CN109529920A - Load boronation titanium catalyst for light paraffins isomerization and preparation method thereof and application method - Google Patents

Load boronation titanium catalyst for light paraffins isomerization and preparation method thereof and application method Download PDF

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CN109529920A
CN109529920A CN201811339876.3A CN201811339876A CN109529920A CN 109529920 A CN109529920 A CN 109529920A CN 201811339876 A CN201811339876 A CN 201811339876A CN 109529920 A CN109529920 A CN 109529920A
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catalyst
isomerization
light paraffins
molecular sieve
load
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CN109529920B (en
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陈金射
张延松
夏道宏
孟祥豹
张新燕
徐翠翠
陈海燕
王相
杜文州
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Shandong University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057Zeolite Beta
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/222Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract

The present invention proposes a kind of load boronation titanium catalyst for light paraffins isomerization and preparation method thereof and application method, belong to light paraffins isomerization field, the catalyst is halogen-free and noble metal, and use low using temperature is preceding to be not necessarily to hydrogen prereduction, both the cost for having reduced catalyst in turn avoids the pollution to environment.Meanwhile the catalyst activity is high, stability is good, it is also higher to the selectivity of isoparaffin.The technical solution includes carrier, and the carrier is made of aluminium oxide and H beta-molecular sieve, and the weight ratio of the aluminium oxide and H beta-molecular sieve is 1:10-10:1;And titanium boride, the 1-30wt% of Zhan Suoshu vehicle weight.The present invention can be applied in the light paraffins isomerization process of C5-C12.

Description

Load boronation titanium catalyst for light paraffins isomerization and preparation method thereof and make Use method
Technical field
The invention belongs to light paraffins isomerization field more particularly to a kind of load boronations for light paraffins isomerization Titanium catalyst and preparation method thereof and application method.
Background technique
For light paraffins isomerization technique, catalyst is a critical issue.Currently, industrial common lightweight Alkane isomerization catalyst is divided into two kinds, Low-temperature catalyst and middle warm type catalyst.
Low form isomerization catalyst often in the catalyst addition halogen (F or Cl) to reduce the use temperature of catalyst, If I -8 catalyst, the catalyst of BP company, Britain and the RD-291 catalyst of Engelhard company of Uop Inc. are reaction Low-temperature catalyst of the temperature at 115-150 DEG C.The advantages of this kind of Low-temperature catalyst, is, catalyst low using temperature Alkane isomerization activity is high.But in the use process of catalyst, halogen can be gradually lost with the progress of reaction, cause to be catalyzed The decline of agent activity, device are corroded.In order to maintain catalytic activity to need constantly to add halide, but so not only can be to equipment Certain corrosion is caused, also can cause environmental pollution;Meanwhile active component used is generally the noble metals such as platinum in catalyst, The preparation cost of catalyst is higher.
Warm type isomerization catalyst is noble metal bifunctional catalyst in common, with the Shell Oil Company, the U.S. and joint The complete isomerization process catalyst series of carbide company are representative, and this kind of catalyst is not active high, selective good, halogen The advantages that plain, but because it need to use H under certain pressure, higher temperature before the use2Active component is reduced to metallic state It can use, operate relatively complicated;In addition, above-mentioned catalyst activity component mainly based on noble metal, also increase it is not small at This burden.
Therefore, how to provide one kind be halogen-free with noble metal and using temperature it is low, it is pre- that hydrogen is not needed before use The Performance of Isomerization Catalysts for Light n-Paraffin of reduction is the important problem that those skilled in the art need to solve.
Summary of the invention
The present invention proposes a kind of load boronation titanium catalyst for light paraffins isomerization and preparation method thereof and uses Method, which is halogen-free and noble metal, and use low using temperature is preceding to be not necessarily to hydrogen prereduction, both reduces catalyst Cost, in turn avoid the pollution to environment.Meanwhile the active height of the catalyst, stability are good, the selection to isoparaffin The good advantage of property.
In order to achieve the above object, the present invention provides a kind of load titanium boride catalysis for light paraffins isomerization Agent, including following components:
Carrier, the carrier are made of aluminium oxide and H beta-molecular sieve, and the weight ratio of the aluminium oxide and H beta-molecular sieve is 1: 10-10:1;With
Titanium boride, the 1-30wt% of Zhan Suoshu vehicle weight.
Preferably, the light paraffins are the n-alkane containing 5-12 carbon atom.
Preferably, the partial size of the catalyst is 0.1mm-1.0mm.
The present invention also provides a kind of according to any of the above-described technical solution for the negative of light paraffins isomerization Carry the preparation method of boronation titanium catalyst, comprising:
H beta-molecular sieve is subjected to thorough roasting under the conditions of 200-600 DEG C, the molecular sieve and aluminium oxide after roasting are in proportion It is uniformly mixed;
Titanium boride is added to be dried under the conditions of 50-100 DEG C after kneading, molding;
Material after drying is ground into particle, the particle is then subjected to thorough roasting in a nitrogen atmosphere, is made Boronation titanium catalyst.
Preferably, the temperature for carrying out thorough roasting in a nitrogen atmosphere is 100-400 DEG C.
The present invention also provides a kind of according to any of the above-described technical solution for the negative of light paraffins isomerization The application method that boronation titanium catalyst carries out light paraffins isomerization is carried, the condition of light paraffins isomerization is carried out are as follows:
Reaction temperature is 230-350 DEG C, reaction pressure 1.0-5.0MPa, hydrogen/oil mol ratio 1.0-6.0, and mass space velocity is 0.5-3.0h-1
Compared with prior art, the advantages and positive effects of the present invention are:
The Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride of the present invention does not use noble metal, without addition halogen Plain component had both reduced the cost of catalyst, in turn avoided the pollution to environment.Catalyst of the present invention is being used for simultaneously It can be used directly when isomerization process, without carrying out pre- hydrogenating reduction, 230 DEG C can be reduced to using temperature, greatly reduced The side reaction occurred in isomerization process improves the yield of isomeric alkane.After tested, catalyst of the present invention is for urging Change light paraffins reaction when, within the said temperature range activity it is higher, the stability of isoparaffin selectivity and catalyst also compared with It is good;In addition, the preparation process of the Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride of the present invention is simple, safety, it is not necessarily to The manufacturing cost of catalyst can be greatly lowered in high temperature and hydrogen.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
The embodiment of the invention provides a kind of load boronation titanium catalysts for light paraffins isomerization, including with the following group Point: carrier, the carrier are made of aluminium oxide and H beta-molecular sieve, and the weight ratio of the aluminium oxide and H beta-molecular sieve is 1:10-10: 1;And titanium boride, the 1-30wt% of Zhan Suoshu vehicle weight.
Boronation titanium catalyst provided by the above embodiment is made of carrier and titanium boride, wherein carrier is by aluminium oxide and H β Molecular sieve composition, H beta-molecular sieve have suitable acid strength, acid distribution and pore structure, provide well for normal alkane isomerization Acid site and reacting environment, while the aluminium oxide in carrier provides meso-hole structure for reaction, is conducive to raw material and product Quickly diffusion;In addition, aluminium oxide is added as binder, catalyst is more easily molded.It is understood that the weight ratio of the two is also It can be 1:9,2:8,3:7,4:6,5:5,6:4,7:3,8:2,9:1 etc., those skilled in the art can carry out within the above range Catalyst needed for any proportion is made.In addition, the present embodiment selects titanium boride to cooperate above-mentioned carrier, main advantage is boronation There is titanium very high abrasion resistance and certain physics, chemical stability can keep good reason under the conditions of differential responses Change property, when preparing catalyst as active component, catalyst has good abrasion resistance, catalytic stability and reproducibility Energy.Meanwhile titanium atom is in underfill state due to its valence layer d orbital electron, is easier to interact with hydro carbons, as metal plus There is good catalytic selectivity when hydrogen/dehydrogenation center.Titanium boride and carrier are combined, stability is prepared Well, activity is high while to the preferable catalyst of isoparaffin selectivity.In addition, the catalyst of the present embodiment does not use noble metal, Without addition halogen component, both reduced the cost of catalyst, and in turn avoided the pollution to environment, can to contain 5-12 carbon The n-alkane of atom carries out high effective isomerization.
In a preferred embodiment, the partial size of the catalyst is 0.1mm-1.0mm.Particle of the present embodiment to catalyst Partial size is defined, too big to avoid particle, increases the interior diffusion effect of catalyst, is reduced catalyst activity, is influenced raw material Conversion ratio;Or particle is too small, increases the pressure drop in reactor, blocking catalyst bed.
The embodiment of the invention also provides a kind of to be used for light paraffins isomerization according to any of the above-described embodiment Load boronation titanium catalyst preparation method, comprising:
H beta-molecular sieve is subjected to thorough roasting under the conditions of 200-600 DEG C, the molecular sieve and aluminium oxide after roasting are in proportion It is uniformly mixed;Titanium boride is added to be dried under the conditions of 50-100 DEG C after kneading, molding;By the material grinding after drying At particle, then by the particle in a nitrogen atmosphere, in 100-400 DEG C of progress thorough roasting, load titanium boride catalysis is made Agent.
The temperature that H beta-molecular sieve is roasted in above-described embodiment can also for 250,300,350,400,450,500, Arbitrary temp value in 550 DEG C or above range, calcining time can differ for 1-5 hours, and those skilled in the art are according to practical anti- Situation is answered to adjust;It is also not specific for drying temperature to limit, be subject to actual drying degree, temperature can also be 60,70, 80, the arbitrary temp value in 90 DEG C or above range;Similarly, roasting in a nitrogen atmosphere is not specific yet limits, with abundant Arbitrary temp value subject to roasting, in 100,200,300,400 DEG C or above range.
The embodiment of the invention also provides a kind of to be used for light paraffins isomerization according to any of the above-described embodiment Load boronation titanium catalyst carry out the application method of light paraffins isomerization, carry out the condition of light paraffins isomerization are as follows: anti- Answering temperature is 230-350 DEG C, reaction pressure 1.0-5.0MPa, hydrogen/oil mol ratio 1.0-6.0, mass space velocity 0.5-3.0h-1。 It should be noted that catalyst described in the present embodiment can be used directly when being used for isomerization process, without carrying out pre-add hydrogen Reduction, can be reduced to 230 DEG C using temperature, can greatly reduce the side reaction occurred in isomerization process, improve isomeric alkane Yield.Wherein, reaction temperature can be the arbitrary temp value in 250,260,280,300,320,340 DEG C or above range, Reaction pressure can for 2.0,3.0, any pressure value in 4.0MPa or above range, hydrogen/oil mol ratio can for 2.0,3.0, 4.0,5.0 or above range in any molar ratio, mass space velocity can be 1.0,1.5,2.0,2.5h-1Or in above range Arbitrary value.
In order to prove that catalyst of the present invention is suitable for the normal alkane isomerization of C5-C12, implementation will be passed through below Example 1-13 is elaborated, wherein embodiment 1-6 is the normal alkane isomerization of C5-C6, raw materials used for pentane/just Hexane, embodiment 7-12 are the normal alkane isomerization of C7-C12, and raw material is followed successively by normal heptane, normal octane, n -nonane, just respectively Decane, n-undecane and n-dodecane.
Embodiment 1
The Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride in the present embodiment includes carrier and accounts for the vehicle weight The titanium boride of 5wt%, wherein the carrier is made of aluminium oxide and H beta-molecular sieve, the weight ratio of the aluminium oxide and H beta-molecular sieve For 1:3.
In the present embodiment load titanium boride Performance of Isomerization Catalysts for Light n-Paraffin the preparation method comprises the following steps:
H beta-molecular sieve is roasted into 4h at 500 DEG C, then by the H after the roasting of the alumina powder of 1 parts by weight and 3 parts by weight Beta-molecular sieve is uniformly mixed, and the titanium boride of 0.2 parts by weight is added, after mixing extruded moulding, after 50 DEG C of dryings, grinds granulating Diameter is the particle of 0.45mm, and under nitrogen atmosphere, 300 DEG C of roasting 2h, catalyst A1 is being made in the particle.
The catalyst A1 that the present embodiment is prepared is 300 DEG C, reaction pressure 1.0MPa in reaction temperature, hydrogen oil mole Than being 2.0, mass space velocity 1.0h-1Under conditions of carry out catalysis C5/C6 isomerization reaction.
Embodiment 2
The Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride in the present embodiment includes carrier and accounts for the vehicle weight The titanium boride of 10wt%, wherein the carrier is made of aluminium oxide and H beta-molecular sieve, the weight of the aluminium oxide and H beta-molecular sieve Than for 1:10.
In the present embodiment load titanium boride Performance of Isomerization Catalysts for Light n-Paraffin the preparation method comprises the following steps:
H beta-molecular sieve is roasted into 6h at 300 DEG C, then will be after the roasting of the alumina powder of 1 parts by weight and 10 parts by weight H beta-molecular sieve is uniformly mixed, and the titanium boride of 1.1 parts by weight is added, after mixing extruded moulding, after 80 DEG C of dryings, grinds granulating Diameter is the particle of 0.8mm, and under nitrogen atmosphere, 350 DEG C of roasting 0.8h, catalyst A2 is being made in the particle.
The catalyst A2 that the present embodiment is prepared is 280 DEG C, reaction pressure 2.0MPa in reaction temperature, hydrogen oil mole Than being 3.0, mass space velocity 2.0h-1Under conditions of carry out catalysis C5/C6 isomerization reaction.
Embodiment 3
The Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride in the present embodiment includes carrier and accounts for the vehicle weight The titanium boride of 15wt%, wherein the carrier is made of aluminium oxide and H beta-molecular sieve, the weight of the aluminium oxide and H beta-molecular sieve Than for 5:1.
In the present embodiment load titanium boride Performance of Isomerization Catalysts for Light n-Paraffin the preparation method comprises the following steps:
H beta-molecular sieve is roasted into 5h at 400 DEG C, then by the H after the roasting of the alumina powder of 5 parts by weight and 1 parts by weight Beta-molecular sieve is uniformly mixed, and the titanium boride of 0.9 parts by weight is added, after mixing extruded moulding, after 100 DEG C of dryings, grinds granulating Diameter is the particle of 1mm, and under nitrogen atmosphere, 280 DEG C of roasting 2.2h, catalyst A3 is being made in the particle.
The catalyst A3 that the present embodiment is prepared is 320 DEG C, reaction pressure 3.0MPa in reaction temperature, hydrogen oil mole Than being 4.0, mass space velocity 3h-1Under conditions of carry out catalysis C5/C6 isomerization reaction.
Embodiment 4
The Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride in the present embodiment includes carrier and accounts for the vehicle weight The titanium boride of 20wt%, wherein the carrier is made of aluminium oxide and H beta-molecular sieve, the weight of the aluminium oxide and H beta-molecular sieve Than for 10:1.
In the present embodiment load titanium boride Performance of Isomerization Catalysts for Light n-Paraffin the preparation method comprises the following steps:
H beta-molecular sieve is roasted into 3h at 600 DEG C, then will be after the roasting of the alumina powder of 10 parts by weight and 1 parts by weight H beta-molecular sieve is uniformly mixed, and the titanium boride of 2.2 parts by weight is added, extruded moulding is ground into after 120 DEG C of dryings after mixing Partial size is the particle of 0.4mm, and under nitrogen atmosphere, 200 DEG C of roasting 3h, catalyst A4 is being made in the particle.
The catalyst A4 that the present embodiment is prepared is 250 DEG C, reaction pressure 4.0MPa in reaction temperature, hydrogen oil mole Than being 5.0, mass space velocity 1h-1Under conditions of carry out catalysis C5/C6 isomerization reaction.
Embodiment 5
The Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride in the present embodiment includes carrier and accounts for the vehicle weight The titanium boride of 1wt%, wherein the carrier is made of aluminium oxide and H beta-molecular sieve, the weight ratio of the aluminium oxide and H beta-molecular sieve For 1:6.
In the present embodiment load titanium boride Performance of Isomerization Catalysts for Light n-Paraffin the preparation method comprises the following steps:
H beta-molecular sieve is roasted into 6.8h at 200 DEG C, then will be after the roasting of the alumina powder of 1 parts by weight and 6 parts by weight H beta-molecular sieve be uniformly mixed, the titanium boride of 0.07 parts by weight is added, extruded moulding after mixing after 150 DEG C of drying, is ground The particle for being 0.2mm at partial size, under nitrogen atmosphere, 400 DEG C of roasting 0.5h, is being made catalyst A5 for the particle.
The catalyst A5 that the present embodiment is prepared is 230 DEG C, reaction pressure 5.0MPa in reaction temperature, hydrogen oil mole Than being 1.0, mass space velocity 2h-1Under conditions of carry out catalysis C5/C6 isomerization reaction.
Embodiment 6
The Performance of Isomerization Catalysts for Light n-Paraffin of load titanium boride in the present embodiment includes carrier and accounts for the vehicle weight The titanium boride of 30wt%, wherein the carrier is made of aluminium oxide and H beta-molecular sieve, the weight of the aluminium oxide and H beta-molecular sieve Than for 8:1.
In the present embodiment load titanium boride Performance of Isomerization Catalysts for Light n-Paraffin the preparation method comprises the following steps:
H beta-molecular sieve is roasted into 3h at 350 DEG C, then by the H after the roasting of the alumina powder of 8 parts by weight and 1 parts by weight Beta-molecular sieve is uniformly mixed, and the titanium boride of 2.7 parts by weight is added, after mixing extruded moulding, after 90 DEG C of dryings, grinds granulating Diameter is the particle of 0.1mm, and under nitrogen atmosphere, 100 DEG C of roasting 4h, catalyst A6 is being made in the particle.
The catalyst A6 that the present embodiment is prepared is 350 DEG C, reaction pressure 2.0MPa in reaction temperature, hydrogen oil mole Than being 6.0, mass space velocity 0.5h-1Under conditions of carry out catalysis C5/C6 isomerization reaction.
Embodiment 7
In the present embodiment by catalyst A1 reaction temperature be 260 DEG C, reaction pressure 1.0MPa, hydrogen/oil mol ratio 3.0, Mass space velocity 2.0h-1Under conditions of carry out catalysis n-heptane isomerization reaction.
Embodiment 8
In the present embodiment by catalyst A1 reaction temperature be 290 DEG C, reaction pressure 3.0MPa, hydrogen/oil mol ratio 3.0, Mass space velocity 0.5h-1Under conditions of carry out catalysis normal octane isomerization reaction.
Embodiment 9
In the present embodiment by catalyst A1 reaction temperature be 310 DEG C, reaction pressure 2.0MPa, hydrogen/oil mol ratio 1.0, Mass space velocity 2.0h-1Under conditions of carry out catalysis n -nonane isomerization reaction.
Embodiment 10
In the present embodiment by catalyst A1 reaction temperature be 330 DEG C, reaction pressure 4.0MPa, hydrogen/oil mol ratio 4.0, Mass space velocity 1.0h-1Under conditions of carry out catalysis n-decane isomerization reaction.
Embodiment 11
In the present embodiment by catalyst A1 reaction temperature be 350 DEG C, reaction pressure 2.0MPa, hydrogen/oil mol ratio 5.0, Mass space velocity 3.0h-1Under conditions of carry out catalysis n-undecane isomerization reaction.
Embodiment 12
In the present embodiment by catalyst A1 reaction temperature be 280 DEG C, reaction pressure 1.0MPa, hydrogen/oil mol ratio 2.0, Mass space velocity 1.0h-1Under conditions of carry out catalysis n-dodecane isomerization reaction.
Performance test
Catalyst normal alkane isomerization performance in above-described embodiment 1-12 is evaluated, reaction product is used Agilent6820 gas chromatograph is analyzed.Wherein, the meter of feed stock conversion X, isoparaffin yield Y, selectivity of product S It calculates and (1-1), (1-2) and (1-3) is shown in by formula:
Y=[B]Product (1-2)
S=Y/X × 100% (1-3)
In formula:
[A]Raw materialFor ratio shared by n-alkane peak area in raw material, %;
[A]ProductFor ratio shared by n-alkane peak area in product, %;
[B]ProductFor ratio shared by the sum of isoparaffin peak areas all in product, %.
Feed stock conversion X, isoparaffin yield Y, the product selection of n-pentane isomerization reaction are catalyzed in embodiment 1-12 Property S the results are shown in Table 1:
Table 1 is catalyzed the feed stock conversion of normal alkane isomerization reaction, isoparaffin yield, selectivity of product
Comparative example
The carrier of catalyst in embodiment 1 is replaced with into mordenite molecular sieve and Y molecular sieve respectively, catalysis is prepared Agent B1 and B2, specific preparation process are as follows:
The dry 1h at 110 DEG C respectively by mordenite molecular sieve and Y molecular sieve, then by the alumina powder of 1 parts by weight With after the roasting of 3 parts by weight mordenite molecular sieve and Y molecular sieve be uniformly mixed respectively, be separately added into the boron of 0.2 parts by weight Change titanium, after mixing extruded moulding, after 50 DEG C of dryings, is ground into the particle that partial size is 0.45mm, then by the particle 200 DEG C, roast 2h under nitrogen atmosphere, catalyst B1 and B2 is respectively prepared.
Using pentane and n-hexane as raw material, by catalyst B1 and B2 respectively under reaction condition same as Example 1 into The evaluation of row catalyst activity is 300 DEG C, reaction pressure 2.0MPa in reaction temperature, hydrogen/oil mol ratio 4.0, quality Air speed 1.0h-1Under conditions of carry out catalysis C5/C6 isomerization reaction.Catalyst B1 and B2 fcc raw material conversion ratio X, isoparaffin Yield Y, selectivity of product S are as shown in table 2.
2 comparative example of table and 1 fcc raw material conversion ratio of embodiment, isoparaffin yield, selectivity of product
The result from above-mentioned table 2 using mordenite molecular sieve and Y molecular sieve it is found that replace H beta-molecular sieve to be prepared Isomerization catalyst, n-alkane conversion ratio, isoparaffin yield are significantly lower than the titanium boride isomery of the embodiment of the present invention 1 Change catalyst, heretofore described catalyst activity component and carrier have more excellent catalysis effect compared with the prior art Fruit.

Claims (6)

1. being used for the load boronation titanium catalyst of light paraffins isomerization, which is characterized in that including following components:
Carrier, the carrier are made of aluminium oxide and H beta-molecular sieve, and the weight ratio of the aluminium oxide and H beta-molecular sieve is 1:10- 10:1;With
Titanium boride, the 1-30wt% of Zhan Suoshu vehicle weight.
2. the load boronation titanium catalyst according to claim 1 for light paraffins isomerization, which is characterized in that described Light paraffins are the n-alkane containing 5-12 carbon atom.
3. the load boronation titanium catalyst of any of claims 1 or 2 for light paraffins isomerization, which is characterized in that described The partial size of catalyst is 0.1mm-1.0mm.
4. the preparation side of the load boronation titanium catalyst according to claim 1-3 for light paraffins isomerization Method characterized by comprising
H beta-molecular sieve is subjected to thorough roasting under the conditions of 200-600 DEG C, the molecular sieve and aluminium oxide after roasting mix in proportion Uniformly;
Titanium boride is added to be dried under the conditions of 50-100 DEG C after kneading, molding;
Material after drying is ground into particle, the particle is then subjected to thorough roasting in a nitrogen atmosphere, boronation is made Titanium catalyst.
5. the preparation method according to claim 4, which is characterized in that the temperature of progress thorough roasting is in a nitrogen atmosphere 100-400℃。
6. the described in any item load boronation titanium catalysts for light paraffins isomerization of claim 1-3 carry out light paraffins The application method of isomerization, which is characterized in that carry out the condition of light paraffins isomerization are as follows:
Reaction temperature is 230-350 DEG C, reaction pressure 1.0-5.0MPa, hydrogen/oil mol ratio 1.0-6.0, mass space velocity 0.5- 3.0h-1
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1584123A (en) * 2004-06-15 2005-02-23 武汉大学 Catalyst for preparing boron hydride by electrolysis and preparing method for catalytic electrode
WO2011094008A1 (en) * 2010-01-27 2011-08-04 Arena Pharmaceuticals, Inc. Processes for the preparation of (r)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid and salts thereof
CN102173807A (en) * 2009-05-08 2011-09-07 李汶军 B4C/SiC functional gradient ceramic and manufacturing method thereof
US20120184794A1 (en) * 2011-01-13 2012-07-19 Uop, Llc Process for isomerizing a feed stream including one or more c4-c6 hydrocarbons
CN103816934A (en) * 2014-03-03 2014-05-28 中国石油大学(华东) C5/C6 alkane isomerization catalyst loaded with nickel boride as well as preparation method and application method thereof
CN203769779U (en) * 2014-04-01 2014-08-13 山东科技大学 Novel semicircular piston entrainment dust-removal device
CN105986323A (en) * 2015-01-30 2016-10-05 中国人民解放军军械工程学院 Method of preparing micro- and nano-scale TiB2 crystal whiskers
CN106631032A (en) * 2016-10-12 2017-05-10 淄博晶亿陶瓷科技有限公司 High-purity titanium diboride powder and preparation method thereof
CN107954817A (en) * 2017-12-04 2018-04-24 万华化学集团股份有限公司 A kind of method for preparing odorlessness isomery dodecane

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1584123A (en) * 2004-06-15 2005-02-23 武汉大学 Catalyst for preparing boron hydride by electrolysis and preparing method for catalytic electrode
CN102173807A (en) * 2009-05-08 2011-09-07 李汶军 B4C/SiC functional gradient ceramic and manufacturing method thereof
WO2011094008A1 (en) * 2010-01-27 2011-08-04 Arena Pharmaceuticals, Inc. Processes for the preparation of (r)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl)acetic acid and salts thereof
US20120184794A1 (en) * 2011-01-13 2012-07-19 Uop, Llc Process for isomerizing a feed stream including one or more c4-c6 hydrocarbons
CN103816934A (en) * 2014-03-03 2014-05-28 中国石油大学(华东) C5/C6 alkane isomerization catalyst loaded with nickel boride as well as preparation method and application method thereof
CN203769779U (en) * 2014-04-01 2014-08-13 山东科技大学 Novel semicircular piston entrainment dust-removal device
CN105986323A (en) * 2015-01-30 2016-10-05 中国人民解放军军械工程学院 Method of preparing micro- and nano-scale TiB2 crystal whiskers
CN106631032A (en) * 2016-10-12 2017-05-10 淄博晶亿陶瓷科技有限公司 High-purity titanium diboride powder and preparation method thereof
CN107954817A (en) * 2017-12-04 2018-04-24 万华化学集团股份有限公司 A kind of method for preparing odorlessness isomery dodecane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIANGGUANGCHEN ET.AL: "Catalytic hydroprocessing of fatty acid methyl esters to renewable alkane fules over Ni/HZSM-5 catalyst", 《CATALYSIS TODAY》 *
孙怀宇等: "C5/C6烷烃异构化机理与催化剂研究进展", 《化工时刊》 *

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