CN106799257A - A kind of alkane isomerization catalyst and preparation method thereof - Google Patents
A kind of alkane isomerization catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 22
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 241000269350 Anura Species 0.000 claims abstract description 29
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 238000002425 crystallisation Methods 0.000 claims description 37
- 230000008025 crystallization Effects 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 12
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007792 addition Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- -1 alkane alkane Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 22
- 239000002808 molecular sieve Substances 0.000 description 18
- 239000003643 water by type Substances 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 238000002386 leaching Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical class CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical class CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229940001007 aluminium phosphate Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003930 superacid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical class [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 101100233056 Caenorhabditis elegans ima-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052721 tungsten 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
-
- 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
-
- 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)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of alkane isomerization catalyst and preparation method thereof.The catalyst is made up of one or two in a kind of SAPO composite molecular screen and group VIII noble metals Pt, Pd, Ir that content is 0.05~5.0wt%.Described SAPO composite molecular screen has SAPO-11 and a kind of multiphase of aluminium silicophosphate salt, and its X-ray diffraction spectrogram has diffraction maximum at least set forth below,Value represents diffraction maximum position,
Description
Technical field
The present invention relates to a kind of alkane isomerization catalyst, and in particular to the alkane isomerization catalyst being made up of a kind of SAPO composite molecular screen and group VIII noble metals that content is 0.05~5.0wt%.
The invention further relates to the preparation method of above-mentioned catalyst.
Background technology
The alkane isomerization catalyst of early stage, predominantly liquid acid catalyst, such as AlCl3- HCl Freunds catalyst, sulfuric acid and liquid superacid catalyst.These liquid acid catalysts have isomerization performance very high, generally when room temperature is to 90 DEG C, can just obtain the conversion ratio close to balance, but selectivity is poor and stability is not enough.Further, since the strong corrosion to equipment and the severe contamination to environment, are eliminated substantially at present.From the forties in last century, difunctional solid catalyst is gradually developed, is applied to alkane isomerization process.
Difunctional solid catalyst is made up of hydrogenation-dehydrogenation component and acid carrier two parts.Hydrogenation-dehydrogenation component can be divided into two classes, including：1st, monometallic or many metal composite systems, such as Pt, Pd, Rh, Ir and Ni；2nd, transient metal sulfide system, such as Ni-Co, Ni-W, Ni-Mo sulfides.Acid carrier can then be divided into following three class：1st, unformed single metal oxides or composite oxides, the Al for such as being processed through halide2O3、SiO2/Al2O3, super acids ZrO2/SO4 2-、WO3/ZrO2Deng；2nd, Si-Al molecular sieve series, such as Y, Beta, ZSM-5, ZSM-22；3rd, aluminium phosphate molecular sieve series, such as SAPO-5, SAPO-11, SAPO-31 and SAPO-41.Compared with unformed oxide and super acids, molecular sieve shows excellent performance in terms of type selectivity, stability, antitoxinization and carbon accumulation resisting ability is selected.Therefore, based on molecular sieve for the isomerization catalyst of carrier is used widely.
Molecular sieve, refers to the material with sieving capacity on molecular dimension.There is the surface nature of regular pore passage structure and uniqueness due to it, catalysis has been widely used in, ion exchange is adsorbed and the field such as separates.The molecular screen material that the mankind recognize earliest is natural zeolite, nineteen forties, Barrer R M et al. realize the artificial synthesized of molecular sieve first, afterwards substantial amounts of molecular screen material in succession by it is artificial synthesized out, however as industrial expansion, many fields are proposed requirement higher, therefore exploitation to the performance of molecular sieve, structureIt is newMolecular screen material it is especially significant.
Aluminium phosphate molecular sieve (AlPO4- n) it is the class developed the eighties in last centuryIt is newMolecular screen material.The skeleton of this molecular sieve analog is strictly by PO4 +And AlO4 -Tetrahedron is alternately constituted, and without the electric charge that can be exchanged, thus without acidity, the application in catalytic reaction is extremely limited.Carry out same order elements with silicon on aluminium phosphate molecular sieve skeleton, you can generation silicoaluminophosphamolecular molecular sieves (SAPO-n) so that its because skeleton electric charge imbalance there is acidity.Simultaneously as also maintaining AlPO4The pore passage structure of-n, makes SAPO-n have huge application prospect in terms of catalysis.At present, existing various SAPO-n are applied to chemical industry process, particularly petroleum refining associated catalytic process.Such as, the application of applications of the SAPO-34 during methanol-to-olefins, and SAPO-11 during diesel modifying and lubricating oil dewaxing etc..
SAPO-11 molecular sieves have AEL structure, belong to rhombic system, and space group is Ima2, and cell parameter isIts skeleton is main by PO4 +、AlO4 -And SiO4Tetrahedron is intertwined to form, and with the one-dimensional straight hole road of oval ten-ring, duct size isIts typical x-ray diffraction patternFigureDataSuch as table 1It is shown.
Table
1
* diffraction peak intensity, w-m:<20；m:20~70；s:70~90；vs:90~100
Synthesis on silicoaluminophosphamolecular molecular sieves SAPO-11, it is seen that in many patent reports, such as US4440871, US4310440, US4943324, US5208005, EP146384, CN99109681 etc..Hydrothermal synthesis method is used in these patents, synthesizes pure phase SAPO-11.Weak acid position and middle strong acidic site are can be only formed on the SAPO-11 molecular sieves prepared due to the design feature of AEL skeletons, the various synthetic methods reported at present, i.e., from NH3Seen in-TPD characterization results, NH3Desorption peaks be only present in 180 and 280 DEG C or so (such asAccompanying drawing 2It is shown), weak acid position and middle strong acidic site are represented respectively.Continue the substitution amount of raising silicon, the quantity of both acidic sites can only be improved, stronger acidic site can not be produced, i.e., in NH3-TPDIn figureThere are 400 DEG C or so of desorption peaks.
During SAPO-11 acts on long chain alkane isomerization, the performance of catalyst is together decided on by the one-dimensional straight hole road of ten-ring and its acidity of SAPO-11.Acid stronger, catalyst activity is higher, and the reaction temperature needed for reaching target conversion is lower.Therefore, SAPO-11 of the synthesis with strong acidic site or the SAPO-11 composite molecular screens with strong acidic site, it would be possible to expand the molecular sieve analog further applying during isomerization and cracking catalysis.More excellent performance will be shown based on the alkane isomerization prepared by the molecular sieve analog.
The content of the invention
It is an object of the invention to provide a kind of alkane isomerization catalyst, it is made up of SAPO composite molecular screen and group VIII noble metals；Wherein, the mass content of group VIII noble metals is 0.05~5.0wt%；
Wherein, SAPO composite molecular screen has the micropore of 0.3~0.7nm, and BET specific surface area is 100~300m2/ g, pore volume is 0.1~0.5mL/g, its x-ray diffraction patternFigureWith diffraction maximum at least set forth below,
2 θ values expression diffraction maximum position, 2 θ/°：8.14 ± 0.2,9.48 ± 0.2,12.49 ± 0.1,13.24 ± 0.2,15.70 ± 0.2,16.32 ± 0.2,17.56 ± 0.2,17.87 ± 0.1,19.02 ± 0.2,20.46 ± 0.2,21.10 ± 0.2,21.66 ± 0.1,22.18 ± 0.2,22.60 ± 0.2,22.76 ± 0.2,23.22 ± 0.2,24.74 ± 0.2,27.86 ± 0.1,28.49 ± 0.1,33.03 ± 0.1,33.41 ± 0.1.
The group VIII noble metals are one or two or three kinds in Pt, Pd or Ir.
The mass content of group VIII noble metals is preferably 0.1~2.0wt%.
The present invention also provides the method for preparing above-mentioned alkane isomerization catalyst, and step is as follows：
A) silicon source, phosphorus source and water are mixed and stirred for uniformly being made precursor mixture A；Precursor mixture A still aging 0~12h at 0~30 DEG C；
B) organic amine is added in the precursor mixture A after still aging, silicon source is added after being stirred until homogeneous, continue to be stirred until homogeneous to form precursor mixture B, in B, silicon source：Phosphorus source：Silicon source：Organic amine is with Al2O3:P2O5:SiO2:Organic amine meter, molar ratio is 1:0.1~5:0.01~5:0.1~5；
C) crystallization under the conditions of obtained precursor mixture B being heated into 120 DEG C~250 DEG C, crystallization time is 8~48h；
D) after crystallization terminates, reactant is cooled to room temperature, is filtered, washed and dried, the solid for obtaining is SAPO composite molecular screen；
E) using one or two or more kinds in dipping, precipitation, addition adhesive bond or mechanical press method, the combination of group VIII noble metals and SAPO composite molecular screen is realized, and in 400~600 DEG C of roastings；
F) preceding in use, the catalyst after roasting is by reduction treatment.
Described phosphorus source is one or two or more kinds in the ammonium phosphate in phosphoric acid or phosphate, monoammonium phosphate or ammonium dihydrogen phosphate；
Described silicon source is one kind or two kinds in boehmite or hydrated alumina；
Described organic amine is one or two or more kinds in fatty amine, aromatic amine, hydramine, quaternary ammonium compound；
The group VIII noble metals are one or two or three kinds in Pt, Pd or Ir.
Described silicon source is one or two or more kinds in gas-phase silica, Ludox, waterglass, solid silicone and amorphous silica.
In step a), optimum condition precursor mixture A still aging 0~8h at 0~25 DEG C.
In step b), in optimum condition precursor mixture B, silicon source：Phosphorus source：Silicon source：Organic amine is with Al2O3:P2O5:SiO2:Organic amine meter, molar ratio is 1:0.5~2:0.1~1:0.5~2.
In step c), optimum condition crystallization temperature is 160 DEG C~220 DEG C, and crystallization time is 12~36h.
Step d)Described organic amine is preferably fatty amine.
The combination of the step e) group VIII noble metals and SAPO composite molecular screen, metal acid, metal acid-salt, chloride, ammino-complex, carbonyl complex or their mixture for using group VIII noble metals are raw material.
Reduction treatment described in step f), reducing atmosphere is hydrogen, or hydrogen and inert gas gaseous mixture, reduction temperature is 100~600 DEG C.
Compared with using the pure SAPO-11 for being currently known means synthesis, SAPO composite molecular screen involved in the present invention has stronger acid and more acid amount.
Therefore, with, based on the catalyst that pure SAPO-11 is carrier, the alkane isomerization catalyst prepared by the present invention has the characteristics that prepared by prior art：
(1) the SAPO-11 crystalline phases with higher-strength, i.e. maintain a large amount of one-dimensional straight hole roads of ten-ring with AEL structure；Meanwhile, also with a kind of crystalline phase of stratiform aluminium silicophosphate salt；
(2) with a large amount of strong acid acidic sites；
(3) when for long chain alkane isomerization reaction, activity is higher, long chain alkane is reached reaction temperature required during high conversion lower.
Brief description of the drawings
Figure 1It is the X-ray diffraction spectrum of pure SAPO-11 prepared by comparative example 1Figure
Figure 2It is the NH of pure SAPO-11 prepared by comparative example 13- TPD is characterizedFigure
Figure 3The X-ray diffraction spectrum of SAPO composite molecular screen in the alkane isomerization catalyst prepared for the embodiment of the present invention 1Figure
Figure 4The NH of SAPO composite molecular screen in the alkane isomerization catalyst prepared for the embodiment of the present invention 13- TPD is characterizedFigure
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, it is to be noted that present invention is not limited thereto.
Comparative example 1
114g aluminium isopropoxides are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The aluminium isopropoxide solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；57g di-n-propylamines are weighed, is dropped in A, stirred；About 45g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 24h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 24h in putting 120 DEG C of baking ovens, and pure SAPO-11 molecular sieves are obtained.Its X-ray diffraction spectrumFigureSuch asAccompanying drawing 1, acid characterization result is such asAccompanying drawing 2；X-ray diffraction peak position is summarized inTable 2。
Comparative example 2
Pure SAPO-11 molecular sieves prepared by the above-mentioned comparative examples 1 of 100g are taken, with 30g γ-Al2O3It is well mixed, add 80g 5wt%HNO3Solution, kneading, extrusion is dried naturally, and 4h is dried at 120 DEG C, 8h is calcined at 550 DEG C molecular sieve carrier is obtained.With Hs of the 10mL containing Pt 0.05g/mL2PtCl6The above-mentioned carriers of solution impregnation 100g, are obtained 0.5wt%Pt/SAPO-11 catalyst, and numbering is A1.Catalytic reaction evaluation result is shown inTable 3。
Embodiment 1
70g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 4h under the conditions of 10 DEG C；57g diisopropylamines are weighed, is dropped in A, stirred；About 45g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 24h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 24h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.Its X-ray diffraction spectrumFigureSuch asAccompanying drawing 3, acid characterization result is such asAccompanying drawing 4；X-ray diffraction peak position is summarized inTable 2。
Embodiment 2
70g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 2h under the conditions of 0 DEG C；57g di-n-propylamines are weighed, is dropped in A, stirred；About 45g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 24h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 20h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.X-ray diffraction peak position is summarized inTable 2。
Embodiment 3
70g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 8h under the conditions of 0 DEG C；57g di-n-propylamines are weighed, is dropped in A, stirred；About 23g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 24h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 18h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.X-ray diffraction peak position is summarized inTable 2。
Embodiment 4
70g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 6h under the conditions of 0 DEG C；57g diisopropylamines are weighed, is dropped in A, stirred；About 66g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 26h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 24h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.X-ray diffraction peak position is summarized inTable 2。
Embodiment 5
70g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 6h under the conditions of 5 DEG C；57g diisopropylamines are weighed, is dropped in A, stirred；About 66g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 26h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 24h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.X-ray diffraction peak position is summarized inTable 2。
Embodiment 6
84g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 6h under the conditions of 0 DEG C；69g diisopropylamines are weighed, is dropped in A, stirred；About 66g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 26h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 24h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.X-ray diffraction peak position is summarized inTable 2。
Embodiment 7
84g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；130g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 8h under the conditions of 5 DEG C；69g di-n-propylamines are weighed, is dropped in A, stirred；About 44g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 200 DEG C, keeps 24h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 24h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.X-ray diffraction peak position is summarized inTable 2。
Embodiment 8
84g boehmites are weighed, is dissolved in 200g deionized waters, be uniformly mixed；156g phosphoric acid is weighed, is dissolved in 100g deionized waters, be well mixed；The boehmite solution that phosphoric acid solution drops to the state of being kept stirring for is formed into precursor mixture A；A is aged 7h under the conditions of 0 DEG C；69g di-n-propylamines are weighed, is dropped in A, stirred；About 66g Ludox (30wt%) is weighed again, is dropped in A, stirred, form precursor mixture B；B is fitted into the reactor that volume is 1L, crystallization is started to warm up, crystallization temperature is 210 DEG C, keeps 24h；After the completion of crystallization, by product washing, filter to filtrate in neutrality, the product for leaching dries 24h in putting 120 DEG C of baking ovens, and SAPO composite molecular screen SC1 is obtained.X-ray diffraction peak position is summarized inTable 2。
Table 2SAPO composite molecular screen X-ray diffraction peak position and intensity in embodiment
Sample reality
Apply example number
* diffraction peak intensity, w-m:<20；m:20~70；s:70~90；vs:90~100
Embodiment 9
The SAPO composite molecular screen of the preparation of 100g embodiments 1 is taken, with 30g γ-Al2O3It is well mixed, add 80g 5wt%HNO3Solution, kneading, extrusion is dried naturally, and 4h is dried at 120 DEG C, 8h is calcined at 550 DEG C molecular sieve carrier is obtained.With Hs of the 10mL containing Pt 0.05g/mL2PtCl6The above-mentioned carriers of solution impregnation 100g, are obtained 0.5wt%Pt/SC1 catalyst, and numbering is B1.Catalytic reaction evaluation result is shown inTable 3。
Embodiment 10
The SAPO composite molecular screen SC1 of the preparation of 100g embodiments 2 is taken, with 30g γ-Al2O3It is well mixed, add 80g 5wt%HNO3Solution, kneading, extrusion is dried naturally, and 4h is dried at 120 DEG C, 8h is calcined at 550 DEG C molecular sieve carrier is obtained.With Hs of the 10mL containing Pt 0.05g/mL2PtCl6The above-mentioned carriers of solution impregnation 100g, are obtained 0.5wt%Pt/SC1 catalyst, and numbering is B2.Catalytic reaction evaluation result is shown inTable 3。
Embodiment 11
The SAPO composite molecular screen SC1 of the preparation of 100g embodiments 3 is taken, with 30g γ-Al2O3It is well mixed, add 80g 5wt%HNO3Solution, kneading, extrusion is dried naturally, and 4h is dried at 120 DEG C, 8h is calcined at 550 DEG C molecular sieve carrier is obtained.With Hs of the 10mL containing Pt 0.05g/mL2PtCl6The PdCl of solution and 10mL containing Pd 0.01g/mL2The above-mentioned carriers of solution impregnation 100g, are obtained 0.5wt%Pt-0.1wt%Pd/SC1 catalyst, and numbering is B3.Catalytic reaction evaluation result is shown inTable 3。
Embodiment 12
The SAPO composite molecular screen SC1 of the preparation of 100g embodiments 4 is taken, with 30g γ-Al2O3It is well mixed, add 80g 5wt%HNO3Solution, kneading, extrusion is dried naturally, and 4h is dried at 120 DEG C, 8h is calcined at 550 DEG C molecular sieve carrier is obtained.With Hs of the 10mL containing Pt 0.05g/mL2PtCl6The PdCl of solution and 10mL containing Pd 0.01g/mL2The above-mentioned carriers of solution impregnation 100g, are obtained 0.5wt%Pt-0.1wt%Pd/SC1 catalyst, and numbering is B4.Catalytic reaction evaluation result is shown inTable 3。
Embodiment 13
The SAPO composite molecular screen SC1 of the preparation of 100g embodiments 5 is taken, with 30g γ-Al2O3It is well mixed, add 80g 5wt%HNO3Solution, kneading, extrusion is dried naturally, and 4h is dried at 120 DEG C, 8h is calcined at 550 DEG C molecular sieve carrier is obtained.With Hs of the 10mL containing Pt 0.05g/mL2PtCl6The PdCl of solution and 10mL containing Pd 0.01g/mL2The above-mentioned carriers of solution impregnation 100g, are obtained 0.5wt%Pt-0.1wt%Pd/SC1 catalyst, and numbering is B5.Catalytic reaction evaluation result is shown inTable 3。
Table 3The evaluation result of different catalysts
| Catalyst | Reaction temperature (DEG C) | Conversion ratio (%) | Isomerisation selectivity (%) | Isomerization yield (%) |
| A1 | 340 | 65.0 | 93.3 | 60.6 |
| B1 | 330 | 91.1 | 80.3 | 73.2 |
| B2 | 325 | 89.7 | 82.5 | 74.0 |
| B3 | 320 | 90.2 | 80.7 | 72.8 |
| B4 | 330 | 90.9 | 79.2 | 72.0 |
| B5 | 325 | 89.5 | 81.6 | 73.0 |
Embodiment 14
Catalytic reaction is evaluated：
Raw material：N-dodecane；Reaction condition：10mL fixed bed reactors, 300~370 DEG C of reaction temperature, reaction pressure 8MPa, air speed 1h-1, hydrogen-oil ratio 200nL/nL.The catalyst for being prepared using above-described embodiment 9-13 respectively, catalyst amount is 8g, and each evaluating catalyst result is listed inTable 3。
Claims (10)
1. a kind of alkane isomerization catalyst, it is characterised in that：By SAPO composite molecular screen and VIII
Race's noble metal composition；
Wherein, the mass content of group VIII noble metals is 0.05~5.0wt%；
Wherein, SAPO composite molecular screen has the micropore of 0.3~0.7nm, and BET specific surface area is
100~300m2/ g, pore volume is 0.1~0.5mL/g, and its X-ray diffraction spectrogram has diffraction at least set forth below
Peak,
2 θ values expression diffraction maximum position, 2 θ/°：8.14 ± 0.2,9.48 ± 0.2,12.49 ± 0.1,13.24 ± 0.2,
15.70 ± 0.2,16.32 ± 0.2,17.56 ± 0.2,17.87 ± 0.1,19.02 ± 0.2,20.46 ± 0.2,21.10 ± 0.2,
21.66 ± 0.1,22.18 ± 0.2,22.60 ± 0.2,22.76 ± 0.2,23.22 ± 0.2,24.74 ± 0.2,27.86 ± 0.1,
28.49 ± 0.1,33.03 ± 0.1,33.41 ± 0.1.
2. catalyst as claimed in claim 1, it is characterised in that：The group VIII noble metals be Pt,
One or two or three kinds in Pd or Ir.
3. catalyst as claimed in claim 1 or 2, it is characterised in that：The quality of group VIII noble metals
Content is 0.1~2.0wt%.
4. the preparation method of the catalyst described in a kind of claim 1, it is characterised in that：Step is as follows：
A) silicon source, phosphorus source and water are mixed and stirred for uniformly being made precursor mixture A；Precursor mixture A exists
Still aging 0~12h at 0~30 DEG C；
B) organic amine is added in the precursor mixture A after still aging, silicon source is added after being stirred until homogeneous,
Continue to be stirred until homogeneous to form precursor mixture B, in B, silicon source：Phosphorus source：Silicon source：Organic amine is with Al2O3:
P2O5:SiO2:Organic amine meter, molar ratio is 1:0.1~5:0.01~5:0.1~5；
C) crystallization under the conditions of obtained precursor mixture B being heated into 120 DEG C~250 DEG C, crystallization time is
8~48h；
D) after crystallization terminates, reactant is cooled to room temperature, is filtered, washed and dried, the solid for obtaining is
SAPO composite molecular screen；
E) using one or two or more kinds in dipping, precipitation, addition adhesive bond or mechanical press method,
The combination of group VIII noble metals and SAPO composite molecular screen is realized, and in 400~600 DEG C of roastings；
F) preceding in use, the catalyst after roasting is by reduction treatment；
Described phosphorus source is the one kind in the ammonium phosphate in phosphoric acid or phosphate, monoammonium phosphate or ammonium dihydrogen phosphate
Or more than two kinds；
Described silicon source is one kind or two kinds in boehmite or hydrated alumina；
The group VIII noble metals are one or two or three kinds in Pt, Pd or Ir；
Described organic amine be fatty amine, aromatic amine, hydramine, quaternary ammonium compound in one kind or two kinds with
On；
Described silicon source is in gas-phase silica, Ludox, waterglass, solid silicone and amorphous silica
One or two or more kinds.
5. according to the preparation method described in claim 4, it is characterised in that：Precursor mixture A in step a)
Still aging 0~8h at 0~25 DEG C.
6. according to the preparation method described in claim 4, it is characterised in that：Precursor mixture B in step b)
In, silicon source：Phosphorus source：Silicon source：Organic amine is with Al2O3:P2O5:SiO2:Organic amine meter, molar ratio is 1:
0.5~2:0.1~1:0.5~2.
7. according to the preparation method described in claim 4, it is characterised in that：Crystallization temperature is in step c)
160 DEG C~220 DEG C, crystallization time is 12~36h.
8. according to the preparation method described in claim 4, it is characterised in that：Described organic amine is fatty amine.
9. according to the preparation method described in claim 4, it is characterised in that：Step e) the group VIIIs are expensive
The combination of metal and SAPO composite molecular screen, using the metal acid of group VIII noble metals, metal acid-salt,
Chloride, ammino-complex, carbonyl complex or their mixture are raw material.
10. according to the preparation method described in claim 4, it is characterised in that：Original place is gone back described in step f)
Reason, reducing atmosphere is hydrogen, or hydrogen and inert gas gaseous mixture, reduction temperature is 100~600 DEG C.
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| CN109465024A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier |
| CN109465021A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MFI type structure molecular sieve as the isomerization catalyst preparation method of carrier |
| CN115672388A (en) * | 2021-07-23 | 2023-02-03 | 中国石油天然气股份有限公司 | Shape selective isomerization catalyst and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109465024A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MTW type structure molecular screen as the isomerization catalyst preparation method of carrier |
| CN109465021A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MFI type structure molecular sieve as the isomerization catalyst preparation method of carrier |
| CN109465024B (en) * | 2017-09-07 | 2021-09-07 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst with MTW type structure molecular sieve as carrier |
| CN109465021B (en) * | 2017-09-07 | 2021-10-08 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst with MFI-structure molecular sieve as carrier |
| CN115672388A (en) * | 2021-07-23 | 2023-02-03 | 中国石油天然气股份有限公司 | Shape selective isomerization catalyst and preparation method and application thereof |
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