CN108126738B - A kind of preparation of Fischer Tropsch waxes hydroisomerisation catalysts and catalyst and application - Google Patents
A kind of preparation of Fischer Tropsch waxes hydroisomerisation catalysts and catalyst and application Download PDFInfo
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- CN108126738B CN108126738B CN201611087754.0A CN201611087754A CN108126738B CN 108126738 B CN108126738 B CN 108126738B CN 201611087754 A CN201611087754 A CN 201611087754A CN 108126738 B CN108126738 B CN 108126738B
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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
- B01J29/70—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
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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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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- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1062—Lubricating oils
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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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The present invention relates to a kind of method for preparing catalyst for Fischer Tropsch waxes hydroisomerization.Specific preparation process is as follows for it: the ZSM-22 molecular sieve after roasting is mixed with the presoma of amorphous oxide first, extrusion, molding and roasting support precursor is made；Liquid hydrocarbon is adsorbed with support precursor, heating treatment is then carried out in an inert atmosphere and obtains carrier of the molecular sieve pore passage by Partial Blocking；In supported on carriers metal active constituent, final catalyst is obtained after dry reduction.Compared with the catalyst made from the prior art, the catalyst using the method for the present invention preparation has better catalytic activity and target product selectivity in Fischer Tropsch waxes hygrogenating isomerization reaction.
Description
Technical field
The invention belongs to molecular sieve catalyst fields, and in particular to a kind of Fischer Tropsch waxes based on ZSM-22 molecular sieve add
Hydrogen isomerization catalyst and preparation method thereof.
Background technique
F- T synthesis (Fischer-Tropsch synthesis) is referred to as FT reaction, is with synthesis gas (CO and H2) be
Raw material synthesizes the technique mistake of the liquid fuel based on paraffin hydrocarbon under the conditions of catalyst (such as iron series, cobalt system) and appropriate reaction
Journey.Traditional F- T synthesis feature is that fraction distribution is wide, and heavy paraffin hydrocarbon content is high, and is straight-chain hydrocarbons.Such heavy paraffin hydrocarbon is solidifying
Solid point is high, is not as suitable as diesel oil or lubricating oil directly uses, therefore, it is necessary to its pour point depression.N-alkane pour point depression is most
Main means are hysomer and cracking, and long-chain normal paraffin is made to be converted into the low isomery of freezing point on bifunctional catalyst
Alkane or small molecule alkane.
Difunctional solid catalyst is made of hydrogenation-dehydrogenation component and acid carrier two parts.Hydrogenation-dehydrogenation component can be with
It is divided into two classes, comprising: 1, monometallic or more metal composite systems, such as Pt, Pd, Rh, Ir and Ni；2, transient metal sulfide body
System, such as Ni-Co, Ni-W, Ni-Mo sulfides.Acid carrier can then be divided into following three classes: 1, unformed single metal oxides or
Composite oxides, the Al such as handled through halide2O3、SiO2/Al2O3, super acids ZrO2/SO4 2-、WO3/ZrO2Deng；2, sial point
Son sieve series, such as Y, Beta, ZSM-5, ZSM-22；3, aluminium phosphate molecular sieve series, such as SAPO-5, SAPO-11, SAPO-31
And SAPO-41 etc..Compared with unformed oxide and super acids, molecular sieve is being selected type selectivity, stability, antitoxinization and is being resisted
Excellent performance is all shown in terms of carbon distribution ability.Therefore, it is answered extensively based on the isomerization catalyst that molecular sieve is carrier
With.The patent documents such as US5882505,2004138051,2005077209, CN1792451,1788844,101245260 are all detailed
Carefully describe using molecular sieve as the preparation method of the alkane isomerization catalyst of carrier.
ZSM-22 molecular sieve is a kind of artificial synthesized high-silica zeolite, belongs to TON topological structure, has one-dimensional ten-ring
Cellular structure, port size areDifferent template synthesis can be used in it.As US4556477 discloses one kind
The method for synthesizing ZSM-22 molecular sieve as template using diethylamine hydrochloride.US4902406, US5707600, US5783168 etc.
Disclose the method that ZSM-22 molecular sieve is synthesized as template using 1,6- hexamethylene diamine.
During ZSM-22 acts on long chain alkane isomerization, the performance of catalyst is one-dimensional by the ten-ring of ZSM-22
Straight hole road and its acidity codetermine.Carbonium ion in the reaction of linear paraffin hydroisomerizing generates and isomerization process exists
It is carried out on acidic site, isomerization activity is poor on too weak acidic site, and it is higher that too strong acidic site then easily leads to Cracking Selectivity；Directly
Mainly in microporous molecular sieve aperture, microporous molecular sieve duct is too deep for the progress of paraffin hydroisomerization, linear paraffin completely or
The probability of most of insertion micropore canals increases, and desorption is obstructed, and increases the probability of insertion end cracking, to easily generate small point
Sub- hydro carbons reduces target product selectivity and yield.
Ideal Fischer Tropsch waxes hydroisomerisation catalysts need to have suitable acidity and micropore distribution.Pass through certain hand
Duan Shixian there is high activity, high isomerization to select preparation the regulation of ZSM-22 molecular sieve carrier acidity and duct depth
Property/yield Fischer Tropsch waxes hydroisomerisation catalysts are very necessary.
Summary of the invention
The purpose of the present invention is to provide a kind of Fischer Tropsch waxes hydroisomerisation catalysts.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst.
To achieve the above object, catalyst provided by the invention is by one of Pt, Pd, Ir in group VIII noble metals
Or it is formed in two kinds of metals, duct containing the ZSM-22 molecular sieve and amorphous oxide of organic matter or carbon distribution.
The catalyst, wherein the total content of organic matter and carbon distribution is 0.5-5wt% in ZSM-22 molecular sieve pore passage；
The catalyst, wherein the preferred total content of organic matter and carbon distribution is 0.8- in ZSM-22 molecular sieve pore passage
3wt%；
The catalyst, wherein unformed oxide be one of amorphous alumina or amorphous silicon oxide or
Two kinds, total content 10-60wt%；
The catalyst, wherein unformed oxide be one of amorphous alumina or amorphous silicon oxide or
Two kinds, preferred total content is 15-40wt%；
Surplus is the carbon/template not removed in ZSM-22 molecular sieve and molecular sieve；
The catalyst, wherein the Micropore volume of catalyst is not higher than 90% that pure ZSM-22 microporous molecular sieve hole holds；
The catalyst, wherein what preferred catalyst Micropore volume held not higher than pure ZSM-22 microporous molecular sieve hole
80%；
The catalyst, wherein one or both of Pt, Pd, Ir in group VIII noble metals metal always contain
Amount is 0.05-5wt%；
The catalyst, wherein one or both of Pt, Pd, Ir in group VIII noble metals metal it is preferred
Total content is 0.1-2wt%；
Catalyst of the present invention has the feature that
It is mesoporous in right amount containing amorphous oxide bring, can intensified response object and product diffusion；Partial organic substances and
Carbon distribution is filled in ZSM-22 molecular sieve pore passage, adjustable molecular sieve duct depth, reach reduce cracking reaction occurrence probability,
Improve the purpose of isomerisation selectivity and yield.
Method for preparing catalyst of the present invention is realized by step in detail below:
(1) the ZSM-22 molecular sieve containing template is dry, roasting removed template method；
(2) presoma of ZSM-22 molecular sieve and amorphous oxide after removed template method described in step (1) is pressed
It is uniformly mixed according to certain ratio, acid solution is then added and carries out kneading, molding, then carrier forerunner is made after drying and roasting
Body；
(3) support precursor described in step (2) is mixed into 0.1-24h at 0-120 DEG C with liquid hydrocarbon；
(4) mixture described in step (3) is filtered, does the support precursor for adsorbing liquid hydrocarbon at 0-200 DEG C
Then dry 0.1-24h is placed it in inert atmosphere or vacuum and is handled, the organic matter and carbon distribution not being removed containing part is made
Carrier；
(5) it by carrier loaded group VIII noble metals active component described in step (4), is then made through dry and reduction
Obtain the catalyst.
The method, wherein template agent content is 0.5-30wt% in the ZSM-22 molecular sieve in step (1)；
The method, wherein the drying temperature of ZSM-22 molecular sieve is 80-150 DEG C in step (1), time 0.5-
12h；
The method, wherein the maturing temperature of ZSM-22 molecular sieve is 300-700 DEG C in step (1), time 2-
40h；
The method, wherein the amorphous oxide presoma in step (2) is the hydrate and/or oxygen of aluminium oxide
The hydrate of SiClx；
The method, wherein the inorganic acid solution in step (2) is aqueous solution of nitric acid or acetic acid aqueous solution, and concentration is
0.1-1.0mol/L；
The method, wherein make ZSM-22 molecular sieve and amorphous using banded extruder, tablet press machine etc. in step (2)
The mixture of compound presoma forms；
The method, wherein ZSM-22 molecular sieve after molding is mixed with amorphous oxide presoma in step (2)
Object naturally dry, and at 80-150 DEG C, dry 0.5-12h；
The method, wherein the ZSM-22 molecular sieve after dry in step (2) is mixed with amorphous oxide presoma
For object at 300-700 DEG C, support precursor is made in roasting 2-40h；
The method, wherein support precursor is mixed with liquid hydrocarbon in step (3)；
The method, wherein liquid hydrocarbon is that alkane, aromatic hydrocarbons, olefines being in a liquid state under room temperature etc. is common in step (3)
One or more of hydrocarbon compound；
The method, wherein the mixing temperature of support precursor and liquid hydrocarbon is 0-120 DEG C in step (3), preferably
Temperature range is 30-100 DEG C；Time is 0.1-24h, preferably 0.5-12h；
The method, wherein the support precursor in step (4) after absorption liquid hydrocarbon dries 0.1- at 0-200 DEG C
For 24 hours, the dry 0.5-12h preferably at 80-150 DEG C；
The method, wherein the ingredient of the inert atmosphere in step (4) is N2, Ar, He etc. will not occur with organic matter
The gas of oxidation reaction；
The method, wherein treatment temperature is 100-800 DEG C under an inert atmosphere or in vacuum in step (4), preferably
Temperature range be 200-600 DEG C；The processing time is 0.1-24h, preferably 2-12h；
The method, wherein organic matter and carbon distribution always contain in ZSM-22 molecular sieve pore passage in the carrier in step (4)
Amount is 0.5-5wt%；
The method, wherein in the carrier in step (4) in ZSM-22 molecular sieve pore passage organic matter and carbon distribution it is preferred
Total content is 0.8-3wt%；
The method, wherein the Micropore volume of carrier holds not higher than pure ZSM-22 microporous molecular sieve hole in step (4)
90%；
The method, wherein preferred carrier Micropore volume is not higher than pure ZSM-22 microporous molecular sieve hole in step (4)
80% held；
The method, wherein one or both of Pt, Pd, Ir in step (5) in group VIII noble metals metal
Total content be 0.05-5wt%；
The method, wherein one or both of Pt, Pd, Ir in step (5) in group VIII noble metals metal
Preferred total content be 0.1-2wt%；
The method, wherein carried noble metal active component is primarily referred to as using Pt, Pd, Ir etc. in step (5)
Metal acid, metal acid-salt, chloride, ammino-complex, carbonyl complex or their mixture of group VIII are raw material, are used
Method including dipping, precipitating, deposition, addition adhesive bonding or mechanical press, realization group VIII noble metals and carrier
In conjunction with；
The method, wherein the drying temperature in step (5) is 20-200 DEG C, drying time 0.1-24h；It is preferred that
Drying temperature be 80-150 DEG C, drying time 0.5-12h；
The method, wherein using one of gases such as hydrogen, carbon monoxide, formaldehyde, hydrazine or two in step (5)
Kind or more with catalyst contact reducing catalyst；
The method, wherein the reduction temperature in step (5) is 100-500 DEG C, time 1-40h.
Catalyst provided by the present invention can be widely applied to the isomerization-visbreaking process of Fischer-Tropsch synthetic.
Compared with prior art, the preparation method of Fischer Tropsch waxes hydroisomerisation catalysts provided by the invention has such as
Lower advantage:
1, a kind of new method for preparing Fischer Tropsch waxes hydroisomerisation catalysts is provided；
2, the isomerization catalyst prepared has the selection of higher isomers in Fischer Tropsch waxes hygrogenating isomerization reaction
Property and yield；
3, the isomerization catalyst prepared can effectively improve Determination of Diesel Oil and lubricating oil in Fischer Tropsch waxes conversion process
Base oil content；
4, the isomerization catalyst prepared can significantly improve the freezing point of obtained diesel oil and lube base oil.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, it is to be noted that the content of present invention is simultaneously
It is not limited to this.
Comparative example 1
The ZSM-22 molecular screen primary powder for taking 120g to contain template roasts for 24 hours under 550 DEG C of air atmospheres, obtains 100g mould
The ZSM-22 molecular sieve that plate agent removes completely；It takes 30g boehmite (hydrate of aluminium oxide) to be mixed with uniformly, is added
80g 5wt%HNO3Solution, kneading are formed with banded extruder, naturally dry, the dry 4h at 120 DEG C, roast 12h at 550 DEG C
Carrier is made.With the H of 5mL 0.05g/mL containing Pt2PtCl6Solution impregnates the above-mentioned carrier of 50g, and naturally dry is simultaneously done at 120 DEG C
Dry 4h uses hydrogen reducing 4h at 500 DEG C, and 0.5wt%Pt/ZSM-22 catalyst, number A1 is made.Catalyst organic matter and product
Carbon content and Micropore volume characterization result are shown in Table 1, and catalysis reaction evaluating the results are shown in Table 3.
Embodiment 1
The ZSM-22 molecular screen primary powder for taking 120g to contain template roasts for 24 hours under 550 DEG C of air atmospheres, obtains 100g mould
The ZSM-22 molecular sieve that plate agent removes completely；It takes 30g boehmite (hydrate of aluminium oxide) to be mixed with uniformly, is added
80g 5wt%HNO3Solution, kneading are formed with banded extruder, naturally dry, the dry 4h at 120 DEG C, roast 12h at 550 DEG C
Support precursor is made；It takes 50g support precursor to mix with 50g benzene, 6h is placed at 25 DEG C, the carrier of absorption benzene is obtained after filtering
Presoma is subsequently placed in quartz ampoule, in 120 DEG C of dry 0.5h in N2Under atmosphere, it is cooled to room temperature after 500 DEG C of processing 4h obtained
Carrier.With the H of 5mL 0.05g/mL containing Pt2PtCl6Solution impregnates the above-mentioned carrier of 50g, naturally dry and the dry 4h at 120 DEG C,
Hydrogen reducing 4h is used at 500 DEG C, and 0.5wt%Pt/ZSM-22-T1 catalyst, number T1 is made.Catalyst organic matter and carbon distribution
Content and Micropore volume characterization result are shown in Table 1, and catalysis reaction evaluating the results are shown in Table 3.
Embodiment 2
The ZSM-22 molecular screen primary powder for taking 120g to contain template roasts for 24 hours under 550 DEG C of air atmospheres, obtains 100g mould
The ZSM-22 molecular sieve that plate agent removes completely；It takes 30g boehmite (hydrate of aluminium oxide) to be mixed with uniformly, is added
80g 5wt%HNO3Solution, kneading are formed with banded extruder, naturally dry, the dry 4h at 120 DEG C, roast 12h at 550 DEG C
Support precursor is made；It takes 50g support precursor to mix with 50g phenol, 6h is placed at 60 DEG C, obtains adsorbing phenol after filtering
Support precursor is subsequently placed in quartz ampoule, in 120 DEG C of dry 0.5h in N2Under atmosphere, it is cooled to room temperature after 500 DEG C of processing 4h
Carrier is made.With the H of 5mL 0.05g/mL containing Pt2PtCl6Solution impregnates the above-mentioned carrier of 50g, and naturally dry is simultaneously done at 120 DEG C
Dry 4h uses hydrogen reducing 4h at 500 DEG C, and 0.5wt%Pt/ZSM-22-T2 catalyst, number T2 is made.Catalyst organic matter
And carbon distribution content and Micropore volume characterization result are shown in Table 1, catalysis reaction evaluating the results are shown in Table 3.
Embodiment 3
The ZSM-22 molecular screen primary powder for taking 120g to contain template roasts for 24 hours under 550 DEG C of air atmospheres, obtains 100g mould
The ZSM-22 molecular sieve that plate agent removes completely；It takes 30g boehmite (hydrate of aluminium oxide) to be mixed with uniformly, is added
80g 5wt%HNO3Solution, kneading are formed with banded extruder, naturally dry, the dry 4h at 120 DEG C, roast 12h at 550 DEG C
Support precursor is made；It takes 50g support precursor to mix with 50g normal octane, 6h is placed at 70 DEG C, obtain adsorbing after filtering just pungent
The support precursor of alkane is subsequently placed in quartz ampoule, in 120 DEG C of dry 0.5h in N2Under atmosphere, it is cooled to after 500 DEG C of processing 4h
Carrier is made in room temperature.With the H of 5mL 0.05g/mL containing Pt2PtCl6Solution impregnates the above-mentioned carrier of 50g, naturally dry and at 120 DEG C
Lower dry 4h uses hydrogen reducing 4h at 500 DEG C, and 0.5wt%Pt/ZSM-22-T3 catalyst, number T3 is made.Catalyst has
Machine object and carbon distribution content and Micropore volume characterization result are shown in Table 1, and catalysis reaction evaluating the results are shown in Table 3.
Embodiment 4
The ZSM-22 molecular screen primary powder for taking 120g to contain template roasts for 24 hours under 550 DEG C of air atmospheres, obtains 100g mould
The ZSM-22 molecular sieve that plate agent removes completely；It takes 30g boehmite (hydrate of aluminium oxide) to be mixed with uniformly, is added
80g 5wt%HNO3Solution, kneading are formed with banded extruder, naturally dry, the dry 4h at 120 DEG C, roast 12h at 550 DEG C
Support precursor is made；It takes 50g support precursor to mix with 50g normal heptane, 6h is placed at 35 DEG C, obtain adsorbing positive heptan after filtering
The support precursor of alkane is subsequently placed in quartz ampoule, in 120 DEG C of dry 0.5h in N2Under atmosphere, it is cooled to after 500 DEG C of processing 4h
Carrier is made in room temperature.With the H of 5mL 0.05g/mL containing Pt2PtCl6Solution impregnates the above-mentioned carrier of 50g, naturally dry and at 120 DEG C
Lower dry 4h uses hydrogen reducing 4h at 500 DEG C, and 0.5wt%Pt/ZSM-22-T4 catalyst, number T4 is made.Catalyst has
Machine object and carbon distribution content and Micropore volume characterization result are shown in Table 1, and catalysis reaction evaluating the results are shown in Table 3.
Embodiment 5
The ZSM-22 molecular screen primary powder for taking 120g to contain template roasts for 24 hours under 550 DEG C of air atmospheres, obtains 100g mould
The ZSM-22 molecular sieve that plate agent removes completely；It takes 30g boehmite (hydrate of aluminium oxide) to be mixed with uniformly, is added
80g 5wt%HNO3Solution, kneading are formed with banded extruder, naturally dry, the dry 4h at 120 DEG C, roast 12h at 550 DEG C
Support precursor is made；It takes 50g support precursor to mix with 50g hexamethylene, 6h is placed at 35 DEG C, absorption hexamethylene is obtained after filtering
The support precursor of alkane is subsequently placed in quartz ampoule, in 120 DEG C of dry 0.5h in N2Under atmosphere, it is cooled to after 500 DEG C of processing 4h
Carrier is made in room temperature.With the H of 5mL 0.05g/mL containing Pt2PtCl6Solution impregnates the above-mentioned carrier of 50g, naturally dry and at 120 DEG C
Lower dry 4h uses hydrogen reducing 4h at 500 DEG C, and 0.5wt%Pt/ZSM-22-T5 catalyst, number T5 is made.Catalyst has
Machine object and carbon distribution content and Micropore volume characterization result are shown in Table 1, and catalysis reaction evaluating the results are shown in Table 3.
Catalyst characterization result in 1. comparative example of table and embodiment
2. Fischer Tropsch waxes feedstock property of table
| Project | Fischer Tropsch waxes |
| Density (15 DEG C), kg/m3 | 812 |
| Distillation, DEG C | |
| Initial boiling point | 262 |
| 10% | 348 |
| 30% | 361 |
| 50% | 414 |
| 70% | 453 |
| 90% | 501 |
| 95% | 578 |
| The end point of distillation | 614 |
| Freezing point, DEG C | 75 |
Evaluating catalyst result in 3. comparative example of table and embodiment
Raw material: Fischer Tropsch waxes, property are shown in Table 2；Reaction condition: 20mL fixed bed reactors, 330 DEG C of reaction temperature, instead
Answer pressure 10MPa, air speed 1h-1, hydrogen-oil ratio 600nL/nL.
As shown in Table 1, made from the pure ZSM-22 molecular sieve and commonsense method compared with catalyst, using made from this method
Catalyst contains a certain amount of organic matter and carbon distribution content, and Micropore volume reduces；
As shown in Table 3, made from the commonsense method compared with catalyst, using catalyst made from this method in F- T synthesis
It can get higher isomerisation selectivity and target product diesel oil and base oil yield in wax hygrogenating isomerization reaction.
Claims (9)
1. a kind of preparation method of Fischer Tropsch waxes hydroisomerisation catalysts, the specific steps are as follows:
(1) the ZSM-22 molecular sieve containing template is dry, roasting removed template method；
(2) the ZSM-22 molecular sieve after removed template method described in step (1) is mixed with the presoma of amorphous oxide
It is even, acid solution is then added and carries out kneading, molding, then support precursor is made after drying and roasting；
(3) support precursor obtained in step (2) is mixed into 0.1-24h at 0-120 DEG C with liquid hydrocarbon；
(4) mixture obtained in step (3) is filtered, makes to adsorb support precursor drying at 0-200 DEG C after liquid hydrocarbon
Then 0.1-24h is placed it in inert atmosphere or vacuum and is handled, the load for not being removed organic matter and carbon distribution containing part is made
Body；
(5) by carrier loaded group VIII noble metals active component described in step (4), institute then is made through dry and reduction
State catalyst；
The ingredient of inert atmosphere in the step (4) is N2, Ar, one or more of He will not occur with liquid hydrocarbon
The gas of oxidation reaction；
The temperature that support precursor is handled under an inert atmosphere or in vacuum in the step (4) is 200-600 DEG C, when processing
Between be 2-12h.
2. the method as described in claim 1, which is characterized in that the amorphous oxide in the step (2) is amorphous
Change one or both of aluminium or amorphous silicon oxide, presoma is in the hydrate of aluminium oxide or the hydrate of silica
It is one or two kinds of.
3. the method as described in claim 1, which is characterized in that acid solution in the step (2) be aqueous solution of nitric acid and/or
Acetic acid aqueous solution, concentration 0.1-1.0mol/L.
4. the method as described in claim 1, which is characterized in that the liquid hydrocarbon in the step (3) is to be in a liquid state under room temperature
One or more of C6-C18 alkane, C6-C18 aromatic hydrocarbons, C6-C18 olefines.
5. the method as described in claim 1, which is characterized in that the carried noble metal active component in the step (5)
It is primarily referred to as metal acid, metal acid-salt, the chloride, ammonia complexing using one or more of Pt, Pd, Ir group VIII
The mixture of one or more of object, carbonyl complex is raw material, using including dipping, precipitating, deposition, addition bonding
The method of agent bonding or mechanical press realizes the combination of group VIII noble metals and carrier.
6. the method as described in claim 1, which is characterized in that noble-metal-supported content is in catalyst in the step (5)
0.05-5.0wt%；Amorphous oxide content is 10-60wt%.
7. the method as described in claim 1, which is characterized in that drying temperature is 80- in the step (1), (2) and (5)
150 DEG C, the time is 0.5-12h；Maturing temperature is 300-700 DEG C in the step (1) and (2), and the time is 2-40h；
Reduction temperature is 100-500 DEG C in the step (5), time 1-40h.
8. a kind of catalyst of any the method preparation of claim 1-7.
9. a kind of application of catalyst described in claim 8, which is characterized in that the catalyst adds hydrogen for Fischer Tropsch waxes
Isomerization reaction.
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1448480A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Isomerization dewaxing catalyst and its prepn. |
| CN1888024A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Hydrocarbon oil processing method |
| CN101475432A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for improving butene double bond isomerization reaction |
| CN105521818A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Hydroisomerization catalyst, its preparation method and use and Fischer-Tropsch synthetic wax hydroisomerization method |
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1448480A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Isomerization dewaxing catalyst and its prepn. |
| CN1888024A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Hydrocarbon oil processing method |
| CN101475432A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for improving butene double bond isomerization reaction |
| CN105521818A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Hydroisomerization catalyst, its preparation method and use and Fischer-Tropsch synthetic wax hydroisomerization method |
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