CN107303506A - A kind of paraffin hydrocarbon selects the preprocess method of type isomerization catalyst - Google Patents
A kind of paraffin hydrocarbon selects the preprocess method of type isomerization catalyst Download PDFInfo
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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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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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/67—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7492—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
Abstract
The invention discloses the preprocess method that a kind of paraffin hydrocarbon selects type isomerization catalyst, including following content：（1）Catalyst precarsor containing amorphous silica-alumina I and active metal component is loaded into the upper bed layer of fixed bed reactors, the catalyst precarsor containing amorphous silica-alumina II and active metal component will be loaded into the lower bed layer of fixed bed reactors；（2）The aqueous solution containing organic amine and halogenated hydrocarbons is passed through, and catalyst precarsor haptoreaction, then be passed through oxygen-containing gas and handled；（3）Aqueous ammonium nitrate solution and catalyst precarsor haptoreaction are passed through, nitrogen is passed through or inert gas is handled；（4）The gas activation processing of hydrogen is passed through, upper bed layer obtains the catalyst that surface is the molecular sieves of ZSM 35, and lower bed layer obtains the catalyst that surface is the molecular sieves of ZSM 23.This method is evenly distributed in the molecular sieve that catalyst surface is formed, and improves the utilization rate of molecular sieve, improves reaction selectivity and activity, while considerably reducing cost, is conducive to environmental protection.
Description
Technical field
The present invention relates to the preprocess method that a kind of paraffin hydrocarbon selects type isomerization catalyst, concretely relate to one kind and contain
The preprocess method of wax stock oil isomerization dewaxing catalyst, is particularly suitable for the hydroisomerization dewaxing process of lubricating oil.
Background technology
Dewaxing reaction is by handling the method that petroleum distillate removes specific hydrocarbon, the hydrocarbon particularly straight chain and slight branch
The alkane for changing chain easily solidifies（Wax）, dewaxing can be realized by solvent extraction and crystallization.In recent years, converted on selective catalysis
And the comparison for removing the technique study of wax is more, in the case where producing lube base oil, catalytic dewaxing is generally adjoint to be not intended to
Viscosity index (VI)（VI）Reduction.Catalytic dewaxing is generally worked by two kinds of mechanism, isomerization and cracking, and VI loss
It is generally related to cracking mechanism.Therefore, the dewaxing catalyst system of exploitation high isomerization selectivity but low Cracking Selectivity is more next
More paid close attention to by people.
Report at present on isomerization dewaxing catalyst is a lot, such as US5990371, US5833837, US5817907,
US5149421, US5135638, US5110445, US4919788, US4419420, US4601993 and US4518485 etc. are
Be related to Isodewaxing Technology, wherein the acidic components used mainly have modenite, SAPO-11, SAPO-31, SAPO-41,
ZSM-23, SSZ-32, TON type molecular sieve etc..US4222855 discloses boiling point in about 450 to 1050 ℉（232 to 566 DEG C）Model
Interior waxy hydrocarbon fraction is enclosed, with being connect comprising aluminosilicate zeolites and the catalyst of hydrogenation metal selected from ZSM-23 and ZSM-35
Touch, preparing has high VI, the lubricating oil of low pour point, the VI values for the dewaxed oil that this method is obtained are much larger than to be obtained with ZSM-5 catalyst
The dewaxed oil obtained.US5075269 is disclosed using acid zeolite ZSM-48, is made especially with organic linear diquaternary amine compound
The ZSM-48 synthesized for structure directing agent as catalyst, can catalytic dewaxing wax hydrocarbon ils to prepare high-viscosity index lubricating oil
Raw material.It is reported that the dewaxed oil is also with higher than the VI of the dewaxed oil by being obtained with ZSM-5.U.S. Patent application 2007/
0029229 discloses a kind of process for dewaxing, and this method includes making hydrocarbon feed under dewaxing conditions and includes the combination of following material
Catalyst contact：Zeolite with MTT framework structure types, such as ZSM-23 and the zeolite with GON framework structure types,
A kind of 12 Yuans ring/8 Yuan ring zeolites with one-dimensional passage, such as GUS-1.It is reported that big with major part boiling point when be used to making
In 1000 ℉（538℃）Hydrocarbon oil crude material dewaxing when, specific combination of zeolites significantly increases heavy wax（Long-chain normal alkane）'s
Conversion ratio, thus reduces the cloud point of product.U.S. Patent application 2007/0029230 discloses a kind of process for dewaxing, this method bag
Including under dewaxing conditions contacts hydrocarbon feed and the catalyst of the combination comprising following material：With MTT framework structure types
Zeolite, such as ZSM-23, and the zeolite with MTW framework structure types, such as ZSM-12, the crystallization of the MTT and MTW zeolites
Granularity is less than 0.1 micron.When for making hydrocarbonaceous charging dewax, it was reported that compared with the viscosity index (VI) of waxy feed, institute
State the viscosity index (VI) that MTT/MTW combination of zeolites improves dewaxed product.
The purpose of isomerization dewaxing is exactly high melting-point wax is converted into the relatively low isoparaffin of fusing point, but isomerisation degree is high
Alkane viscosity index (VI) decline it is also a lot, so must just control the isomerisation degree of wax molecule, this is just urged isomerization dewaxing
The Acidity and pore structure and hydrogenation component of agent acidic components propose strict requirements.Acidic components will have in general
Moderate strength, more and with space restriction effect the pore structure of acid amount, and active metal component has quickly hydrogenation/de-
Hydrogen activity, prevents further isomery or even the cracking of tertiary carbonium ion.Although these above-mentioned materials have the acidity of moderate strength
Center and the pore structure matched with wax molecule, have obvious space to limit to highly-branched chain isomerous body, can be to a certain degree
On make paraffin hydrocarbon occur isomerization reaction, but be due in catalyst preparation process, can make most acid centre be coated to
Lid, obtained acidity of catalyst is weaker, and activity and selectivity is relatively low.And for lube cut, due to wherein containing very multiple
Miscellaneous component, is not that identical molecule participates in reaction, so just occurring that some are adapted to for the molecular sieve with homogeneous structural
The problem of property, the catalysis material of good match is capable of to a kind of molecule, may be less desirable for other component.Cause
This, this is desirable to a catalyst while having shape-selective cracking and isomerization multi-functional, and if using single molecular sieve
Good effect is not reached.
ZSM-35 molecular sieve is a kind of mesopore zeolite with FER type skeletons, due to the two-dimensional channel with square crossing
System, with more preferable cracking activity and lower level of deactivation；And ZSM-23 molecular screen has the general framework of opening up of MTT structures,
Because the one-dimensional channels that its ten-ring is constituted are the mutually parallel channels that are not crosslinked, free a diameter of 0.56 × 0.45nm, exactly by
In its unique pore passage structure, the molecular sieve analog shows very high catalytic activity and choosing in alkene and alkane isomerization reaction
Selecting property, with the incomparable superiority of other catalyst, there is good application prospect.
Synthetic method on ZSM-23 and ZSM-35 molecular sieve has had many reports, is typically all in alkaline environment
Under, organic amine is structure directing agent, at a certain temperature crystallization certain time.Substantial amounts of contain can be produced in this building-up process
There are the industrial wastewaters such as organic amine and alkali, it is difficult to carry out harmless treatment, not only greatly improve molecular sieve production cost, Er Qiezao
Into serious environmental pollution, use it and greatly limited.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides the preprocess method that a kind of paraffin hydrocarbon selects type isomerization catalyst,
The SiO that this method passes through upper and lower two bed catalyst precursors2And Al2O3Mol ratio is different, is formed in catalyst precursor surface
Two distinct types of molecular sieve.Both molecular sieves have different pore passage structure and acidic character, and embody good
Cooperative effect.This method is evenly distributed in the molecular sieve that catalyst surface is formed, and improves the utilization rate of molecular sieve, is conducive to production
The diffusion of thing, improve reaction selectivity and activity, while considerably reducing Catalyst Production cost, it is to avoid conventional synthesis point
The generation of the intractable waste water of the sieved journey of son, is conducive to environmental protection.
The paraffin hydrocarbon of the present invention selects the preprocess method of type isomerization catalyst, including following content：
（1）Catalyst precarsor containing amorphous silica-alumina I and active metal component is loaded into the upper bed layer of fixed bed reactors,
Catalyst precarsor containing amorphous silica-alumina II and active metal component will be loaded into the lower bed layer of fixed bed reactors；Without fixed
Type sial I SiO2And Al2O3Mol ratio is 5 ~ 25, amorphous silicon aluminium II SiO2And Al2O3Mol ratio is 26 ~ 200；
（2）The aqueous solution containing organic amine and halogenated hydrocarbons is passed through, the catalyst precarsor haptoreaction with upper and lower two beds, then
Oxygen-containing gas is passed through to be handled；
（3）It is passed through aqueous ammonium nitrate solution and step（2）Catalyst precarsor haptoreaction after processing, then passes to nitrogen or inertia
Gas is handled；
（4）The gas activation processing of hydrogen is passed through, upper bed layer obtains the catalyst that surface is ZSM-35 molecular sieve, and lower bed layer is obtained
To the catalyst that surface is ZSM-23 molecular screen.
In the inventive method, step（1）Described amorphous silicon aluminium I SiO2And Al2O3Mol ratio be 5 ~ 20, without fixed
Type sial II SiO2And Al2O3Mol ratio be 30 ~ 150；Described active metal component is platinum or/and palladium, preferably platinum,
On the basis of the final catalyst weight of corresponding bed, active component content is calculated as 0.1% ~ 10% with metal, preferably 0.1% ~
2%, more preferably 0.2% ~ 1.0%.
In the inventive method, step（1）The preparation method of described catalyst precarsor can be prepared according to prior art, typically
Process is as follows：Aluminum hydroxide solid elastomer powder, white carbon, sesbania powder are sufficiently mixed, peptizing agent is then added（Sodium hydroxide solution）,
Kneading is plastic paste, extruded moulding, through drying, calcination process, then supported active metals component, drying and
Calcination process, obtains catalyst precarsor.Specific preparation condition can be determined according to this area Conventional wisdom.
In the inventive method, step（2）The organic amine compound be one kind in pyrrolidines, isopropylamine and isobutyl amine or
It is several, preferably pyrrolidines and isopropylamine；Described halogenated hydrocarbons is that the halogenated hydrocarbons of 1 ~ 3 carbon atom is one or more of, preferably
CH3I、CH3CHCl2Or CHCl3In one or more, the concentration of halogenated hydrocarbons in aqueous be 0.01 ~ 2 mol/L, be preferably
0.1~1mol/L。
In the inventive method, step（2）Described organic amine and the mol ratio of halogenated hydrocarbons are 0.5 ~ 5, preferably 1 ~ 3.
In the inventive method, step（2）The inlet amount and caltalyst of the described aqueous solution containing organic amine and halogenated hydrocarbons
Product is than being 0.1 ~ 10, preferably 0.5 ~ 5；Haptoreaction condition is：Reaction pressure be 0.2 ~ 10MPa, preferably 0.5 ~ 5MPa, instead
It is 150 ~ 220 DEG C to answer temperature, and preferably 170 ~ 200 DEG C, the reaction time is 12 ~ 100 hours, preferably 24 ~ 72 hours.
In the inventive method, step（2）Described is passed through 400 ~ 600 DEG C of the temperature that oxygen-containing gas is handled, during processing
Between be 4 ~ 12 hours, gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）100~1000；It is wherein described
Oxygen-containing gas for air, the mixture or oxygen of oxygen and nitrogen and inert gas mixture in one kind, oxygen is in gas
Volume fraction in phase is 5% ~ 50%.
In the inventive method, step（3）The inlet amount of the aqueous solution containing ammonium nitrate and the volume ratio of catalyst are 0.1
~10:1, preferably 1 ~ 5:1, the wherein mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%；Haptoreaction condition is：Instead
It is 0.2 ~ 10MPa, preferably 0.5 ~ 5MPa to answer pressure；Reaction temperature is the boiling temperature less than water at this pressure, is preferably
20~100℃；Time is 1 ~ 24 hour, preferably 2 ~ 12 hours.
In the inventive method, step（3）Described is passed through the temperature 100 DEG C ~ 300 that nitrogen or inert gas are handled
DEG C, processing time is 4 ~ 12 hours, gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）100~1000.
In the inventive method, step（4）The hydrogen gas can be pure hydrogen or the hydrogen containing inert gas, its
Hydrogen volume degree in middle hydrogen-containing gas is 5% ~ 100%, preferably 50% ~ 100%；Activation process condition is：Pressure
For 0.2 ~ 10MPa, preferably 0.5 ~ 5MPa, temperature is 200 ~ 600 DEG C, and preferably 250 ~ 500 DEG C, the time is 0.5 ~ 24 hour,
Preferably 1 ~ 12 hour, more preferably 2 ~ 8 hours.
In step in the inventive method（4）Afterwards, reaction mass is passed directly into reactor, it is different that progress paraffin hydrocarbon selects type
Structureization is reacted.
The catalyst that the inventive method is obtained selects type isomerization reaction applied to paraffin hydrocarbon, and general process conditions are as follows：
0.5 ~ 4.0h of volume space velocity-1, reaction temperature is 200 ~ 400 DEG C, and reaction pressure is 2 ~ 20MPa, and hydrogen hydrocarbon mol ratio is 2 ~ 10；Wherein
It is the technical process that long straight-chain alkane is converted into branched paraffin that described paraffin hydrocarbon, which selects type isomerization reaction,.Wherein paraffin
Feedstock oil used in the reaction of hydrocarbon selective isomerization is waxy feeds oil, generally comprises diesel oil, AGO, VGO, white oil, hydrogenation and splits
Change tail oil and lube cut etc., the higher feedstock oil of the wax content that is particularly suitable for use in, wax content is generally more than 50%, preferably
Wax content is between 50% ~ 80%.
The inventive method is by preparing catalyst precarsor（Mainly amorphous silicon aluminium surface）, catalyst precarsor and organic amine
Compound water solution and the contact of halogen compounds mixture, under certain temperature and pressure, pass through two beds above and below control
SiO2And Al2O3Mol ratio, reactor overlying catalyst precursor surface formed with intersect duct ZSM-35 molecules
Sieve, forms on the surface of reactor lower catalyst agent precursor and is suitable to selective isomerization reaction ZSM-23 molecular screen.Due to both
The pore passage structure of molecular sieve and acid difference, and embody good cooperative effect.During the course of the reaction, high wax stock is first
Contacted with upper strata ZSM-35 molecular sieve catalyst, first will the long direct-connected alkane generating unit point cracking reaction in part, then with reactor
The ZSM-23 molecular screen catalyst contact of layer shape selectivity, carries out isomerization reaction.For lube oil hydrotreating process, particularly
When handling high wax stock, with incomparable superiority.Not only have lube base oil high income, viscosity index (VI) high and
The characteristics of pour point is low.And this method can also improve the utilization rate of molecular sieve, catalyst can be considerably reduced into production cost, kept away
Exempt from the generation of the intractable waste water of conventional synthesis molecular sieve process, be conducive to environmental protection.
Embodiment
The technology of the present invention is described further below by embodiment, but should not be construed as being limited to this scope.
Embodiment 1
（1）By 600 grams of white carbons, 94 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）With 20 grams of sesbanias
Powder is sufficiently mixed, the sodium hydroxide solution that then addition 380ml concentration is 0.1M, abundant kneading, and making paste can
Thing is moulded, forming diameter is 1.5mm cylindrical bars on banded extruder, and the cylindrical bars are dried 16 hours at 100 DEG C, then in air
550 DEG C of roastings obtain catalyst carrier in 4 hours in atmosphere, with containing H2PtCl6Solution saturation impregnates said catalyst carrier, so
100 DEG C of dryings 8 hours again afterwards, 500 DEG C are calcined 3 hours in air atmosphere, and the catalyst containing 0.5wt%Pt is made.It is catalyzed
Agent precursor A.SiO in the catalyst2And Al2O3Mol ratio be 14.100ml catalyst is taken, is filled after being diluted with 100ml quartz sands
Insert the upper bed layer of pilot-plant reactor.
By 600 grams of white carbons, 30 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）With 20 grams of fields
Cyanines powder is sufficiently mixed, and then adds the sodium hydroxide solution that 380ml concentration is 0.1M, and abundant kneading makes paste
Plastic, forming diameter is 1.5mm cylindrical bars on banded extruder, and the cylindrical bars are dried 16 hours at 100 DEG C, then in sky
550 DEG C of roastings obtain catalyst carrier in 4 hours in gas atmosphere, with containing H2PtCl6Solution saturation impregnates said catalyst carrier,
Then 100 DEG C of dryings 8 hours again, 500 DEG C are calcined 3 hours in air atmosphere, and the catalyst containing 0.5wt%Pt is made.Urged
Agent precursor A.SiO in the catalyst2And Al2O3Mol ratio be 45.100ml catalyst is taken, after being diluted with 100ml quartz sands
The lower bed layer of pilot-plant reactor is packed into, the evaluation of catalyst is carried out.
（2）It is 2MPa, 180 DEG C of temperature, CH in treatment fluid in pressure3CHCl2Concentration is 0.2 Mol/L, pyrrolidines and NaF
Mol ratio is 2, feed volume air speed（The volume and the ratio of catalyst fed per hour）2.0h-1, 36 hours processing times.So
After stop into treatment fluid, with gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）800 speed is passed through
Air, improves temperature to 550 DEG C, the retention time is to start Temperature fall after 6 hours.
（3）When temperature is reduced to 60 DEG C, starts to be passed through the aqueous solution containing ammonium nitrate into beds under normal pressure, enter
Material volume space velocity is 2.0h-1, stop water inlet after being kept for 4 hours, with gas agent volume ratio（Into the volume and the dress of catalyst of gas
Fill out volume ratio）500 speed is passed through nitrogen, improves temperature to 200 DEG C, the retention time is to stop within 4 hours being passed through nitrogen.
（4）Under conditions of pressure 1MPa, 200 DEG C of temperature, with gas agent volume ratio（Into the volume and catalyst of gas
Admission space ratio）800 speed is passed through pure hydrogen, improves temperature to 420 DEG C, the retention time is to carry out activation of catalyst in 4 hours.
（5）Under conditions of pressure 5MPa, 380 DEG C of temperature, hydrogen hydrocarbon mol ratio is 4, using volume space velocity as 6.0h-1Into
Feedstock oil in table 1, carries out evaluating catalyst, negates and answer the product of 4 hours to be analyzed, evaluation result is shown in Table 2.
Embodiment 2
Be the same as Example 1, difference is step（1）In be loaded into fixed bed reactors upper and lower two beds catalyst
SiO in precursor2And Al2O3Mol ratio be respectively 8 and 50, CH in treatment fluid3I replaces CH3CHCl2, pyrrolidines and CH3I's
Mol ratio is 3.Evaluation result is shown in Table 2.
Embodiment 3
Be the same as Example 1, difference is step（1）In be loaded into fixed bed reactors upper and lower two beds catalyst
SiO in precursor2And Al2O3Mol ratio be respectively 5 and 30, step（2）CH in treatment fluid3CHCl2Concentration is 0.6, isopropylamine
Substituted pyrrolidin, volume space velocity is 4.0 h-1, 28 hours processing times, air-treatment temperature is 580 DEG C, and the time is 4 hours.Comment
Valency the results are shown in Table 2.
Embodiment 4
Be the same as Example 1, difference is step（1）In be loaded into fixed bed reactors upper and lower two beds catalyst
SiO in precursor2And Al2O3Mol ratio be respectively 15 and 90, step（3）In the aqueous solution containing ammonium nitrate feed volume it is empty
Speed is 1.0 h-1, flooding time 8 hours, temperature is 25 DEG C, and nitrogen gas agent volume ratio is 300,300 DEG C of temperature, and the time is 6 small
When.Evaluation result is shown in Table 2.
Embodiment 5
Be the same as Example 1, difference is step（1）In be loaded into fixed bed reactors upper and lower two beds catalyst
SiO in precursor2And Al2O3Mol ratio be respectively 20 and 60, step（4）Pressure be 0.5MPa, reduction temperature be 240 DEG C,
Gas is the mixture of hydrogen and nitrogen（Wherein hydrogen volume degree is 60%）, gas agent volume ratio is 600, during reduction
Between be 2 hours.Evaluation result is shown in Table 2.
Comparative example 1
By 600 grams of white carbons, 30 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）With 20 grams of sesbania powders
It is sufficiently mixed, then adds the sodium hydroxide solution that 380ml concentration is 0.1M, abundant kneading makes paste plastic
Thing, forming diameter is 1.5mm cylindrical bars on banded extruder, and the cylindrical bars are dried 16 hours at 100 DEG C, then in air gas
550 DEG C of roastings obtain catalyst carrier in 4 hours in atmosphere.With containing H2PtCl6Solution saturation impregnates said catalyst carrier, then
100 DEG C of dryings 8 hours again, 500 DEG C are calcined 3 hours in air atmosphere, and the catalyst containing 0.5wt%Pt is made.In the catalyst
SiO2And Al2O3Mol ratio be 45.Appreciation condition be the same as Example 1, evaluation result is shown in Table 2.
Comparative example 2
（1）Prepare E-2a catalyst
By 100 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）, 20 grams of ZSM-35 molecular sieve and 6 grams of fields
Cyanines powder is sufficiently mixed, and then adds the salpeter solution that 70ml concentration is 0.2M, and abundant kneading makes paste plastic
Thing, extrudes a diameter of 1.5mm cylindrical bars, cylindrical bars are dried 16 hours at 100 DEG C, then in air atmosphere on banded extruder
In 550 DEG C of roastings obtain catalyst carrier within 4 hours.With containing H2PtCl6Solution saturation impregnates said catalyst carrier, Ran Houzai
100 DEG C of dryings 8 hours, 500 DEG C of roasting 3h, are made the catalyst containing 0.5wt%Pt, sample number into spectrum E-2a in air atmosphere.
（2）Prepare E-2b catalyst
By 100 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）, 40 grams of ZSM-23 molecular screen and 6 grams of fields
Cyanines powder is sufficiently mixed, and then adds the salpeter solution that 70ml concentration is 0.2M, and abundant kneading makes paste plastic
Thing, extrudes a diameter of 1.5mm cylindrical bars, cylindrical bars are dried 16 hours at 100 DEG C, then in air atmosphere on banded extruder
In 550 DEG C of roastings obtain catalyst carrier within 4 hours.With containing H2PtCl6Solution saturation impregnates said catalyst carrier, Ran Houzai
100 DEG C of dryings 8 hours, 500 DEG C of roasting 3h, are made the catalyst containing 0.5wt%Pt, sample number into spectrum E-2b in air atmosphere.
（3）E-2a and E-2b catalyst 100ml are taken respectively, and fixed bed reaction is loaded respectively after being diluted with 100ml quartz sands
Device（Two beds up and down）Middle carry out catalytically active assessment.Appreciation condition be the same as Example 1, evaluation result is shown in Table 2.
Comparative example 3
（1）By 600 grams of white carbons, 94 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）With 20 grams of sesbanias
Powder is sufficiently mixed, the sodium hydroxide solution that then addition 380ml concentration is 0.1M, abundant kneading, and making paste can
Thing is moulded, forming diameter is 1.5mm cylindrical bars on banded extruder, and the cylindrical bars are dried 16 hours at 100 DEG C, then in air
550 DEG C of roastings obtain catalyst carrier in 4 hours in atmosphere, with containing H2PtCl6Solution saturation impregnates said catalyst carrier, so
100 DEG C of dryings 8 hours again afterwards, 500 DEG C are calcined 3 hours in air atmosphere, and the catalyst containing 0.5wt%Pt is made.It is catalyzed
Agent precursor A.SiO in the catalyst2And Al2O3Mol ratio be 14.100ml catalyst is taken, is filled after being diluted with 100ml quartz sands
Insert in pilot-plant reactor, carry out the evaluation of catalyst.
（2）It is 2MPa, 180 DEG C of temperature, CH in treatment fluid in pressure3CHCl2Concentration is 0.2 Mol/L, pyrrolidines and NaF
Mol ratio is 2, feed volume air speed（The volume and the ratio of catalyst fed per hour）2.0h-1, 36 hours processing times.So
After stop into treatment fluid, with gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）800 speed is passed through
Air, improves temperature to 550 DEG C, the retention time is to start Temperature fall after 6 hours.
（3）When temperature is reduced to 60 DEG C, starts to be passed through the aqueous solution containing ammonium nitrate into beds under normal pressure, enter
Material volume space velocity is 2.0h-1, stop water inlet after being kept for 4 hours, with gas agent volume ratio（Into the volume and the dress of catalyst of gas
Fill out volume ratio）500 speed is passed through nitrogen, improves temperature to 200 DEG C, the retention time is to stop within 4 hours being passed through nitrogen.
（4）Under conditions of pressure 1MPa, 200 DEG C of temperature, with gas agent volume ratio（Into the volume and catalyst of gas
Admission space ratio）800 speed is passed through pure hydrogen, improves temperature to 420 DEG C, the retention time is to carry out activation of catalyst in 4 hours.
（5）Under conditions of pressure 5MPa, 380 DEG C of temperature, hydrogen hydrocarbon mol ratio is 4, using volume space velocity as 6.0h-1Into
Feedstock oil in table 1, carries out evaluating catalyst, negates and answer the product of 4 hours to be analyzed, evaluation result is shown in Table 2.
Comparative example 4
（1）By 600 grams of white carbons, 30 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）With 20 grams of sesbanias
Powder is sufficiently mixed, the sodium hydroxide solution that then addition 380ml concentration is 0.1M, abundant kneading, and making paste can
Thing is moulded, forming diameter is 1.5mm cylindrical bars on banded extruder, and the cylindrical bars are dried 16 hours at 100 DEG C, then in air
550 DEG C of roastings obtain catalyst carrier in 4 hours in atmosphere, with containing H2PtCl6Solution saturation impregnates said catalyst carrier, so
100 DEG C of dryings 8 hours again afterwards, 500 DEG C are calcined 3 hours in air atmosphere, and the catalyst containing 0.5wt%Pt is made.It is catalyzed
Agent precursor A.SiO in the catalyst2And Al2O3Mol ratio be 45.100ml catalyst is taken, is filled after being diluted with 100ml quartz sands
Insert in pilot-plant reactor, carry out the evaluation of catalyst.
（2）It is 2MPa, 180 DEG C of temperature, CH in treatment fluid in pressure3CHCl2Concentration is 0.2 Mol/L, pyrrolidines and NaF
Mol ratio is 2, feed volume air speed（The volume and the ratio of catalyst fed per hour）2.0h-1, 36 hours processing times.So
After stop into treatment fluid, with gas agent volume ratio（Into the volume and the admission space ratio of catalyst of gas）800 speed is passed through
Air, improves temperature to 550 DEG C, the retention time is to start Temperature fall after 6 hours.
（3）When temperature is reduced to 60 DEG C, starts to be passed through the aqueous solution containing ammonium nitrate into beds under normal pressure, enter
Material volume space velocity is 2.0h-1, stop water inlet after being kept for 4 hours, with gas agent volume ratio（Into the volume and the dress of catalyst of gas
Fill out volume ratio）500 speed is passed through nitrogen, improves temperature to 200 DEG C, the retention time is to stop within 4 hours being passed through nitrogen.
（4）Under conditions of pressure 1MPa, 200 DEG C of temperature, with gas agent volume ratio（Into the volume and catalyst of gas
Admission space ratio）800 speed is passed through pure hydrogen, improves temperature to 420 DEG C, the retention time is to carry out activation of catalyst in 4 hours.
（5）Under conditions of pressure 5MPa, 380 DEG C of temperature, hydrogen hydrocarbon mol ratio is 4, using volume space velocity as 6.0h-1Into
Feedstock oil in table 1, carries out evaluating catalyst, negates and answer the product of 4 hours to be analyzed, evaluation result is shown in Table 2.
The feedstock oil main character of table 1.
The evaluation result of table 2.
The evaluation result of table 2 is shown, compared with comparative catalyst, the catalyst provided using the present invention, for lubricating oil
In the hydroprocessing processes of cut, when lube base oil pour point is close, C5 +Liquid is received and lube base oil yield is all improved
5wt% or so, the viscosity index (VI) of product is improved more than 10 units, illustrates catalyst of the present invention in processing crude lube stock process
In, effect, which has, to be significantly improved.
Claims (12)
1. a kind of paraffin hydrocarbon selects the preprocess method of type isomerization catalyst, it is characterised in that including following content：（1）It will contain
The catalyst precarsor of amorphous silica-alumina I and active metal component is loaded into the upper bed layer of fixed bed reactors, will contain to whether there is and determine
The catalyst precarsor of shape sial II and active metal component is loaded into the lower bed layer of fixed bed reactors；Amorphous silicon aluminium I's
SiO2And Al2O3Mol ratio is 5 ~ 25, amorphous silicon aluminium II SiO2And Al2O3Mol ratio is 26 ~ 200；（2）It is passed through containing organic
The aqueous solution of amine and halogenated hydrocarbons, the catalyst precarsor haptoreaction with upper and lower two beds, then be passed through at oxygen-containing gas
Reason；（3）It is passed through aqueous ammonium nitrate solution and step（2）Catalyst precarsor haptoreaction after processing, then passes to nitrogen or inertia
Gas is handled；（4）The gas activation processing of hydrogen is passed through, upper bed layer obtains the catalysis that surface is ZSM-35 molecular sieve
Agent, lower bed layer obtains the catalyst that surface is ZSM-23 molecular screen.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described amorphous silicon aluminium I SiO2And Al2O3
Mol ratio be 5 ~ 20, amorphous silicon aluminium II SiO2And Al2O3Mol ratio be 30 ~ 150；Described active metal component is
Platinum or/and palladium, on the basis of the final catalyst weight of corresponding bed, active component content is calculated as 0.1% ~ 10% with metal.
3. in accordance with the method for claim 1, it is characterised in that：Step（2）The organic amine compound is pyrrolidines, isopropyl
One or more in amine and isobutyl amine.
4. in accordance with the method for claim 1, it is characterised in that：Step（2）Described halogenated hydrocarbons is the halogen of 1 ~ 3 carbon atom
One or more of for hydrocarbon, the concentration of halogenated hydrocarbons in aqueous is 0.01 ~ 2 mol/L.
5. in accordance with the method for claim 1, it is characterised in that：Step（2）Described organic amine and the mol ratio of halogenated hydrocarbons
For 0.5 ~ 5.
6. in accordance with the method for claim 1, it is characterised in that：Step（2）It is described water-soluble containing organic amine and halogenated hydrocarbons
The inlet amount of liquid is 0.1 ~ 10 with catalyst volume ratio；Haptoreaction condition is：Reaction pressure is 0.2 ~ 10MPa, reaction temperature
For 150 ~ 220 DEG C, the reaction time is 12 ~ 100 hours.
7. in accordance with the method for claim 1, it is characterised in that：Step（2）Described is passed through what oxygen-containing gas was handled
400 ~ 600 DEG C of temperature, processing time is 4 ~ 12 hours, gas agent volume ratio 100 ~ 1000.
8. in accordance with the method for claim 1, it is characterised in that：Step（3）The inlet amount of the aqueous solution containing ammonium nitrate
Volume ratio with catalyst is 0.1 ~ 10:1, the wherein mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%；Haptoreaction
Condition is：Reaction pressure is 0.2 ~ 10MPa, and reaction temperature is the boiling temperature less than water at this pressure, and the time is 1 ~ 24 small
When.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described is passed through nitrogen or inert gas progress
100 ~ 300 DEG C of the temperature of processing, processing time is 4 ~ 12 hours, gas agent volume ratio 100 ~ 1000.
10. in accordance with the method for claim 1, it is characterised in that：Step（4）The activation process condition is：Pressure is 0.2
~ 10MPa, temperature is 200 ~ 600 DEG C, and the time is 0.5 ~ 24 hour.
11. in accordance with the method for claim 1, it is characterised in that：In step（4）Afterwards, it is passed directly into reactor anti-
Material is answered, paraffin hydrocarbon is carried out and selects type isomerization reaction.
12. in accordance with the method for claim 11, it is characterised in that：Process conditions are as follows：0.5 ~ 4.0h of volume space velocity-1, instead
It is 200 ~ 400 DEG C to answer temperature, and reaction pressure is 2 ~ 20MPa, and hydrogen hydrocarbon mol ratio is 2 ~ 10.
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| CN112126462A (en) * | 2020-07-20 | 2020-12-25 | 中国科学院大连化学物理研究所 | Lubricating oil base oil prepared from Fischer-Tropsch synthetic wax as raw material and preparation method thereof |
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