CN106563440A - Crystal-grain-distribution-controlled light alkane dehydrogenation catalyst and preparation method thereof - Google Patents
Crystal-grain-distribution-controlled light alkane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN106563440A CN106563440A CN201611001100.1A CN201611001100A CN106563440A CN 106563440 A CN106563440 A CN 106563440A CN 201611001100 A CN201611001100 A CN 201611001100A CN 106563440 A CN106563440 A CN 106563440A
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a crystal-grain-distribution-controlled light alkane dehydrogenation catalyst and a preparation method of the crystal-grain-distribution-controlled light alkane dehydrogenation catalyst. In the preparation process of the crystal-grain-distribution-controlled light alkane dehydrogenation catalyst, crystal grains of a main active component are controlled through the dipping temperature and a surfactant, and the obtained catalyst has different kinds of crystal grain size distribution; and according to the crystal grain distribution of the main active component, chromium oxide, in the catalyst, the chromium oxide crystal grains close to the center of the catalyst are large in size, and the chromium oxide crystal grains close to the outer surface of the catalyst are small in size. The crystal-grain-distribution-controlled light alkane dehydrogenation catalyst takes the advantage of different crystal grain sizes in the alkane dehydrogenation, the activity and the stability of the catalyst are improved, catalyst deactivation is slowed down, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to belong to dehydrogenation preparation field, and in particular to a kind of catalysis of manufacturing olefin by low-carbon alkane dehydrogenation
Agent and preparation method, particularly improve the catalyst preparation of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation activity and stability and use
Method.
Background technology
Low-carbon alkene, such as propylene and isobutene. are important Organic Chemicals, and such as current propylene demand is larger, and tradition is raw
Production. art can not meet the market demand, thus the emerging low-carbon alkene production technology for substituting includes dehydrogenating propane (PDH), methanol system
Five kinds of emerging techniques such as alkene (MTO, MTP), DCC (DCC), olefin cracking and olefin(e) disproportionation.Comparatively speaking,
Dehydrogenating low-carbon alkane technical advantage becomes apparent from, and it is few etc. excellent that it possesses technology maturation, good product quality, high conversion rate, by-product
Point.The catalyst of preparation of olefin through light alkane dehydrogenation is broadly divided into two classes, chromium-based catalysts and platinum-group noble metals catalyst.At present
Industrialized dehydrogenating low-carbon alkane propylene production technology is mainly the Oleflex techniques of Uop Inc. of the U.S., using platinum catalysis
Agent, has the advantages that good stability, but expensive；Also Catofin techniques of U.S. Lummus companies, using chromium, system urges
Agent, its low price is low to raw material impurity requirement, is suitable to internal sources present situation in short supply.
Research shows, for loaded catalyst, its maximum activity and selectivity are carried with metal or metal-oxide at it
The distribution of body and grain size are closely related.It is to obtain good catalytic performance in general catalyst preparation process, pursues activity
Component crystal grain is uniformly distributed.Chinese patent CN1522178 disclose a kind of high surface, smooth uniform surface form,
In the little transition metal based catalysts of whole granule and crystallite dimension, its preparation method is big in a kind of pH to this equiblibrium mass distribution of cobalt-based
Prepare in 7.0 nonacidic solutions, initiation material is nonacid transient metal complex, and the product for obtaining is a kind of metal
Be uniformly distributed in whole catalyst granules, with smooth uniform surface form and heating when the slow catalyst of grain growth.China
Patent CN103447038A discloses the preparation method that a kind of mesoporous TiO2 loads nanometer iron catalyst, by improving preparation technology
Condition, effectively delays the fast hydrolyzing-polycondensation reaction of butyl titanate so that nano-iron particle crystal grain refinement is uniformly mesoporous
Generate in TiO2 catalyst duct, solve nano-iron particle and pile up agglomeration traits in mesoporous TiO2 catalyst surfaces, it is effectively slow
The reuniting effect of nano iron particles has been solved, its aerial stability and non-oxidizability has been improve, the light of the catalyst has been improved
Catalytic efficiency.Chinese patent CN103769157A is the invention discloses a kind of preparation method of hydrogenation catalyst.Existed using two steps
Parallel-flow precipitation prepares catalyst precursor under different condition, and beneficial to catalyst stable framing structure is formed, and adopts supercritical
Dry technology, the catalyst for making preparation has bigger specific surface and the pore size distribution more concentrated, and metal component is in dry process
In there is no the clustering phenomena of nanoparticle, while the grain size in catalyst is more uniform, pore size distribution is relatively concentrated, and is improve and is urged
The reactivity and selectivity of agent and stability.
Dehydrogenating low-carbon alkane reaction is limited by thermodynamical equilibrium, is typically carried out under conditions of high temperature, low pressure, and too high is anti-
Answer temperature so that the side reaction of dehydrogenation reaction such as cracking reaction and deep dehydrogenation aggravate, and cause selectivity to decline；Also make simultaneously
It is serious into catalyst surface carbon distribution, have a strong impact on catalyst activity.Although chromia-alumina catalyst is in dehydrogenation reaction process
Middle initial reaction activity is higher, as used in dehydrogenating propane reaction, initial stage conversion ratio up to 50%～60%, initial stage selectivity
Up to 92%～96%.But being changed by carbon distribution and active component is affected, catalyst is used 2 years or so, catalyst
Conversion ratio be down to 35%～40%, selectivity is down to 80%～85%.Therefore need further to change dehydrogenation
Enter.
Chromium system catalyst for dehydrogenation of low-carbon paraffin belongs to loaded catalyst, it is considered that with the increase of load capacity, oxidation
Chromium crystal grain gradually increases, and low-carbon alkanes conversion ratio declines, while the selectivity of alkene is improved, olefin yields gradually increase, and are catalyzed
Agent activity is raised with the increase of load capacity.But when chromium oxide load capacity is further improved, olefin yields are likely to occur not
It is further added by, or even the phenomenon that can be reduced.For dehydrogenation of hydrocarbons catalyst, optimal conditions are answered to prepare the catalysis of suitable grain size
Agent, it is considered that catalyst activity component crystal grain is little can to improve alkane conversion, but the selectivity of alkene is relatively low；And be catalyzed
Agent active component crystal grain is then conducive to improving the olefine selective of catalyst greatly, but the conversion ratio of alkane can be affected to improve.Cause
This current chromium system dehydrogenation technology of preparing is so that the catalyst activity component prepared possesses suitable grain size,
To carry out balance optimizing in alkane conversion and olefine selective, the catalyst dehydrogenation activity prepared also has been thus resulted in steady
Qualitative difference, it is impossible to reach the purpose for preferably obtaining more polyene.
The present invention obtains more preferable catalysis activity, in changing catalyst to solve to increase chromium system dehydrogenation stability
Main active component chromium oxide crystal grain distribution so that the crystal grain of catalyst inner layer chromium oxide is less, the chromium oxide of catalyst outer layer is brilliant
Grain is larger.Catalyst inner layer active component crystal grain is less, using alkane conversion is improved, when product leaves catalyst inner layer
And when chromium oxide crystal grain larger outer layer, can have less chance further to react, so as to the overall alkene for improving catalyst
Hydrocarbon-selective so that catalyst has higher alkane conversion, and reduces reactant deep dehydrogenation, so as to reduce catalyst product
Carbon, improves catalyst stability.
The content of the invention
For currently used for the chromium-based catalysts of dehydrogenating low-carbon alkane, in use dehydrogenation activity stability is poor, no
The purpose for preferably obtaining more polyene can be reached, the invention discloses a kind of dehydrogenating low-carbon alkane catalysis of control crystal grain distribution
Agent and preparation method thereof so that the catalyst has while catalyst activity during dehydrogenating low-carbon alkane keeps stable
Have the advantages that inactivation is slow, carbon accumulation resisting ability is strong.
A kind of catalyst for dehydrogenation of low-carbon paraffin of control crystal grain distribution of the present invention, the catalyst activity component is using dipping
Mode is loaded on carrier, and active component content is uniformly distributed in the catalyst, wherein main active component chromium oxide is in catalyst
Middle size of microcrystal has following characteristics：Chromium oxide size of microcrystal is larger at close catalyst center, and outside catalyst
Chromium oxide size of microcrystal is less at surface.
In catalyst of the present invention, described main active component chromium oxide size of microcrystal is in catalyst section
The heart is not less than 15 nanometers；Main active component chromium oxide size of microcrystal is being not more than 12 nanometers near catalyst surface.
Catalyst of the present invention, wherein it is preferred that with aluminium oxide as carrier, chromium oxide is the main active component of catalyst,
One or more in Li, Na, K, Zr is auxiliary agent.The weight/mass percentage composition of each component is in catalyst：The oxygen of active component chromium
Compound is 1～40wt%, preferably 10～30wt%；The oxide content of auxiliary element be 0.01～10wt%, preferably 0.1
～8wt%；Remaining is carrier, and carrier is aluminium oxide.
Present invention also offers the preparation method of the catalyst for dehydrogenation of low-carbon paraffin of above-mentioned control crystal grain distribution, including it is following
Step：
1) impregnation liquid configuration：Prepare dipping solution containing chromium, the surface activity containing 0.01wt%～5wt% in impregnation liquid
Agent；
2) catalyst activity component load：The first step：Catalyst dipping is carried out under room temperature after 1～120 minute, is slowly heated
To after 40 DEG C～150 DEG C, 1～180 minute is incubated；
3) in 80 DEG C～180 DEG C dryings 1～24 hour, then in 550 DEG C～900 DEG C roastings 1～24 hour, lower alkanes are obtained
Hydrocarbon dehydrogenation.
In above-mentioned preparation method, described surfactant is citric acid, maleic acid, trichloroacetic acid, acetic acid, three ethanol
The combination of one or more in amine, imidazoline, polyacrylamide.Belong to water miscible or dissolve in more than 50 DEG C water-soluble
Liquid.
The remarkable advantage of technology of the present invention is：(1) for catalyst for dehydrogenation of low-carbon paraffin difference grain size to catalysis
The impact of activity has nuance, catalyst activity component is loaded on catalyst by the way of step impregnation, and has
There are different active component size of microcrystal；(2) activity over catalysts component grain size possesses different distributions, can effectively carry
The conversion ratio of high dehydrating alkanes, and the selectivity of alkene is improved to greatest extent, reduce side reaction and occur；(3) catalyst activity group
Divide crystal grain different, also can preferably reduce the migration of active component and the impact of sintering under reaction condition, improve catalyst stabilization
Property.
Specific embodiment
Below will by specific embodiment, the invention will be further described, but the invention is not limited in these enforcement
Example.
The preparation method of the carrier of catalyst in the embodiment of the present invention, including：By aluminium hydroxide powder with account for alumina powder
Weight fraction is 0.5～5% sesbania powder mix homogeneously, and add mass concentration carries out kneading for 1～30% dust technology, is mixed
The time is pinched for 10min～10h, molding is finally carried out on forming machine again, the carrier after molding after room temperature dries in the air 1～12h, then
Dry 1～8h in 80～150 DEG C, last 500～1000 DEG C of 1～12h of roasting in Muffle furnace of the carrier of drying obtain final
Carrier.
Prepare the molding that alumina catalyst support is used machine include tablet machine, rolling granulators, pellet processing machine, moulding machine,
Banded extruder etc..The shape of molding rear oxidation aluminium mixture includes spherical, lamellar, cylinder, star, trilobal, quatrefoil.
The preparation of embodiment of the present invention catalyst for dehydrogenation of low-carbon paraffin is using infusion process come supported active metals and auxiliary agent, bag
Include following steps：
1) impregnation liquid is prepared：It is dense 2 kinds of different chromium oxides to be prepared using the presoma of the presoma containing chromium, alkali metal containing and Zr
The chromium-containing solution of degree, and water miscible surfactant is added in impregnation liquid so that containing 0.01%～5% in impregnation liquid
Surfactant；
The presoma containing chromium that uses of configuration impregnation liquid include chromic acid, sodium chromate, sodium dichromate, potassium dichromate, Ammonium bichromate.,
The combination of one or more in chromic nitrate, chromium+oxalic acid, chromic tartrate, Chlorizate chromium and chromium acetate.
The alkali metal containing presoma that configuration impregnation liquid is used includes alkali-metal nitrate, sulfate, chloride, oxalates
In the combination of one or more, alkali metal used includes the combination of one or more in Li, Na and K.
The compound containing Zr elements that configuration impregnation liquid is used includes zirconium nitrate, nitric acid oxidation zirconium, zirconium carbonate, basic carbonate
The combination of one or more in zirconium, zirconium chloride.
Surfactant used by configuration impregnation liquid can use water miscible cationic surfactant, anionic surface
Activating agent, nonionic surfactant and zwitterionic surfactant, specifically include using citric acid, maleic acid, trichlorine
The combination of one or more in acetic acid, acetic acid, triethanolamine, imidazoline, polyacrylamide.
The content of promoter metal in impregnation liquid, it is catalyst weight to control auxiliary agent metal oxides total amount in catalyst
0.5%～8%.
2) active component is supported in two temperature ranges and carries out, and carries out catalyst at room temperature first and impregnates 1～120 point
Zhong Hou, preferably 1～60 minute；Slow heating impregnation liquid is incubated 1～180 minute to after 40 DEG C～150 DEG C.
Hot submersion liquid can adopt heating in water bath, the mode such as electrical heating or steam heating may also be employed, in heating process
Can stir, it would however also be possible to employ the mode of standing is slowly heated, but heating process is unwell 180 minutes.
3) after dipping is finished, the material for soaking in 80 DEG C～180 DEG C dryings 1～24 hour, then 550 DEG C～900
DEG C roasting 1～24 hour, obtains catalyst for dehydrogenation of low-carbon paraffin.
Calcination atmosphere is air or the air containing 5%～80% vapor, preferably 600 DEG C～750 DEG C of sintering temperature, roasting
Preferably 4～12 hours time.
Through chromium system dehydrogenation prepared by as above step, characterized with electron probe, scanning electron microscope or projection Electronic Speculum etc.
Means carry out catalyst section grain form and size is characterized, it is possible to find the particle diameter distribution of its crystal grain is in catalyst section
On.By the measurable grain size of above means, distribution situation of the size of microcrystal from catalyst kernel of section to edge is obtained.
Here catalyst kernel of section can be the figure of a point, or a various straight lines or curve connection, positioned at cutting
Face center.
So that catalyst section is as circle as an example, the center of catalyst is its center of circle.By above catalyst preparation step
The catalyst for obtaining, its crystal grain distribution is that catalyst inner layer chromium oxide crystal grain is larger, and by paracentral size of microcrystal 15 are not less than
Nanometer, preferably more than 20 nanometers；And near catalyst outer layer be catalyst surface chromium oxide size of microcrystal it is less, catalyst
Outer surface chromium oxide crystal grain is not more than less than 12 nanometers, preferably less than 10 nanometers.
For catalyst section is not circular catalyst, its central point can be the figure being made up of line segment and curve.
The intersection point that catalyst section edges each point inwardly intersects along normal direction constitutes its kernel of section.Walked by above catalyst preparation
Suddenly the catalyst for obtaining, its crystal grain distribution is that catalyst inner layer chromium oxide crystal grain is larger, and size of microcrystal is not less than 15 nanometers, preferably
For more than 20 nanometers, and it is less near the chromium oxide size of microcrystal of catalyst outer layer, and size of microcrystal is not more than 12 nanometers, preferably
Less than 10 nanometers.
Although passing through according to being distributed from the inside to surface according to the catalyst activity component grain size of above-mentioned steps preparation
The different thin layers of scraping carry out chemical constituent analysis, as a result show, chromic oxide content keeps being uniformly distributed in the catalyst.Scraped
Thin layer it is maximum be less than 0.5 millimeter, the thickness for being scraped carries out chemical constituent analysis, shows active component along catalyst enough
Content distribution of the section center of circle to catalyst edge.
When catalyst of the present invention is used for dehydrogenating low-carbon alkane, typically dehydrogenation is carried out under the reaction temperature higher than 500 DEG C anti-
Should, the generic condition of reaction is reaction pressure：- 0.1～1MPa, 500～680 DEG C of reaction temperature, low-carbon alkanes gas space velocity is
200～2000h-1.
Because chromium-based catalysts carbon distribution is very fast, the mode of operation of interval is industrially typically adopted.Dehydrogenation reaction in the present invention
Process and coke combustion are alternately.Wherein certain embodiments are carried out 1～20 minute, be switched to Burning Coke on Catalyst process carry out 0～
40 minutes, preferably 5～40 minutes.At 500～700 DEG C, reaction pressure is normal pressure or negative pressure for reaction temperature control.
The low-carbon alkanes raw material that catalyst of the present invention is suitable for is liquefied petroleum gas of the low-carbon alkanes content more than 80%,
Raw material low-carbon alkanes refer to the alkane gaseous mixture of below the C4 of arbitrary proportion, the particularly mixed gas of propane and butane.Individually
During with propane as raw material, in 0.01～0.5MPa of reaction pressure, 570～600 DEG C of reaction temperature, propane feed gas gas space velocity
Under conditions of 200～500h-1, conversion of propane is more than 55%, and Propylene Selectivity is higher than 90%；1 is pressed with propane and butane:1
When mixed alkanes are raw material, in 0.03～0.5MPa of reaction pressure, 550～580 DEG C of reaction temperature, mixed gas air speed 200～
Under conditions of 500h-1, the conversion ratio of mixed alkanes generates the selectivity of alkene also more than 90% more than 60%
Comparative example 1
It is prepared by carrier.By a certain amount of boehmite powder body 300g, silica powder 5g, sesbania powder 3g mix homogeneously,
Carry out kneading for 10% dust technology mixed solution with mass concentration again, the kneading time is 60min, Φ is finally used on banded extruder again
The orifice plate of 4mm carries out molding, and after room temperature dries in the air 8h, then at 120 DEG C of drying 4h, the carrier of drying is finally in horse for the carrier after molding
Not 850 DEG C of roasting 6h in stove, obtain carrier 1, and its water absorption rate is 52.3%.
Prepare impregnation liquid containing chromium：Chromic nitrate 10.6g, chromic anhydride 21.6g, Sodium Chloride 1.5g, sodium nitrate are weighed in beaker
2.0g, zirconyl nitrate 2.8g, add 40ml deionized water dissolving to be made into impregnation liquid；
Dipping：25g carrier A are taken, room temperature descended volume impregnation 120 minutes, hydro-thermal heats beaker to 45 DEG C, impregnates 165 points
Clock；Then in 85 DEG C of dryings 6 hours, then the roasting 6h under 660 DEG C of air atmospheres, obtains finished catalyst A and is catalyzed as a comparison
Agent.
The crystal grain distribution of the active component chromium oxide of catalyst A is shown in Table 1.
Catalyst activity test condition：Using 20ml fixed bed minisize reaction evaluation systems, take 20 milliliters to load internal diameter is 8
Dehydrogenating propane reactivity worth test is carried out in the stainless steel reactor of millimeter.
Catalytic performance test condition：Unstripped gas mass space velocity of the unstripped gas containing propane 97% is 400h-1, and reaction pressure is
0.01MPa, reaction temperature is 600 DEG C, and dehydrogenation reaction is carried out 12 minutes, is passed through air regenesis 18 minutes, after to carry out dehydrogenation again anti-
Should, so circulation is carried out.Every time dehydrogenation reaction is carried out to chromatograph sample analysis when 8 minutes, and the catalytic performance test of catalyst A is tied
Fruit is shown in Table 1.
Embodiment 1
Prepare impregnation liquid：Chromic nitrate 10.6g, chromic anhydride 21.6g, Sodium Chloride 1.5g, sodium nitrate 2.0g, nitre are weighed in beaker
Sour oxygen zirconium 2.8g, adds 40ml deionized water dissolving, adds 0.5 gram of citric acid and is made into impregnation liquid；
Dipping：25g carriers 1 are taken, room temperature descended volume impregnation 120 minutes, hydro-thermal heats beaker to 45 DEG C, impregnates 165 points
Clock；Then in 85 DEG C of dryings 6 hours, then the roasting 6h under 660 DEG C of air atmospheres, obtains finished catalyst B.
The crystal grain distribution of the active component chromium oxide of catalyst B is shown in Table 1.
, with comparative example 1, evaluation result is shown in Table 1 for catalyst B activity test condition and appreciation condition.
Embodiment 2
Prepare impregnation liquid：Weigh Ammonium bichromate. 18.6g, chromic anhydride 13.2g, potassium sulfate 0.5g, sodium nitrate 2.6g, acetic acid 4.5
Milliliter is put in beaker, adds 35ml deionized water dissolving to be made into impregnation liquid；
Dipping：45g carriers 1 are taken, room temperature volumetric impregnates 120 minutes, heating in water bath beaker impregnates 95 points to 65 DEG C
Clock；Then in 125 DEG C of dryings 12 hours, then the roasting 4h under 750 DEG C of air atmospheres, obtains finished catalyst C.
The crystal grain distribution of the active component chromium oxide of catalyst C is shown in Table 1.
With embodiment 1, catalytic performance test the results are shown in Table 1 to the performance evaluation condition of catalyst C.
Embodiment 3
Prepare impregnation liquid：Weigh chromic nitrate 27.5g, chromium+oxalic acid 4.6g, chromic anhydride 16.8g, sodium nitrate 1.5g, imidazoline 0.3g
In being put into beaker, 50ml deionized water dissolving is added uniformly to be made into impregnation liquid；
Dipping：45g carriers 1 are taken, room temperature descended volume impregnation 3 minutes, heating beaker impregnates 120 minutes to 90 DEG C；Then
In 150 DEG C of dryings 12 hours, then the roasting 4h under 860 DEG C of air atmospheres, obtained finished catalyst D.
The crystal grain distribution of the active component chromium oxide of catalyst D is shown in Table 1.
, with comparative example 1, evaluation result is shown in Table 1 for catalyst D active testings condition and appreciation condition.
Embodiment 4
Prepare impregnation liquid：Weigh chromic nitrate 46.6g, chromium+oxalic acid 3.6g, chromic tartrate 2.5g, potassium oxalate 1.5g, polypropylene
Amide 0.1g is put in beaker, adds 30ml deionized water dissolving to be uniformly made into impregnation liquid；
Dipping：55g carriers 1 are taken, room temperature descended volume impregnation 12 minutes, hydro-thermal heats beaker to 65 DEG C, impregnates 180 points
Clock；In 175 DEG C of dryings 8 hours, then the roasting 6h under 560 DEG C of air atmospheres, obtained finished catalyst E.
The crystal grain distribution of the active component chromium oxide of catalyst E is shown in Table 1.
With embodiment 1, Evaluation results are shown in Table 1 to the performance evaluation condition of catalyst E.
The dehydrating alkanes performance of the different catalysts of table 1
Claims (5)
1. it is a kind of control crystal grain distribution catalyst for dehydrogenation of low-carbon paraffin, it is characterized by：The active component based on chromium oxide, activity
Component is loaded on carrier by the way of dipping, and active component content is uniformly distributed in the catalyst, and wherein chromium oxide is being urged
Size of microcrystal has following characteristics in agent：Chromium oxide size of microcrystal is larger at close catalyst center, and near catalysis
Agent outer surface chromium oxide size of microcrystal is less.
2. according to the catalyst described in claim 1, it is characterised in that described chromium oxide size of microcrystal is cutting near catalyst
Face center is not less than 15 nanometers；Chromium oxide size of microcrystal is being not more than 12 nanometers near catalyst surface.
3. catalyst according to claim 1, it is characterised in that with aluminium oxide as carrier, chromium oxide is the catalyst
The main active component of catalyst, one or more in Li, Na, K, Zr is auxiliary agent；The weight/mass percentage composition of each component in catalyst
For：The oxide of active component chromium is 1～40wt%, and the oxide content of auxiliary element is 0.01～10wt%, and remaining is load
Body, carrier is aluminium oxide.
4. a kind of preparation method of the catalyst for dehydrogenation of low-carbon paraffin described in claim 1, comprises the following steps：
1) impregnation liquid configuration：Prepare dipping solution containing chromium, the surfactant containing 0.01wt%～5wt% in impregnation liquid；
2) catalyst activity component load：The first step：Catalyst dipping is carried out under room temperature after 1～120 minute, 40 are slowly heated to
DEG C～150 DEG C after, be incubated 1～180 minute；
3) in 80 DEG C～180 DEG C dryings 1～24 hour, then in 550 DEG C～900 DEG C roastings 1～24 hour, low-carbon alkanes are obtained and is taken off
Hydrogen catalyst.
5. according to the preparation method described in claim 4, it is characterised in that described surfactant be citric acid, maleic acid,
The combination of one or more in trichloroacetic acid, acetic acid, triethanolamine, imidazoline, polyacrylamide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109289831A (en) * | 2018-10-09 | 2019-02-01 | 天津科技大学 | The catalyst of preparing propylene by dehydrogenating propane and preparation method thereof with high anti-carbon |
| CN109529811A (en) * | 2018-12-29 | 2019-03-29 | 杨斌 | Alumina support, salic carried catalyst preparation method and catalyst application |
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