is only used for explaining the present invention, any limitation of the invention is not constituted.
By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive and explanatory
Vocabulary, rather than limited vocabulary.The present invention can be modified within the scope of the claims by regulation, and
The present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it be related to specific method,
Material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, the present invention can be extended to other
All methods and applications with identical function.
Claims (13)
1. a kind of catalyst that propylene is prepared for propane direct dehydrogenation, including carrier, the active component being carried on the carrier
And auxiliary agent；Wherein, the carrier is nano flake MFI structure molecular sieve, and the auxiliary agent is comprising in group iib metallic element
At least one and alkali earth metal at least one.
2. catalyst according to claim 1, it is characterised in that the active component comprising in platinum group extremely
Few one kind, is preferably selected from least one in platinum, palladium, osmium, iridium, ruthenium and rhodium, preferably platinum and/or palladium；And/or
The group iib metallic element is zinc and/or cadmium, preferably zinc, and the alkali earth metal is magnesium and/or calcium.
3. catalyst according to claim 1 and 2, it is characterised in that the weight meter based on the catalyst,
The content of the carrier is 80-99wt%, preferably 92-99.7wt%；The content of the active component is calculated as with metallic element
0.01-5.0wt%, preferably 0.1-1.0wt%；The content of the auxiliary agent is calculated as 0.02-15.0wt% with metallic element, preferably
0.2-10.0wt%；Wherein, the content of preferably described group iib metallic element be 0.01-10.0wt%, preferably 0.1-5.0wt%,
The content of the alkali earth metal is 0.01-5.0wt%, preferably 0.1-2.0wt%.
4. the catalyst according to any one in claim 1-3, it is characterised in that in the XRD spectrum of the molecular sieve
In, there is diffraction maximum for 7.8 °, 8.7 ° and 22.5-25 ° in 2 θ；The thickness of thin layer of the molecular sieve is 5-50nm.
5. the catalyst according to any one in claim 1-4, it is characterised in that the molecular sieve passes through following steps
Prepare：By template, silicon source, silicon source, alkali metal hydroxide and sour mixing soluble in water, gel is obtained；Gel is existed
Crystallization is carried out under uniform temperature, product is obtained；Product is dried and is calcined again, nano flake MFI knots are obtained
Structure molecular sieve；Wherein,
The template is the asymmetric bi-quaternary ammonium salt of dication surfactant, its molecular formula such as formula (a)：
In formula (a), n values are 10,12,14,16,18,20 or 22, m value are 1,2,3,4,5,6,7
Or 8, p value are 6 or 8, X are halogen, preferred bromine.
6. catalyst according to claim 5, it is characterised in that counted by 4000mol of water, the template is with halogen
5-20mol is calculated as, the silicon source is calculated as 50-600mol with element silicon, and source of aluminium is calculated as 1-3mol, the acid with aluminium element
It is 30-50mol, and the alkali metal hydroxide is calculated as 20-80mol with alkali metal；
Preferably, the silicon source includes at least one in Ludox, white carbon and waterglass, and source of aluminium includes aluminum sulfate, nitre
At least one in sour aluminium, boehmite and aluminium isopropoxide, the alkali metal hydroxide is NaOH and/or hydroxide
Potassium.
7. the catalyst according to claim 5 or 6, it is characterised in that the temperature of the crystallization is 120-180 DEG C,
It is preferred that 140-160 DEG C, the time of the crystallization is 80-180h.
8. the catalyst according to any one in claim 5-7, it is characterised in that the dry temperature is
80-150℃；The temperature of the roasting is 400-700 DEG C, preferably 500-600 DEG C；The time of the roasting is 4-10h.
9. as described in any one in claim 1-8 catalyst preparation method, comprise the following steps：By nano flake MFI
Structure molecular screen impregnated in the aqueous solution of platinum group metal compounds, group iib metallic compound and alkaline earth metal compound, then
Through drying and being calcined, combination of molecular sieve is obtained, obtain catalyst prod.
10. method according to claim 9, it is characterised in that based on molecular sieve meter, the group iib metallization
The consumption of compound is calculated as 0.01-12.0wt%, preferably 0.1-6.0wt% with group iib metallic element；The platinum group metal compounds
Consumption 0.01-7wt%, preferably 0.1-2wt% are calculated as with platinum group；The consumption of the alkaline earth metal compound is with alkaline earth
Metallic element is calculated as 0.01-6wt%, preferably 0.1-3wt%；
Preferably, the group iib metallic compound is at least one in zinc chloride, zinc nitrate and zinc sulfate；The platinum family gold
Category compound is chloroplatinic acid；The compound of the alkali earth metal is at least one in calcium chloride, magnesium nitrate and barium nitrate.
11. method according to claim 9 or 10, it is characterised in that the dry temperature is 80-150 DEG C, described
The temperature of roasting is 400-700, and preferably 450-600 DEG C, the time of the roasting is 2-14h.
12. catalyst as described in any one in claim 1-8 or according to any one methods described system in claim 9-11
Application of the standby catalyst in propane direct dehydrogenation prepares propylene reaction.
13. applications according to claim 12, it is characterised in that the application includes there is propane in the catalyst
Under carry out dehydrogenation reaction, wherein the temperature of the dehydrogenation reaction is 400-800 DEG C, preferably described propane feed mass space velocity is
2.0-5.0h-1。
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