CN109465031B - Preparation method of isomerization catalyst taking AFO type structure molecular sieve as carrier - Google Patents
Preparation method of isomerization catalyst taking AFO type structure molecular sieve as carrier Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 119
- 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 119
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000012298 atmosphere Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 229910052799 carbon Inorganic materials 0.000 claims description 42
- 230000008021 deposition Effects 0.000 claims description 26
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 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
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 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
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 52
- 239000011148 porous material Substances 0.000 abstract description 19
- 238000011068 loading method Methods 0.000 abstract description 6
- 239000012188 paraffin wax Substances 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 21
- 239000005416 organic matter Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000001179 sorption measurement 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- -1 silicon aluminum molecular sieve series Chemical class 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 238000012360 testing method Methods 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2791—Catalytic processes with metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an isomerization catalyst taking an AFO type structure molecular sieve as a carrier. The preparation method comprises the following specific steps: firstly, carrying out partial demoulding agent treatment on template-containing molecular sieve raw powder with an AFO type structure in an inert atmosphere at 50-300 ℃; and further treating the molecular sieve with AFO type structure after partial template removing agent in oxygen-containing atmosphere at 50-400 ℃, then loading metal active components on the obtained molecular sieve carrier, and drying and reducing to obtain the target catalyst. The removal mode of the template agent in the molecular sieve carrier is controlled, so that the acid property and the pore canal property of the molecular sieve carrier are effectively regulated and controlled. Compared with the catalyst prepared by the prior art, the catalyst prepared by the method has higher isomerization selectivity and isomer yield in the normal paraffin isomerization reaction.
Description
Technical Field
The invention belongs to the fields of petrochemical industry, fine chemical industry and molecular sieve catalysts, and particularly relates to a preparation method and application of an isomerization catalyst taking an AFO type structure molecular sieve as a carrier.
Background
The bifunctional solid catalyst is widely applied to alkane hydroisomerization process and consists of a hydrogenation-dehydrogenation component and an acidic carrier. Wherein, the hydrogenation-dehydrogenation component is mainly a VIII group metal such as Pt, Pd, Rh, Ir, Ni and the like; acidic carriers can be classified into the following three categories: 1. amorphous single metal oxides or composite oxides such as halide-treated Al2O3, SiO2/Al2O3, superacids ZrO2/SO42-, WO3/ZrO2, and the like; 2. silicon aluminum molecular sieve series, such as Y, Beta, ZSM-5, etc.; 3. the aluminum phosphate molecular sieves, such as SAPO-5, SAPO-11, SAPO-31, SAPO-41, and the like. Compared with amorphous oxides and super acids, the molecular sieve shows excellent performances in the aspects of shape selection selectivity, stability, poisoning resistance and carbon deposition resistance. Therefore, isomerization catalysts using molecular sieves as carriers are widely used. Patent documents such as US5882505, 2004138051, 2005077209, CN1792451, 1788844, 101245260, etc. all describe in detail the preparation of catalysts for the hydroisomerization of alkanes, supported on molecular sieves.
In the process of the molecular sieve acting on the hydroisomerization of long-chain alkane, the performance of the catalyst is determined by the combination of the pore canal and the acidity of the catalyst. The generation of carbon positive ions and the isomerization process in the normal paraffin hydroisomerization reaction are mainly carried out on an acid site at an orifice, and the distribution of an isomerization product is mainly determined by the space confinement effect of microporous pore channels of the molecular sieve. The distribution and quantity of the acid sites of the molecular sieve obviously influence the performance of the catalyst, wherein the isomerization activity on the weak acid sites is poor, and the cracking is easily caused by the strong acid sites, so that the selectivity and the yield of a target product are reduced. The ideal alkane hydroisomerization catalyst needs to have more medium-strength acid sites and micropore quantity, and can obtain higher isomerization selectivity and higher yield of the isomeric hydrocarbon in the alkane isomerization reaction.
The acidity and micropores of the molecular sieve result from the removal of the organic templating agent from the molecular sieve. The organic template agent in the molecular sieve is removed by adopting a high-temperature roasting method, namely: the synthesized molecular sieve is directly roasted at high temperature (not lower than 450 ℃) in oxygen-containing atmosphere such as air and the like to completely remove the template agent. For example, Liu et al calcination treatment at 550 ℃ for 8h in an air atmosphere to remove the template hexanediamine (J.Catal.2016,335,11) from ZSM-22; wang et al calcinate at 550 deg.C for 3h in air atmosphere to remove template agent pyrrolidine (Ind. Eng. chem. Res.2016,55,6069) in ZSM-23; liu et al remove the template dipropylamine (J.colloid Interf.Sci.2014,418,193) in SAPO-11 by roasting at 600 ℃ for 6h in air atmosphere; philippaerts et al remove the templating agent tetrapropylammonium bromide in ZSM-5 by calcination treatment at 550 ℃ for 24h in an air atmosphere (J.Catal.2010,270, 172).
Although the organic template agent can be thoroughly removed by high-temperature roasting in the air atmosphere, the template agent can generate steam and local high temperature and high pressure by oxidative combustion in the roasting process, so that the framework structure of the molecular sieve is damaged, and the pore channel property and the acidic property of the molecular sieve are influenced. For example, Corma et al have found that high temperature (not less than 450 ℃) calcination during calcination of molecular sieves to remove templating agents causes dealumination of the molecular sieves, framework collapse, reduction of micropores, and affects surface acidity (j.catal.1994,148, 569). Ward et al found that high temperature (not less than 450 ℃) calcination resulted in the destruction of structural hydroxyl groups, resulting in a change in the distribution and number of acid sites of the molecular sieve, a decrease in acid sites of moderate strength, and an increase in strong acid sites (j.catal.1968,11,251).
SAPO-41 and MeAPO-41(Me ═ Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni) molecular sieves are a class of artificially synthesized silicoaluminophosphate microporous molecular sieves, belong to AFO topological structures, have one-dimensional ten-membered ring channel structures, and have pore sizes of about
It can be synthesized by using different templates. Because of the characteristic and moderate acidity of one-dimensional pore channel, the supported catalyst taking the supported catalyst as the carrier shows excellent performance in the hydroisomerization reaction of long-chain alkane. Similar to the molecular sieve demolding means, the template agent in the molecular sieve is usually removed by high-temperature (not lower than 450 ℃) calcination in the preparation of the catalyst taking the AFO type molecular sieve as the carrier, and the conventional high-temperature (not lower than 450 ℃) calcination demolding means influences the distribution of acid sites, the acid amount and the number of micropores on the AFO type molecular sieve, so that the number of micropores is reduced, the acid sites with medium strength are reduced, the acid sites with strong strength are increased, and the performance of the catalyst is further influenced. Therefore, the removal mode of the template agent in the molecular sieve is controlled by a new means, so that the carrier acid of the SAPO-41 and MeAPO-41(Me ═ Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni) molecular sieve is realizedThe control of the distribution of properties and the amount of acid and the number of micropores is essential for the preparation of a paraffin hydroisomerization catalyst with high isomerization selectivity/yield.
The invention provides a preparation method of a catalyst which takes an AFO type structure molecular sieve as a carrier and removes a template agent through step-by-step low-temperature (not higher than 450 ℃) roasting and hydrogenation reduction. The molecular sieve containing the template agent is respectively subjected to two-step low-temperature roasting processes in an inert atmosphere and an oxygen-containing atmosphere to partially remove the template agent (so that the template agent is decomposed in the low-temperature roasting process to generate active carbon species including carbon deposition and organic matters); then loading metal, and removing active carbon species generated in the low-temperature roasting process by catalytic hydrogenation of the loaded metal in the reduction process. Compared with the traditional high-temperature demoulding method, the method can reduce the damage degree of the high-temperature (not lower than 450 ℃) roasting to the framework structure of the molecular sieve, reserve the framework acid site with medium strength on the molecular sieve, and simultaneously inhibit the formation of strong acid site when hydroxyl is removed due to the high-temperature roasting. Therefore, the prepared catalyst has more medium-strength acid sites and larger micropore volume, and shows better isomerization selectivity and yield in the alkane isomerization process.
Disclosure of Invention
The invention aims to provide a preparation method of an isomerization catalyst taking an AFO type structure molecular sieve as a carrier.
The invention also relates to the application of the catalyst in the isomerization reaction of the alkane.
Specifically, the preparation method of the catalyst provided by the invention is characterized in that: the isomerization catalyst is prepared by roasting an AFO type structure molecular sieve carrier at a lower temperature (not higher than 450 ℃), in an inert atmosphere and an oxygen-containing atmosphere, then loading metal, and then drying and reducing the metal, and comprises the following steps:
(1) roasting the molecular sieve raw powder containing the template agent and having an AFO type structure for 0.5-24h at 50-300 ℃ in an inert atmosphere such as one or more of nitrogen, helium, neon and argon, and controlling the content of carbon deposition and organic matters in the roasted molecular sieve to be 0.5-10 wt% of the weight of the molecular sieve;
(2) roasting the molecular sieve roasted in the step (1) for 0.5-24h in oxygen-containing atmosphere such as one or more of air, oxygen and ozone at 50-400 ℃, and controlling the content of carbon deposition and organic matters in the roasted molecular sieve to be 0.2-8 wt% of the weight of the molecular sieve;
(3) and (3) loading the VIII group noble metal active component on the molecular sieve calcined in the step (2), drying, and reducing for 1-12h at the temperature of 100-450 ℃ in a reducing atmosphere to prepare the isomerization catalyst.
In the method provided by the invention, the molecular sieve with an AFO type structure is one or more of SAPO-41 and MeAPO-41(Me ═ Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni);
the template agent in the steps (1) and (2) of the method provided by the invention is organic amine filled in pore channels of an AFO type structure molecular sieve, which is derived from the self-synthesis process of the AFO type structure molecular sieve, and comprises but is not limited to tetrabutylammonium hydroxide, di-n-propylamine, diisopropylamine, diethylamine, di-n-butylamine, diisobutylamine and other organic amines or a mixture thereof;
the noble metal active component loading process in the step (3) of the method provided by the invention adopts conventional operations in the field, including but not limited to impregnation, precipitation, deposition, adhesive bonding or mechanical pressing and the like, so that the VIII group noble metal precursor is dispersed on the carrier to realize the combination of the VIII group noble metal and the carrier; the metal precursors used include, but are not limited to, metal acids, metal acid salts, chlorides, ammonia complexes, carbonyl complexes, or mixtures thereof;
the inert atmosphere in the step (1) of the method provided by the invention is one or more of nitrogen, helium, neon and argon;
the roasting temperature in the step (1) of the method provided by the invention is 50-300 ℃, which is lower than the temperature required for completely removing the template agent in the molecular sieve, and the optimal treatment temperature is 100-300 ℃;
the roasting time in the step (1) of the method provided by the invention is 0.5-24h, and the preferable roasting time is 1-12 h;
the roasting atmosphere in the step (2) of the method provided by the invention is an oxygen-containing atmosphere, such as one or more of air, oxygen and ozone;
the roasting temperature in the step (2) of the method provided by the invention is 50-400 ℃, is lower than the temperature required for completely removing the template agent in the molecular sieve, and preferably is 200-350 ℃;
in the step (2) of the method provided by the invention, the roasting time is 0.5-24h, and preferably 1-12 h;
the method provided by the invention comprises the following steps that (1) in the roasting process, a template agent in AFO type molecular sieve raw powder is partially removed, and the content of carbon deposition and organic matters in the roasted AFO type molecular sieve is controlled to be 0.5-10 wt% of the total weight of the molecular sieve;
in the method, the template agent in the AFO type molecular sieve raw powder is partially removed in the roasting process in the step (1), and the content of carbon deposition and organic matters in the roasted AFO type molecular sieve is controlled to be 0.5-8 wt% of the total weight of the molecular sieve;
in the method provided by the invention, the template agent in the AFO type molecular sieve raw powder is further removed in the roasting process in the step (2), and the content of carbon deposit and organic matters in the roasted AFO type molecular sieve is controlled to be 0.2-8 wt% of the total weight of the molecular sieve;
in the method provided by the invention, the template agent in the AFO type molecular sieve raw powder is further removed in the roasting process in the step (2), and the content of carbon deposition and organic matters in the roasted AFO type molecular sieve is controlled to be 0.2-5 wt% of the total weight of the molecular sieve carrier;
the roasting process in the step (2) of the method provided by the invention further removes the template agent in the AFO type molecular sieve raw powder; controlling the pore volume of the roasted AFO type molecular sieve to be not more than 90 percent, preferably not more than 80 percent of the molecular sieve carrier completely removed by the template;
in the step (3) of the method provided by the invention, the active component of the VIII group noble metal is one or more of Pt, Pd, Ir, Ru, Rh and other elements, and the content of the VIII group metal is 0.05-5.0wt.%, preferably 0.1-3.0 wt.%;
the drying temperature in the step (3) of the method is 20-200 ℃, and the drying time is 0.5-24 h; preferably, the drying temperature is 70-150 ℃, and the drying time is 2-8 h;
the reduction mode in step (3) of the method provided by the invention is a conventional operation in the field, and generally, the catalyst is reduced by contacting one or two of reducing atmosphere such as hydrogen and carbon monoxide with the catalyst;
the reduction temperature in the step (3) of the method is 100-450 ℃, and the reduction time is 1-12 h; the preferable reduction temperature is 200-400 ℃, and the preferable reduction time is 2-8 h;
in the reduction process in the step (3) of the method provided by the invention, carbon deposit and organic matters generated in the steps (1) and (2) are removed by catalytic hydrogenation under the action of loaded metal.
The catalyst provided by the invention can be widely applied to the processing processes of petroleum fractions, biomasses and Fischer-Tropsch synthesis products, such as the processes of isomerization pour point depression, isomerization dewaxing and the like.
Compared with the traditional preparation method of the catalyst by roasting at high temperature (not lower than 450 ℃) and demoulding, the preparation method of the catalyst provided by the invention has the following advantages:
1. the roasting and demolding temperature of the molecular sieve carrier is reduced, and the energy consumption in the preparation process of the catalyst is reduced;
2. the template agent in the molecular sieve is completely removed in the reduction process, so that the prepared catalyst has higher micropore volume and medium-strength acid content;
3. the prepared isomerization catalyst has higher isomerization selectivity and isomer yield in the isomerization reaction of the alkane.
Detailed Description
The invention will be further described with reference to specific examples, but it should be understood that the invention is not limited thereto.
The measurement of the acid amount of the sample was carried out on a Micromeritics AutoChem2920 chemisorption instrument. The sample is firstly treated in situ for 60min under the condition of introducing He at 350 ℃ on an adsorption instrument, then the temperature of a sample tube is reduced to 100 ℃, NH3 is introduced, after adsorption saturation, He is introduced for purging for 60min, after a TCD detector base line is stable, the temperature is increased to 700 ℃ at 10 ℃/min, and an NH3 desorption curve is recorded. The acid position with the desorption temperature of 250-450 ℃ is assigned as medium-strong acid, the acid position with the desorption temperature of more than 450 ℃ is assigned as strong acid, and the acid amount is calculated according to an NH3 concentration calibration curve and an NH3 desorption peak area.
And determining the carbon deposition and organic matter content of the sample according to the thermogravimetric analysis result. The samples were subjected to thermogravimetric measurements using an instrument of type STA 449F3, NETZSCH company, germany. The measurement conditions were as follows: the sample loading was 20mg and the temperature was raised from 40 ℃ to 900 ℃ at a rate of 10 ℃/min in an air atmosphere (flow 20 ml/min). The carbon deposition and organic matter content of the sample are weight loss amounts of more than 200 ℃ in the thermogravimetric result of the sample.
The pore volume measurements of the samples were performed on a Micromeritics ASAP2420 physisorption instrument. Before testing, the samples were subjected to vacuum treatment at 200 ℃ for 6h, and then subjected to N2 adsorption and desorption isotherms at liquid nitrogen temperature. The micropore volume of the sample was calculated by the t-plot method.
The catalyst evaluation is carried out in a stainless steel tube fixed bed reactor, 10mL of the prepared catalyst is loaded in the reactor, the temperature is raised to the reaction temperature under the hydrogen atmosphere, the raw oil n-tetradecane is introduced for reaction, and the product is analyzed by gas chromatography. Reaction conditions are as follows: the reaction temperature is 300-.
Comparative example
120g of SAPO-41 molecular sieve raw powder (with the Si content of 0.6 wt.%) containing tetrabutylammonium hydroxide template (with the content of 10 wt.%) is roasted at 550 ℃ for 18h in an air atmosphere to obtain about 100g of SAPO-41 molecular sieve carrier with the template completely removed, wherein the content of carbon and organic matters in the molecular sieve carrier is 0, and the micropore volume is 0.046cm 3/g. 50g of the above support was impregnated with 5mL of a solution of H2PtCl6 containing 0.05g/mL of Pt, air dried naturally and dried at 120 ℃ for 4H, and reduced with hydrogen at 400 ℃ for 4H to obtain a 0.5 wt.% Pt/SAPO-41 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the content of medium strong acid is 0.47mmol/g, the content of strong acid is 0.27mmol/g, and the pore volume of micropores is 0.044cm 3/g. The carbon deposition, organic matter content and micropore volume of the molecular sieve catalyst, the characterization results of medium-strong acid quantity, strong acid quantity and micropore volume of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 1
Taking 120g of SAPO-41 molecular sieve raw powder (same as a comparative example, the Si content is 0.6 wt.%) containing a tetrabutylammonium hydroxide template (the content is 10 wt.%), roasting at 210 ℃ for 12h in a nitrogen atmosphere, and enabling the carbon and organic matter content of the molecular sieve to be 6.9 wt.%; and continuously roasting for 6 hours at 250 ℃ in the air atmosphere to obtain about 105g of SAPO-41 molecular sieve carrier with the partially removed template agent, wherein the volume of carbon and organic matters loaded by the molecular sieve is 5.0wt.%, and the pore volume of micropores is 0.011cm 3/g. 50g of the above support was impregnated with 5mL of a solution of H2PtCl6 containing 0.05g/mL of Pt, air dried naturally and dried at 120 ℃ for 4H, and reduced with hydrogen at 400 ℃ for 4H to obtain a 0.5 wt.% Pt/SAPO-41 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the content of medium strong acid is 0.72mmol/g, the content of strong acid is 0.11mmol/g, and the pore volume of micropores is 0.052cm 3/g. The carbon deposition, organic matter content and micropore volume of the molecular sieve catalyst, the characterization results of medium-strong acid quantity, strong acid quantity and micropore volume of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 2
120g of MgAPO-41 molecular sieve raw powder (the Mg content is 0.05 wt.%) containing tetrabutylammonium hydroxide template (the content is 12 wt.%) of the molecular sieve weight is roasted for 6h at 220 ℃ in a nitrogen atmosphere, and the carbon and organic matter content of the molecular sieve after roasting is 8.0 wt.%; and then roasting for 12 hours at 350 ℃ in the air atmosphere to obtain about 105g of MgAPO-41 molecular sieve carrier with the template partially removed, wherein the carbon and organic matter content of the molecular sieve carrier volume is 2.8 wt.%, and the micropore volume is 0.025cm 3/g. 50g of the carrier is soaked in 5mL of H2PtCl6 solution containing Pt0.05g/mL, naturally dried and dried at 120 ℃ for 4H, and reduced by hydrogen at 400 ℃ for 2H to prepare 0.5 wt.% of Pt/MgAPO-41 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the content of medium strong acid is 0.74mmol/g, the content of strong acid is 0.10mmol/g, and the pore volume of micropores is 0.051cm 3/g. The carbon deposition, organic matter content and micropore volume of the molecular sieve catalyst, the characterization results of medium-strong acid quantity, strong acid quantity and micropore volume of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 3
Taking 120g of ZnAPO-41 molecular sieve raw powder (the Zn content is 1 wt.%) containing a di-n-butylamine template (the content is 20 wt.%), roasting at 250 ℃ for 2h in a nitrogen atmosphere, wherein the carbon and organic matter content of the molecular sieve after roasting is 7.6 wt.%; and roasting at 200 ℃ in an ozone atmosphere for 12 hours to obtain about 105g of ZnAPO-41 molecular sieve carrier with the template agent partially removed, wherein the content of carbon and organic matters in the carrier volume of the molecular sieve is 2.7 wt.%, and the pore volume of micropores is 0.026cm 3/g. 50g of the above support was impregnated with 5mL of a solution of H2PtCl6 containing 0.05g/mL of Pt, air dried naturally and dried at 120 ℃ for 4H, and reduced with hydrogen at 200 ℃ for 8H to produce a 0.5 wt.% Pt/ZnAPO-41 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the content of medium strong acid is 0.71mmol/g, the content of strong acid is 0.10mmol/g, and the pore volume of micropores is 0.053cm 3/g. The carbon deposition, organic matter content and micropore volume of the molecular sieve catalyst, the characterization results of medium-strong acid quantity, strong acid quantity and micropore volume of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 4
120g of CoAPO-41 molecular sieve raw powder (the Co content is 1.5 wt.%) containing a di-n-butylamine template (the content is 6 wt.%) of the molecular sieve weight is roasted for 8 hours at 300 ℃ in a nitrogen atmosphere, and the carbon and organic matter content of the molecular sieve after roasting is 4.8 wt.%; and then roasting for 12 hours at 250 ℃ in an ozone atmosphere to obtain about 101g of CoAPO-41 molecular sieve carrier with the template agent partially removed, wherein the content of carbon and organic matters in the carrier volume of the molecular sieve is 0.5 wt.%, and the pore volume of micropores is 0.043cm 3/g. 50g of the above support was impregnated with 5mL of a solution of 0.05g/mL Pt in H2PtCl6, air dried naturally and dried at 120 ℃ for 4H and reduced with hydrogen at 300 ℃ for 4H to produce 0.5 wt.% Pt/CoAPO-41 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the content of medium strong acid is 0.75mmol/g, the content of strong acid is 0.09mmol/g, and the pore volume of micropores is 0.056cm 3/g. The carbon deposition, organic matter content and micropore volume of the molecular sieve catalyst, the characterization results of medium-strong acid quantity, strong acid quantity and micropore volume of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
Example 5
Taking 120g of MnAPO-41 molecular sieve raw powder (the Mn content is 5 wt.%) containing diisobutylamine and diethylamine template (the content is 10 wt.%), roasting at 250 ℃ for 6h in a nitrogen atmosphere, and enabling the content of carbon and organic matters in the molecular sieve to be 5.8 wt.% after roasting; and roasting at 250 ℃ in an ozone atmosphere for 4 hours to obtain about 105g of MnAPO-41 molecular sieve carrier with the partially removed template agent, wherein the content of carbon and organic matters in the volume of the molecular sieve carrier is 3.4 wt.%, and the pore volume of micropores is 0.021cm 3/g. 50g of the above support was impregnated with 5mL of H2PtCl6 solution containing Pt0.05g/mL, air dried naturally and dried at 120 ℃ for 4H, and reduced with hydrogen at 350 ℃ for 4H to give 0.5 wt.% Pt/MnAPO-41 catalyst. The content of carbon deposition and organic matters in the catalyst is 0, the content of medium strong acid is 0.76mmol/g, the content of strong acid is 0.08mmol/g, and the pore volume of micropores is 0.054cm 3/g. The carbon deposition, organic matter content and micropore volume of the molecular sieve catalyst, the characterization results of medium-strong acid quantity, strong acid quantity and micropore volume of the catalyst are shown in table 1, and the catalytic reaction evaluation results are shown in table 2.
TABLE 1 characterization results of catalysts in comparative examples and examples
TABLE 2 evaluation results of catalysts in comparative examples and examples
| Normal tetradecane conversion (%) | Isomeric tetradecane Selectivity (%) | Yield (%) of isomeric tetradecane | |
| Comparative example | 88 | 65 | 57 |
| Example 1 | 90 | 77 | 69 |
| Example 2 | 92 | 76 | 70 |
| Example 3 | 93 | 77 | 72 |
| Example 4 | 92 | 78 | 72 |
| Example 5 | 93 | 79 | 73 |
As can be seen from Table 1, the carbon and organic contents of the AFO structure molecular sieve carrier (SAPO-41) after the plate-removing agent is removed by the conventional method in the comparative example are 0, and the AFO structure molecular sieve carriers (SAPO-41 and MeAPO-41) obtained by the partial plate-removing agent method in the examples 1 to 5 contain a small amount of carbon and organic matters. But the carbon deposit and organic matter contained in the catalyst are completely removed after the catalyst is reduced. The effect is: examples 1-5 using the process of the present invention, the catalysts obtained had higher amounts of medium and lower amounts of strong acid, while having greater micropore volume than the catalysts prepared by the conventional process of the comparative example.
As can be seen from Table 2, the catalysts obtained in examples 1 to 5 using the present process can achieve higher isomerization selectivity and yield in the hydroisomerization of paraffins than the catalysts obtained by the conventional process in the comparative example.
Claims (9)
1. A method for preparing an isomerization catalyst with an AFO type structure molecular sieve as a carrier is characterized in that the AFO type structure molecular sieve carrier is roasted in two steps in an inert atmosphere and an oxygen-containing atmosphere, then a metal is loaded, and the isomerization catalyst is prepared by drying and reducing, and comprises the following steps:
(1) roasting the molecular sieve raw powder containing the template agent and having an AFO type structure for 0.5-24h at 50-300 ℃ in an inert atmosphere gas such as one or more of nitrogen, helium, neon and argon, and controlling the content of carbon deposition and organic matters in the roasted molecular sieve to be 0.5-10 wt% of the weight of the molecular sieve;
(2) roasting the molecular sieve roasted in the step (1) for 0.5-24h in oxygen-containing atmosphere such as one or more of air, oxygen and ozone at 50-400 ℃, and controlling the content of carbon deposition and organic matters in the roasted molecular sieve to be 0.2-8 wt% of the weight of the molecular sieve;
(3) the molecular sieve roasted in the step (2) is loaded with VIII group noble metal active components, and is reduced for 1-12h at the temperature of 100-450 ℃ in a reducing atmosphere after being dried to prepare the isomerization catalyst;
the molecular sieve with the AFO type structure is one or more of SAPO-41 and MeAPO-41(Me = one or more of Zn, Mg, Mn, Co, Cr, Cu, Cd and Ni, and the mass content of the molecular sieve is 0.05-5 wt.%).
2. The method of claim 1, wherein: the roasting temperature in the step (1) is 100-.
3. The method of claim 1, wherein: the roasting temperature in the step (2) is 200-350 ℃, and the roasting time is 1-12 h.
4. The method of claim 1, wherein: the content of carbon deposition and organic matters in the molecular sieve roasted in the step (1) is 0.5-8 wt% of the weight of the molecular sieve.
5. The method of claim 1, wherein: the content of carbon deposition and organic matters in the molecular sieve roasted in the step (2) is 0.2-5 wt% of the weight of the molecular sieve.
6. The method of claim 1, wherein: the active component of the VIII group noble metal in the step (3) is one or more than two of Pt, Pd, Ir, Ru, Rh and other elements, and the content of the VIII group metal is 0.05-5.0 wt.%.
7. The method of claim 1, wherein: the drying temperature in the step (3) is 50-200 ℃; the drying time is 0.5-24 h.
8. The method of claim 1, wherein: the reducing atmosphere in the step (3) is one or two of hydrogen and carbon monoxide; the reduction temperature is 200 ℃ and 400 ℃, and the reduction time is 2-8 h.
9. The method of claim 1, wherein: the template agent in the molecular sieve raw powder in the step (1) is one or more than two of tetrabutyl ammonium hydroxide, di-n-propylamine, diisopropylamine, diethylamine, di-n-butylamine and diisobutylamine, and the content of the template agent is 0.5-20 wt% of the weight of the molecular sieve.
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