CN109465021A - A kind of preparation method of isomerization catalyst with MFI type structural molecular sieve as carrier - Google Patents
A kind of preparation method of isomerization catalyst with MFI type structural molecular sieve as carrier Download PDFInfo
- Publication number
- CN109465021A CN109465021A CN201710800187.7A CN201710800187A CN109465021A CN 109465021 A CN109465021 A CN 109465021A CN 201710800187 A CN201710800187 A CN 201710800187A CN 109465021 A CN109465021 A CN 109465021A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- content
- carrier
- mfi type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000012298 atmosphere Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 238000009826 distribution Methods 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000010792 warming Methods 0.000 description 8
- 239000003708 ampul Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 150000001722 carbon compounds Chemical class 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229940094933 n-dodecane Drugs 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005985 Hofmann elimination reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
-
- 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
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of using MFI type structure molecular sieve as the preparation method of the isomerization catalyst of carrier.Specific step is as follows for catalyst preparation: carrying out part demoulding processing to the molecular screen primary powder with MFI type structure first at 100-400 DEG C；It again will be on the group VIII noble metals active component molecular sieve that is carried on that treated；Then reduction obtains final catalyst in hydrogen atmosphere.By the removing mode of template in control molecular sieve carrier, the Effective Regulation of catalyst metals property, Acidity and pore properties is realized.Compared with the catalyst made from the prior art, high reactivity and isomers yield are shown in normal alkane isomerization reaction using catalyst made from the method for the present invention.
Description
Technical field
The invention belongs to petrochemical industry, fine chemistry industry and molecular sieve catalyst fields, and in particular to one kind is with MFI type structure
Molecular sieve is the isomerization catalyst preparation method and application of carrier.
Technical background
Alkane isomerization reaction has a very important role during the quality-improving of oil product.Light paraffins add hydrogen
Isomerization can produce high-octane gasoline blend component, and long chain alkane hydroisomerization is mainly used for improving boat coal, bavin
The low temperature fluidity of oil and lubricating oil.Currently, it is negative by carrier of molecular sieve for being applied to the state-of-the-art catalyst of the reaction
Carrier has plus the bifunctional catalyst of the metal component of (de-) hydrogen performance.US4710485,5135638,5282598,
The patent documents such as CN1792451,1788844,101245260 all report the alkane isomerization catalyst using molecular sieve as carrier
Preparation.
In alkane isomerization reaction process, metal position mainly provides hydrogenation/dehydrogenation performance, the acidic site of molecular sieve carrier
Isomerization/cracking performance is provided, the cellular structure of molecular sieve provides shape-selective function.The isomerization performance of catalyst by its metal,
Acid and duct codetermines.
Generally, using molecular sieve as the acidity and duct template in molecular sieve of the isomerization catalyst of carrier
Removing.The method of template is usually to be roasted in air atmosphere using the temperature not less than 500 DEG C in removing molecular sieve.
For example, template di-n-propylamine (J.Colloid of the Liu et al. in air atmosphere in 600 DEG C of calcination process 6h removing SAPO-11
Interf.Sci.2014,418,193.)；Template of the Liu et al. in air atmosphere in 550 DEG C of calcination process 8h removing ZSM-22
Agent hexamethylene diamine (J.Catal.2016,335,11.)；Wang etc. is in air atmosphere in 550 DEG C of calcination process 3h removing ZSM-23
Template pyrrolidines (Ind.Eng.Chem.Res.2016,55,6069.).
In above-mentioned roasting knockout course, it is high that vapor part with caused by that oxidizing fire reaction generates occurs for template
Warm high pressure can destroy the skeleton structure of molecular sieve, influence the pore properties and Acidity of molecular sieve.Corma etc. has found 540 DEG C of roastings
Burning demoulding will lead to molecular sieve and dealuminzation phenomenon occurs, influence the surface acidity (J.Catal.1994,148,569.) of molecular sieve.
The discoveries such as Ward roasting calcining temperature is higher than 500 DEG C of destructions that will cause Y molecular sieve structural hydroxyl, so that molecular sieveAcid (B acid) amount is reduced, and Lewis acid (L acid) amount increases (J.Catal.1968,11,251.).
MFI-type molecular sieve has three-dimensional ten-ring duct, its skeleton is made of two kinds of intersection channel systems, straight tube duct
Port size be aboutThe port size in " Z " font duct is aboutIt is with MFI-type molecular sieve
The loaded catalyst of carrier shows excellent performance in long chain alkane hygrogenating isomerization reaction.With above-mentioned release method
It is similar, often divided using higher temperature (being not less than 500 DEG C) removing in preparation using MFI-type molecular sieve as the catalyst of carrier
Template in son sieve.For example, the template in air atmosphere in 550 DEG C of calcination process certain time removing ZSM-5 such as Kim
Agent is prepared Pt/ZSM-5 isomerization catalyst (J.Catal.2013,301,187.).This roasting knockout course influences MFI type
Acid bit distribution, quantity and Micropore volume on molecular sieve reduce acid amount and Micropore volume.Therefore, pass through new tool control
The stripping means in the molecular sieve analog are made, realize the regulation to Acidity and pore properties with MFI type structure molecular sieve, it is right
Have the hydroisomerisation catalysts of high isomers yield very necessary in preparation.
Studies have shown that the metallicity (hydrogenation/dehydrogenation performance) of catalyst is related to the load situation of metal.Generally,
The distance between metal position and acidic site are closer, and the hydrogenation/dehydrogenation performance of catalyst is better.Since MFI-type molecular sieve is unique
One-dimensional straight cellular structure and narrow port size, the acidic site to work in isomerization process are predominantly located at molecular sieve outer surface
Aperture near.On the catalyst using MFI-type molecular sieve as carrier, acidity that the metal position of outer surface is worked due to distance
Position is closer, is capable of providing better hydrogenation/dehydrogenation performance.And preparation method conventional at present is difficult to control the load of metal component
Position.Therefore, the method for the outer surface that exploitation control metal component is carried on MFI type structure molecular sieve is particularly significant.
The present invention proposes a kind of using MFI type structure molecular sieve as the preparation method of the isomerization catalyst of carrier.Pass through elder generation
Segment template agent in roasting removing molecular sieve, then carried metal active component, is thoroughly taken off using the reduction process of catalyst
Except the template in molecular sieve.Firstly, roasting under 100-400 DEG C of relative low temperature, the template in molecular sieve passes through
The reactions such as Hofmann elimination generate active carbon species, are an endothermic processes.Then, molecular sieve carried hydrogenation metal component,
It is restored in hydrogen or hydrogeneous atmosphere；The active carbon species in molecular sieve are removed by catalytic hydrogenation at hydro carbons in this process.This
Invention makes full use of the reduction process of catalyst to demould, and the carbon species hydrogenation and removing in molecular sieve is compared with the oxygen in customary preparation methods
It is small to change removing heat release, and anhydrous steam generates, framework of molecular sieve structural damage is acted on small.
Meanwhile the load situation of metal component can also be controlled using the method for the present invention.In 50-400 DEG C of relative low temperature
The active carbon species of lower roasting, generation are blocked in the duct of molecular sieve, and the organic matter and impurity of outer surface absorption are then taken off
It removes, the hydroxyl of molecular sieve outer surface is exposed.Thus, in the loading process of metal component, metal component is due to molecular sieve
Duct blocks and cannot be introduced into the duct of molecular sieve, can only interact with the hydroxyl of molecular sieve outer surface, final
The catalyst of molecular sieve supported external surface is distributed only over to metal component.
To sum up, made from the conventional method compared with catalyst, had more using catalyst made from the method for the present invention
High acid amount and Micropore volume, metal component are distributed in the outer surface of molecular sieve, show in isomerization process higher
Reactivity and isomers yield.
Summary of the invention
The purpose of the present invention is to provide a kind of using MFI type structure molecular sieve as the preparation side of the isomerization catalyst of carrier
Method.
Specifically, the present invention provides a kind of using MFI type structure molecular sieve as the isomerization catalyst preparation method of carrier,
It is characterized by: the segment template agent in first roasting removing molecular sieve, then carried metal active component, utilizes catalyst reduction
Process thoroughly removes the template in molecular sieve, and isomerization catalyst is made, includes the following steps,
(1) by containing template, the molecular screen primary powder with MFI type structure at 100-400 DEG C calcination process 0.5-
18h, carbon distribution and content of organics are the 0.5-20wt.% of molecular sieve in the molecular sieve after roasting；
(2) by the molecular sieve carried group VIII noble metals active component after roasting in (1), group VIII noble metals component
Content be 0.05-10wt.%；
(3) in a reducing atmosphere by the sample after carried metal component in (2), 150-450 DEG C of reduction 0.5-12h is made
Isomerization catalyst.
Treatment temperature described in method and step (1) provided by the present invention is 150-400 DEG C, and the processing time is 1-12h；
Carbon distribution and content of organics are point in molecular sieve after roasting described in method and step (1) provided by the present invention
The 0.5-17wt.% of son sieve weight；
Calcination process process described in method and step (1) provided by the present invention is generally in oxygen-containing atmosphere (such as air, oxygen
Gas, ozone etc.) in carry out, can also be in inert atmosphere (such as nitrogen, argon gas) or reducing atmosphere (such as hydrogen, hydrogen sulfide, an oxygen
Change carbon etc.) in carry out；
Reduction temperature described in method and step (3) provided by the present invention is 200-400 DEG C, recovery time 1-8h；
Reducing atmosphere described in method and step (3) provided by the present invention is that hydrogen or hydrogen and other gases are (such as lazy
Property gas, alkane, alkene etc.) gaseous mixture；
Group VIII noble metals active component described in method and step (2) provided by the present invention or step (3) be Pt,
One or more of elements such as Pd, Ir；
Group VIII noble metals content described in method and step (2) provided by the present invention is 0.05-5.0wt.%；
Molecular sieve described in method provided by the present invention with MFI type structure is ZSM-5, Me-ZSM-5 (Me=
Zn, Mg, Mn, Co, Cr, Cu, Fe, Cd or Ni etc.), one or more of Silicalite, FZ-1 and NU-4 etc..
The load of metal component described in method and step (2) provided by the present invention uses the operation side of this field routine
Method including but not limited to impregnates, precipitates, deposition, the addition operation such as adhesive bonding or mechanical press, making group VIII noble metals
Presoma is scattered on carrier, realizes the combination of group VIII noble metals and carrier；The metal precursor used includes but unlimited
In metal acid, metal acid-salt, chloride, ammino-complex, carbonyl complex or their mixture；
In the present invention, active carbon species react in the reduction process of catalyst with hydrogen, mainly generate it is hydrocarbon or
Hydronitrogen；And in conventional roasting process, oxidizing fire mainly occurs with oxygen for the template in molecular sieve, main raw
At carbon oxygen or oxynitrides；
It will be needed after on the metal component molecular sieve that is carried on that treated described in method and step (2) provided by the present invention
It is dried, the dry operating method for using this field routine, including but not limited to heat drying, freeze-drying is overcritical
Dry etc., common method is 40-300 DEG C of drying temperature, preferably 60-200 DEG C of drying temperature in air atmosphere；When dry
Between 0.5-24h, preferably drying time 1-8h；
Catalyst provided by the present invention can be widely applied to petroleum distillate, biomass, Fischer-Tropsch synthetic it is processed
Journey, such as isomerization-visbreaking, the processes such as isomerization dewaxing.
It is provided by the invention using MFI type structure molecular sieve as the preparation of the catalyst of carrier with conventional preparation method ratio
Method has the advantages that
1. reducing the roasting calcining temperature of molecular sieve carrier, the energy consumption in catalyst preparation process is reduced；
2. making full use of the template in reduction process removing molecular sieve, reduce knockout course to framework of molecular sieve structure
Destruction, the catalyst being prepared has high Micropore volume and acid amount；
3. the isomerization catalyst of preparation is in alkane isomerization reaction with high activity and isomers yield.
Specific embodiment
The present invention is described further for embodiment below, but the invention is not limited to the following embodiments
In.Meanwhile embodiment has been merely given as realizing the partial condition of this purpose, being not meant to must satisfy these conditions just can be with
Reach this purpose.
The test of catalyst acid amount carries out on Micromeritics AutoChem2920 chemical adsorption instrument.Sample first exists
In-situ treatment 60min under the conditions of 350 DEG C of logical He, is then down to 100 DEG C for sample cell temperature, is passed through NH on adsorption instrument3, to be adsorbed
After saturation, lead to He and purge 60min, after waiting TCD detector baseline steady, rises to 700 DEG C with 10 DEG C/min, record NH3Desorption
Curve.The acid amount of sample is according to NH3Concentration correction curve and NH3Calculated by peak area is desorbed and obtains.
The carbon distribution and content of organics of sample are determined according to thermal gravimetric analysis results.Using German NETZSCH company STA
449F3 type instrument carries out thermogravimetric measurement to sample.Determination condition: sample sample-loading amount is the 10mg, (flow in air atmosphere
20ml/min) 900 DEG C are warming up to from 40 DEG C with the heating rate of 10 DEG C/min.The carbon distribution and content of organics of sample are sample heat
It is greater than 200 DEG C of weight loss in weight result.
The hole of catalyst holds measurement and carries out on Micromeritics ASAP2420 physical adsorption appearance.Before test, sample
The vacuumize process 6h at 200 DEG C, then carries out N under liquid nitrogen temperature2The measurement of absorption and desorption isotherm.The micropore of sample
Kong Rong is calculated by t-plot method.
Evaluating catalyst carries out in stainless steel fixed bed reactors, and the catalyst 1.0mL of preparation is taken to be loaded in reactor,
It is warming up to reaction temperature in a hydrogen atmosphere, logical feedstock oil n-dodecane is reacted, and product is by gas chromatographic analysis.React item
Part: 180-280 DEG C of reaction temperature, normal pressure, n-dodecane liquid hourly space velocity (LHSV) 1.0h-1, hydrogen-oil ratio (mol/mol) is 15.
Comparative example
The ZSM-5 molecular sieve original powder (17.3wt.% that template agent content is molecular sieve) that 20g contains template is set
In quartz ampoule, for 24 hours, cooled to room temperature obtains the ZSM-5 that template removes completely for 550 DEG C of roastings in air atmosphere
Molecular sieve carrier, carbon distribution and content of organics are 0 in molecular sieve carrier.With the H of 5.0mL 0.001g/mL containing Pt2PtCl6Solution
Impregnate the above-mentioned molecular sieve carrier of 5g.Sample after dipping dries 2h at 120 DEG C, and 400 DEG C of reduction 4h, obtain in hydrogen atmosphere
0.5wt.%Pt/ZSM-5 catalyst.Carbon distribution and content of organics are 0 in catalyst, and the acid amount having is 1.02mmol/g, micro-
Kong Kongrong is 0.092cm3/g.Carbon distribution and content of organics, the acid amount of catalyst and Micropore volume table in molecular sieve and catalyst
Sign the results are shown in Table 1, and catalysis reaction evaluating the results are shown in Table 2.
Embodiment 1
By 20g ZSM-5 molecular sieve original powder identical with comparative example (17.3wt.% that template agent content is molecular sieve)
It is placed in quartz ampoule, in air atmosphere, 5 DEG C/min is warming up to 150 DEG C, roasts 4h at such a temperature, then naturally cools to
Room temperature, the ZSM-5 molecular sieve carrier that obtains that treated, carbon distribution and content of organics are 15.8wt.% in molecular sieve carrier.With
The H of 5.0mL 0.001g/mL containing Pt2PtCl6Solution impregnates the above-mentioned molecular sieve carrier of 5g.Sample after dipping is dry at 120 DEG C
2h, 300 DEG C of reduction 4h, obtain 0.5wt.%Pt/ZSM-5 catalyst in hydrogen atmosphere.Carbon distribution and organic matter contain in catalyst
Amount is 0, and the acid amount having is 1.65mmol/g, Micropore volume 0.141cm3/g.Carbon distribution and organic in molecular sieve and catalyst
Object content, the acid amount of catalyst and Micropore volume characterization result are shown in Table 1, and catalysis reaction evaluating the results are shown in Table 2.
Embodiment 2
By Cr-ZSM-5 molecular screen primary powder that 20g contains template, (template agent content is molecular sieve
The content of 17.8wt.%, Cr are 0.9wt.%) it is placed in quartz ampoule, in air atmosphere, 5 DEG C/min is warming up to 230 DEG C,
12h is roasted at this temperature, then cooled to room temperature, obtain that treated Cr-ZSM-5 molecular sieve carrier, molecular sieve carrier
Middle carbon distribution and content of organics are 14.0wt.%.With the H of 5.0mL 0.001g/mL containing Pt2PtCl6Solution impregnates the above-mentioned molecule of 5g
Sieve carrier.Sample after dipping dries 2h at 120 DEG C, and 400 DEG C of reduction 6h, obtain 0.5wt.%Pt/Cr- in hydrogen atmosphere
ZSM-5 catalyst.Carbon distribution and content of organics are 0 in catalyst, and the acid amount having is 1.54mmol/g, and Micropore volume is
0.136cm3/g.Carbon distribution and content of organics, the acid amount of catalyst and Micropore volume characterization result are shown in molecular sieve and catalyst
Table 1, catalysis reaction evaluating the results are shown in Table 2.
Embodiment 3
By Co-ZSM-5 molecular screen primary powder that 20g contains template, (template agent content is molecular sieve
The content of 17.5wt.%, Co are 1.2wt.%) it is placed in quartz ampoule, in air atmosphere, 5 DEG C/min is warming up to 300 DEG C,
2h is roasted at this temperature, then cooled to room temperature, the Co-ZSM-5 molecular sieve carrier that obtains that treated, in molecular sieve carrier
Carbon distribution and content of organics are 10.9wt.%.With the H of 5.0mL 0.001g/mL containing Pt2PtCl6Solution impregnates the above-mentioned molecular sieve of 5g
Carrier.Sample after dipping dries 2h at 120 DEG C, and 400 DEG C of reduction 6h, obtain 0.5wt.%Pt/Co- in hydrogen atmosphere
ZSM-5 catalyst.Carbon distribution and content of organics are 0 in catalyst, and the acid amount having is 1.37mmol/g, and Micropore volume is
0.123cm3/g.Carbon distribution and content of organics, the acid amount of catalyst and Micropore volume characterization result are shown in molecular sieve and catalyst
Table 1, catalysis reaction evaluating the results are shown in Table 2.
Embodiment 4
By Cu-ZSM-5 molecular screen primary powder that 20g contains template, (template agent content is molecular sieve
The content of 18.3wt.%, Cu are 2.1wt.%) it is placed in quartz ampoule, in air atmosphere, 5 DEG C/min is warming up to 400 DEG C,
1h is roasted at this temperature, then cooled to room temperature, the Cu-ZSM-5 molecular sieve carrier that obtains that treated, in molecular sieve carrier
Carbon distribution and content of organics are 6.3wt.%.With the H of 5.0mL 0.001g/mL containing Pt2PtCl6Solution impregnates the above-mentioned molecular sieve of 5g
Carrier.Sample after dipping dries 2h at 120 DEG C, and 200 DEG C of reduction 8h, obtain 0.5wt.%Pt/Cu- in hydrogen atmosphere
ZSM-5 catalyst.Carbon distribution and content of organics are 0 in catalyst, and the acid amount having is 1.15mmol/g, and Micropore volume is
0.106cm3/g.Carbon distribution and content of organics, the acid amount of catalyst and Micropore volume characterization result are shown in molecular sieve and catalyst
Table 1, catalysis reaction evaluating the results are shown in Table 2.
Embodiment 5
By Ni-ZSM-5 molecular screen primary powder that 20g contains template, (template agent content is molecular sieve
The content of 17.4wt.%, Ni are 1.4wt.%) it is placed in quartz ampoule, in nitrogen atmosphere, 5 DEG C/min is warming up to 150 DEG C,
8h is roasted at this temperature, then cooled to room temperature, the Ni-ZSM-5 molecular sieve carrier that obtains that treated, in molecular sieve carrier
Carbon distribution and content of organics are 15.7wt.%.With the H of 5.0mL 0.001g/mL containing Pt2PtCl6Solution impregnates the above-mentioned molecular sieve of 5g
Carrier.Sample after dipping dries 2h at 120 DEG C, and 400 DEG C of reduction 8h, obtain 0.5wt.%Pt/Ni- in hydrogen atmosphere
ZSM-5 catalyst.Carbon distribution and content of organics are 0 in catalyst, and the acid amount having is 1.70mmol/g, and Micropore volume is
0.144cm3/g.Carbon distribution and content of organics, the acid amount of catalyst and Micropore volume characterization result are shown in molecular sieve and catalyst
Table 1, catalysis reaction evaluating the results are shown in Table 2.
Embodiment 6
By Sn-ZSM-5 molecular screen primary powder that 20g contains template, (template agent content is molecular sieve
The content of 16.9wt.%, Sn are 1.4wt.%) it is placed in quartz ampoule, in hydrogen atmosphere, 5 DEG C/min is warming up to 200 DEG C,
6h is roasted at this temperature, then cooled to room temperature, the Sn-ZSM-5 molecular sieve carrier that obtains that treated, in molecular sieve carrier
Carbon distribution and content of organics are 15.3wt.%.With the H of 5.0mL 0.001g/mL containing Pt2PtCl6Solution impregnates the above-mentioned molecular sieve of 5g
Carrier.Sample after dipping dries 2h at 120 DEG C, and 400 DEG C of reduction 1h, obtain 0.5wt.%Pt/Sn- in hydrogen atmosphere
ZSM-5 catalyst.Carbon distribution and content of organics are 0 in catalyst, and the acid amount having is 1.67mmol/g, and Micropore volume is
0.141cm3/g.Carbon distribution and content of organics, the acid amount of catalyst and Micropore volume characterization result are shown in molecular sieve and catalyst
Table 1, catalysis reaction evaluating the results are shown in Table 2.
The characterization result of molecular sieve, catalyst in 1 comparative example of table and embodiment
The reaction evaluating result of 2 comparative example of table and the catalyst in embodiment
When a reaction temperature is 200 DEG C, n-dodecane conversion ratio on catalyst；
In b n-dodecane isomerization reaction, the maximum isomers yield of catalyst.
As shown in Table 1, carbon distribution and content of organics is 0 in the molecular sieve for using conventional method to demould in comparative example,
Containing a certain amount of in the molecular sieve obtained in embodiment 1-6 using 150-400 DEG C of the present invention roasting molecular screen primary powder
Carbon distribution and organic matter.But after catalyst reduction, contained carbon distribution and organic matter are removed completely.The effect of generation are as follows: with comparison
Catalyst made from conventional method is compared in example, and embodiment 1-6 uses method of the invention, and gained catalyst has high acid amount
With big Micropore volume.
As shown in Table 2, made from the comparative example conventional method compared with catalyst, the method for the present invention is used in embodiment 1-6
The catalyst being prepared shows high reactivity and isomers yield in alkane hygrogenating isomerization reaction.
Claims (9)
1. a kind of using MFI type structure molecular sieve as the isomerization catalyst preparation method of carrier, it is characterised in that: in 100-400
DEG C roasting MFI type structure molecular screen primary powder, then carried metal active component, then restored and isomerization catalyst is made, including
Following steps,
(1) by calcination process 0.5-18h, control at 100-400 DEG C containing template, the molecular screen primary powder with MFI type structure
Carbon distribution and content of organics are the 0.5-20wt.% of molecular sieve in molecular sieve after system roasting,
(2) by the molecular sieve carried group VIII noble metals active component after roasting in (1), group VIII noble metals component contains
Amount is 0.05-10wt.%,
(3) in a reducing atmosphere by the sample after load group VIII noble metal component in (2), 150-450 DEG C of reduction 0.5-
Isomerization catalyst is made in 12h.
2. according to the method described in claim 1, it is characterized by: treatment temperature in the step (1) is 150-400 DEG C,
The processing time is 1-12h.
3. method according to claim 1, it is characterised in that: in the molecular sieve in the step (1) after control roasting
Carbon distribution and content of organics are the 0.5-17wt.% of molecular sieve.
4. method according to claim 1, it is characterised in that: the reduction temperature in the step (3) is 200-400
DEG C, recovery time 1-8h.
5. method according to claim 1, it is characterised in that: the reducing atmosphere in the step (3) is hydrogen or hydrogen
Gas and other gases (alkane of one of such as inert gas gas such as nitrogen, helium, neon, argon gas or two kinds or more, C1-C4
Hydrocarbon, one of the alkene etc. of C1-C4 or two kinds or more) gaseous mixture, the volume content of hydrogen is 5-100%.
6. method according to claim 1, it is characterised in that: the group VIII in the step (2) or step (3) is expensive
Metal active constituent is one of elements such as Pt, Pd, Ir or two kinds or more.
7. method according to claim 2, it is characterised in that: the group VIII noble metals content in the step (2)
For 0.05-5.0wt.%.
8. method according to claim 1, it is characterised in that: the molecular sieve with MFI type structure is ZSM-
5, (one of Me=Zn, Mg, Mn, Co, Cr, Cu, Fe, Cd or Ni etc. or two kinds or more, mass content is Me-ZSM-5
0.05-5wt.%), one of Silicalite, FZ-1 and NU-4 etc. or two kinds or more.
9. according to the method described in claim 1, it is characterized by: template is organic in the step (1) molecular screen primary powder
One or more of amine, quaternary ammonium salt, metal organic complex etc., content-are the 0.5- of molecular sieve
25wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710800187.7A CN109465021B (en) | 2017-09-07 | 2017-09-07 | A kind of preparation method of isomerization catalyst with MFI type structural molecular sieve as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710800187.7A CN109465021B (en) | 2017-09-07 | 2017-09-07 | A kind of preparation method of isomerization catalyst with MFI type structural molecular sieve as carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109465021A true CN109465021A (en) | 2019-03-15 |
| CN109465021B CN109465021B (en) | 2021-10-08 |
Family
ID=65657578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710800187.7A Active CN109465021B (en) | 2017-09-07 | 2017-09-07 | A kind of preparation method of isomerization catalyst with MFI type structural molecular sieve as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109465021B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058639A (en) * | 2021-03-09 | 2021-07-02 | 中国原子能科学研究院 | Noble metal catalyst with ZSM-5 as carrier and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1311554A (en) * | 1970-07-08 | 1973-03-28 | Gulf Research Development Co | Isomerization of hydrocarbons |
| CN1721074A (en) * | 2005-06-27 | 2006-01-18 | 中国科学院大连化学物理研究所 | A kind of hydroisomerization catalyst and preparation method thereof |
| CN102658197A (en) * | 2012-05-16 | 2012-09-12 | 浙江师范大学 | Catalyst for normal paraffin hydroisomerization reaction and preparation method as well as application thereof |
| CN104857983A (en) * | 2015-04-30 | 2015-08-26 | 北京化工大学 | Load type metal mesoporous molecular sieve noble metal catalyst and preparation method thereof |
| CN105217649A (en) * | 2015-10-26 | 2016-01-06 | 中国科学院广州能源研究所 | A kind of two steps in low temperature removes the method for organic formwork agent and realizes the device of the method |
| WO2016005312A1 (en) * | 2014-07-07 | 2016-01-14 | Shell Internationale Research Maatschappij B.V. | Isomerization catalyst |
| CN106799257A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | A kind of alkane isomerization catalyst and preparation method thereof |
| CN107020147A (en) * | 2017-04-25 | 2017-08-08 | 天津大学 | A kind of MFI structure sheet molecular sieve catalyst, the preparation method and the usage of package metals oxide or metal nanoparticle |
-
2017
- 2017-09-07 CN CN201710800187.7A patent/CN109465021B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1311554A (en) * | 1970-07-08 | 1973-03-28 | Gulf Research Development Co | Isomerization of hydrocarbons |
| CN1721074A (en) * | 2005-06-27 | 2006-01-18 | 中国科学院大连化学物理研究所 | A kind of hydroisomerization catalyst and preparation method thereof |
| CN102658197A (en) * | 2012-05-16 | 2012-09-12 | 浙江师范大学 | Catalyst for normal paraffin hydroisomerization reaction and preparation method as well as application thereof |
| WO2016005312A1 (en) * | 2014-07-07 | 2016-01-14 | Shell Internationale Research Maatschappij B.V. | Isomerization catalyst |
| CN104857983A (en) * | 2015-04-30 | 2015-08-26 | 北京化工大学 | Load type metal mesoporous molecular sieve noble metal catalyst and preparation method thereof |
| CN105217649A (en) * | 2015-10-26 | 2016-01-06 | 中国科学院广州能源研究所 | A kind of two steps in low temperature removes the method for organic formwork agent and realizes the device of the method |
| CN106799257A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | A kind of alkane isomerization catalyst and preparation method thereof |
| CN107020147A (en) * | 2017-04-25 | 2017-08-08 | 天津大学 | A kind of MFI structure sheet molecular sieve catalyst, the preparation method and the usage of package metals oxide or metal nanoparticle |
Non-Patent Citations (1)
| Title |
|---|
| 刘波等: "Pt-ZSM-5/Pd-ZSM-5催化剂对正丁烷异构化反应性能的影响", 《工业催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058639A (en) * | 2021-03-09 | 2021-07-02 | 中国原子能科学研究院 | Noble metal catalyst with ZSM-5 as carrier and preparation method and application thereof |
| CN113058639B (en) * | 2021-03-09 | 2022-06-28 | 中国原子能科学研究院 | Noble metal catalyst with ZSM-5 as carrier and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109465021B (en) | 2021-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Hydrodeoxygenation of bio-oil over Pt-based supported catalysts: Importance of mesopores and acidity of the support to compounds with different oxygen contents | |
| WO2013147190A1 (en) | Method for dewaxing hydrocarbon oil and method for producing lubricating-oil base oil | |
| JP2015077575A (en) | Hydrocarbon synthesis catalyst, and hydrocarbon production device using the same and method for producing hydrocarbon | |
| CN111215134B (en) | Preparation method of shape selective isomerism catalyst based on AEL type structure molecular sieve | |
| CN108126736B (en) | Alkane isomerization catalyst, preparation and application | |
| CN111215131B (en) | A kind of preparation method of shape-selective isomerization catalyst based on MTW structure molecular sieve | |
| CN109465023A (en) | A kind of preparation method of isomerization catalyst with MTT structure molecular sieve as carrier | |
| CN109465028B (en) | A kind of preparation method of isomerization catalyst with AEL type structural molecular sieve as carrier | |
| CN109465029B (en) | Preparation method of isomerization catalyst taking AFI type structure molecular sieve as carrier | |
| CN109465021A (en) | A kind of preparation method of isomerization catalyst with MFI type structural molecular sieve as carrier | |
| CN111215133B (en) | A kind of preparation method of shape-selective isomerization catalyst based on AFI structure molecular sieve | |
| CN109465024B (en) | A kind of preparation method of isomerization catalyst with MTW structure molecular sieve as carrier | |
| CN109465030B (en) | Preparation method of isomerization catalyst taking ATO type structure molecular sieve as carrier | |
| CN109465025B (en) | A kind of preparation method of isomerization catalyst with *BEA structure molecular sieve as carrier | |
| CN111229296B (en) | Preparation method of shape-selective isomerization catalyst based on MFI-type structure molecular sieve | |
| CN111229292B (en) | Preparation method of shape selective isomerization catalyst based on FAU-type structure molecular sieve | |
| CN111215135B (en) | Preparation method of shape selective heterogeneous catalyst based on AFO type structure molecular sieve | |
| CN105732284A (en) | Selective hydrogenation method of carbon three-fraction | |
| CN109465020B (en) | A kind of preparation method of isomerization catalyst with FAU type structure molecular sieve as carrier | |
| CN109465026A (en) | A kind of preparation method of isomerization catalyst with TON type structure molecular sieve as carrier | |
| Dzhikiya et al. | A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization | |
| CN109465031A (en) | A kind of preparation method of isomerization catalyst with AFO type structural molecular sieve as carrier | |
| CN111229306B (en) | Preparation method of shape selective isomerization catalyst based on MTT type structure molecular sieve | |
| CN111229307B (en) | Preparation method of shape selective isomerization catalyst based on TON type structure molecular sieve | |
| CN111229308B (en) | Preparation method of shape-selective isomerization catalyst based on BEA structure molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |