CN109465024A - It is a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier - Google Patents
It is a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier Download PDFInfo
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- CN109465024A CN109465024A CN201710799857.8A CN201710799857A CN109465024A CN 109465024 A CN109465024 A CN 109465024A CN 201710799857 A CN201710799857 A CN 201710799857A CN 109465024 A CN109465024 A CN 109465024A
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- molecular sieve
- catalyst
- roasting
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- carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000002808 molecular sieve Substances 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 238000009826 distribution Methods 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- -1 4-propyl bromide Chemical compound 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- AUBSNUSTVUZGCC-UHFFFAOYSA-N [NH4+].[Br-].C(C)[PH3+].[Br-] Chemical compound [NH4+].[Br-].C(C)[PH3+].[Br-] AUBSNUSTVUZGCC-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 42
- 230000008569 process Effects 0.000 description 20
- 230000002378 acidificating effect Effects 0.000 description 12
- 238000001354 calcination Methods 0.000 description 10
- 239000005416 organic matter Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRVPDGGTLNKOBZ-UHFFFAOYSA-M triethyl(methyl)azanium;bromide Chemical compound [Br-].CC[N+](C)(CC)CC GRVPDGGTLNKOBZ-UHFFFAOYSA-M 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 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
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J29/70—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
- B01J29/7469—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
-
- B01J35/633—
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier.Specific step is as follows for preparation method: first at inert atmosphere and 50-300 DEG C, carrying out the processing of part Template removal to the sieve original powder containing template molecule with MTW type structure；Again at oxygen-containing atmosphere and 50-400 DEG C, further Template removal processing is carried out to the molecular sieve after the Template removal of part with MTW type structure, then the carried metal active component on obtained molecular sieve carrier, obtains final catalyst by dry and reduction.By the removing mode of template in control molecular sieve carrier, the Effective Regulation of its Acidity and pore properties is realized.Compared with the catalyst made from the prior art, there is higher isomerisation selectivity and isomers yield in normal alkane isomerization reaction using the catalyst of the method for the present invention preparation.
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 MTW type structure
Molecular sieve is the isomerization catalyst preparation method and application of carrier.
Background technique
Difunctional solid catalyst is widely used in alkane hydroisomerization process, by hydrogenation-dehydrogenation component and acidity
Carrier two parts composition.Wherein, hydrogenation-dehydrogenation component is mainly group VIII metal such as Pt, Pd, Rh, Ir and Ni etc.；Acidity carries
Body 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, Si-Al molecular sieve series, such as Y, Beta, ZSM-5；3, phosphoric acid
Aluminum molecular screen series, such as SAPO-5, SAPO-11, SAPO-31 and SAPO-41.Compared with unformed oxide and super acids,
Molecular sieve all shows excellent performance in terms of selecting type selectivity, stability, antitoxinization and carbon accumulation resisting ability.Therefore, with
Molecular sieve is that the isomerization catalyst of carrier is used widely.US5882505,2004138051,2005077209,
The alkane hydroisomerizing using molecular sieve as carrier is all described in detail in the patent documents such as CN1792451,1788844,101245260
Change the preparation method of catalyst.
During molecular sieve acts on long chain alkane hydroisomerization, the performance of catalyst is total to by its duct and acidity
With decision.Carbonium ion in the reaction of n-alkane hydroisomerizing generates and its isomerization process is mainly enterprising in aperture acidic site
Row, and the distribution of isomerized products is then mainly determined by the space confinement effect in microporous molecular sieve duct.Acidic zeolite bit distribution
And quantity significantly affects catalyst performance, wherein isomerization activity is poor on faintly acid position, and highly acid position then easily leads to cracking, makes
Target product selectivity and yield reduce.Ideal alkane hydroisomerisation catalysts need to have more moderate strength acidic site
With micropore quantity, higher isomerisation selectivity and isohydrocarbon yield can be obtained in alkane isomerization reaction.
The acidity of molecular sieve and micropore are from the removing of organic template agent from molecular sieve.Organic formwork agent in molecular sieve
Remove the method for generalling use high-temperature roasting, it may be assumed that by the obtained molecular sieve of synthesis directly the oxygen-containing atmospheres such as air high temperature (no
Lower than 450 DEG C) it roasts with complete removed template method.For example, Liu et al. 550 DEG C of calcination process 8h in air atmosphere remove ZSM-
Template hexamethylene diamine (J.Catal.2016,335,11) in 22；550 DEG C of calcination process 3h removings in air atmosphere such as Wang
Template pyrrolidines (Ind.Eng.Chem.Res.2016,55,6069) in ZSM-23；Liu et al. is 600 DEG C in air atmosphere
Calcination process 6h removes the template di-n-propylamine (J.Colloid Interf.Sci.2014,418,193) in SAPO-11；
550 DEG C of calcination process in air atmosphere such as Philippaerts remove the template 4-propyl bromide in ZSM-5 for 24 hours
(J.Catal.2010,270,172)。
Although can thoroughly remove organic formwork agent, in roasting process, mould in the roasting of air atmosphere high temperature
Plate agent can occur oxidizing fire and generate vapor and local high temperature and pressure, destroy the skeleton structure of molecular sieve, influence molecular sieve
Pore properties and acid properties.For example, the discovery such as Corma is during molecular sieve roasts removed template method, high temperature (is not less than
450 DEG C) roasting will lead to molecular sieve and dealuminzation phenomenon, generation structure collapse, micropore reduction occurs, and influence its surface acidity
(J.Catal.1994,148,569).The discovery such as Ward high temperature (being not less than 450 DEG C) roasting will cause the destruction of structural hydroxyl, make
The acid bit distribution sum number amount for obtaining molecular sieve changes, and the acidic site of moderate strength is reduced, and strong acidic site increases
(J.Catal.1968,11,251)。
ZSM-12, NU-13, CZH-5, TPZ-12, VS-12, Theta-3 molecular sieve are that a kind of artificial synthesized alumina silicate is micro-
Porous molecular sieve belongs to MTW topological structure, has one-dimensional twelve-ring cellular structure, and port size is aboutIt can
It is synthesized using different templates.Because of the characteristic and moderate acidity of its one-dimensional channels, using it as the loaded catalyst of carrier
Excellent performance is shown in long chain alkane hygrogenating isomerization reaction.It is similar with previous molecular sieve demoulding means, with MTW type point
Son sieve is that the catalyst preparation of carrier often uses the template in high temperature (not less than 450 DEG C) roasting removing molecular sieve, this
Conventional high temperature (being not less than 450 DEG C) roasting demoulding means influence acid bit distribution, acid amount and number cells on MTW type molecular sieve
Amount reduces micropore quantity, and the acidic site of moderate strength is reduced, and strong acidic site increases, and then influences the performance of catalyst.Cause
This, the removing mode of template in the molecular sieve analog is controlled by new tool, with this realize to ZSM-12, NU-13, CZH-5,
TPZ-12, VS-12, Theta-3 etc. have the regulation of the molecular sieve carrier acid distribution of MTW structure, acid amount and micropore quantity,
Have high isomerization selectivity/yield alkane hydroisomerisation catalysts very necessary preparation.
The present invention proposes one kind using MTW type structure molecular screen as carrier, by step low-temperature (be not higher than 450 DEG C) roasting and
Hydrogenating reduction is with the method for preparing catalyst of removed template method.It sieves containing template molecule not in inert atmosphere and oxygen-containing atmosphere
In, by two step low-temperature bake processes, removing template partly (makes template occur to divide during low-temperature bake
Solution, generates active carbon species, including carbon distribution and organic matter)；Then carried metal, and it is active to generate low-temperature bake in the process
Carbon species are removed in reduction process by institute's carried metal catalytic hydrogenation.This method, can compared with conventional high-temperature release method
Mitigate the degree destroyed by high temperature (being not less than 450 DEG C) roasting to framework of molecular sieve structure, retains moderate strength on molecular sieve
Skeleton acidic site, while inhibiting the formation because of strong acidic site when high-temperature roasting removes hydroxyl.Thus, obtained catalyst has
More moderate strength acidic sites and bigger Micropore volume show better isomerization selection during alkane isomerization
Property and yield.
Summary of the invention
The purpose of the present invention is to provide a kind of using MTW type structure molecular screen as the isomerization catalyst preparation side of carrier
Method.
The invention further relates to application of the above-mentioned catalyst in alkane isomerization reaction.
Specifically, above-mentioned method for preparing catalyst provided by the invention is characterized in that: by MTW type structure molecular screen carrier
Under lower temperature (being not higher than 450 DEG C), two one-step bakings are carried out in inert atmosphere and oxygen-containing atmosphere, then carried metal, then pass through
Dry and reduction, is made the isomerization catalyst, comprising the following steps:
(1) by containing template, the molecular screen primary powder with MTW type structure inert atmosphere for example nitrogen, helium, neon,
One or more of argon gas at 50-300 DEG C, roasts 0.5-24h, carbon distribution and organic matter contain in the molecular sieve after control roasting
Amount is the 0.5-10wt.% of molecular sieve；
(2) by the molecular sieve after roasting in step (1) in one or more of oxygen-containing atmosphere such as air, oxygen, ozone,
At 50-400 DEG C, 0.5-24h is roasted, carbon distribution and content of organics are the 0.2- of molecular sieve in the molecular sieve after control roasting
8wt.%；
(3) by the molecular sieve carried group VIII noble metals active component after roasting in step (2), after drying, also
In Primordial Qi atmosphere, at 100-450 DEG C, 1-12h is restored, the isomerization catalyst is made.
In method provided by the present invention with MTW type structure molecular sieve be ZSM-12, NU-13, CZH-5, TPZ-12,
One or more of VS-12, Theta-3；
Template described in method and step (1) provided by the present invention and (2) is to fill out in MTW type structure molecular screen duct
The organic amine filled derives from MTW type structure molecular screen itself synthesis process, including but not limited to tetraethyl ammonium hydroxide, four
Propyl ammonium hydroxide, tetraethylammonium bromide, 4-propyl bromide, methyl triethylammonium hydroxide, methyl triethylammonium bromide etc.
Organic amine or their mixture；
Carried noble metal active component described in method and step (3) provided by the present invention is conventional using this field
Operation including but not limited to impregnates, precipitates, deposition, the addition operation such as adhesive bonding or mechanical press, making the expensive gold of group VIII
Belong to predecessor to be scattered on carrier, realizes the combination of group VIII noble metals and carrier；The metal precursor used includes but not
It is limited to metal acid, metal acid-salt, chloride, ammino-complex, carbonyl complex or their mixture；
Inert atmosphere described in method and step (1) provided by the present invention is nitrogen, helium, neon, one in argon gas
Kind is several；
Maturing temperature in method and step (1) provided by the present invention is 50-300 DEG C, complete lower than template in molecular sieve
The temperature that full removing needs, 100-300 DEG C of preferred process temperature；
Calcining time described in method and step (1) provided by the present invention is 0.5-24h, and preferably calcining time is 1-
12h；
Calcination atmosphere described in method and step (2) provided by the present invention is oxygen-containing atmosphere, such as air, oxygen, ozone
One or more of；
Maturing temperature in method and step (2) provided by the present invention is 50-400 DEG C, complete lower than template in molecular sieve
The temperature that full removing needs, 200-350 DEG C of preferred process temperature；
Calcining time described in method and step (2) provided by the present invention is 0.5-24h, and preferably calcining time is 1-
12h；
Roasting process described in method and step (1) provided by the present invention makes the template in MTW type molecular screen primary powder
It partly removes, carbon distribution and content of organics are the 0.5- of molecular sieve total weight in the MTW type molecular sieve after controlling the roasting
10wt.%；
Roasting process described in method and step (1) provided by the present invention makes the template in MTW type molecular screen primary powder
It partly removes, preferred carbon distribution and content of organics are molecular sieve total weight in the MTW type molecular sieve after controlling the roasting
0.5-8wt.%；
Roasting process described in method and step (2) provided by the present invention makes the template in MTW type molecular screen primary powder
It further removes, carbon distribution and content of organics are molecular sieve total weight in the MTW type molecular sieve after controlling the roasting
0.2-8wt.%；
Roasting process described in method and step (2) provided by the present invention makes the template in MTW type molecular screen primary powder
It further removes, preferred carbon distribution and content of organics are molecular sieve carrier in the MTW type molecular sieve after controlling the roasting
The 0.2-5wt.% of total weight；
Roasting process described in method and step (2) provided by the present invention makes the template in MTW type molecular screen primary powder
Further remove；The type microporous molecular sieve hole MTW after controlling the roasting holds the molecular sieve removed completely no more than template
The 90% of carrier, preferably no greater than 80%；
Group VIII noble metals active component described in method and step (3) provided by the present invention be Pt, Pd, Ir, Ru,
One or more of elements such as Rh, group VIII tenor are 0.05-5.0wt.%, preferably tenor 0.1-
3.0wt.%；
Drying temperature described in method and step (3) provided by the present invention is 20-200 DEG C, drying time 0.5-
24h；It is preferred that drying temperature is 70-150 DEG C, preferably drying time is 2-8h；
Reduction mode described in method and step (3) provided by the present invention is this field routine operation, is usually used
One or both of reducing atmosphere such as hydrogen, carbon monoxide contacts reducing catalyst with catalyst；
Reduction temperature described in method and step (3) provided by the present invention is 100-450 DEG C, recovery time 1-12h；
It is preferred that reduction temperature is 200-400 DEG C, the preferably recovery time is 2-8h；
Reduction process described in method and step (3) provided by the present invention by the carbon distribution generated in step (1) and (2) and
Organic matter removes under the action of institute's carried metal through catalytic hydrogenation.
Catalyst provided by the present invention can be widely applied to petroleum distillate, biomass, the processing in Fischer-Tropsch synthetic
Process, such as isomerization-visbreaking, the processes such as isomerization dewaxing.
Compared with the method for preparing catalyst of conventional high-temperature (being not less than 450 DEG C) roasting demoulding, catalysis provided by the invention
Agent preparation 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. removing the template in molecular sieve completely using reduction process, make the catalyst of preparation that there is higher micropore hole
Hold and moderate strength acid amount；
3. the isomerization catalyst of preparation has higher isomerisation selectivity and isomers in alkane isomerization reaction
Yield.
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.
The test of sample acid amount carries out on Micromeritics AutoChem2920 chemical adsorption instrument.Sample is first being inhaled
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 attached instrument3, to be adsorbed full
With rear, logical He purging 60min, after waiting TCD detector baseline steady, 700 DEG C are risen to 10 DEG C/min, record NH3Desorption is bent
Line.The acidic site that desorption temperature is 250-450 DEG C is attributed to middle strong acid, and acidic site of the desorption temperature greater than 450 DEG C is attributed to by force
Acid, acid amount 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 449
F3 type instrument carries out thermogravimetric measurement to sample.Determination condition: sample sample-loading amount is 20mg, (the flow 20ml/ in air atmosphere
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 thermogravimetric knot
It is greater than 200 DEG C of weight loss in fruit.
The hole of sample holds measurement and carries out on Micromeritics ASAP2420 physical adsorption appearance.Before test, sample exists
Vacuumize process 6h at 200 DEG C, then carries out N under liquid nitrogen temperature2The measurement of absorption and desorption isotherm.The micropore hole of sample
Appearance is calculated by t-plot method.
Evaluating catalyst carries out in stainless steel tube fixed bed reactors, takes the catalyst 10mL of preparation loaded on reactor
In, it is warming up to reaction temperature in a hydrogen atmosphere, logical feedstock oil n-tetradecane is reacted, and product is by gas chromatographic analysis.Instead
Answer condition: 290-360 DEG C of reaction temperature, 10MPa, n-tetradecane liquid hourly space velocity (LHSV) 1.0h-1, hydrogen-oil ratio (mol/mol) is 15.
Comparative example
120g is taken to contain the ZSM-12 molecule of tetraethyl ammonium hydroxide template (10wt.% that content is molecular sieve)
Original powder is sieved, 18h is roasted under 550 DEG C of air atmospheres, obtains the ZSM-12 molecular sieve carrier that about 100g template removes completely, this point
Carbon distribution and content of organics are 0 in son sieve carrier, Micropore volume 0.050cm3/g.With the H of 5mL 0.05g/mL containing Pt2PtCl6
Solution impregnates the above-mentioned carrier of 50g, naturally dry and the dry 4h at 120 DEG C, uses hydrogen reducing 4h at 500 DEG C, is made
0.5wt.%Pt/ZSM-12 catalyst.Carbon distribution and content of organics are 0 in catalyst, and possessed middle strong acid amount is
0.53mmol/g, strong acid amount are 0.32mmol/g, Micropore volume 0.048cm3/g.Molecular sieve catalyst carbon distribution and organic matter contain
Amount, Micropore volume, middle strong acid amount, strong acid amount and the Micropore volume characterization result of catalyst are shown in Table 1, and catalysis reaction evaluating result is shown in
Table 2.
Embodiment 1
120g is taken to contain the ZSM-12 molecule of tetraethyl ammonium hydroxide template (10wt.% that content is molecular sieve)
It sieves original powder (identical as comparative example), roasts 12h under 210 DEG C of nitrogen atmospheres, molecular sieve carrier carbon distribution and content of organics after roasting
For 7.2wt.%；6h is roasted under 250 DEG C of air atmospheres, the ZSM-12 for obtaining about 105g template partial removal is molecular sieve supported
Body, the molecular sieve carrier carbon distribution and content of organics are 5.0wt.%, Micropore volume 0.013cm3/g.Contain Pt with 5mL
The H of 0.05g/mL2PtCl6Solution impregnates the above-mentioned carrier of 50g, and naturally dry simultaneously dries 4h at 120 DEG C, at 400 DEG C also with hydrogen
0.5wt.%Pt/ZSM-12 catalyst is made in former 4h.Carbon distribution and content of organics are 0 in catalyst, possessed middle strong acid amount
For 0.81mmol/g, strong acid amount is 0.17mmol/g, Micropore volume 0.056cm3/g.Molecular sieve catalyst carbon distribution and organic matter
Content, Micropore volume, middle strong acid amount, strong acid amount and the Micropore volume characterization result of catalyst are shown in Table 1, are catalyzed reaction evaluating result
It is shown in Table 2.
Embodiment 2
120g is taken to contain the TPZ-12 molecule of tetraethyl ammonium hydroxide template (12wt.% that content is molecular sieve)
Original powder is sieved, roasts 6h under 220 DEG C of nitrogen atmospheres, molecular sieve carrier carbon distribution and content of organics are 8.0wt.% after roasting；Then at
12h is roasted under 350 DEG C of air atmospheres, obtains the TPZ-12 molecular sieve carrier of about 105g template partial removal, this is molecular sieve supported
Volume carbon and content of organics are 2.9wt.%, Micropore volume 0.029cm3/g.With the H of 5mL 0.05g/mL containing Pt2PtCl6
Solution impregnates the above-mentioned carrier of 50g, naturally dry and the dry 4h at 120 DEG C, uses hydrogen reducing 2h at 400 DEG C, is made
0.5wt.%Pt/TPZ-12 catalyst.Carbon distribution and content of organics are 0 in catalyst, and possessed middle strong acid amount is
0.85mmol/g, strong acid amount are 0.15mmol/g, Micropore volume 0.055cm3/g.Molecular sieve catalyst carbon distribution and organic matter contain
Amount, Micropore volume, middle strong acid amount, strong acid amount and the Micropore volume characterization result of catalyst are shown in Table 1, and catalysis reaction evaluating result is shown in
Table 2.
Embodiment 3
120g is taken to contain the NU-13 molecular sieve of tetraethylammonium bromide template (20wt.% that content is molecular sieve)
Original powder roasts 2h under 250 DEG C of nitrogen atmospheres, and molecular sieve carrier carbon distribution and content of organics are 7.6wt.% after roasting；Then at 200
12h is roasted under DEG C ozone atmosphere, obtains the NU-13 molecular sieve carrier of about 105g template partial removal, the molecular sieve supported volume
Carbon and content of organics are 2.8wt.%, Micropore volume 0.030cm3/g.With the H of 5mL 0.05g/mL containing Pt2PtCl6Solution
The above-mentioned carrier of 50g, naturally dry and the dry 4h at 120 DEG C are impregnated, hydrogen reducing 8h is used at 200 DEG C, 0.5wt.%Pt/ is made
NU-13 catalyst.Carbon distribution and content of organics are 0 in catalyst, and possessed middle strong acid amount is 0.87mmol/g, and strong acid amount is
0.14mmol/g, Micropore volume 0.057cm3/g.Molecular sieve catalyst carbon distribution and content of organics, Micropore volume, catalyst
Middle strong acid amount, strong acid amount and Micropore volume characterization result be shown in Table 1, catalysis reaction evaluating the results are shown in Table 2.
Embodiment 4
Take VS-12 points that 120g contains methyl triethylammonium hydroxide template (6wt.% that content is molecular sieve)
Son sieves original powder, roasts 8h under 300 DEG C of nitrogen atmospheres, and molecular sieve carrier carbon distribution and content of organics are 5.1wt.% after roasting；Again
12h is roasted under 250 DEG C of ozone atmospheres, obtains the VS-12 molecular sieve carrier of about 101g template partial removal, this is molecular sieve supported
Volume carbon and content of organics are 0.5wt.%, Micropore volume 0.046cm3/g.With the H of 5mL 0.05g/mL containing Pt2PtCl6
Solution impregnates the above-mentioned carrier of 50g, naturally dry and the dry 4h at 120 DEG C, uses hydrogen reducing 4h at 300 DEG C, is made
0.5wt.%Pt/VS-12 catalyst.Carbon distribution and content of organics are 0 in catalyst, and possessed middle strong acid amount is
0.88mmol/g, strong acid amount are 0.13mmol/g, Micropore volume 0.060cm3/g.Molecular sieve catalyst carbon distribution and organic matter contain
Amount, Micropore volume, middle strong acid amount, strong acid amount and the Micropore volume characterization result of catalyst are shown in Table 1, and catalysis reaction evaluating result is shown in
Table 2.
Embodiment 5
120g is taken to contain the Theta-3 of methyl triethylammonium bromide template (10wt.% that content is molecular sieve)
Molecular screen primary powder roasts 6h under 250 DEG C of nitrogen atmospheres, and molecular sieve carrier carbon distribution and content of organics are 6.2wt.% after roasting；
4h is roasted under 250 DEG C of ozone atmospheres, obtains the Theta-3 molecular sieve carrier of about 105g template partial removal, the molecule
It sieves carrier carbon distribution and content of organics is 3.2wt.%, Micropore volume 0.021cm3/g.With 5mL 0.05g/mL's containing Pt
H2PtCl6Solution impregnates the above-mentioned carrier of 50g, naturally dry and the dry 4h at 120 DEG C, uses hydrogen reducing 4h at 350 DEG C, is made
0.5wt.%Pt/Theta-3 catalyst.Carbon distribution and content of organics are 0 in catalyst, and possessed middle strong acid amount is
0.92mmol/g, strong acid amount are 0.12mmol/g, Micropore volume 0.056cm3/g.Molecular sieve catalyst carbon distribution and organic matter contain
Amount, Micropore volume, middle strong acid amount, strong acid amount and the Micropore volume characterization result of catalyst are shown in Table 1, and catalysis reaction evaluating result is shown in
Table 2.
Catalyst characterization result in 1. comparative example of table and embodiment
Evaluating catalyst result in 2. comparative example of table and embodiment
As shown in Table 1, using the product of MTW structure molecular screen carrier (ZSM-12) after conventional method Template removal in comparative example
Carbon and content of organics are 0, the MTW structural molecule obtained in embodiment 1-5 using Template removal method in part of the present invention
It sieves and contains a small amount of carbon distribution and organic matter in carrier (ZSM-12, TPZ-12, NU-13, VS-12, Theta-3).But catalyst reduction
Afterwards, contained carbon distribution and organic matter are removed completely.The effect of generation are as follows: with catalyst phase made from conventional method in comparative example
Than embodiment 1-5 uses method of the present invention, and gained catalyst has higher middle strong acid acid amount and lower strong acid acid
Amount, while there is bigger Micropore volume.
As shown in Table 2, made from the conventional method in comparative example compared with catalyst, using our legal system in embodiment 1-5
The catalyst obtained can get higher isomerisation selectivity and yield in alkane hygrogenating isomerization reaction.
Claims (10)
1. a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier, which is characterized in that by MTW type knot
Structure molecular sieve carrier carries out two one-step bakings in inert atmosphere and oxygen-containing atmosphere, then carried metal, then through dry and reduction, system
Obtain the isomerization catalyst, comprising the following steps:
(1) by containing template, the molecular screen primary powder with MTW type structure inert atmosphere gases for example nitrogen, helium, neon,
One of argon gas or two kinds or more at 50-300 DEG C, roast 0.5-24h, carbon distribution and organic in the molecular sieve after control roasting
Object content is the 0.5-10wt.% of molecular sieve；
(2) by the molecular sieve after roasting in step (1) in one of oxygen-containing atmosphere such as air, oxygen, ozone or two kinds or more,
At 50-400 DEG C, 0.5-24h is roasted, carbon distribution and content of organics are the 0.2- of molecular sieve in the molecular sieve after control roasting
8wt.%；
(3) by the molecular sieve carried group VIII noble metals active component after roasting in step (2), after drying, in also Primordial Qi
In atmosphere, at 100-450 DEG C, 1-12h is restored, the isomerization catalyst is made.
2. according to the method described in claim 1, it is characterized by: the molecular sieve with MTW type structure be ZSM-12,
One of NU-13, CZH-5, TPZ-12, VS-12, Theta-3 or two kinds or more.
3. according to the method described in claim 1, it is characterized by: being roasted 100-300 DEG C of maturing temperature in the step (1)
Time is 1-12h.
4. according to the method described in claim 1, it is characterized by: being roasted 200-350 DEG C of maturing temperature in the step (2)
Time is 1-12h.
5. method according to claim 1, it is characterised in that: carbon distribution in the molecular sieve in the step (1) after roasting
And content of organics is the 0.5-8wt.% of molecular sieve.
6. method according to claim 1, it is characterised in that: carbon distribution in the molecular sieve in the step (2) after roasting
And content of organics is the 0.2-5wt.% of molecular sieve.
7. method according to claim 1, it is characterised in that: the group VIII noble metals activity in the step (3)
Group is divided into one of elements such as Pt, Pd, Ir, Ru, Rh or two kinds or more, and group VIII tenor is 0.05-5.0wt.%.
8. method according to claim 1, it is characterised in that: the drying temperature in the step (3) is 50-200 DEG C；
Drying time is 0.5-24h.
9. method according to claim 1, it is characterised in that: the reducing atmosphere in the step (3) is hydrogen, an oxygen
Change one or both of carbon；Reduction temperature is 200-400 DEG C, recovery time 2-8h.
10. according to the method described in claim 1, it is characterized by: template is tetrem in the step (1) molecular screen primary powder
Base ammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, 4-propyl bromide, methyl triethylammonium hydroxide, methyl three
One of ethyl phosphonium bromide ammonium or two kinds or more, content are the 0.5-20wt.% of molecular sieve.
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