CN108745408A - The preparation method of EU-1/ZSM-48 composite molecular sieve catalysts - Google Patents
The preparation method of EU-1/ZSM-48 composite molecular sieve catalysts Download PDFInfo
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- CN108745408A CN108745408A CN201810532834.5A CN201810532834A CN108745408A CN 108745408 A CN108745408 A CN 108745408A CN 201810532834 A CN201810532834 A CN 201810532834A CN 108745408 A CN108745408 A CN 108745408A
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- molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/703—MRE-type, e.g. ZSM-48
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Abstract
The present invention provides a kind of EU-1/ZSM-48 compound eutectics molecular sieve catalyst preparation methods, EU-1/ZSM-48 compound eutectic molecular sieves are synthesized by hydro-thermal method, by the EUO structures of EU-1 molecular sieves and the MRE structure compositions of ZSM-48 molecular sieves, in the reaction of hexadecane hydrocarbon hydroisomerization, although showing highest conversion ratio on EU-1 molecular sieves, highest selectivity is shown on ZSM-48 molecular sieves, but shows best catalytic performance on EU-1/ZSM-48 compound eutectic molecular sieves.And the catalytic performance of EU-1/ZSM-48-200, compared with the ZSM-48-200 with same silica alumina ratio, catalytic performance has dramatically different.
Description
Technical field
The invention belongs to molecular sieve catalysts to synthesize field, more particularly to EU-1/ZSM-48 composite molecular sieve catalysts
It prepares.
Background technology
Coming few decades oil will be the main source of fossil fuel energy, and a big industry and fortune are realized by continuous
Defeated required demand for fuel.Due to the development of auto industry and new energy, the demand to different fuel and lubricating oil, in the past 30
It is almost doubled in year.In petroleum industry, hydroisomerization is an important catalytic process, and it is high that this has been applied to production
Octane gasoline and oligomeric diesel oil and the viscosity characteristics for improving waxy feed, such as loose wax.
Hygrogenating isomerization reaction is catalyzed by bifunctional catalysis' agent comprising metal and acidic site.According to isomerization
The basic principle of mechanism, normal paraffin hydrocarbons dehydrogenation on metallic site form alkene and are protonated on acidic site as corresponding
Alkyl carbon ion.In recent years, various acid have been supported applied to SiO2–Al2O3, 10 ZrO2With comprising Y, Beta, ZSM-5,
The isomerization reaction of ZSM-22, ZSM-23, SAPO-11, SAPO-41 molecular sieve.However, using point of one-dimensional ten-ring structure
Sub- sieve ratio large pore molecular sieve is particularly suited for isomerization, because monobranched hydrocarbons can more freely disperse, 10 membered ring channels can be with
The formation for inhibiting branched chain hydrocarbon leads to higher isomerisation selectivity to be easily broken by form selective.ZSM-48 makees
For one of most promising candidate of hydrogen isomerization reaction, due to its unique pore passage structure, as n-hexane hydrogen isomerization
Acidity is supported.In work in our prior, improve catalysis by reducing silica alumina ratio and the alkali treatment modifying of ZSM-48 synthesis
Performance.ZSM-48 is with HMBr2It is synthesized as structure directing agent, in our subsequent experiments, eutectic ZSM-48/EU-1 molecular sieves
It can be crystallized in low silica-alumina ratio, however EU-1 can be with HMBr2As structure directing agent under more low silica-alumina ratio hydrothermal crystallizing.
EU-1 has one-dimensional bull's eye duct, and the acidity as n-hexane hydrogen isomerization is supported.ZSM-48 and EU-1 is reported different as hydrogen
The acid of structure support, but eutectic ZSM-48/EU-1 be not applied to before research.The catalytic performance of eutectic molecular sieve is not
It is same as corresponding individual molecular sieve.
Before this, we are absorbed in 10 annular distance road molecular sieves of synthesis, and have studied different 10 membered ring channel molecular sieves pair
The influence of its mechanical impurity.By mechanical agitation, the catalytic performance of ZSM-48 can be improved, but the catalytic performance of ZSM-48
Do not improve fundamentally, therefore be prepared for the ZSM-48 of low silica-alumina ratio, the catalytic performance for fundamentally improving ZSM-48 is one
A good selection.Eutectic ZSM-48/EU-1 is synthesized with more low silica-alumina ratio, but is not suitable for catalysis reaction.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of EU-1/ZSM-48 composite molecular sieve catalysts.
To achieve the above object, the present invention provides a kind of preparation method of EU-1/ZSM-48 composite molecular sieve catalysts,
Include the following steps：
1. by Al (NO3)3• 9H2O is mixed and stirred for deionized water until obtaining transparent aluminum nitrate solution；By 50wt%
Stirring in aluminum nitrate solution is added until obtaining uniform solution in NaOH solution, adds hexamethyl ammonium bromide（HMBr2）, wait for molten
Liquid is stirring evenly and then adding into Ludox, then stirs the mixture for uniformly obtaining gel；
2. 200 DEG C of crystallization 72h, product centrifugation, washing, 60 DEG C are dried overnight, 550 DEG C of roasting 4h；
3. by step, 2. calcined solids use NH4NO3Solion exchanges three times, using NH4NO3The behaviour that solion exchanges
It is as condition：The NH of 5wt% is used in 85 DEG C of water-baths4NO3Solution treatment 8h, filtering and washing dry obtained solid；
4. 550 DEG C of roasting 4h of products therefrom are to get EU-1/ZSM-48 coexisting molecular sieves 3. step is handled after.
Preferably, step 1. in gained gel mole group become 60SiO2 :xAl2O3 : 10Na2O : 15HMBr2 :
3000H2O, x=0.24-0.6.
The beneficial effect comprise that：The present invention has studied different SiO2/Al2O3The ZSM-48/EU-1 symbiosis system of value
System and its hexadecane hydrocarbon hydrogen isomerization catalytic performance, the eutectic molecular sieve of the ZSM-48/EU-1 of different silica alumina ratios with it is opposite
The individual molecular sieve physical property answered is different.EU-1/ZSM-48 compound eutectic molecular sieves in the present invention are synthesized by hydro-thermal method, by
The EUO structures of EU-1 molecular sieves and the MRE structure compositions of ZSM-48 molecular sieves, in the reaction of hexadecane hydrocarbon hydroisomerization,
Although showing highest conversion ratio on EU-1 molecular sieves, highest selectivity is shown on ZSM-48 molecular sieves,
Best catalytic performance is shown on EU-1/ZSM-48 compound eutectic molecular sieves.And the catalytic performance of EU-1/ZSM-48-200 with
ZSM-48-200 with same silica alumina ratio is compared, and catalytic performance has dramatically different.
Description of the drawings
Fig. 1 is the XRD diagram for preparing all samples prepared by embodiment 1-5；Fig. 2 is all of embodiment 1-4 preparations
The NH of sample3- TPD schemes, and abscissa is temperature in fig. 2, and ordinate is that ammonolysis inhales peak.
Specific implementation mode
The present invention is further explained in the light of specific embodiments, and but the scope of the present invention is not limited thereto.
Embodiment 1
Al (the NO of 0.22g3)3·9H2The deionized water of O and 18.02g is mixed and stirred for until obtaining clear solution；By 1.37g
NaOH（50wt%）Solution is added in aluminum nitrate solution and stirs until obtaining a uniform solution；The pregnancy of 1.55g is added
Base ammonium bromide（HMBr2）, wait for that solution is stirring evenly and then adding into the Ludox of 5.71g, then obtain mixture hand operated mixing within 5 minutes
To gel（Prepared gel molar ratio is 30 SiO2:0.3Al2O3:9.0 Na2O:4.5 HMBr2:1335 H2O）, 180 DEG C dynamic
State crystallization 48h；Final product centrifuges, washing, and the whole night, 550 DEG C roast 4h for 60 DEG C of dryings one；Obtained solid ion exchange is three times
（The NH of 5wt% is used in 85 DEG C of water-baths4NO3Solution treatment 8h, filtering and washing）, obtained solid is dried, 550 DEG C of roasting 4h are
Obtain the H-type EU-1-100 molecular sieves that silica alumina ratio is 100.
Embodiment 2
By the dibromo pentane of 15g（DBP）With the trimethylamine ethanol solution of 31.1g（33wt%, TMA）It is dissolved in 75ml absolute ethyl alcohols
In, make TMA/DBP=2.5:1, mixture flows back a night, cooling, washing, 70 DEG C of dryings；Al (the NO of 0.144g are added3)3·
9H2The NaOH solution of 0.64g 50wt% is added until obtain a transparent solution in the deionized water of O and 17.93g, stirring,
The pentamethyl ammonium bromide of 1.24g is added（PMBr2）, wait for that solution is stirring evenly and then adding into the tetraethyl orthosilicate of 4.96g, stirring is straight
It all volatilizees to all ethyl alcohol（Gained gel molar ratio is 30 SiO2:0.15 Al2O3:5.0 Na2O:4.5 HMBr2:1200
H2O）, 200 DEG C of crystallization 72h, final product centrifugation, washing, the whole night, 550 DEG C of roasting 4h, obtained solid ion is handed over for 60 DEG C of dryings one
It changes three times（The NH of 5wt% is used in 85 DEG C of water-baths4NO3Solution treatment 8h, filtering and washing）, obtained solid is dried, 550 DEG C of roastings
It burns 4h and obtains the H-type ZSM-48-200 molecular sieves that silica alumina ratio is 200.
Embodiment 3
By the dibromo pentane of 15g（DBP）With the trimethylamine ethanol solution of 31.1g（33wt%, TMA）It is dissolved in 75ml absolute ethyl alcohols
In, make TMA/DBP=2.5:1, mixture flows back a night, cooling, washing, 70 DEG C of dryings；Al (the NO of 0.144g are added3)3·
9H2The NaOH solution of 0.64g 50wt% is added until obtain a transparent solution in the deionized water of O and 17.93g, stirring,
The pentamethyl ammonium bromide of 1.24g is added（PMBr2）, wait for that solution is stirring evenly and then adding into the tetraethyl orthosilicate of 4.96g, stirring is straight
It all volatilizees to all ethyl alcohol（Prepared gel molar ratio is 30 SiO2:0.12 Al2O3:5.0 Na2O:4.5 HMBr2:
1200 H2O）, 200 DEG C of crystallization 72h, final product centrifugation, washing, the whole night, 550 DEG C roast 4h, obtained solid for 60 DEG C of dryings one
Ion exchange is three times（The NH of 5wt% is used in 85 DEG C of water-baths4NO3Solution treatment 8h, filtering and washing）, obtained solid is dried,
550 DEG C of roasting 4h obtain the H-type ZSM-48-250 molecular sieves that silica alumina ratio is 200.
Embodiment 4
Al (the NO of 0.29g3)3• 9H2The deionized water of O and 40g is mixed and stirred for until obtaining clear solution；By 1.52g's
NaOH（50wt%）Solution is added in aluminum nitrate solution and stirs until obtaining a uniform solution；The hexamethyl of 5.16g is added
Ammonium bromide（HMBr2）, wait for that solution is stirring evenly and then adding into the Ludox of 11.42g, then obtain mixture hand operated mixing within 5 minutes
To gel（Gel molar ratio is 60SiO2 :0.4Al2O3 : 10Na2O : 15HMBr2 : 3000H2O）, 200 DEG C of crystallization 72h,
Final product centrifuges, washing, and the whole night, 550 DEG C of roasting 4h, obtained solid ion exchange is three times for 60 DEG C of dryings one（In 85 DEG C of water-baths
The middle NH with 5wt%4NO3Solution treatment 8h, filtering and washing）, obtained solid is dried, 550 DEG C of roasting 4h are to get silica alumina ratio
150 EU-1/ZSM-48-150 eutectic molecular sieves.
Embodiment 5
Al (the NO of 0.22g3)3• 9H2The deionized water of O and 40g is mixed and stirred for until obtaining clear solution；By 1.52g's
NaOH（50wt%）Solution is added in aluminum nitrate solution and stirs until obtaining a uniform solution；The hexamethyl of 5.16g is added
Ammonium bromide（HMBr2）, wait for that solution is stirring evenly and then adding into the Ludox of 11.42g, then obtain mixture hand operated mixing within 5 minutes
To gel（Gel molar ratio is 60SiO2 :0.3Al2O3 : 10Na2O : 15HMBr2 : 3000H2O）, 200 DEG C of crystallization 72h,
Final product centrifuges, washing, and the whole night, 550 DEG C of roasting 4h, obtained solid ion exchange is three times for 60 DEG C of dryings one（In 85 DEG C of water-baths
The middle NH with 5wt%4NO3Solution treatment 8h, filtering and washing）, obtained solid is dried, 550 DEG C of roasting 4h are to get silica alumina ratio
200 EU-1/ZSM-48-200 coexisting molecular sieves.
Fig. 1 is the XRD diagram for preparing all samples prepared by embodiment 1-5, and abscissa is angle, ordinate in Fig. 1
For crystallinity.Different aluminium contents results in the synthesis of different molecular sieve in gel, and EU-1 is synthesized with higher aluminium content,
And lower aluminium content is conducive to the crystallization of ZSM-48.Eutectic EU-1/ZSM-48 molecular sieves are shown compared with EU-1 and ZSM-48
Different peaks XRD, with SiO2/Al2O3Ratio increases, and the characteristic peak of EU-1 fades away, and the peak of ZSM-48 gradually increases,
The variation of characteristic peak shows that the synthesis of eutectic EU-1/ZSM-48 molecular sieves is because when eutectic EU-1/ZSM-48 molecular sieves are EU-
When the physical mixture of 1 and ZSM-48, two kinds of skeletons can be detected.Eutectic EU-1/ZSM-48 molecular sieves and EU-1 and
ZSM-48 is relatively low compared to crystallinity, and the variation of crystallinity influences acidity and catalyst activity, but the reduction of crystallinity has no effect on
Catalyst choice.
Fig. 2 is the NH of all samples prepared by embodiment 1-43- TPD schemes, and abscissa is temperature in fig. 2, and ordinate is
Ammonolysis inhales peak.EU-1-100, EU-1/ZSM-48-150, EU-1/ZSM-48-200, ZSM-48-250 are all shown typical
Low temperature, medium temperature, the desorption peak of high temperature, in low temperature, medium temperature, the different desorption peak of three kinds of high temperature corresponds to weak acid respectively, middle acid, by force
Acid.The strong acid of ZSM-48-250 is 430 DEG C, has stronger acidity, strong acid to reach maximum value and be with ZSM-48-250, EU-1-100
430℃；The weak acid of ZSM-48-250 and EU-1-100 has similar trend, the weak acid amount of 4 samples to be all higher than strong acid with strong acid
With weak acid amount, show that this 4 kinds of samples are weakly acidic.
Claims (4)
1. a kind of preparation method of EU-1/ZSM-48 composite molecular sieve catalysts, it is characterised in that include the following steps：
1. by Al (NO3)3• 9H2O is mixed and stirred for deionized water until transparent aluminum nitrate solution is obtained, by 50wt%
Stirring in aluminum nitrate solution is added until obtaining uniform solution in NaOH solution, adds hexamethyl ammonium bromide（HMBr2）, wait for molten
Liquid is stirring evenly and then adding into Ludox, then stirs the mixture for uniformly obtaining gel；
2. 200 DEG C of crystallization 72h, product centrifugation, washing, 60 DEG C are dried overnight, 550 DEG C of roasting 4h；
3. by step, 2. calcined solids use NH4NO3Solion exchanges three times, dry；
4. 550 DEG C of roasting 4h of products therefrom are to get EU-1/ZSM-48 coexisting molecular sieves 3. step is handled after.
2. the preparation method of EU-1/ZSM-48 composite molecular sieve catalysts as described in claim 1, it is characterised in that：Using
NH4NO3Solion exchange operating condition be：The NH of 5wt% is used in 85 DEG C of water-baths4NO3Solution treatment 8h, filtering and washing.
3. the preparation method of EU-1/ZSM-48 composite molecular sieve catalysts as described in claim 1, it is characterised in that：Step is 1.
Mole group of middle gained gel becomes 60SiO2 :xAl2O3 : 10Na2O : 15HMBr2 : 3000H2O, x=0.24-0.6.
4. as EU-1/ZSM-48 composite molecular sieve catalysts are prepared in claim 1-3 either method.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109772447A (en) * | 2019-01-18 | 2019-05-21 | 太原大成环能化工技术有限公司 | A kind of isomerization of C-8 aromatics composite molecular sieve catalyst and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109772447A (en) * | 2019-01-18 | 2019-05-21 | 太原大成环能化工技术有限公司 | A kind of isomerization of C-8 aromatics composite molecular sieve catalyst and preparation method thereof |
| CN109772447B (en) * | 2019-01-18 | 2022-04-12 | 太原大成环能化工技术有限公司 | Composite molecular sieve catalyst for isomerization of carbon octa-arene and preparation method thereof |
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Application publication date: 20181106 |