CN110180530A - A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof - Google Patents
A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof Download PDFInfo
- Publication number
- CN110180530A CN110180530A CN201910590249.5A CN201910590249A CN110180530A CN 110180530 A CN110180530 A CN 110180530A CN 201910590249 A CN201910590249 A CN 201910590249A CN 110180530 A CN110180530 A CN 110180530A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon
- preparation
- low
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to catalyst fields, and in particular to a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof.The catalyst includes the chromium oxide of 2-8wt%, the auxiliary agent of 0.5-1.0wt% and the modified active high-area carbon of surplus, and the weight percentage of the chromium oxide is in terms of chromium.The present invention is carrier using the modified activated carbon successively handled through microwave modification, sour modification and alkali modification, and the surface of catalyst is made to have suitable acidity and Cr6+/Cr3+Ratio, there is suitable interaction force, catalyst has excellent activity, selectivity and stability on the whole between carrier and active component.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation side
Method.
Background technique
Low-carbon alkene, one of the basic material such as propylene as chemical industry can be used to produce high molecular polymer, alkene
A series of downstream chemical product such as hydrocarbon oxide.Simultaneously as the mankind give bigger attention to the environment that it is depended on for existence, draw
Sent out the unleaded of gasoline, MTBE (methyl tertiary butyl ether(MTBE)) as the modifier of octane number and it is noticeable, demand is got over
Come it is bigger, to promote the growth of isobutene demand.To sum up, due to the rapid growth of downstream product in recent years, to low
The demand of carbon olefin etc. increasingly increases.Currently, the catalytic cracking process and naphtha steam cracking technique of petroleum are low-carbon alkene
The main source of hydrocarbon, but with the growing tension of petroleum resources, traditional low-carbon alkene production technology has been difficult to meet quickly
The low-carbon alkene demand of growth, therefore develop new low-carbon alkene production technology and seem very urgent.This is for alleviating low-carbon
Alkene imbalance between supply and demand, optimization China's energy and chemical industry structure etc. have important strategic importance.
Currently, catalyst for manufacturing olefin by low-carbon alkane dehydrogenation mainly has noble metal catalyst and base metal oxide catalyst two
Major class, co-catalyst used have K2O、K2CO3With MgO etc..The former is with Pt-Sn/Al disclosed in United States Patent (USP) US4827066A2O3
Catalyst (i.e. the Oleflex technique catalyst of UOP) is representative, although the conversion ratio of catalyst, selectivity and stability are all
Very well, but due to having used noble metal platinum, cause catalyst cost very high, greatly improve production cost.The latter is with Britain
Cr disclosed in patent GB2162082A2O3/Al2O3Catalyst (i.e. the Catofin technique catalyst of ABB Lummus Crest)
To represent, although the conversion ratio of catalyst, selectivity are preferably, and the lower production costs of catalyst, there is certain anti-poisoning energy
Power, but catalyst inactivation is quickly, and frequent regeneration is needed in use process, leads to the energy consumption of the technique very big (regeneration period 15-
30min)。
A kind of loaded platinum-tin catalyst for low-carbon alkanes catalytic dehydrogenation as disclosed in Chinese patent CN1185352A
PtSn/MgAl (O), carrier are MgAl (O) composite oxides, and the molar ratio of Mg and Al are 2:1-15:1, and Pt is carrier MgAl
(O) molar ratio of the 0.2 to 1.2% of weight, Pt and Sn are 0.5:1~1.5:1.The catalyst has dehydrogenation of isobutane reaction
Higher selective isobutene (97-98%), and have stronger resistance to deactivation, but due to having used noble metal platinum, cause to urge
Agent cost is obviously higher.
A kind of preparing propylene by dehydrogenating propane catalyst, is advised as disclosed in Chinese patent CN109331810A with doped sno_2
Whole meso-porous alumina is as carrier, using chromium oxide as active component, with alkali metal oxide, alkaline earth oxide and fourth officer
Family metal oxide is auxiliary agent；With the poidometer of the aluminium oxide, the content of the tin oxide is 0.5~1.5%, the oxidation
The load capacity of chromium is 5~20%, Cr6+/Cr3+Ratio is 0.5~0.6, the load capacity of the alkali metal oxide is 0.05~
1.0%, the load capacity of the alkaline earth oxide is 0.05~1.0%, the load capacity of the fourth officer family metal oxide
It is 0.05~3.0%.The invention can make tin oxide abundant by the way that tin oxide is added during forming alumina backbone structure
It is entrained in alumina backbone, to effectively have adjusted the sour structure of aluminium oxide, and by Cr6+/Cr3+Ratio control 0.5~
In the range of 0.6, to inhibit the generation of carbon distribution, there is good high-temperature stability, after 120min, the conversion of propane
Rate can also be maintained at 40% or more.
A kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin as disclosed in Chinese patent CN108786831A, (1) is by Cr
Soluble salt and the soluble salt of La be dissolved in benzoic acid solution, obtain the maceration extract containing Cr and La；(2) step (1) is obtained
Maceration extract impregnated carrier, it is then dry, roast, obtain dehydrogenation.This method by by active component Cr species with help
Agent La is formed under acid environment using benzoic acid as the macromolecule complex of ligand, and Cr and La close to each other are formed in carrier surface
Cluster, by strong interaction caused by wherein so that Cr species are stable in the presence of the surface of alumina catalyst support, catalysis
Agent still possesses higher dehydrogenation activity after multiple circular regeneration.Cr species are largely present at the biggish duct in aperture, can be
Greater activity is still kept under higher carbon deposition quantity, one way operation cycle of catalyst is extended, reduces device operating cost.
A kind of Cr of preparing isobutene through dehydrogenation of iso-butane as disclosed in Chinese patent CN102962054A2O3Catalyst, wherein living
Property component Cr2O34~25% are calculated as by mass percentage, remaining is mesoporous carbon；The specific surface area of the mesoporous carbon be 900~
3200m2/ g, most probable pore size are 2.5~9.5nm, and Kong Rong is in 1.1~3.5ml g-1, mesoporous is 70~100%.The invention
By using mesoporous carbon as carrier, the surface area of catalyst carrier and the diffusion rate of product isobutene are improved,
Under 570-660 DEG C of reaction temperature, the conversion ratio of iso-butane is up to 26.3~58.4%.
In general, the activity of existing catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, anti-carbon performance, stability etc.
There are still various shortcomings, therefore need to develop performance of new generation more preferably catalyst for manufacturing olefin by low-carbon alkane dehydrogenation with right
The industrial production of chemical industry provides more favorable supporting function.
Summary of the invention
For this purpose, technical problems to be solved in this application are how not improve production cost, i.e., aoxidized with base metal
Under the premise of object-chromium oxide is active component, activity, the selectivity of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation are improved as much as possible
And stability.
In order to solve the above technical problems, present inventor is by the research conscientiously with effort, it was found that available to change
Property active carbon be carrier, when subsequent load active component, make that there is suitable phase interaction between carrier and active component
Firmly, so that Cr in catalyst on the one hand can be regulated and controled6+/Cr3+Ratio within the appropriate range, on the other hand, utilize active carbon
The acidic functionality and basic functionality of suitable proportion present in surface, can be during supported chromium oxide to chromium group
Dividing has suitable adsorption capacity, and can have suitable adsorption capacity to low-carbon alkanes raw material in catalytic reaction process, thus
Not only it had been avoided that in reaction process that chromium oxide occurred to reunite and lead to active reduction, but also the reaction of raw material and the expansion of product can be promoted
It dissipates, avoids the generation of side reaction and the formation of carbon distribution.
Technical scheme is as follows: the invention discloses a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, including 2-
The chromium oxide of 8wt%, the auxiliary agent of 0.5-1.0wt% and the modified active high-area carbon of surplus, the weight percent of the chromium oxide contain
Amount is in terms of chromium；The auxiliary agent is selected from one or more oxidations of alkali metal, alkaline-earth metal, rare earth metal, Sn, Bi etc.
Object.
In the catalyst, the content of chromium oxide is more preferably 2-5wt%.
The modified active high-area carbon is the modified active successively handled through microwave modification, sour modification and alkali modification
Charcoal.Its preparation process includes the following steps:
A) charing process
Raw material is cleaned, is dried, is then carbonized in Muffle furnace, obtain active carbon precursor, then crushed, be ground up, sieved；
B) microwave modification is handled
The active carbon precursor that step a) is obtained, which is packed into microwave generator, carries out microwave modification processing；
C) high-temperature activation
The active carbon precursor that step b) is obtained, places into Muffle furnace and is activated；
D) sour modification
Step c) the active carbon precursor obtained is totally immersed in the mixed solution of hypochlorous acid and nitric acid, is carried out at immersion
Reason, then washing, drying；
E) alkali modification is handled
Step d) the active carbon precursor obtained is totally immersed in sodium hydroxide solution, immersion treatment is carried out, then washes
It washs, dry, can be prepared by modified activated carbon.
The raw material of the modified active high-area carbon can be timber, fruit stone, coal and semicoke, wherein preferably shell, such as coconut palm
Shell or almond can make final modified active carbon surface obtained have the acidic functionality of more suitable proportion using it as raw material
And basic functionality.
Drying temperature in the step a) is preferably 60-150 DEG C, and drying time is preferably 20-60min；Carbonization process
Middle to use temperature programming, heating rate is preferably 5-20 DEG C/min, is first warming up to 300 DEG C, keeps 12-24h, then proceedes to heat up
To 500 DEG C, 12-24h is kept；650 DEG C are finally warming up to, 12-18h is kept.
Active carbon precursor in the step a) crosses 50-80 mesh sieve.
Microwave power is preferably 510-680W in the step b), and microwave radiation (the i.e. microwave modification processing) time is preferably
5-10min。
Activation temperature in the step c) is preferably 700-750 DEG C, activation time 3-5h.
Hypochlorous acid in the step d) and in the mixed solution of nitric acid, hypochlorous acid concentration is preferably 1-1.5mol/L, nitre
Acid concentration is preferably 2-3mol/L.Soaking time is preferably 0.5-2h；Drying temperature is preferably 60-100 DEG C, and drying time is preferred
For 30-60min.
The concentration of sodium hydroxide solution in the step e) is preferably 1-1.5mol/L, and soaking time is preferably 2-6h,
Drying temperature is preferably 60-100 DEG C, and drying time is preferably 30-60min.
Present inventor it has been investigated that, it is advanced before high-temperature activation by the precursor after being carbonized to activated carbon
The processing of row microwave modification, can be such that the micropore and mesoporous of many occlusions in active carbon opens, and can avoid in subsequent high temperature activation process
Duct collapses.So absorbent charcoal carrier can be made to form suitable cellular structure, and facilitate raw material and product and reacting
Diffusion in journey.
Through research it has also been found that, sour modification and alkali modification processing are successively carried out to the active carbon after high-temperature activation, can be had
Destination carries out modulation to the oxygen-containing acid functional group of activated carbon surface and the type and quantity of oxygen-containing basic functionality etc.
Suction-operated of active carbon during supported chromium oxide active component to it is influenced, so that catalyst on the one hand can be regulated and controled
Surface acidity and Cr6+/Cr3+Ratio within the appropriate range, such as make Cr6+/Cr3+Ratio 0.30-0.45 range it
It is interior, so as in the case of holding catalyst high initial activity, moreover it is possible to be effectively reduced the deactivation rate of catalyst；It is another
Aspect makes have suitable interaction force between carrier and active component, aoxidizes so as to be effectively prevented from reaction process
Chromium occurs sintering and reunites and lead to active reduction.It can also making catalyst in catalytic reaction process to low-carbon alkanes original
Expect that there is suitable adsorption capacity to avoid generation and the carbon distribution of side reaction to can promote the reaction of raw material and the diffusion of product
Formation.
The invention also discloses a kind of preparation methods of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, include the following steps:
1) modified active high-area carbon is prepared first；
2) composition for pressing final catalyst, weighs the soluble precursor salt of soluble chromic salts, auxiliary agent, deionized water is added to prepare
At maceration extract；
3) maceration extract made from step 2) is impregnated on modified active high-area carbon made from step 1)；Then dry, roasting
It burns, is subsequently reduced to room temperature, can be prepared by catalyst prod.
Soluble chromic salts in the step 2) is selected from one of chromic nitrate, chromium+oxalic acid, chromium sulfate, chromium chloride etc. or more
Kind.
Chromium ion concentration is 0.5-2.0mol/L in the maceration extract of the step 2), and the concentration of metal ions of auxiliary agent is 0.1-
0.5mol/L。
Drying temperature in the step 3) is preferably 100-150 DEG C, and drying time is preferably 4-8h；Maturing temperature is preferred
It is 500-600 DEG C, calcining time is preferably 4-6h.
In the preparation method of the application, catalyst shape and mechanical strength can also be wanted in the process according to specifically used
It asks, and introduces forming step after step 3), common molding mode can be used, such as compression forming, extrusion molding, rotate into
Type etc. can also introduce suitable common shaping assistant, the bonding of such as methylcellulose etc as needed in forming process
The extrusion aid etc. of the lubricant of agent, graphite, paraffin etc, sesbania powder etc.
Disclosed herein as well is the catalyst for manufacturing olefin by low-carbon alkane dehydrogenation in low-carbon alkanes catalytic dehydrogenation alkene work
Application in skill, reactor used can be fixed bed reactors, moving-burden bed reactor or fluidized-bed reactor, reaction condition
Are as follows: reaction temperature is 500-650 DEG C, reaction pressure 0.1-0.5MPa, air speed 500-5000h-1。
Compared with prior art, the application has the beneficial effect that
1, the catalyst of the application makes the surface of catalyst have suitable acid by using modified activated carbon as carrier
Degree and Cr6+/Cr3+Ratio, there is suitable interaction force, catalyst has excellent on the whole between carrier and active component
Different activity, selectivity and stability.
2, the catalyst of the application for noble metal catalyst, is dropped significantly using chromium oxide as active component
Low production cost.
3, the content of chromium oxide is lower in the catalyst of the application, more friendly to environment, can reduce chromium base well and urge
Agent is in preparation, use process and dead catalyst treatment process due to the loss of inevitable chromium and to the bad shadow of environment
It rings.
4, the application first carries out microwave modification processing by the precursor after carbonizing to activated carbon before high-temperature activation, can
The micropore and mesoporous of many occlusions in active carbon are opened, duct is can avoid in subsequent high temperature process and collapses, can so make
Absorbent charcoal carrier forms suitable cellular structure, and facilitates the diffusion of raw material and product during the reaction.
5, the application can be in the case of holding catalyst high initial activity, moreover it is possible to be effectively reduced the inactivation of catalyst
Rate；And chromium oxide in reaction process can be effectively prevented from, sintering occurs and reunites and leads to active reduction.
6, the application can make catalyst have suitable adsorption capacity to low-carbon alkanes raw material in catalytic reaction process, from
And can promote the reaction of raw material and the diffusion of product, avoid the generation of side reaction and the formation of carbon distribution.
Other advantage will be partly show in the following description, and can be partly able to by specific embodiment
Understand.Especially by point out in the dependent claims Chemical composition that, method and combinations thereof, will realize and obtain down
State advantage.It should be appreciated that general description and detailed description below above is merely exemplary and illustrative, rather than
It is restrictive.
Complementary definition
Material, compound, composition and component described herein, can be used for method and composition described herein,
Or it can be in connection or the production that can be used for implementing the method and prepare the composition or obtained as the method
Product.It should be appreciated that when disclosing combination, subset, interaction, the group etc. of these materials, although may not clearly have
Body refers to each and collective combinations and arrangement of these compounds, but specifically considers and describe wherein in this application
Each.For example, if open and a certain adjuvant component is discussed, and a variety of alternative actual forms of the component are discussed,
Then unless there is specific opposite instruction, each combination of possible adjuvant component and actual form is otherwise specifically considered
And arrangement.The concept is suitable for all aspects of the application, is including but not limited to making and using disclosed composition
Step in method.Therefore, if there is the multiple other steps that can be executed, then it should be appreciated that these other steps
Each can be executed by the combination of any specific embodiment or multiple embodiments of disclosed method, and
Each such combination is specifically considered, they should be considered as disclosing.
In claims in this specification and its later, refer to many terms, they should be defined as with
Lower meaning:
It must be noted that unless context is in addition clearly stipulate that otherwise such as institute in this specification and appended claims
Not only may include a referring to thing with, singular " one ", "/kind " and " should/described ", but may include multiple referring to thing (i.e.
Two or more, including two).Thus, for example, referring to that " pH adjusting agent " may include single pH adjusting agent or two
Kind or more mixture of pH adjusting agent, etc..
" optional " or " optionally " mean that the event then described or situation can occur or will not occur, and the description
Including the wherein event or the situation happened and the situation not occurred.For example, phrase " optional adjuvant component " is anticipated
Refer to that the adjuvant component may exist, can also be not present, and the description covers in composition comprising adjuvant component and group
Close two kinds of situations for not including adjuvant component in object.
Unless otherwise specified, therefore it and may include in the model about that the numberical range in the application, which is,
Enclose outer value.The numberical range can be expressed as in the application from " about " particular value and/or to " about " another particular value.
When stating such range comprising from one particular value and/or to another particular value.Similarly, when by making
When a certain particular value being expressed as approximation with antecedent " about ", it should be understood that its cover the particular value itself and by
In measurement or calculate caused technical field tolerance range.It is also understood that each in numberical range
Endpoint is important in the relationship with another endpoint and independently of another endpoint.
The parts by weight of element-specific or component in composition or product are referred in specification and last claims
Refer to the weight relationships stated in composition or product between the element or component and any other element or component with parts by weight.
Therefore, in the composition comprising 2 parts by weight of component X and 5 parts by weight of component Y, X and Y exist with the weight ratio of 2:5, and nothing
It whether include that other component exists with the ratio by composition.
Unless context in addition clearly stipulate that or have other meanings, or context or technical field based on context
The hint of interior ways customary, all scores and percentage otherwise referred in the application are by weight, and the weight of component
Total weight of the percentage based on the composition comprising the component or product.
"comprising", " comprising ", " having " and the similar terms referred in the application are not intended to exclude any optional group
Divide, the presence of step or program, regardless of whether specifically disclosing any optional component, step or program.It is doubted in order to avoid any
It asks, unless may include otherwise that one or more are additional by using all methods that term "comprising" requires there are state otherwise
Step, equipment part or component part and/or substance.In contrast, term " by ... form " exclude be not specifically delineated or
Any component, step or the program enumerated.Unless otherwise stated, otherwise term "or" refers to individually and in any combination
The member enumerated.
In addition, the side that the content of any referenced patent document or non-patent literature is all quoted in its entirety in the application
Formula is incorporated herein, especially with respect to disclosed in fields definition (any definition not provided specifically with the application not
Under unanimous circumstances) and common sense.
Specific embodiment
Iing is proposed the following example is to provide how to be made and evaluate the application institute to those skilled in the art
Entire disclosure and the description of compound state and claimed, composition, product, device and/or method,
And it is intended only to be illustrative, is not intended to be limiting the range that applicant is considered as its invention.Effort has been made to ensure
About the accuracy of digital (such as amount, temperature etc.), but it is contemplated that some errors and deviation.Unless otherwise specified, no
Then number is parts by weight, and temperature is DEG C to indicate or under environment temperature, and pressure is atmospheric pressure or close to atmospheric pressure.
There are reaction condition (such as concentration of component, required solvent, solvent mixture, temperature, pressure and other reaction ranges) and
It can be used for optimizing a variety of variations and combination of the condition of the product purity and yield that obtain by the method.It will only need
Reasonable routine experiment optimizes such method condition.
Embodiment 1:
Modified active high-area carbon is prepared first:
Coconut husk raw material is cleaned, 40min is dried at 80 DEG C, is then carbonized in Muffle furnace, is first warming up in carbonization process
300 DEG C, 16h is kept, then proceedes to be warming up to 500 DEG C, keeps 16h；650 DEG C are finally warming up to, 14h is kept, heating rate is
10 DEG C/min, active carbon precursor is obtained, is then crushed, ground 60 mesh.Progress microwave in microwave generator is then charged into change
Property processing, microwave power 680W, radiated time 5min；It places into Muffle furnace and activates 5h at 700 DEG C.It is then immersed in
In the mixed solution of hypochlorous acid and nitric acid, wherein hypochlorous acid concentration is 1.2mol/L, concentration of nitric acid 2.5mol/L, impregnates 1h,
It then washs, dry 60min at 60 DEG C.It is totally immersed in the sodium hydroxide solution that concentration is 1.5mol/L, is impregnated again
2h then washs, dries 50min at 70 DEG C, can be prepared by modified active high-area carbon
The 2.1wt%, auxiliary agent K of catalyst weight are accounted for by chromium oxide in catalyst (in terms of Cr element)2The content of O accounts for
0.9wt% weighs Cr (NO3)3·9H2O, KNO3Deionized water is added to be configured to mixed solution；Chromium ion concentration is in mixed solution
0.6mol/L, potassium concentration 0.3mol/L.
Maceration extract is impregnated into modified active high-area carbon, the filter cake obtained after filtering is dried into 8h at 100 DEG C, then in horse
Not in furnace, 6h is roasted at 500 DEG C, is subsequently reduced to room temperature, can be prepared by catalyst prod.
Embodiment 2
Modified active high-area carbon is prepared first:
Almond raw material is cleaned, 40min is dried at 80 DEG C, is then carbonized in Muffle furnace, is first warming up in carbonization process
300 DEG C, 16h is kept, then proceedes to be warming up to 500 DEG C, keeps 16h；650 DEG C are finally warming up to, 14h is kept, heating rate is
15 DEG C/min, active carbon precursor is obtained, is then crushed, ground 70 mesh.Progress microwave in microwave generator is then charged into change
Property processing, microwave power 600W, radiated time 7min；It places into Muffle furnace and activates 4h at 725 DEG C.It is then immersed in
In the mixed solution of hypochlorous acid and nitric acid, wherein hypochlorous acid concentration is 1.2mol/L, concentration of nitric acid 2.5mol/L, impregnates 1h,
It then washs, dry 45min at 80 DEG C.It is totally immersed in the sodium hydroxide solution that concentration is 1.2mol/L, is impregnated again
3h then washs, dries 45min at 75 DEG C, can be prepared by modified active high-area carbon
The 3.0wt%, auxiliary agent K of catalyst weight are accounted for by chromium oxide in catalyst (in terms of Cr element)2The content of O accounts for
0.7wt% weighs Cr (NO3)3·9H2O, KNO3Deionized water is added to be configured to mixed solution；Chromium ion concentration is in mixed solution
1.0mol/L, potassium concentration 0.25mol/L.
Maceration extract is impregnated into modified active high-area carbon, the filter cake obtained after filtering is dried into 6h at 120 DEG C, then in horse
Not in furnace, 5h is roasted at 550 DEG C, is subsequently reduced to room temperature, can be prepared by catalyst prod.
Embodiment 3
Modified active high-area carbon is prepared first:
Coconut husk raw material is cleaned, 40min is dried at 80 DEG C, is then carbonized in Muffle furnace, is first warming up in carbonization process
300 DEG C, 16h is kept, then proceedes to be warming up to 500 DEG C, keeps 16h；650 DEG C are finally warming up to, 14h is kept, heating rate is
10 DEG C/min, active carbon precursor is obtained, is then crushed, ground 60 mesh.Progress microwave in microwave generator is then charged into change
Property processing, microwave power 680W, radiated time 5min；It places into Muffle furnace and activates 3h at 750 DEG C.It is then immersed in
In the mixed solution of hypochlorous acid and nitric acid, wherein hypochlorous acid concentration is 1.2mol/L, concentration of nitric acid 2.5mol/L, impregnates 1h,
It then washs, dry 30min at 100 DEG C.It is totally immersed in the sodium hydroxide solution that concentration is 1.5mol/L, is impregnated again
2h then washs, dries 40min at 90 DEG C, can be prepared by modified active high-area carbon
The 7.8wt%, auxiliary agent K of catalyst weight are accounted for by chromium oxide in catalyst (in terms of Cr element)2The content of O accounts for
0.6wt% weighs Cr (NO3)3·9H2O, KNO3Deionized water is added to be configured to mixed solution；Chromium ion concentration is in mixed solution
1.8mol/L, potassium concentration 0.15mol/L.
Maceration extract is impregnated into modified active high-area carbon, the filter cake obtained after filtering is dried into 8h at 100 DEG C, then in horse
Not in furnace, 6h is roasted at 500 DEG C, is subsequently reduced to room temperature, can be prepared by catalyst prod.
Comparative example 1
Preparation process is substantially the same manner as Example 2, and difference is only that: in the modifying process of active carbon, high-temperature activation being walked
Suddenly it adjusts to alkali treatment.
Comparative example 2
Preparation process is substantially the same manner as Example 2, and difference is only that: being omitted at alkali modification in the modifying process of active carbon
Manage step.
Comparative example 3
Preparation process is substantially the same manner as Example 2, and difference is only that: is omitted at sour be modified in the modifying process of active carbon
Manage step.
Comparative example 4
Preparation process is substantially the same manner as Example 2, and difference is only that: microwave modification is omitted in the modifying process of active carbon
Processing step.
Comparative example 5
Preparation process is substantially the same manner as Example 2, and difference is only that: directlying adopt mesoporous carbon (commercially available commodity CMK-1)
As carrier.
Comparative example 6
Preparation process is substantially the same manner as Example 2, and difference is only that: directlying adopt aluminium oxide (ZL201110196192.4
Disclosed aluminium oxide) it is used as carrier.
Catalytic performance test
The catalytic performance of catalyst obtained by embodiment 1-3, comparative example 1-6 is tested respectively, test result is such as
Shown in table 1.Wherein the service life refers to the time that can be used continuously in the case that the activity and selectivity of catalyst is basically unchanged.
Above-mentioned Catalyst packing is taken to be reacted in fixed bed reactors, actual conditions are as follows: 550 DEG C, 0.1Mpa, 500h-1
(V/V), unstripped gas is propane.
Table 1- catalyst performance test result
The catalyst that can be seen that the application from the test result of table 1 is successively modified through microwave modification, acid due to using
It is carrier with the modified activated carbon that alkali modification is handled, so that the catalyst tool of the catalyst of the application compared with the existing technology
There are more excellent activity, selectivity and stability.
In text of the statement, various publications are referred to.Disclosures of these publications full text is accordingly with reference side
During formula is incorporated herein, so that compound, composition and method described herein is described more fully with.
Various modifications and change can be made to compound described herein, composition and method.In view of specification and
The practice of compound, composition and method disclosed in the present application, compound described herein, composition and method it is other
Aspect will be evident.Specification and example are intended to be considered as illustrative.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, the chromium oxide including 2-8wt%, the auxiliary agent of 0.5-1.0wt% and remaining
The modified active high-area carbon of amount, the weight percentage of the chromium oxide is in terms of chromium.
2. catalyst for manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, the content of the chromium oxide is 2-5wt%.
3. catalyst for manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, the auxiliary agent is selected from alkali metal, alkaline earth gold
Category, rare earth metal, Sn, Bi one or more oxides.
4. the preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1-3, including it is as follows
Step:
1) modified active high-area carbon is prepared first；
2) composition for pressing final catalyst, weighs the soluble precursor salt of soluble chromic salts, auxiliary agent, deionized water is added to be configured to soak
Stain liquid；
3) maceration extract made from step 2) is impregnated on modified active high-area carbon made from step 1)；Then dry, roasting, with
After be down to room temperature, can be prepared by catalyst prod.
5. the preparation method according to claim 4, the process that modified active high-area carbon is prepared in the step 1) includes such as
Lower step:
A) charing process
Raw material is cleaned, is dried, is then carbonized in Muffle furnace, obtain active carbon precursor, then crushed, be ground up, sieved；
B) microwave modification is handled
The active carbon precursor that step a) is obtained, which is packed into microwave generator, carries out microwave modification processing；
C) high-temperature activation
The active carbon precursor that step b) is obtained, places into Muffle furnace and is activated；
D) sour modification
Step c) the active carbon precursor obtained is totally immersed in the mixed solution of hypochlorous acid and nitric acid, immersion treatment is carried out,
Then washing, drying；
E) alkali modification is handled
Step d) the active carbon precursor obtained is totally immersed in sodium hydroxide solution, immersion treatment is carried out, then washing, baking
It is dry, it can be prepared by modified activated carbon.
6. preparation method according to claim 5, the raw material in the step a) is preferably shell；It is used in carbonization process
Temperature programming, heating rate are preferably 5-20 DEG C/min, are first warming up to 300 DEG C, keep 12-24h, then proceed to be warming up to 500
DEG C, keep 12-24h；650 DEG C are finally warming up to, 12-18h is kept.
7. preparation method according to claim 5, hypochlorous acid in the step d) and in the mixed solution of nitric acid, secondary chlorine
Acid concentration is preferably 1-1.5mol/L, and concentration of nitric acid is preferably 2-3mol/L.Soaking time is preferably 0.5-2h.
8. preparation method according to claim 5, the concentration of the sodium hydroxide solution in the step e) is preferably 1-
1.5mol/L, soaking time are preferably 2-6h.
9. the preparation method according to claim 4, chromium ion concentration is 0.5-2.0mol/ in the maceration extract of the step 2)
L, the concentration of metal ions of auxiliary agent are 0.2-2mol/L.
10. the preparation method according to claim 4 can introduce forming step after step 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910590249.5A CN110180530B (en) | 2019-07-02 | 2019-07-02 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910590249.5A CN110180530B (en) | 2019-07-02 | 2019-07-02 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110180530A true CN110180530A (en) | 2019-08-30 |
| CN110180530B CN110180530B (en) | 2023-05-05 |
Family
ID=67724678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910590249.5A Active CN110180530B (en) | 2019-07-02 | 2019-07-02 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110180530B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403458A (en) * | 2020-11-26 | 2021-02-26 | 高化学（江苏）化工新材料有限责任公司 | Double-activity-center propane dehydrogenation catalyst and preparation method and application thereof |
| CN115779885A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Light hydrocarbon dehydrogenation catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949992A (en) * | 2011-08-26 | 2013-03-06 | 中国石油化工股份有限公司 | Alkali metal modified Cr2O3 catalyst and preparation method thereof |
| CN103769078A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst for alkene production and its preparation method and application |
| CN107486195A (en) * | 2016-06-13 | 2017-12-19 | 中国石油天然气股份有限公司 | The preparation method of catalyst for dehydrogenation of low-carbon paraffin |
| CN107970913A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of chromium-bismuth catalyst of preparing propylene by dehydrogenating propane, preparation method and application |
| CN109331810A (en) * | 2018-08-22 | 2019-02-15 | 天津科技大学 | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane |
| CN109926038A (en) * | 2019-02-28 | 2019-06-25 | 高化学（江苏）化工新材料有限责任公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
-
2019
- 2019-07-02 CN CN201910590249.5A patent/CN110180530B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949992A (en) * | 2011-08-26 | 2013-03-06 | 中国石油化工股份有限公司 | Alkali metal modified Cr2O3 catalyst and preparation method thereof |
| CN103769078A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst for alkene production and its preparation method and application |
| CN107486195A (en) * | 2016-06-13 | 2017-12-19 | 中国石油天然气股份有限公司 | The preparation method of catalyst for dehydrogenation of low-carbon paraffin |
| CN107970913A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of chromium-bismuth catalyst of preparing propylene by dehydrogenating propane, preparation method and application |
| CN109331810A (en) * | 2018-08-22 | 2019-02-15 | 天津科技大学 | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane |
| CN109926038A (en) * | 2019-02-28 | 2019-06-25 | 高化学（江苏）化工新材料有限责任公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
Non-Patent Citations (4)
| Title |
|---|
| JIAN FEI DING，ET AL.: "Coupling dehydrogenation of isobutane in the presence of carbon dioxide over chromium oxide supported on active carbon", 《CHINESE CHEMICAL LETTERS》 * |
| MELTEM DOĞAN，ET AL.: "İzobütan dehidrojenasyonunun CrOx/AC katalizörler üzerinde incelenmesi", 《JOURNAL OF THE FACULTY OF ENGINEERING AND ARCHITECTURE OF GAZI UNIVERSITY》 * |
| 周安宁等: "《洁净煤技术》", 28 February 2018, 中国矿业大学出版社 * |
| 宋永辉，等编著: "《提金氰化废水处理理论与方法》", 31 March 2015, 冶金工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403458A (en) * | 2020-11-26 | 2021-02-26 | 高化学（江苏）化工新材料有限责任公司 | Double-activity-center propane dehydrogenation catalyst and preparation method and application thereof |
| CN115779885A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Light hydrocarbon dehydrogenation catalyst and preparation method and application thereof |
| CN115779885B (en) * | 2021-09-10 | 2024-05-03 | 中国石油化工股份有限公司 | Light hydrocarbon dehydrogenation catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110180530B (en) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106512994B (en) | Anti-carbon deposition catalyst for preparing propylene by platinum-based propane dehydrogenation and preparation method thereof | |
| CN103212411B (en) | High-performance catalyst for preparing olefin through dehydrogenation of light alkane and preparation method thereof | |
| CN105582977B (en) | A kind of preparation method of dehydrogenation | |
| CN105312046B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for improving its activity and stability | |
| CN109126808A (en) | A kind of additive modification copper-based catalysts and preparation method and applications | |
| CN107519911A (en) | It is a kind of to prepare nickel-base catalyst and its application in methanation reaction using organic molecule additive | |
| CN107890870A (en) | A kind of carbon dioxide and water methanation catalyst and its preparation method and application | |
| CN104209123A (en) | Light alkane dehydrogenation catalyst containing silver and boron and preparation method thereof | |
| CN110180530A (en) | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof | |
| CN105727930A (en) | Catalyst for propylene production using propane dehydrogenation and preparation method and application of catalyst | |
| CN114272950A (en) | CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof | |
| CN111111675A (en) | Ni-CeO2Process for preparing catalyst | |
| CN111389405B (en) | Method for preactivating methane vapor hydrogen production catalyst | |
| CN104289219B (en) | Preparation method for low carbon alkane dehydrogenation catalyst | |
| CN101993336B (en) | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition | |
| CN107715862A (en) | A kind of anti-carbon chromium base catalyst for preparing propylene with propane dehydrogenation, preparation method and application | |
| CN107398281A (en) | A kind of FCC regenerated flue gas denitration catalyst, preparation method and its usage | |
| CN113398920B (en) | Ultra-long cerium dioxide nanorod-loaded manganese oxide low-temperature denitration catalyst and preparation method thereof | |
| CN110272327A (en) | A kind of method of manufacturing olefin by low-carbon alkane dehydrogenation | |
| CN107537485A (en) | Catalyst of isopentane dehydrogenation iso-amylene and preparation method thereof | |
| CN112206811B (en) | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof | |
| CN112958075A (en) | Ce-doped sodium-manganese composite oxide catalyst and preparation method and application thereof | |
| CN113058613A (en) | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof | |
| CN107115863A (en) | A kind of preparation method of acetic acid preparation of ethanol by hydrogenating Pt Sn/Li Al O catalyst | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230420 Address after: 163000 Hongwei Park, Daqing High tech Zone, Daqing City, Heilongjiang Province (No. A-01-2, South Third Road West) Applicant after: Daqing svanda New Material Co.,Ltd. Address before: 277500 Yikang North Road, Shannan Street, Tengzhou City, Zaozhuang City, Shandong Province (second floor of business building of Shandong Fuhui Metal Structure Engineering Co., Ltd.) Applicant before: Tengzhou Jingtengxinhui New Material Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |