CN106732753A - The preparation method of temp isomerizing catalyst in a kind of C5, C6 - Google Patents
The preparation method of temp isomerizing catalyst in a kind of C5, C6 Download PDFInfo
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- CN106732753A CN106732753A CN201611030582.3A CN201611030582A CN106732753A CN 106732753 A CN106732753 A CN 106732753A CN 201611030582 A CN201611030582 A CN 201611030582A CN 106732753 A CN106732753 A CN 106732753A
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- citric acid
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- aluminum oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 8
- ZXWHANCSQZVZCM-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;methanol Chemical compound OC.OC(=O)CC(O)(C(O)=O)CC(O)=O ZXWHANCSQZVZCM-UHFFFAOYSA-N 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- IYJGDVCRVLXCAS-UHFFFAOYSA-N [O-2].[Al+3].S Chemical compound [O-2].[Al+3].S IYJGDVCRVLXCAS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000006317 isomerization reaction Methods 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000009938 salting Methods 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- -1 Hydrogen hydrocarbon Chemical class 0.000 description 5
- 125000003963 dichloro group Chemical group Cl* 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
-
- B01J35/396—
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention discloses the preparation method of temp isomerizing catalyst in a kind of C5, C6, belong to light paraffins isomerization field.Preparation method of the invention carries out pre- modified, then platinum-impregnated salting liquid using citric acid methanol solution to catalyst carrier prepared by h-mordenite/aluminum oxide.By above-mentioned operation, the conversion ratio and selectivity of catalyst can be effectively improved, and then obtain high performance middle temperature C5, C6 isomerization catalyst.
Description
Technical field
The invention belongs to light paraffins isomerization field, and in particular to catalysis material based on a kind of use molecular sieve
Warm type isomerization catalyst and preparation method thereof in C5, C6.
Background material
The advantages of isomery C5, C6 (double side chain C6) are with its high-octane rating, environment optimization, is front end cut in ultra-clean gasoline
Middle important component.Isomerization technique studies numerous both at home and abroad, in, based on low temperature isomery, wherein, low temperature isomery is at home
Count set commercial plant to be currently running, because operating condition is extremely harsh, for some factories, it is preferred that middle temperature isomery is relative
Scheme.In middle temperature heterogeneous catalyst customary preparation methods, with mercerising molecular sieve as catalytic matrix, made using noble metal such as platinum, palladium
It is catalyst plus/dehydrogenation active component.Numerous inventive points, patent CN are proposed to the catalyst in existing finding patent
99105790.2 disclose a kind of catalyst for isomerizing light hydrocarbon and preparation method thereof, and CN 201410075578.3 discloses one kind
The C5C6 alkane isomerization catalysts and its preparation and application of nickel borides are loaded, CN03122849.6 discloses a kind of low-carbon (LC)
Alkane isomerization catalyst and preparation method, CN20140723154.3 disclose a kind of C5, C6 isomerization catalyst and its preparation
Method, the preparation expense of catalyst is can obviously reduce according to the patent.
For C5, C6 isomerization catalyst, noble-metal-supported and dispersion be catalyst activity height core, high degree of dispersion
Noble metal effectively can be matched with acid site, the molecular sieve in catalyst mainly provides acid site, and noble metal active component is provided
Hydrogenation/dehydrogenation center.Sour amount higher, suitable acid strength, metal dispersity higher are preferable C5, C6 isomerization catalytics
Agent.
Noble-metal-supported, United States Patent (USP) US4710485,5135638,5282598,5376260, using infusion process or from
Sub- exchange process.United States Patent (USP) US7141529B2,5246566 are disclosed using alkali metal or alkaline-earth metal to molecular sieve modified, are adjusted
The method of molecular sieve acid amount is saved to improve the selectivity of catalyst.Chinese patent CN1448480A discloses one kind with SAPO-11
Molecular sieve is the preparation method of the catalyst of main carriers, and molecular sieve is retained to catalyst carrier pretreatment by using organic amine
Acidity improves the activity of catalyst.
For isomerization catalyst, noble-metal-supported and dispersion be catalyst preparation technology core point, generally recognize
The molecular sieve outer surface of the effective channel surfaces of catalyst is exposed to for optimal for noble metal is evenly distributed on.To reach this purpose,
Common practice is to use infusion process, but dipping process is likely to result in part metals and is deposited in trickle, non-effective duct,
Lose catalytic action.
The content of the invention
For above-mentioned technical problem, the invention provides the preparation method of temp isomerizing catalyst in a kind of C5, C6.This hair
The method of bright use pre-preg auxiliary agent, the characteristics of make full use of auxiliary agent, reach as much as possible realize metal in effective duct and
The purpose of the molecular sieve surface enrichment in duct.
The present invention is the preparation method of temp isomerizing catalyst in a kind of C5, C6, and the preparation method uses following steps：
1) h-mordenite is mixed with aluminum oxide, adds appropriate aqueous solution of nitric acid, kneading and compacting to dry, roast
After burning, carrier is prepared into, wherein molecular sieve accounts for the 40%~95% of carrier gross weight；Aluminum oxide be low-sulfur, without sulphur aluminum oxide；
2) Vehicle element uses citric acid-methanol system, through incipient impregnation auxiliary agent citric acid-methyl alcohol after, 50~
0.5h~5h is dried for the first time at 170 DEG C；Dried sample incipient impregnation tetraammineplatinum chloride solution, then 250 DEG C~
After 600 DEG C carry out second drying, at 250 DEG C~600 DEG C, heating rate is that 0.1 DEG C/min~3 DEG C/min roastings are prepared
Catalyst；
Wherein Citric Acid Dosage is the 0.1%~10% of vehicle weight, and quantity of methyl alcohol regards carrier hole in citric acid-methanol system
Depending on appearance, i.e., in dipping, methanol usage meets the amount of carrier incipient impregnation requirement to citric acid-methanol solution.The ammonia of dichloro four
Platinum solution ph control range 6~10 is closed, platinum amount is the 0.1%~0.5% of carrier.
In technical solutions according to the invention, silica alumina ratio (silica and the aluminum oxide of described h-mordenite
Mol ratio) it is 15~30, sodium oxide content is between 10~2000ppm；Molecular sieve accounts for preferably the 60%~90% of carrier gross weight.
Citric acid amount used is preferably 0.2%~5%, more preferably 0.3%~4% for vehicle weight.
First time drying temperature is preferably set to 60~100 DEG C, more preferably 70~90 DEG C.
Using incipient impregnation tetraammineplatinum chloride solution, platinum amount is preferably the 0.2%~0.4% of carrier.
Tetraammineplatinum chloride solution ph control range preferably 7~9.
Catalyst bar after dipping, carry out after drying after baking temperature be preferably 300 DEG C~550 DEG C, heating rate
Preferably 0.2~2 DEG C/min.
The catalyst that the inventive method is prepared, due to being pre-processed to carrier, citric acid-methanol solution dipping
After carrier, through low temperature drying, there is esterification, it is the body of main functional group to form hydroxyl, carboxyl, ester group in carrier surface
System, promotes dispersion of the noble metal in carrier surface.The catalyst of preparation, rationally, crystal grain is small, and decentralization is high, urges for Metal Distribution
The catalytic performance of agent is splendid, and compared to catalyst prepared by other infusion processes, activity is significantly improved.
Specific embodiment
Middle temp isomerizing catalyst prepared by C5, C6 prepared by the present invention is carried out further with reference to embodiment
Bright and elaboration, but it is not intended to limit the present invention.
The activity that the present invention provides catalyst can be evaluated with the following method：
Catalyst activity is evaluated in micro fixed-bed reactor.By the catalyst breakage after roasting to 40~60 mesh, dress
In entering miniature reactor reaction pipe (internal diameter is 15mm), 300 DEG C of reduction activations of pure hydrogen.Raw material n-hexane as reaction raw materials,
Squeezed into reactor through constant-flux pump.Reaction pressure is 2.0MPa, and reaction temperature is 260 DEG C.Hydrogen hydrocarbon mol ratio 2:1~4:1, preferably
Hydrogen ester mol ratio 2.5:1~3.0:1, volume space velocity is 0.5~1.5h during liquid-1, preferably liquid when volume space velocity be 0.5~1.0h-1, concrete technology condition can be carried out specifically chosen according to feedstock property and product requirement by ability domain knowledge.
Equally, during using pentane as reaction raw materials, squeezed into reactor through constant-flux pump.Reaction pressure is 2.0MPa,
Reaction temperature is 260 DEG C.Hydrogen hydrocarbon mol ratio 2:1~4:1, preferably hydrogen ester mol ratio 2.5:1~3.0:1, volume space velocity is during liquid
0.5~1.5h-1, preferably liquid when volume space velocity be 0.5~1.0h-1, concrete technology condition can will according to feedstock property and product
Ask carried out by ability domain knowledge it is specifically chosen.
Embodiment 1
The h-mordenite (sodium oxide content 10ppm, butt 97.5%) of 82.05g silica alumina ratios 15 and the SB of 26.67g
Powder (butt 75%) is mixed, and adds appropriate aqueous solution of nitric acid, kneading and compacting after dry, roasting, to be prepared into carrier, carrier
Molecular sieve：Aluminum oxide=80:20 (weight ratios).The citric acid for taking 0.10 ± 0.01g is dissolved in 55g methyl alcohol, forms solution, will
In the solution, after standing 2h, 50 DEG C dry the carrier impregnation of foregoing preparation, after constant temperature time 0.5h, incipient impregnation dichloro
Four ammino platinum, platinum amount is the 0.1% of vehicle weight, and maceration extract pH value 6, the catalyst bar after dipping is carried out secondary after drying
Roasting, temperature is 250 DEG C, and heating rate is 0.1 DEG C/min.Catalyst after roasting is finished catalyst of the present invention.
Embodiment 2~4
, with embodiment 1, difference is that the ratio of molecular sieve and aluminum oxide in embodiment 2~4 is respectively 40 for other:60、70:
30、95:5。
Embodiment 5
, with embodiment 1, difference is that silica alumina ratio is 30 for other.
Embodiment 6
, with embodiment 1, difference is molecular sieve sodium oxide content 2000ppm for other.
Embodiment 7
The h-mordenite (sodium oxide content 500ppm, butt 97.5%) of 82.05g silica alumina ratios 15 and the SB of 26.67g
Powder (butt 75%) is mixed, and adds appropriate aqueous solution of nitric acid, kneading and compacting after dry, roasting, to be prepared into carrier, carrier
Molecular sieve：Aluminum oxide=80:20 (weight ratios).The citric acid for taking 1.50 ± 0.01g is dissolved in 54g methyl alcohol, forms solution, will
In the solution, after standing 2h, 80 DEG C dry the carrier impregnation of foregoing preparation, after constant temperature time 3h, incipient impregnation dichloro four
Ammino platinum, platinum amount is the 0.3% of vehicle weight, and maceration extract pH value 8, the catalyst bar after dipping carries out secondary roasting after drying
Burn, temperature is 400 DEG C, heating rate is 0.3 DEG C/min.Catalyst after roasting is finished catalyst of the present invention.It is real
Apply example 8
, with embodiment 7, difference is that citric acid amount is 10.00 ± 0.01g, with ethanol as solvent, ethanol consumption for other
46g。
Embodiment 9
, with embodiment 7, difference is 0.4% that platinum amount is vehicle weight for other.
Embodiment 10
, with embodiment 7, it is 600 DEG C that difference is catalyst bar after baking temperature for other, heating rate control 2 DEG C/
min。
Embodiment 11
Parallel evaluation is carried out to catalyst prepared by above-described embodiment 1~10, appreciation condition is：By the catalyst after roasting
40~60 mesh are crushed to, are fitted into microreactor reaction tube (internal diameter is 15mm), 300 DEG C of reduction activations of pure hydrogen.Respectively with
Raw material pentane, n-hexane are squeezed into reactor as reaction raw materials through constant-flux pump.Reaction pressure is 2.0MPa, reaction temperature
260 DEG C, 24h is sampled once, is sampled four times, three average values after taking.Hydrogen hydrocarbon mol ratio 2.5:1, volume space velocity is 1.0h during liquid-1.Concrete outcome is shown in Table 1.Data in result include conversion ratio, selectivity.
The evaluation result of catalyst prepared by the different embodiments of table 1
Note：1. conversion ratio is calculated with pentane, n-hexane
2. selective：100%* isopentane/(isopentane+C4+C4-) (with pentane as raw material)；
100%* isomeries hexane/(isomery hexane+C5+C5-) (with n-hexane as raw material) comparative example 1
Comparative example 1
Comparative example 1 is prepared according to the method for embodiment 1, difference is the carrier after being calcined, direct incipient impregnation dichloro four
Ammino platinum, platinum amount is the 0.1% of vehicle weight, and maceration extract pH value 6, the catalyst bar after dipping carries out secondary roasting after drying
Burn, temperature is 250 DEG C, heating rate is 0.1 DEG C/min.Catalyst after roasting is the catalyst of comparative example 1.
Comparative example 2
Comparative example 2 is prepared according to the method for embodiment 7, difference is the direct ammonia of incipient impregnation dichloro four of carrier after being calcined
Platinum is closed, platinum amount is the 0.3% of vehicle weight, and maceration extract pH value 8, the catalyst bar after dipping carries out after baking after drying,
Temperature is 400 DEG C, and heating rate is 0.3 DEG C/min.Catalyst after roasting is finished catalyst of the present invention.
Comparative example 1,2 is shown in Table 2 using the same process conditions of embodiment 11, evaluation result.
The evaluation result of catalyst prepared by the different comparative examples of table 2
Through Data Comparison, the conversion ratio and selectivity of comparative example are inferior to the data of correspondence embodiment, show institute of the present invention
The catalyst of preparation has advance.
Claims (9)
1. in a kind of C5, C6 temp isomerizing catalyst preparation method, it is characterised in that comprise the following steps：
1) h-mordenite is mixed with aluminum oxide, adds aqueous solution of nitric acid, kneading and compacting after dry, roasting, to prepare
Into carrier；The silica alumina ratio of wherein described h-mordenite is 15~30, and sodium oxide content is 10~2000ppm, and Hydrogen
Modenite accounts for the 40%~95% of carrier gross weight, and aluminum oxide is low-sulfur, without sulphur aluminum oxide；
2) carrier dries 0.5h~5h for the first time using citric acid-methyl alcohol pretreatment at 50~170 DEG C；Dried sample
Incipient impregnation tetraammineplatinum chloride solution, then after carrying out second drying at 250 DEG C~600 DEG C, at 250 DEG C~600 DEG C two
Secondary roasting prepares catalyst, and roasting heating rate is 0.1 DEG C/min~3 DEG C/min；Wherein Citric Acid Dosage is carrier weight
The 0.1%~10% of amount, depending on carrier pore volume, citric acid-methanol solution amount meets carrier incipient impregnation needs to quantity of methyl alcohol；
6~10, platinum amount is the 0.1wt%~0.5wt% of carrier to the control of tetraammineplatinum chloride solution ph.
2. method according to claim 1, it is characterised in that described h-mordenite account for carrier gross weight 60%~
90%.
3. method according to claim 1, it is characterised in that described Citric Acid Dosage for vehicle weight 0.2%~
5%.
4. method according to claim 3, it is characterised in that described Citric Acid Dosage for vehicle weight 0.3%~
4%.
5. method according to claim 1, it is characterised in that described first time drying temperature is 60~100 DEG C.
6. method according to claim 5, it is characterised in that described first time drying temperature is 70~90 DEG C.
7. method according to claim 1, it is characterised in that described platinum amount is the 0.2wt%~0.4wt% of carrier.
8. method according to claim 1, it is characterised in that described tetraammineplatinum chloride solution ph is 7~9.
9. method according to claim 1, it is characterised in that the catalyst bar after described dipping carries out two after drying
Secondary sintering temperature is 300 DEG C~550 DEG C, and heating rate is 0.2~2 DEG C/min.
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| CN87103444A (en) * | 1987-04-29 | 1988-11-30 | 环球油品公司 | Composite catalyst for paraffin isomerization |
| CN1044053A (en) * | 1989-01-13 | 1990-07-25 | 中国石油化工总公司石油化工科学研究院 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof |
| CN105709810A (en) * | 2014-12-03 | 2016-06-29 | 南京克米斯璀化工科技有限公司 | C5C6 isomerization catalyst and preparation method thereof |
| CN104525247A (en) * | 2015-01-26 | 2015-04-22 | 南开大学 | Preparation method used for preparing biological jet fuel hydrogenation deoxidization and hydrogenation isomerization catalysts by castor oil |
| US20160263562A1 (en) * | 2015-03-10 | 2016-09-15 | California Institute Of Technology | Methods to produce molecular sieves with lta topology and compositions derived therefrom |
| CN105562105A (en) * | 2016-01-05 | 2016-05-11 | 中国石油大学(华东) | Metallocene loaded catalyst for C5/C6 alkane isomerization, preparation method and application method thereof |
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