CN106732753B - 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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- CN106732753B CN106732753B CN201611030582.3A CN201611030582A CN106732753B CN 106732753 B CN106732753 B CN 106732753B CN 201611030582 A CN201611030582 A CN 201611030582A CN 106732753 B CN106732753 B CN 106732753B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 8
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 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 Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 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
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- -1 Hydrogen hydrocarbon Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000006185 dispersion Substances 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
- 230000003197 catalytic effect Effects 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 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
- 229910052784 alkaline earth metal Inorganic materials 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
- 235000019441 ethanol Nutrition 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000005070 sampling Methods 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparation methods of temp isomerizing catalyst in a kind of C5, C6, belong to light paraffins isomerization field.Preparation method of the invention carries out pre- modification, then platinum-impregnated salting liquid to h-mordenite/aluminium oxide preparation catalyst carrier using citric acid-methanol solution.By above-mentioned operation, the conversion ratio and selectivity of catalyst can be effectively improved, and then obtains high performance medium temperature C5, C6 isomerization catalyst.
Description
Technical field
The invention belongs to light paraffins isomerization fields, and in particular to it is a kind of using molecular sieve as basic catalysis material
Warm type isomerization catalyst and preparation method thereof in C5, C6.
Background material
The advantages that isomery C5, C6 (double branch C6) are with its high-octane rating, environment optimization, is front end fraction in ultra-clean gasoline
Middle important component.Isomerization technique study both at home and abroad it is numerous, in, based on low temperature isomery, wherein low temperature isomery is at home
Have number set commercial plant to be currently running, because operating condition is extremely harsh, for some factories, it is preferred that medium temperature isomery is opposite
Scheme.In medium temperature heterogeneous catalyst customary preparation methods, using mercerising molecular sieve as catalytic matrix, made using noble metal such as platinum, palladium
For catalyst plus/dehydrogenation active component.Numerous inventive points, patent CN are proposed to the catalyst in patent seen in existing
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 catalyst and its preparation and application of nickel borides are loaded, CN03122849.6 discloses a kind of low-carbon
Alkane isomerization catalyst and preparation method, CN20140723154.3 disclose a kind of C5, C6 isomerization catalyst and its preparation
Method can obviously reduce the preparation expense of catalyst 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 can effectively be matched with acid site, the molecular sieve in catalyst mainly provides acid site, and noble metal active component provides
Hydrogenation/dehydrogenation center.Higher acid amount, suitable acid strength, higher metal dispersity are ideal 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 or alkaline earth metal to molecular sieve modified, tune
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, by retaining molecular sieve to catalyst carrier pretreatment using organic amine
Acidity improves the activity of catalyst.
For isomerization catalyst, noble-metal-supported and dispersion be catalyst preparation technology core point, usually recognize
It is optimal for being evenly distributed on for noble metal and being exposed to the molecular sieve outer surface of the effective channel surfaces of catalyst.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 subtle, non-effective duct,
Lose catalytic action.
Summary of the invention
In view of the above technical problems, the present invention provides the preparation methods of temp isomerizing catalyst in a kind of C5, C6.This hair
The bright method using pre-preg auxiliary agent, the characteristics of making full use of auxiliary agent, reach as much as possible realize metal in effective duct and
The purpose of molecular sieve surface enrichment in duct.
The present invention is the preparation method of temp isomerizing catalyst in a kind of C5, C6, which uses following steps:
1) h-mordenite is mixed with aluminium oxide, appropriate aqueous solution of nitric acid, kneading and compacting, dry, roasting is added
After burning, it is prepared into carrier, wherein molecular sieve accounts for the 40%~95% of carrier gross weight；Aluminium oxide is low-sulfur, without sulphur aluminium oxide；
2) Vehicle element uses citric acid-methanol system, after incipient impregnation auxiliary agent citric acid-methanol, 50~
0.5h~5h is dried at 170 DEG C for the first time；Sample incipient impregnation tetraammineplatinum chloride solution after drying, then 250 DEG C~
After 600 DEG C carry out second of drying, at 250 DEG C~600 DEG C, heating rate is that 0.1 DEG C/min~3 DEG C/min roasting is 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., for citric acid-methanol solution in dipping, methanol usage meets the amount of carrier incipient impregnation requirement.Four ammonia of dichloro
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, the silica alumina ratio of the h-mordenite be (silica and aluminium oxide
Molar 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 that vehicle weight is preferably 0.2%~5%, more preferably 0.3%~4%.
First time drying temperature is preferably set to 60~100 DEG C, more preferable 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 item after dipping, carrying out after baking temperature after drying is preferably 300 DEG C~550 DEG C, heating rate
Preferably 0.2~2 DEG C/min.
The catalyst that the method for the present invention is prepared, due to being pre-processed to carrier, citric acid-methanol solution dipping
After carrier, through low temperature drying, esterification occurs, forms hydroxyl, carboxyl, the body that ester group is main functional group in carrier surface
System, promotes noble metal in the dispersion of carrier surface.The catalyst of preparation, Metal Distribution is reasonable, and crystal grain is small, and dispersion degree is high, urges
The catalytic performance of agent is splendid, compares other catalyst prepared by infusion process, and activity significantly improves.
Specific embodiment
Middle temp isomerizing catalyst prepared by C5, C6 prepared by the present invention is carried out further below 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
Enter in miniature reactor reaction pipe (internal diameter 15mm), 300 DEG C of reduction activations of pure hydrogen.Raw material n-hexane as reaction raw materials,
It is squeezed into reactor through constant-flux pump.Reaction pressure is 2.0MPa, and reaction temperature is 260 DEG C.Hydrogen hydrocarbon molar ratio 2:1~4:1, preferably
Hydrogen ester molar ratio 2.5:1~3.0:1, volume space velocity is 0.5~1.5h when liquid-1, preferably liquid when volume space velocity be 0.5~1.0h-1, concrete technology condition can be specifically chosen according to feedstock property and product requirement by ability domain knowledge.
Equally, it when using pentane as reaction raw materials, is squeezed into reactor through constant-flux pump.Reaction pressure is 2.0MPa,
Reaction temperature is 260 DEG C.Hydrogen hydrocarbon molar ratio 2:1~4:1, preferably hydrogen ester molar ratio 2.5:1~3.0:1, volume space velocity is when liquid
0.5~1.5h-1, preferably liquid when volume space velocity be 0.5~1.0h-1, concrete technology condition can want according to feedstock property and product
It asks and is specifically chosen by ability domain knowledge.
Embodiment 1
The SB of h-mordenite (sodium oxide content 10ppm, the butt 97.5%) and 26.67g of 82.05g silica alumina ratio 15
Powder (butt 75%) is mixed, and appropriate aqueous solution of nitric acid is added, and kneading and compacting is prepared into carrier, carrier after dry, roasting
Molecular sieve: aluminium oxide=80:20 (weight ratio).It takes the citric acid of 0.10 ± 0.01g to be dissolved in 55g methanol, forms solution, it will
The carrier impregnation of aforementioned preparation is in the solution, and after standing 2h, 50 DEG C are dried, after constant temperature time 0.5h, incipient impregnation dichloro
Four ammino platinum, platinum amount are the 0.1% of vehicle weight, maceration extract pH value 6, and the catalyst item after dipping carries out secondary after drying
Roasting, temperature are 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
Other are in embodiment 2~4 that the ratio of molecular sieve and aluminium oxide is respectively 40:60,70 with embodiment 1, difference:
30、95:5。
Embodiment 5
, with embodiment 1, difference is that silica alumina ratio is 30 for other.
Embodiment 6
Other are molecular sieve sodium oxide content 2000ppm with embodiment 1, difference.
Embodiment 7
The SB of h-mordenite (sodium oxide content 500ppm, the butt 97.5%) and 26.67g of 82.05g silica alumina ratio 15
Powder (butt 75%) is mixed, and appropriate aqueous solution of nitric acid is added, and kneading and compacting is prepared into carrier, carrier after dry, roasting
Molecular sieve: aluminium oxide=80:20 (weight ratio).It takes the citric acid of 1.50 ± 0.01g to be dissolved in 54g methanol, forms solution, it will
The carrier impregnation of aforementioned preparation is in the solution, and after standing 2h, 80 DEG C are dried, after constant temperature time 3h, incipient impregnation dichloro four
Ammino platinum, platinum amount are the 0.3% of vehicle weight, maceration extract pH value 8, and the catalyst item after dipping carries out secondary roasting after drying
It burns, temperature is 400 DEG C, and 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 for other, uses ethyl alcohol as solvent, ethanol consumption
46g。
Embodiment 9
, with embodiment 7, difference is that platinum amount is the 0.4% of vehicle weight for other.
Embodiment 10
With embodiment 7, difference is that catalyst after baking temperature is 600 DEG C for other, heating rate control 2 DEG C/
min。
Embodiment 11
The catalyst prepared to above-described embodiment 1~10 is evaluated in parallel, evaluation condition are as follows: by the catalyst after roasting
40~60 mesh are crushed to, are fitted into microreactor reaction tube (internal diameter 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, sampling is primary for 24 hours, samples four times, average value three times after taking.Hydrogen hydrocarbon molar ratio 2.5:1, volume space velocity is 1.0h when liquid-1.Concrete outcome is shown in Table 1.As a result the data in include conversion ratio, selectivity.
The evaluation result of the catalyst of the different embodiment preparations of table 1
Note: 1. conversion ratios are calculated with pentane, n-hexane
2. selectivity: 100%* isopentane/(isopentane+C4+C4-) (using pentane as raw material)；
100%* isomery hexane/(isomery hexane+C5+C5-) (using n-hexane as raw material) comparative example 1
Comparative example 1
Comparative example 1 is prepared according to 1 method of embodiment, difference is the carrier after roasting, direct incipient impregnation dichloro four
Ammino platinum, platinum amount are the 0.1% of vehicle weight, maceration extract pH value 6, and the catalyst item after dipping carries out secondary roasting after drying
It burns, temperature is 250 DEG C, and 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 7 method of embodiment, difference is direct four ammonia of incipient impregnation dichloro of carrier after roasting
Close platinum, platinum amount is the 0.3% of vehicle weight, maceration extract pH value 8, and the catalyst item 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 Examples 1 and 2 uses the same process conditions of embodiment 11, and evaluation result is shown in Table 2.
The evaluation result of the catalyst of the different comparative example preparations of table 2
Through data comparison, the conversion ratio and selectivity of comparative example are inferior to the data of corresponding embodiment, show institute of the present invention
The catalyst of preparation has advance.
Claims (9)
1. the preparation method of temp isomerizing catalyst in a kind of C5, C6, which comprises the steps of:
1) h-mordenite is mixed with aluminium oxide, aqueous solution of nitric acid is added, kneading and compacting is prepared after dry, roasting
At carrier；Wherein the silica alumina ratio of the 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 aluminium oxide is low-sulfur, without sulphur aluminium oxide；
2) carrier dries 0.5h~5h using citric acid-methanol pretreatment for the first time at 50~170 DEG C；Sample after drying
Incipient impregnation tetraammineplatinum chloride solution, then after 250 DEG C~600 DEG C progress, second of drying, at 250 DEG C~600 DEG C two
Catalyst is prepared in secondary roasting, 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, for quantity of methyl alcohol depending on carrier hole appearance, citric acid-methanol solution amount meets carrier incipient impregnation needs；
For the control of tetraammineplatinum chloride solution ph 6~10, platinum amount is 0.1wt%~0.5wt% of carrier.
2. the method according to claim 1, wherein the h-mordenite account for carrier gross weight 60%~
90%.
3. the method according to claim 1, wherein the Citric Acid Dosage be vehicle weight 0.2%~
5%.
4. according to the method described in claim 3, it is characterized in that, the Citric Acid Dosage be vehicle weight 0.3%~
4%.
5. the method according to claim 1, wherein the first time drying temperature is 60~100 DEG C.
6. according to the method described in claim 5, it is characterized in that, the first time drying temperature is 70~90 DEG C.
7. the method according to claim 1, wherein the platinum amount is 0.2wt%~0.4wt% of carrier.
8. the method according to claim 1, wherein the tetraammineplatinum chloride solution ph is 7~9.
9. the method according to claim 1, wherein the catalyst item after the dipping carries out two after drying
Secondary maturing temperature is 300 DEG C~550 DEG C, and heating rate is 0.2~2 DEG C/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
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| US9821297B2 (en) * | 2015-03-10 | 2017-11-21 | California Institute Of Technology | Methods to produce molecular sieves with LTA topology and compositions derived therefrom |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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