CN102513146A - Catalyst for compounding 2, 6-dimethylnaphthalene and preparing method thereof - Google Patents
Catalyst for compounding 2, 6-dimethylnaphthalene and preparing method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 26
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 title abstract description 18
- 238000013329 compounding Methods 0.000 title abstract 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000004964 aerogel Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 13
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 13
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000499 gel Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- 238000005804 alkylation reaction Methods 0.000 abstract description 9
- 239000002808 molecular sieve Substances 0.000 abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 abstract 2
- 239000004966 Carbon aerogel Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 230000029936 alkylation Effects 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical class C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 7
- 239000011280 coal tar Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005120 petroleum cracking Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 101000579647 Penaeus vannamei Penaeidin-2a Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- -1 naphthalene compound Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for compounding 2, 6-dimethylnaphthalene and a preparing method thereof. The weight ratio of main components of the catalyst is: Na 2O 0.25-0.5 parts, SiO 2 1.0 parts, tetrapropyl ammonium bromide (TPABr) 0.05-0.2 parts, Al2O3 0.01-0.03 parts, Fe2O3 0.01-0.03 parts, H2PO4- 0.03-0.06 parts and carbon aerogel 22-45 parts. The catalyst for compounding the 2, 6-dimethylnaphthalene and the preparing method of the catalyst are used in an alkylation reaction of 2-methylnaphthalene and methanol, the selectivity and yield of the 2, 6-dimethylnaphthalene respectively reach 50% and 17% and are obviously better than those of a common molecular sieve catalyst.
Description
Technical field
The present invention relates to a kind of catalyst, especially a kind of Synthetic 2 that is used for, the Catalysts and its preparation method of 6-dimethylnaphthalene.
Background technology
2,6-dialkyl group naphthalene is as the important intermediate of synthesized high-performance polyester material, generate after its oxidation 2, the PEN (PEN) that 6-naphthalenedicarboxylic acid and ethylene glycol polymerization make is a kind of novel polyester-type material.Compare with PETG (PET) at present commonly used, PEN performance aspect numerous all is superior to PET, is the substitute of following PET.The key that PEN commercially produces is a starting monomer 2, the source of 6-naphthalenedicarboxylic acid and cost.The principal element that restricting current PEN comes into the market on a large scale is the raw material of synthetic PEN---2, and 6-dialkyl group naphthalene costs an arm and a leg.
Contain naphthalene compound with other and compare, 2, the 6-dimethylnaphthalene is simple and do not have the carbon atom loss and the most economical with its easy oxidation, oxidizing process, and therefore cheap, the process of exploitation is simple 2, and 6-dimethylnaphthalene technology is the basis of realizing PEN large-scale production.Some major companies of the world have begun to be correlated with 2, the R&D work of 6-dimethylnaphthalene.
2,6-dimethylnaphthalene synthesis technique comprises two types of direct extraction method and chemical synthesis.Direct extraction method is to be raw material with coal tar wash oil, pyrolysis gas oil and petroleum cracking heavy aromatics etc., through series of process direct separation such as rectifying, crystallizations, but because in coal tar wash oil and the petroleum cracking heavy aromatics 2; 6-dimethylnaphthalene content is merely 1-2 wt%, also be difficult to satisfy reality to the PEN development need even all utilize, and dimethylnaphthalene isomer is many; Separation difficulty, efficient are low; Can not be as 2,6-dimethylnaphthalene main source must be through the chemical synthesis preparation.
Chemical synthesis comprises that with toluene, xylenes, naphthalene, methyl naphthalene and multi-methylnaphthalene etc. be raw material, through series of chemical preparation 2,6-dimethylnaphthalene process.Contain methyl naphthalene component abundant, relative low price (comprising 1-methyl naphthalene and 2-methyl naphthalene) in the coal tar, so the rational and efficient use of methyl naphthalene has significant effects for the value that promotes coal tar and the development of Coal Chemical Industry industry.At present; Amoco and Mitsubishi are only to have two families to realize 2 in the world, 6-dimethylnaphthalene suitability for industrialized production enterprise, and the technology of employing all is raw material with the ortho-xylene; Through preparing 2 with processes such as butadiene side chain alkylation, dehydrocyclization, dehydroaromatizationof, isomerization; The 6-dimethylnaphthalene needs each step intermediate product separated and can carry out just that next step is synthetic, therefore has the process complicacy, process route is long and problems such as cost height.
2 of the synthetic high added value of zeolite catalysis 2-methyl naphthalene and methanol alkylation selectivity, 6-dimethylnaphthalene have advantages such as process route is short, raw material sources are extensive, low price, are a kind of synthetic routes with potentiality to be exploited, thereby are to study focus at present.
Summary of the invention
The technical problem that the present invention will solve provides a kind of Synthetic 2 that is used for, and the Catalysts and its preparation method of 6-dimethylnaphthalene is used for 2-methyl naphthalene and methanol alkylation Synthetic 2, the reaction of 6-dimethylnaphthalene, obtain desirable 2,6-dimethylnaphthalene yield.
For solving the problems of the technologies described above, among the present invention respectively the weight proportion of this catalyst component be: Na
20.25～0.5 part of O, SiO
21.0 part, 0.05～0.2 part of TPABr, Al
2O
30.01～0.03 part, Fe
2O
30.01～0.03 part, H
2PO
4 -0.03～0.06 part with 22～45 parts of charcoal-aero gels.
The weight proportion of the preferred catalyst component of the present invention is: Na
20.32 part of O, SiO
21.0 part, 0.1 part of TPABr, Al
2O
30.01 part, Fe
2O
30.0163 part, H
2PO
4 -0.0489 30 parts of part and charcoal-aero gels.
The inventive method adopts following processing step preparation:
(1) calculates also raw materials weighing NaOH, waterglass, TPAOH (aq, 20%), Al (NO according to the proportioning of each composition
3)
39H
2O, Fe
2(SO
4)
3, NaH
2PO
4And charcoal-aero gel;
(2) waterglass and NaOH solution are mixed, add TPAOH solution, stir;
(3) with Al (NO
3)
39H
2O solution and above-mentioned mixed liquor mix, and add Fe again
2(SO
4)
3, stir;
(4) in above-mentioned mixed liquor, add NaH
2PO
4Solution, dry charcoal-aero gel is added in the back that stirs, and stirs;
(5) with the aging gel that obtains of said mixture, gel carries out crystallization and obtains sample then;
(6) described sample is through suction filtration, washing, drying, and template is removed in last, roasting, makes described catalyst.
Add NaH in the said step of the inventive method (4)
2PO
4Stir 1～3h behind the solution, add the charcoal-aero gel of 120 ℃ of down dry 3～6h then.
In the said step of the inventive method (5), the aging at normal temperatures 20～25h of mixture, the gained gel is in 175 ℃ of following crystallization 70～75h.
In the said step of the inventive method (6), template is removed in 550 ℃ of following roastings at last in 120 ℃ of drying 3～5h in sample washing back, makes catalyst.
Adopt the beneficial effect that technique scheme produced to be: the present invention is a kind of methyl naphthalene alkylation catalyst; The alkylated reaction that is used for 2-methyl naphthalene and methyl alcohol; Target product 2; The selectivity of 6-dimethylnaphthalene and yield reach 50% and 17% respectively, obviously are superior to existing common molecular sieve catalyst.
The specific embodiment
Below in conjunction with specific embodiment the present invention is done further detailed explanation.
The ZSM-5 zeolite molecular sieve is a kind of desirable 2-methyl naphthalene alkylation catalyst material, but in use has 2-methyl naphthalene conversion ratio and 2, problem such as lower and easy inactivation of 6-dimethylnaphthalene selectivity.After the process modification makes it possess special composition and pore passage structure, can obtain desirable catalytic effect.
2,6-dimethylnaphthalene molecule has and ZSM-5 zeolite cavity similar sizes, runs into very big diffusional resistance during molecule turnover ZSM-5, and this situation hinders finishes carbon precursor disengaging catalyst activity position, makes catalyst carbon deposit make its inactivation.Fe is a transition metal, and atomic size is bigger than Al, introduces zeolitic frameworks, can increase pore volume, reduces the current resistance of molecule, reduces carbon deposit, improves catalyst life.Simultaneously, behind the Al element with the Fe instead of part, the ZSM-5 acid strength is improved, and can increase catalytic activity, improves 2-methyl naphthalene conversion ratio.
Through discovering, in the building-up process of zeolite, adding charcoal-aero gel can increase the zeolite pore volume, thereby obviously improves the conversion ratio of 2-methyl naphthalene.But excessive charcoal-aero gel can reduce the mesoporous content of zeolite on the contrary, causes the total pore volume of zeolite to reduce, thereby reduces the conversion ratio of 2-methyl naphthalene.After the charcoal-aero gel addition acquires a certain degree; Mesoporous amount minimizing causes reactant and the product diffusion in catalyst to reduce; The selectivity that less molecule is generated improves, and 2, the molecular dimension of 6-dimethylnaphthalene is compared less with most of homologue; Help zeolite to 2, the 6-dimethylnaphthalene select the shape effect.Therefore the addition of charcoal-aero gel has a suitable scope.
Comprehensive 2-methyl naphthalene conversion ratio and 2,, the 6-dimethylnaphthalene is double factor optionally, and the weight proportion of each composition of catalyst provided by the invention is: sodium oxide molybdena (Na
2O) 0.25～0.5 part, silica (SiO
2) 1.0 parts, 0.05～0.2 part of 4-propyl bromide (TPABr), aluminium oxide (Al
2O
3) 0.01～0.03 part, di-iron trioxide (Fe
2O
3) 0.01～0.03 part, dihydrogen phosphate (H
2PO
4 -) 0.03～0.06 part with 22～45 parts of charcoal-aero gels.
Embodiment 1: originally be used for Synthetic 2, the catalyst of 6-dimethylnaphthalene adopts following preparation method.
By weight Na
2O:SiO
2: TPAOH:Al
2O
3: Fe
2O
3: H
2PO
4 -: charcoal-aero gel=0.32:1.0:0.1:0.01:0.0163:0.0489:30, calculate and take by weighing raw material NaOH, waterglass, TPAOH (aq, 20%), Al (NO
3)
39H
2O, Fe
2(SO
4)
3, NaH
2PO
4And charcoal-aero gel.
Waterglass NaOH solution is mixed, add TPAOH (aq), stir; With Al (NO
3)
39H
2O solution and above-mentioned mixed liquor mix, and add Fe again
2(SO
4)
3, stir; In above-mentioned mixed liquor, add NaH
2PO
4Solution behind the powerful stirring 2h, adds 120 ℃ of charcoal-aero gels of dry 5h down, stirs; With the aging at normal temperatures 22h of said mixture, the gained gel is in 175 ℃ of following crystallization 72h.Through suction filtration, deionized water fully washs with above-mentioned gained sample, in 120 ℃ of dry 4h, and removes template in 550 ℃ of following roastings, makes this catalyst.Through detecting, the weight proportion of each composition in this catalyst is: Na
20.32 part of O, SiO
21.0 part, 0.1 part of TPABr, Al
2O
30.01 part, Fe
2O
30.0163 part, H
2PO
4 -0.0489 30 parts of part, charcoal-aero gels.
At 400 ℃, 2-methyl naphthalene mass space velocity is 0.5 h
-1, under the condition of 2-methyl naphthalene: methyl alcohol: mesitylene=1:1:3 (mol ratio), above-mentioned catalyst is used for 2-methyl naphthalene and methanol alkylation Synthetic 2, in the reaction of 6-dimethylnaphthalene.Through reaction in 8 hours, the selectivity of 2-methyl naphthalene, dimethylnaphthalene selectivity, 2,6/2,7-DMN ratio, 2, the selectivity of 6-DMN and yield can reach 44%, 78%, 2.7,49% and 17% respectively.
Embodiment 2: originally be used for Synthetic 2, the catalyst of 6-dimethylnaphthalene adopts following preparation method.
By weight Na
2O:SiO
2: TPAOH:Al
2O
3: Fe
2O
3: H
2PO
4 -: charcoal-aero gel=0.25:1.0:0.2:0.02:0.01:0.06:22, calculate and take by weighing raw material NaOH, waterglass, TPAOH (aq, 20%), Al (NO
3)
39H
2O, Fe
2(SO
4)
3, NaH
2PO
4And charcoal-aero gel.
Waterglass NaOH solution is mixed, add TPAOH (aq), stir; With Al (NO
3)
39H
2O solution and above-mentioned mixed liquor mix, and add Fe again
2(SO
4)
3, stir; In above-mentioned mixed liquor, add NaH
2PO
4Solution behind the powerful stirring 1h, adds 120 ℃ of charcoal-aero gels of dry 6h down, stirs; With the aging at normal temperatures 20h of said mixture, the gained gel is in 175 ℃ of following crystallization 70h.Through suction filtration, deionized water fully washs with above-mentioned gained sample, in 120 ℃ of dry 5h, and removes template in 550 ℃ of following roastings, makes this catalyst.Through detecting, the weight proportion of each composition in this catalyst is: Na
20.25 part of O, SiO
21.0 part, 0.2 part of TPABr, Al
2O
30.02 part, Fe
2O
30.01 part, H
2PO
4 -0.06 22 parts of part, charcoal-aero gels.
Adopt embodiment 1 described process conditions, above-mentioned catalyst is used for 2-methyl naphthalene and methanol alkylation Synthetic 2, in the reaction of 6-dimethylnaphthalene.Through reaction in 8 hours, the selectivity of 2-methyl naphthalene, dimethylnaphthalene selectivity, 2,6/2,7-DMN ratio, 2, the selectivity of 6-DMN and yield can reach 45%, 79%, 2.8,47% and 18% respectively.
Embodiment 3: originally be used for Synthetic 2, the catalyst of 6-dimethylnaphthalene adopts following preparation method.
By weight Na
2O:SiO
2: TPAOH:Al
2O
3: Fe
2O
3: H
2PO
4 -: charcoal-aero gel=0.5:1.0:0.05:0.03:0.03:0.03:45, calculate and take by weighing raw material NaOH, waterglass, TPAOH (aq, 20%), Al (NO
3)
39H
2O, Fe
2(SO
4)
3, NaH
2PO
4And charcoal-aero gel.
Waterglass NaOH solution is mixed, add TPAOH (aq), stir; With Al (NO
3)
39H
2O solution and above-mentioned mixed liquor mix, and add Fe again
2(SO
4)
3, stir; In above-mentioned mixed liquor, add NaH
2PO
4Solution behind the powerful stirring 3h, adds 120 ℃ of charcoal-aero gels of dry 3h down, stirs; With the aging at normal temperatures 25h of said mixture, the gained gel is in 175 ℃ of following crystallization 75h.Through suction filtration, deionized water fully washs with above-mentioned gained sample, in 120 ℃ of dry 3h, and removes template in 550 ℃ of following roastings, makes this catalyst.Through detecting, the weight proportion of each composition in this catalyst is: Na
20.5 part of O, SiO
21.0 part, 0.05 part of TPABr, Al
2O
30.03 part, Fe
2O
30.03 part, H
2PO
4 -0.03 45 parts of part, charcoal-aero gels.
Adopt embodiment 1 described process conditions, above-mentioned catalyst is used for 2-methyl naphthalene and methanol alkylation Synthetic 2, in the reaction of 6-dimethylnaphthalene.Through reaction in 8 hours, the selectivity of 2-methyl naphthalene, dimethylnaphthalene selectivity, 2,6/2,7-DMN ratio, 2, the selectivity of 6-DMN and yield can reach 44%, 77%, 2.6,48% and 17% respectively.
Claims (6)
1. one kind is used for Synthetic 2, and the catalyst of 6-dimethylnaphthalene is characterized in that, this catalyst predominant quantity proportioning is: Na
20.25～0.5 part of O, SiO
21.0 part, 0.05～0.2 part of TPABr, Al
2O
30.01～0.03 part, Fe
2O
30.01～0.03 part, H
2PO
4 -0.03～0.06 part with 22～45 parts of charcoal-aero gels.
2. the Synthetic 2 that is used for according to claim 1, the catalyst of 6-dimethylnaphthalene is characterized in that, this catalyst predominant quantity proportioning is: Na
20.32 part of O, SiO
21.0 part, 0.1 part of TPABr, Al
2O
30.01 part, Fe
2O
30.0163 part, H
2PO
4 -0.0489 30 parts of part and charcoal-aero gels.
3. claim 1, the 2 described Synthetic 2s that are used for; The Preparation of catalysts method of 6-dimethylnaphthalene; It is characterized in that the processing step of this method is: also raw materials weighing NaOH, waterglass, TPAOH (aq, 20%), Al (NO are calculated according to the proportioning of each composition in (1)
3)
39H
2O, Fe
2(SO
4)
3, NaH
2PO
4And charcoal-aero gel;
(2) waterglass and NaOH solution are mixed, add TPAOH solution, stir;
(3) with Al (NO
3)
39H
2O solution and above-mentioned mixed liquor mix, and add Fe again
2(SO
4)
3, stir;
(4) in above-mentioned mixed liquor, add NaH
2PO
4Solution, dry charcoal-aero gel is added in the back that stirs, and stirs;
(5) with the aging gel that obtains of said mixture, gel carries out crystallization and obtains sample then;
(6) described sample is through suction filtration, washing, drying, and template is removed in last, roasting, makes described catalyst.
4. the Synthetic 2 that is used for according to claim 3, the Preparation of catalysts method of 6-dimethylnaphthalene is characterized in that: add NaH in the said step (4)
2PO
4Stir 1～3h behind the solution, add the charcoal-aero gel of 120 ℃ of down dry 3～6h then.
5. the Synthetic 2 that is used for according to claim 3, the Preparation of catalysts method of 6-dimethylnaphthalene is characterized in that: in the said step (5), the aging at normal temperatures 20～25h of mixture, the gained gel is in 175 ℃ of following crystallization 70～75h.
6. according to claim 3, the 4 or 5 described Synthetic 2s that are used for; The Preparation of catalysts method of 6-dimethylnaphthalene is characterized in that: in the said step (6), sample washing back is in 120 ℃ of drying 3～5h; Remove template in 550 ℃ of following roastings at last, make catalyst.
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