CN108421563A - Hydroisomerisation catalysts and preparation method thereof - Google Patents
Hydroisomerisation catalysts and preparation method thereof Download PDFInfo
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- CN108421563A CN108421563A CN201710080814.4A CN201710080814A CN108421563A CN 108421563 A CN108421563 A CN 108421563A CN 201710080814 A CN201710080814 A CN 201710080814A CN 108421563 A CN108421563 A CN 108421563A
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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Abstract
The present invention relates to a kind of hydroisomerisation catalysts and preparation method thereof, which includes：(1) water soluble salt of hydrogenation metal active component and organic complexing agent are loaded on carrier using infusion process, then it is dried, roasts, obtain semi-finished product catalyst, the roasting condition so that on the basis of the total amount of semi-finished product catalyst, carbon content is 0.03 0.5 weight % in semi-finished product catalyst；(2) to contain the solution of organic complexing agent as maceration extract, semi-finished product catalyst obtained by step (1) is impregnated, is then dried and without roasting；Wherein, the carrier contains inorganic refractory oxides and mesoporous molecular sieve.Hydroisomerisation catalysts obtained by this method have higher activity and isomerisation selectivity.
Description
Technical field
The present invention relates to the preparation methods of hydroisomerisation catalysts and hydroisomerisation catalysts obtained by this method.
Background technology
The environmental consciousness being increasingly enhanced and the environmental regulation being increasingly stringenter force oil refining circle more to focus on clean fuel life
Produce technological development.Future market vehicle fuel is intended to " super-low sulfur ", and the fuel that cannot meet discharge standard will be unable into entering the market
.Hydrogen addition technology plays more and more important work as a kind of effective desulfurization means in the production of fuel for cleaning vehicle
With wherein efficient hydrogenation catalyst is then the core technology of hydrogen addition technology, therefore, is developed new with higher activity and selectivity
Type hydroisomerisation catalysts then become most urgent one of the demand of petroleum refining industry.
Prepared by hydroisomerisation catalysts generally use infusion process, that is, use and contain required active component (such as Ni, Mo, Co, W
Deng) solution, impregnate certain carrier, the method for being dried, roasting or not roasting later.
CN103551162A discloses a kind of diesel hydrogenation for removal sulphur denitrification catalyst, the composition of catalyst include carrier, auxiliary agent,
Active metal；Carrier is Al2O3-ZrO2-TiO2-SiO2Multivariant oxide complex carrier；Auxiliary agent is phosphorus；It is with nickel, cobalt, molybdenum and tungsten
Active component；Weight percent content of each component on the basis of catalyst be：In terms of oxide, 1~6wt% of cobalt oxide；Oxygen
Change 1~15wt% of nickel, 2~12wt% of molybdenum oxide, 12~35wt% of tungsten oxide, 1.5~5wt% of auxiliary agent phosphorus pentoxide；Catalysis
Kong Rong ≮ 0.2mL/g of agent, specific surface area are ≮ 140m2/ g, mechanical strength ≮ 15N/mm；Each component is in carrier in complex carrier
In shared proportion be respectively：Titanium oxide accounts for 2~15wt%, and silica accounts for 2~20wt%, and zirconium oxide accounts for 5~15wt%；Surplus
For aluminium oxide.The catalyst is made by step impregnation method：Co-impregnated solution is divided into isometric two parts, dipping carries in two steps
Body, and all roasted after the completion of each step dipping.
CN103657667A discloses a kind of preparation method of new macroporous structure catalyst for heavy oil hydrogenation demetal, special
Sign is：It specifically comprises the following steps：1) preparation of Aluminum sol；2) asphaltic residue powder and Aluminum sol are mixed with macropore knot
Structure catalyst carrier；3) catalyst carrier after molding is used to two step impregnations of isometric branch；It is finally made and urges
Agent.Two step infusion processes of the preparation method are specially：The first step first impregnates Mo, and second step impregnates Ni, also, in maceration extract not
Including organic complexing agent.
The two step infusion processes provided by the prior art make hydroisomerisation catalysts activity increase, but improve degree
It is limited.
CN100469440C, CN102909027A are disclosed by introducing organic dispersing agent into carrier in preparation process
Or complexing agent (such as ethylene glycol, oxalic acid, citric acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid) is prepared for Ni-W-Mo ternary metals and adds
Hydrogen isomerization catalyst.With existing method provide catalyst compared with, obtained by catalyst have better hydrofinishing
Energy.But there is still a need for further increase catalyst activity.
Invention content
For the relatively low disadvantage of prior art hydroisomerisation catalysts activity, the present invention provides a kind of new hydroisomerizing
Change the preparation method of catalyst and hydroisomerisation catalysts obtained by this method, hydroisomerization obtained by this method
Catalyst has higher activity and isomerisation selectivity.
It was found by the inventors of the present invention that above-mentioned complexing dipping technique, by introducing complexing agent in dipping process, and low
The lower drying of temperature can weaken active component and carrier interaction, improve metal dispersity, change metal vulcanization sequence, be formed
The activity phase of more high activities simultaneously improves activated centre number.But it is dry due to using low temperature in dipping technique is complexed
Dry, there is no the process Jing Guo high-temperature roasting, metallic compound is still present in carrier surface in the form of metallic salt, activity
Component and carrier function power are weaker, cause under high temperature and pressure and the hydrogenation conditions of severe raw material, metal was reacting
Constantly assemble in journey, auxiliary agent effect weakens, and activated centre number is reduced, and latent active declines, therefore catalyst is active, steady
Qualitative decline.Although and the catalyst stability for using high-temperature roasting method to prepare is preferable, active component and carrier active force
Relatively strong, the latent active in activated centre is relatively low, and due to the not dispersion of complexing agent and iris action, active component platelet is larger,
Activated centre number is less, and activity is very low.
By research it has furthermore been found that by two step preparation catalysts, the first step impregnates the present inventor
It is respectively used to introduce hydrogenation metal active component and organic complexing agent with second step dipping, being added in first step dipping process has
Machine complexing agent is simultaneously run through roasting and is converted into charcoal, can not only improve the activity of catalyst, and can effectively for a long time
The high activity for keeping catalyst, to greatly improve the service life of catalyst.Speculate that its reason may be because the first step is soaked
The organic complexing agent being added during stain, the presence of organic complexing agent hinder the aggregation of active metal in roasting process, make it
That disperses is more uniform；Meanwhile roasting can make metallic compound be converted into metal oxide after first step dipping, make organic network
Mixture is converted into charcoal, to keep the combination between active metal and carrier more secured, improves the activity and stabilization of catalyst
Property.And the organic complexing agent being added in second step dipping process is covered in catalyst surface, can effectively prevent active metal
Aggregation in sulfidation improves metal dispersity, is more advantageous to be formed with higher active II class activity phase and shape
At more activated centres, to the further very high activity of catalyst.Therefore, which can effectively solve conventional impregnation method
With the technological deficiency of existing complexing infusion process.
As a result, the present invention also provides a kind of preparation method of hydroisomerisation catalysts, which includes following step
Suddenly：
(1) water soluble salt of hydrogenation metal active component and organic complexing agent are loaded on carrier using infusion process, so
After be dried, roast, obtain semi-finished product catalyst, the roasting condition makes on the basis of the total amount of semi-finished product catalyst,
Carbon content is 0.03-0.5 weight % in semi-finished product catalyst；
(2) to contain the solution of organic complexing agent as maceration extract, semi-finished product catalyst obtained by step (1) is soaked
Then stain is dried and without roasting；
Wherein, the carrier contains inorganic refractory oxides and mesoporous molecular sieve.
In addition, the method for the present invention additionally provides the hydroisomerisation catalysts made from the above method.
Hydroisomerisation catalysts prepared by method using the present invention have both higher catalytic activity and selectivity and
Activity stability, for example, the conversion ratio of catalyst S3 prepared in accordance with the method for the present invention is 45%, isomerisation selectivity is
64.6%, far above the isomerization using 35.4% conversion ratio that reference agent D2 is obtained made from conventional impregnation method and 52.6%
Selectivity illustrates that the hydroisomerisation catalysts made from method provided by the present invention have higher hydrogenation activity and isomery
Selectivity.And method provided by the invention is easy to operate, and therefore, method of the invention has preferable prospects for commercial application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the preparation method of hydroisomerisation catalysts provided by the invention, which includes the following steps：
(1) water soluble salt of hydrogenation metal active component and organic complexing agent are loaded on carrier using infusion process, so
After be dried, roast, obtain semi-finished product catalyst, the roasting condition makes on the basis of the total amount of semi-finished product catalyst,
Carbon content is 0.03-0.5 weight % in semi-finished product catalyst；
(2) to contain the solution of organic complexing agent as maceration extract, semi-finished product catalyst obtained by step (1) is soaked
Then stain is dried and without roasting；
Wherein, the carrier contains inorganic refractory oxides and mesoporous molecular sieve.
In accordance with the present invention it is preferred that step (1) described roasting condition makes on the basis of the total amount of semi-finished product catalyst,
Carbon content is 0.04-0.4 weight % in semi-finished product catalyst.
In the present invention, it can be obtained by controlling the intake of calcination temperature and imflammable gas in roasting condition
Above-mentioned carbon content, the imflammable gas can be various oxygen contents be not less than 20 volume % gas, as air, oxygen with
And it is one or more in their mixed gas.
Relative to every gram of carrier, the rate that is passed through of the imflammable gas is not less than 0.2 l/h.The combustibility gas
Body is passed through, and on the one hand meets the condition of burning so that the salt of active metal component is converted into oxide, and organic complexing agent is made to turn
Turn to charcoal；On the other hand the carbon dioxide and water and other compositions that burning is formed can also be emitted, to avoid being deposited on
It causes to hinder the vacancy of active phase on catalyst.
Under preferable case, relative to every gram of carrier, the rate that is passed through of imflammable gas is 0.2-20 ls/h, preferably
0.3-10 ls/h.
In accordance with the present invention it is preferred that the temperature of step (1) described roasting is 350-500 DEG C, and preferably 360-450 DEG C, roasting
The time of burning is 0.5-8h, preferably 1-6h.It controls calcination temperature and can guarantee organic complexing agent energy or more within the above range
It states content range charcoal is formed on carrier, obtains semi-finished product catalyst.
In accordance with the present invention it is preferred that the molar ratio of step (1) organic complexing agent and metal active constituent is 0.03-
2：1, preferably 0.08-1.5:1, further preferably 0.1-1.4：1, it is still more preferably 0.5-1.3：1.
In accordance with the present invention it is preferred that step (1) and the molar ratio of step (2) organic complexing agent are 1：0.25-4, preferably
1：0.5-2.
In the present invention, organic complexing agent described in step (1) and step (2) may be the same or different, preferably
Ground, the organic complexing agent are one or more in oxygen-containing and/or itrogenous organic substance.
The oxygen containing organic matter is preferably selected from one or more in Organic Alcohol, organic acid.
The Organic Alcohol is preferably the polyalcohol of binary or more, still more preferably for the polyalcohol of carbon atom number 2-6 or
Its oligomer or polymer, as one or more in ethylene glycol, glycerine, polyethylene glycol, diethylene glycol, butanediol.It is described
The molecular weight of polyethylene glycol is preferably 200-1500.
The organic acid is preferably the compound containing one or more COOH groups of C2-C7, is specifically as follows acetic acid, horse
Come one or more in sour, oxalic acid, aminotriacetic acid, 1,2- 1,2-diaminocyclohexane tetraacetic acids, citric acid, tartaric acid, malic acid.
The nitrogenous organic matter is preferably selected from one or more in organic amine, organic ammonium salt.
The organic amine is preferably the compound containing one or more NH groups of C2-C7, can be primary amine, secondary amine or uncle
Amine, particularly preferably ethylenediamine.
The organic ammonium salt is preferably EDTA.
Specifically, the organic complexing agent specifically preferred according to the invention is ethylene glycol, glycerine, (molecular weight is excellent for polyethylene glycol
Be selected as 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- 1,2-diaminocyclohexane tetraacetic acids,
It is one or more in citric acid, tartaric acid, malic acid, ethylenediamine and EDTA.
Preferably, organic complexing agent described in step (1) is one or more in organic acid, it is highly preferred that step
(1) one or more in aliphatic acid of the organic complexing agent selected from C2-C7.Using organic acid as the organic of step (1)
Complexing agent can be obtained with higher active hydroisomerisation catalysts.
There is no particular limitation to the drying condition by the present invention, can be various drying conditions commonly used in the art, step
Suddenly drying condition described in (1) and step (2) may be the same or different.
Preferably, step (1) described drying temperature is 100-250 DEG C, time 1-12h.
Preferably, step (2) described drying temperature is 100-200 DEG C, time 1-12h.
In accordance with the present invention it is preferred that the dosage of the hydrogenation metal active component makes, with hydroisomerisation catalysts
On the basis of total amount, in terms of oxide, the content of hydrogenation metal active component is 10-60 weight %, preferably 15-50 weight %,
Further preferably 20-40 weight %.
In accordance with the present invention it is preferred that with elemental metal, a concentration of 0.2- of the water soluble salt of hydrogenation metal active component
8mol/L, preferably 0.2-5mol/L are still more preferably 0.2-2mol/L.A concentration of various hydrogenation metal activity herein
The respective concentration of water soluble salt rather than total concentration of component.
The water soluble salt of the hydrogenation metal active component can be that various solubility meet load requirement or in hydrotropy
The water soluble compound for the hydrogenation metal active component that solubility is met the requirements can be formed in the presence of agent in water, such as can
To be one or more in nitrate, chloride, sulfate, carbonate, preferably nitrate.
In accordance with the present invention it is preferred that the hydrogenation metal active component at least one is selected from vib metals element, extremely
It is few a kind of selected from group VIII metallic element.
According to the present invention, the vib metals element is preferably molybdenum and/or tungsten.
According to the present invention, the group VIII metallic element is preferably cobalt and/or nickel.
In accordance with the present invention it is preferred that the compound of the element containing vib metals can be selected from ammonium molybdate, ammonium paramolybdate, partially
It is one or more in ammonium tungstate, molybdenum oxide and tungsten oxide.
The compound of the metallic element containing group VIII can be selected from the nitrate of group VIII metal, group VIII metal
Chloride, the sulfate of group VIII metal, the formates of group VIII metal, the acetate of group VIII metal, Section VIII
The carbonic acid of the phosphate of race's metal, the citrate of group VIII metal, the oxalates of group VIII metal, group VIII metal
Salt, the subcarbonate of group VIII metal, the hydroxide of group VIII metal, the phosphate of group VIII metal,
The molybdenum of the phosphide of group VIII metal, the sulfide of group VIII metal, the aluminate of group VIII metal, group VIII metal
It is one or more in the water-soluble oxide of hydrochlorate, the tungstates of group VIII metal and group VIII metal.
Preferably, the compound of the metallic element containing group VIII is selected from the oxalates of group VIII metal, group VIII gold
The nitrate of category, the sulfate of group VIII metal, the acetate of group VIII metal, the chloride of group VIII metal,
The carbonate of group VIII metal, the subcarbonate of group VIII metal, the hydroxide of group VIII metal, group VIII gold
The water-soluble oxygen of the phosphate of category, the molybdate of group VIII metal, the tungstates of group VIII metal and group VIII metal
It is one or more in compound.
The compound of the metallic element containing group VIII can be selected from but not limited to nickel nitrate, nickel sulfate, nickel acetate, alkali formula carbon
It is one or more in sour nickel, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.
According to the present invention, the mode of loading of the hydrogenation metal active component is not particularly limited.
In accordance with the present invention it is preferred that the load of the hydrogenation metal active component is that hydrogenation metal is lived by infusion process
Property component loads on carrier.
According to the present invention, loading to the sequence on carrier to hydrogenation metal active component, there is no particular limitation, Ke Yitong
It crosses and also may be used on all hydrogenation metal active component mutual loads to carrier containing the solution impregnating carrier there are many water soluble salt
To prepare the solution step impregnation carrier containing water soluble salt respectively, hydrogenation metal active component is loaded on carrier successively.
When using step impregnation, preferably it is dried after each dipping and preferably further roasts.It is dry and roasting
Mode and condition are referred to the prior art and are selected.
According to the present invention, the mode of loading of the organic complexing agent is not particularly limited.Organic complexing agent can be with
One or more co-formulations in the water soluble salt of hydrogenation metal active component can also individually match at maceration extract impregnated carrier
Maceration extract impregnated carrier is made, preferably the former.
According to the present invention, the infusion process can be incipient impregnation, or supersaturation dipping, to the dipping
Temperature is not particularly limited, and can be the attainable various temperature of maceration extract institute, the time of dipping is not particularly limited, as long as
Upper the desired amount of required component can be loaded, such as：The temperature of dipping can be 15-60 DEG C, and dip time can be 0.5-5
Hour.
According to the present invention, the carrier contains inorganic refractory oxides and mesoporous molecular sieve.According to the present invention, term " nothing
Machine refractory oxides " refer under oxygen or oxygen-containing atmosphere, decomposition temperature not less than 300 DEG C (such as：Decomposition temperature is 300-
1000 DEG C) inorganic oxygen-containing compound.
According to the present invention, the inorganic refractory oxides can be various inorganic refractory oxides commonly used in the art.Institute
Aluminium oxide, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-can be for example selected from by stating inorganic refractory oxides
Magnesia, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia,
Titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia
With it is one or more in silica-alumina, zirconia.
A preferred embodiment of the invention, the inorganic refractory oxides are aluminium oxide, further preferred institute
It is aluminium oxide and mesoporous molecular sieve (i.e. aluminium oxide-mesoporous molecular sieve) to state carrier.
A preferred embodiment of the invention, on the basis of the total amount of the carrier, mesoporous point in the carrier
The content of son sieve is 2-75 weight %, preferably 5-60 weight %.
A preferred embodiment of the invention, the carrier is aluminium oxide and mesoporous molecular sieve, with the carrier
Total amount on the basis of, in the carrier content of mesoporous molecular sieve be 2-75 weight %, preferably 5-60 weight %, aluminium oxide
Content is 25-98 weight %, preferably 40-95 weight %.
In the present invention, the mesoporous molecular sieve refers to the zeolite molecular sieve for having ten-ring pore structure, is preferably selected from SAPO-
11, one kind in SAPO-31, SAPO-41, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57 or
It is a variety of.It is one or more in further preferred SAPO-11, ZSM-5, ZSM-22 etc..
Wherein aluminium oxide is more preferably and obtains after a kind of roasting of hydrated alumina (aluminium hydroxide) glue compound
Aluminium oxide.
One preferred method for preparing aluminium oxide-mesoporous molecular sieve, be by the precursor of aluminium oxide and/or aluminium oxide with
Mesoporous molecular sieve mixing, roasting obtain.The carrier can be made into various easily operated moldings depending on different requirements, such as micro-
Ball, spherical shape, tablet or bar shaped etc..Molding can carry out according to a conventional method, for example, it may be by institute's aluminium oxide and/or its precursor
It is mixed with mesoporous molecular sieve, prepared by the method for extruded moulding and roasting.Wherein, the precursor of the aluminium oxide can be selected from various
One or more of hydrated alumina, Aluminum sol.Appropriate extrusion aid and/or adhesive can be added in extrusion molding, so
Extrusion molding afterwards.The extrusion aid, the type of peptizing agent and dosage are known to those skilled in the art, and this will not be repeated here.Institute
The roasting stated uses method and condition customary in the art, if calcination temperature can be 350-650 DEG C；Preferably 400-600 DEG C,
Roasting time is 2-6 hours, preferably 3-5 hours.
Catalyst of the present invention using when it is general be first reduced into metallic state in a hydrogen atmosphere, restoring method can be this
Method known to field technology personnel.Such as：With V (hydrogen)：V (catalyst)=95-105,1-5 DEG C/min rate heat up also
Original stops 3-5h at 300-400 DEG C.
The present invention also provides hydroisomerisation catalysts made from a kind of preparation method by the present invention.
Compared with catalyst prepared by conventional method, the hydroisomerisation catalysts made from method provided by the present invention
With higher hydrogenation activity and stereoselectivity, the isomerization reaction of the various feedstock oils containing linear paraffin is can be applied to, including
But following reaction is not limited：Hydrocracking tail oil isomerization-visbreaking, biology boat coal drop freezing point, Fischer Tropsch waxes pour point depressing etc..
In the present invention, dry weight refers to the weight measured by roasting sample 4 hours at 600 DEG C.
Below by way of the specific embodiment implementation process that the present invention will be described in detail and generated advantageous effect, it is intended to help
Where reader more clearly understands the Spirit Essence of the present invention, but any restriction cannot be constituted to the practical range of the present invention.
Rigaku electric machine industry Co., Ltd. 3271E type Xray fluorescence spectrometers are used in following embodiment, to catalysis
The content of each element carries out analysis measurement in agent.Carbon content uses the production of HORIBA companies of Japan in catalyst semi-finished product
EMIA-320V carbon and sulfur analytical instruments carry out analysis measurement.Unless stated otherwise, the aluminium oxide used in embodiment is by sinopec
The RPB-90 that Chang Ling catalyst branch is produced, silicaalumina carrier are to be produced by German Condea companies
Siral40。
Preparation example 1
The preparation of mesoporous molecular sieve：SAPO-11 molecular sieves are synthesized according to the method for embodiment in US4440871 16.It weighs
440.0g distilled water, (the Chang Ling refinery company catalyst plant life of 144.0g boehmites is added in 230.6g phosphoric acid (85 weight %)
The dry glue powder of production, 71 weight % of butt), it stirs evenly, obtains mixture P1.Weigh the four positive fourth of hydroxyl of a concentration of 40 weight %
Amine aqueous solution 649.2g, smoke silica gel (silica content 92.8 weight %, 7.2 weight % of water content) 26.0g, stir evenly,
Obtain mixture P2.Mixture P1 and P2 are mixed, 102.0g di-n-propylamines are added under stiring, obtain reaction mixture.It will
Reaction mixture is packed into the reaction kettle of teflon seal, and 200 DEG C of crystallization 24 hours are filtered, washed solid product into
Property, 120 DEG C of drying obtain SAPO-11 molecular sieves (85.0 weight % of net content).
The preparation of aluminium oxide-mesoporous catalyst-support：By 150 grams of SAPO-11 molecular sieves, 850 grams of butt boehmites
(Shandong Aluminum Plant produces, trade name SD powder, 69 weight % of butt) and 30 grams of sesbania powder mixing, it is 1.6 millis to be extruded into circumscribed circle diameter
The mesoporous molecular sieve in carrier Z1, carrier Z1 is made in the trilobal item of rice, 120 DEG C of drying, 550 DEG C of roasting temperatures 3 hours
Content is 15.0 weight %.
Preparation example 2
By 50 grams of SAPO-11 molecular sieves, (Shandong Aluminum Plant produces 950 grams of butt boehmites, trade name SD powder, butt
69 weight %) and 30 grams of sesbania powder mixing, it is extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of drying, 550 DEG C of temperature
The lower roasting of degree 3 hours, the content that the mesoporous molecular sieve in carrier Z2, carrier Z2 is made is 5.0 weight %.
Preparation example 3
By 600 grams of SAPO-11 molecular sieves, (Shandong Aluminum Plant produces 400 grams of butt boehmites, trade name SD powder, butt
69 weight %) and 30 grams of sesbania powder mixing, it is extruded into the trilobal item that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of drying, 550 DEG C of temperature
The lower roasting of degree 3 hours, the content that the mesoporous molecular sieve in carrier Z3, carrier Z3 is made is 60.0 weight %.
Embodiment 1
Weigh respectively 54 grams of molybdenum trioxides, 19 grams of basic cobaltous carbonates, 20 grams of phosphoric acid, 20 grams of citric acids be put into 140 grams go from
In sub- water, heating stirring dissolves to obtain clarification dipping solution, impregnates 200 grams of carrier Z1 using the above-mentioned solution of saturation infusion process,
Dip time is 2 hours, then, 2 hours dry at 120 DEG C, then roasts it in the state of being passed through air stream, roasts
It is 400 DEG C to burn temperature, and the time is 2 hours, and relative to every gram of carrier, the rate that is passed through of air is 2 ls/h, obtains semi-finished product
The carbon content of catalyst Z 1-S1, Z1-S1 are shown in Table 1；5 grams of ethyl alcohol are added in 150 grams of deionized waters, clear solution is stirred to get,
Z1-S1 is impregnated using the above-mentioned solution of saturation infusion process, dip time is 2 hours, and then, dry 3 hours, obtain at 110 DEG C
To catalyst S1.On the basis of the total amount of S1, in terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Comparative example 1
Hydroisomerisation catalysts are prepared using method same as Example 1, unlike, obtained by embodiment 1
Hydroisomerisation catalysts S1 is roasted 3 hours at 400 DEG C, obtains catalyst D1, in catalyst D1, on the basis of the total amount of D1,
In terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Embodiment 2
Weigh respectively 54 grams of molybdenum trioxides, 21 grams of basic nickel carbonates, 13 grams of phosphoric acid, 30 grams of citric acids be put into 140 grams go from
In sub- water, heating stirring dissolves to obtain clarification dipping solution, impregnates 200 grams of carrier Z2 using the above-mentioned solution of saturation infusion process,
Dip time is 2 hours, then, 2 hours dry at 150 DEG C, then roasts it in the state of being passed through air stream, roasts
It is 360 DEG C to burn temperature, and the time is 3 hours, and relative to every gram of carrier, the rate that is passed through of air is 10 ls/h, obtains semi-finished product
The carbon content of catalyst Z 2-S2, Z2-S2 are shown in Table 1；30 grams of citric acids are added in 150 grams of deionized waters, it is molten to stir to get clarification
Liquid impregnates Z2-S2 using the above-mentioned solution of saturation infusion process, and dip time is 2 hours, then, dry 3 hours at 150 DEG C,
Obtain hydroisomerisation catalysts S2.On the basis of the total amount of S2, in terms of oxide, the content of hydrogenation metal active component is shown in Table
1。
Embodiment 3
30 grams of nickel nitrates, 45 grams of ammonium metatungstates (hydrate, molecular weight 3037 are same as below) and 15 grams of grass are weighed respectively
Acid is put into 140 grams of deionized waters, and stirring and dissolving obtains clear solution, impregnates 200 grams using the above-mentioned solution of saturation infusion process
Carrier Z3, dip time are 2 hours, then, 2 hours dry at 120 DEG C, then carry out it in the state of being passed through air stream
Roasting, calcination temperature are 450 DEG C, and the time is 4 hours, and relative to every gram of carrier, the rate that is passed through of air is 0.3 l/h, is obtained
Carbon content to semi-finished product catalyst Z 3-S3, Z3-S3 is shown in Table 1；10 grams of diethylene glycol (DEG)s are put into 150 grams of deionized waters, are stirred
To clear solution, Z3-S3 is impregnated using the above-mentioned solution of saturation infusion process, dip time is 2 hours, then, in 120 DEG C of dryings
6 hours, obtain catalyst S3.On the basis of the total amount of S3, in terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Comparative example 2
30 grams of nickel nitrates, 45 grams of ammonium metatungstates, 15 grams of oxalic acid and 10 grams of diethylene glycol (DEG)s are weighed respectively is put into 140 grams of deionized waters
In, stirring and dissolving obtains clear solution, impregnates 200 grams of carrier Z3 using the above-mentioned solution of saturation infusion process, dip time is 2 small
When, it is then 2 hours dry at 120 DEG C, obtain catalyst D2.On the basis of the total amount of D2, in terms of oxide, hydrogenation metal activity
The content of component is shown in Table 1.
Comparative example 3
Hydroisomerisation catalysts are prepared according to the method for embodiment 3, unlike, carrier Z3 is replaced by aluminium oxide, is obtained
To catalyst D3.On the basis of the total amount of D3, in terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Comparative example 4
According to embodiment 3 method prepare hydroisomerisation catalysts, unlike, carrier Z3 by identical weight oxidation
Silicon-alumina support replaces, and obtains catalyst D4.On the basis of the total amount of D4, in terms of oxide, hydrogenation metal active component
Content is shown in Table 1.
Embodiment 4
Hydroisomerisation catalysts are prepared using method same as Example 3, unlike, metal active constituent dipping
To after carrier, when being roasted to it, calcination temperature is 480 DEG C, and the time is 6 hours.Charcoal contains in obtained catalyst semi-finished product
Amount is shown in Table 1, and in obtained catalyst S4, on the basis of the total amount of S4, in terms of oxide, the content of hydrogenation metal active component is shown in
Table 1.
Embodiment 5
Hydroisomerisation catalysts are prepared using method same as Example 3, unlike, relative to every gram when roasting
The rate that is passed through of carrier, air is 1.0 ls/h, in obtained catalyst S5, on the basis of the total amount of S5, and in terms of oxide,
The content of hydrogenation metal active component is shown in Table 1.
Embodiment 6
Hydroisomerisation catalysts are prepared using method same as Example 3, unlike, step (1) and step (2)
The amount ratio of organic complexing agent is by 15 grams：10 grams are changed to 5 grams：20 grams, in obtained catalyst S6, on the basis of the total amount of S6,
In terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Table 1
Test example 1
In this test example, the hydroisomerisation catalysts and comparative example that are prepared using method provided by the present invention are carried
The catalytic activity and selectivity of the hydroisomerisation catalysts of confession are evaluated in accordance with the following methods, evaluation result such as the following table 2 institute
Show.
The catalytic performance test of catalyst carries out on the continuous micro device of high pressure.By the catalyst S1 of 1.5g 40-60 mesh
(S2 or S3 or S4 or S5 or S6 or D1 or D2 or D3 or D4) is fitted into the flat-temperature zone of fixed-bed micro-devices, is passed through hydrogen, is risen
Temperature restores 4h, is then cooled to reaction temperature to 360 DEG C, starts into n-decane, reaction feed mass space velocity is 2.0h-1, hydrogen hydrocarbon
Molar ratio is 3000.Start sampling analysis after stablizing 1.5h.
Quantitative analysis is carried out to product using the TRACE GC-2000 gas chromatographs of CE companies.Chromatographic column selects capillary
Tubing string, chromatographic condition are：Capillary column (OV-17, non-polar column), internal diameter 0.32mm, long 25m, split ratio 40:1, program liter
Temperature；Fid detector.According to the analysis result of gas and fluid sample, conversion ratio and selectivity are calculated.Each embodiment and comparative example
The hydroisomerizing evaluation result of obtained catalyst is as shown in table 2.
Table 2
The result of table 2 can illustrate, the hydroisomerisation catalysts prepared than existing methods, catalyst provided by the invention
With considerably better hydrogenation activity and hydroisomerizing selection activity.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of preparation method of hydroisomerisation catalysts, the preparation method include：
(1) water soluble salt of hydrogenation metal active component and organic complexing agent are loaded on carrier using infusion process, then into
Row is dry, roasting, obtains semi-finished product catalyst, and the roasting condition makes on the basis of the total amount of semi-finished product catalyst, half at
Carbon content is 0.03-0.5 weight % in product catalyst；
(2) to contain the solution of organic complexing agent as maceration extract, semi-finished product catalyst obtained by step (1) is impregnated, so
After be dried and without roasting；
Wherein, the carrier contains inorganic refractory oxides and mesoporous molecular sieve.
2. preparation method according to claim 1, wherein step (1) described roasting condition makes with semi-finished product catalyst
Total amount on the basis of, in semi-finished product catalyst carbon content be 0.04-0.4 weight %.
3. preparation method according to claim 1 or 2, wherein roasting is under conditions of being passed through gas described in step (1)
The temperature for carrying out, and roasting is 350-500 DEG C, preferably 360-450 DEG C；The time of roasting is 0.5-8h, preferably 1-6h；Phase
For every gram of carrier, the rate that is passed through of gas is 0.2-20 ls/h, preferably 0.3-10 ls/h.
4. according to the preparation method described in any one of claim 1-3, wherein in step (1), organic complexing agent and metal
The molar ratio of active component is 0.03-2：1, preferably 0.08-1.5：1.
5. according to the preparation method described in any one of claim 1-4, wherein step (1) and step (2) organic complexing agent
Molar ratio be 1：0.25-4.
6. according to the preparation method described in any one of claim 1-5, wherein step (1) organic complexing agent and step
Suddenly (2) described organic complexing agent is identical or different, and the organic complexing agent is selected from oxygen containing organic matter and/or nitrogenous organic
One or more in object, the oxygen containing organic matter is preferably selected from one or more in Organic Alcohol, organic acid, and nitrogenous has
Machine object is preferably selected from one or more in organic amine, organic ammonium salt.
7. preparation method according to claim 6, wherein it is 2-7's that step (1) described organic complexing agent, which is carbon atom number,
It is one or more in organic acid.
8. preparation method according to any one of claims 1-7, wherein the dosage of the hydrogenation metal active component
So that on the basis of the total amount of hydroisomerisation catalysts, in terms of oxide, the content of hydrogenation metal active component is 10-60
Weight %, preferably 15-50 weight %.
9. according to the preparation method described in any one of claim 1-8, wherein the hydrogenation metal active component is at least
One kind being selected from group VIII metallic element selected from vib metals element and at least one, and the vib metals element is preferred
For molybdenum and/or tungsten, the group VIII metallic element is preferably cobalt and/or nickel；The inorganic refractory oxides are selected from gamma oxidation
Aluminium, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica-oxidation
Thorium, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-oxidation
One kind in thorium, silica-alumina-titania, silicaalumina-magnesia and silica-alumina, zirconia or
It is a variety of.
10. according to the preparation method described in any one of claim 1-9, wherein on the basis of the total amount of the carrier, institute
The content for stating mesoporous molecular sieve in carrier is 2-75 weight %, preferably 5-60 weight %.
11. according to the preparation method described in any one of claim 1-10, wherein the carrier is aluminium oxide and mesoporous point
Son sieve, on the basis of the total amount of the carrier, the content of mesoporous molecular sieve is 2-75 weight %, preferably 5-60 in the carrier
The content of weight %, aluminium oxide are 25-98 weight %, preferably 40-95 weight %.
12. according to the preparation method described in any one of claim 1-11, wherein the mesoporous molecular sieve refers to having ten
The zeolite molecular sieve of first ring pore structures, be preferably selected from SAPO-11, SAPO-31, SAPO-41, ZSM-5, ZSM-11, ZSM-22,
It is one or more in ZSM-23, ZSM-35, ZSM-48, ZSM-57.
13. the hydroisomerisation catalysts made from the preparation method described in any one of claim 1-12.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111151269A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrodesulfurization catalyst |
| CN112742395A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrogenation dealdehyding catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853777A (en) * | 2005-04-21 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst and production thereof |
| CN102909027A (en) * | 2012-09-19 | 2013-02-06 | 中国海洋石油总公司 | Preparation method of catalyst by ultralow-sulfur hydrofining |
| WO2014071686A1 (en) * | 2012-11-08 | 2014-05-15 | 中国石油化工股份有限公司 | Hydrogenation catalyst and manufacturing method therefor and use thereof |
| CN104941654A (en) * | 2015-05-21 | 2015-09-30 | 中国石油大学(北京) | Aluminum oxide based hydrorefining catalyst as well as preparation method and application thereof |
| CN106031881A (en) * | 2015-03-12 | 2016-10-19 | 中国石油化工股份有限公司 | A hydrogenation catalyst and applications thereof |
-
2017
- 2017-02-15 CN CN201710080814.4A patent/CN108421563B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853777A (en) * | 2005-04-21 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst and production thereof |
| CN102909027A (en) * | 2012-09-19 | 2013-02-06 | 中国海洋石油总公司 | Preparation method of catalyst by ultralow-sulfur hydrofining |
| WO2014071686A1 (en) * | 2012-11-08 | 2014-05-15 | 中国石油化工股份有限公司 | Hydrogenation catalyst and manufacturing method therefor and use thereof |
| CN106031881A (en) * | 2015-03-12 | 2016-10-19 | 中国石油化工股份有限公司 | A hydrogenation catalyst and applications thereof |
| CN104941654A (en) * | 2015-05-21 | 2015-09-30 | 中国石油大学(北京) | Aluminum oxide based hydrorefining catalyst as well as preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111151269A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrodesulfurization catalyst |
| CN111151269B (en) * | 2018-11-08 | 2023-02-03 | 中国石油化工股份有限公司 | Preparation method of hydrodesulfurization catalyst |
| CN112742395A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrogenation dealdehyding catalyst and preparation method and application thereof |
| CN112742395B (en) * | 2019-10-31 | 2023-04-07 | 中国石油化工股份有限公司 | Hydrogenation dealdehyding catalyst and preparation method and application thereof |
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