CN103664490B - The method of alkylation of toluene methanol - Google Patents
The method of alkylation of toluene methanol Download PDFInfo
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- CN103664490B CN103664490B CN201210325066.9A CN201210325066A CN103664490B CN 103664490 B CN103664490 B CN 103664490B CN 201210325066 A CN201210325066 A CN 201210325066A CN 103664490 B CN103664490 B CN 103664490B
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Abstract
The present invention relates to a kind of method of alkylation of toluene methanol, when mainly solution prior art carries out alkylation of toluene methanol reaction, improve the optionally obvious problem of simultaneous reactions activity decrease.The present invention, by adopting with toluene and methyl alcohol for raw material, with catalyst exposure, generates dimethylbenzene and water; Catalyzer wherein used, comprises following component with weight parts: a) core-shell molecular sieve of Si modification of 5 ~ 95 parts; B) binding agent of 5 ~ 95 parts; Wherein, the nuclear phase of the core-shell molecular sieve of described Si modification is ZSM-5 molecular sieve, and shell is Silicalite-1 molecular sieve, is coated with silicon dioxide layer outside shell; Wherein, the weight ratio of core/shell is (0.01 ~ 3): 1; Silicon dioxide layer is that the technical scheme of 1 ~ 30% of core-shell molecular sieve weight solves this problem preferably, can be used in the industrial production of alkylation of toluene methanol reaction.
Description
Technical field
The present invention relates to a kind of alkylation of toluene methanol method.
Background technology
P-Xylol is the important source material of synthetic polyester fibers, current industrial main employing toluene disproportionation and C
9accordance transfer, xylene isomerization and toluene select the methods such as disproportionation to produce.Because the p-Xylol content in its product is by thermodynamic control, the equilibrium concentration of p-Xylol in all xylene isomers only accounts for about 24%, and between isomer, boiling point is close, and separation condition is harsh, and equipment requirements is high.In toluene selective disproportionation reaction, need could generate the p-Xylol of a molar purity more than 85% with two mole toluene, toluene utilization ratio is lower.And react at toluene and methanol alkylation and directly synthesize in the p-Xylol technique of high density, toluene utilization ratio is high, and product is easy to be separated, and thus this technique has good Development volue.
Alkylation of toluene methanol reaction is with usually all adopting acidic molecular sieve to make catalyzer, and the strength of acid of ZSM-5 distributes can in very large range regulate and control with acid, and therefore ZSM-5 is the molecular screen material extensively adopted in research.But, the acid sites of ZSM-5 molecular sieve outside surface is disadvantageous to selecting shaped reaction usually, alkylated reaction is there is and generates p-Xylol in toluene and methyl alcohol in molecular sieve crystal, p-Xylol spreads out from the duct of ZSM-5 at first, but there is acidic site in molecular sieve outer surface, particularly the ratio of small crystal grain molecular sieve outer surface acidity position is larger, and p-Xylol further isomery under the effect at outer surface acidity center turns to m-xylene and o-Xylol.In prior art, can by modifying the generation reducing this reaction to molecular sieve outer surface, to improve the selectivity of molecular sieve shape selective catalytic reaction.
US Patent No. 4088605, US4788374 and US4868146 report the molecular sieve shell at ZSM-5 or ZSM-3 outside surface crystallization total silicon, and this shell can under the prerequisite not affecting nuclear phase molecular sieve pore passage diffusion and Acidity, modulation outer surface properties.
CN1927463A relates to a kind of chemical reaction deposit to modify the method for ZSM-5 zeolite outer surface acidity.The feature of the method is that estersil and molecular sieve react in airtight container at 140-170 DEG C, then cools, and roasting obtains.The effect of the method and benefit are that the utilization ratio of estersil is high, a load is only needed for micron ZSM-5, the contraposition of catalyzer is selected to reach more than 90%, and needs twice chemical reaction deposit for nano-ZSM-5, and para-selectivity can reach more than 90%.But the method is while modification outside is acid, meeting Partial Blocking duct, causes catalyst activity greatly to reduce.
Summary of the invention
Technical problem to be solved by this invention be prior art carry out alkylation of toluene methanol reaction time, improving the optionally obvious problem of simultaneous reactions activity decrease, provide a kind of method of new alkylation of toluene methanol.The method has while having compared with highly selective, the advantage that activity decrease is less.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of alkylation of toluene methanol, with toluene and methyl alcohol for raw material, with to reaction in the gas of inertia for carrier gas, be 300 ~ 500 DEG C in temperature of reaction, reaction pressure is 0 ~ 1 MPa, and air speed is 1 ~ 10 hour
-1, the mol ratio of toluene and methyl alcohol is (10:1) ~ (1:3), and the mol ratio of carrier gas and methylbenzene methanol total amount is under the condition of (1:1) ~ (5:1), reaction raw materials and catalyst exposure, generates dimethylbenzene and water; Catalyzer wherein used, comprises following component with weight parts:
A) core-shell molecular sieve of Si modification of 5 ~ 95 parts;
B) binding agent of 5 ~ 95 parts;
Wherein, the nuclear phase of the core-shell molecular sieve of described Si modification is ZSM-5 molecular sieve, and shell is Silicalite-1 molecular sieve, is coated with silicon dioxide layer outside shell; Wherein, the weight ratio of core/shell is (0.01 ~ 3): 1; Silicon dioxide layer is 1 ~ 30% of core-shell molecular sieve weight.
In technique scheme, nuclear phase ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2o
3preferable range is 10 ~ 350, and more preferably scope is 20 ~ 300.The weight ratio preferable range of core/shell is (0.02 ~ 2): 1, and more preferably scope is (0.03 ~ 1.5): 1.Silicon dioxide layer weight preferable range is 2 ~ 25% of core-shell molecular sieve weight, and more preferably scope is 3 ~ 22%.In catalyzer, binding agent preferred version is be selected from least one in silicon sol or silicon oxide.Temperature of reaction preferable range is 320 ~ 480 DEG C, and more preferably scope is 350 ~ 450 DEG C.In raw material, the mol ratio of toluene and methyl alcohol is preferable range is (8:1) ~ (1:2), and more preferably scope is (6:1) ~ (1:1).Carrier gas preferred version is nitrogen.
The preparation method of the catalyzer in the present invention is as follows: the binding agent of the core-shell molecular sieve of Si modification and aequum is carried out kneading, shaping, dry, roasting, obtains finished catalyst.Wherein, the preparation method of the core-shell molecular sieve of Si modification comprises the following steps:
1) shell liquid is prepared: tetraethoxy, organic formwork agent R and water are mixed, mole consisting of of mixture: H
2o/SiO
2=20 ~ 120, R/SiO
2=0.01 ~ 0.3; Wherein, organic formwork agent R is selected from least one in TPAOH, 4-propyl bromide, methylamine, ethamine, propylamine or butylamine;
2) nuclear phase ZSM-5 molecular sieve is added in above-mentioned shell liquid, in 130 ~ 210 DEG C of crystallization 1 ~ 36 hour, through cooling, filter, dry, obtain core-shell molecular sieve; Wherein, the weight ratio of nuclear phase ZSM-5 molecular sieve and shell liquid is 1:(5 ~ 250);
3) mixed with silicon source by core-shell molecular sieve, in 140 ~ 180 DEG C of crystallization 1 ~ 10 hour, roasting products therefrom, obtained the core-shell molecular sieve of described Si modification; Wherein, the weight ratio in core-shell molecular sieve and silicon source is 1:(1 ~ 2); Described silicon source, with weight parts, comprises following component:
A) at least one be selected from tetraethoxy, positive silicic acid propyl ester or butyl silicate of 1 ~ 100 part;
B) at least one dispersion agent be selected from normal hexane, hexanaphthene, normal heptane, suberane, octane or cyclooctane of 0 ~ 99 part.
In technique scheme, in step 1), a mole composition preferable range for mixture is: H
2o/SiO
2=30 ~ 100, R/SiO
2=0.03 ~ 0.2.Step 2) in, crystallization temperature preferable range is 140 ~ 200 DEG C, and crystallization time preferable range is 2 ~ 24 hours.In step 3), crystallization temperature preferable range is 150 ~ 170 DEG C, and crystallization time preferable range is 2 ~ 9 hours.In step 3), with weight parts, the consumption preferable range being selected from least one in tetraethoxy, positive silicic acid propyl ester or butyl silicate is 5 ~ 95 parts, and the consumption preferable range being selected from least one dispersion agent in normal hexane, hexanaphthene, normal heptane, suberane, octane or cyclooctane is 5 ~ 95 parts.
In the inventive method, catalyst activity main body is made owing to adopting the core-shell molecular sieve of Si modification, this main body is at nuclear phase ZSM-5 molecular sieve surface growth total silicon Silicalite-1 shell, shell is under the prerequisite not affecting nuclear phase molecular sieve pore passage diffusion and Acidity, can effective modulation outer surface acidity matter, thus in alkylation of toluene methanol reaction, there is certain selectivity.But, be inadequate only by elimination outer surface acidity, also need to modify the selectivity that just can reach industrial application and require to aperture.The present invention is by carrying out Si modification to core-shell molecular sieve, and the template in the process of Si modification in core-shell molecular sieve shell can effectively prevent from depositing SiO
2to the blocking in duct, thus effectively reduce the loss of the catalytic activity in modifying process.Be 6:1 in methylbenzene methanol mol ratio, temperature of reaction is 380 DEG C, and air speed is 3 hours
-1condition under, the selection of p-Xylol is more than 90%, and the loss of catalyst activity is less than 18%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[comparative example 1]
[comparative example 1] is used for SiO is described
2/ Al
2o
3be that the ZSM-5 molecular sieve of 150 is as the preparation of active constituent catalyst.
Take silicon sol as binding agent, by 10 grams of Hydrogen ZSM-5 molecular sieves, 6 grams of silicon sol, 0.1 gram of sesbania powder and 2 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[comparative example 2]
[comparative example 2] is used for illustrating that nuclear phase is SiO
2/ Al
2o
3be the ZSM-5 molecular sieve of 150, shell is the preparation of core-shell molecular sieve as active constituent catalyst of Silicalite-1 mutually.
The TPAOH of 50 gram 25%, 260 grams of tetraethoxys, 1574 grams of water mixing are made into shell liquid, and stir 4 hours, in shell liquid, each component molar is than being H
2o/SiO
2=70, R/SiO
2=0.05.By 10 grams of good for ion-exchange SiO
2/ Al
2o
3be 150 Hydrogen ZSM-5 molecular sieve add in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 DEG C of crystallization 8 hours.At the end of crystallization, chilling, filters, and washing, is drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.13:1, and its XRD analysis result conforms to data in literature.
Get 10 grams of these core-shell molecular sieves, 6 grams of silicon sol, 0.1 gram of sesbania powder and 2 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[comparative example 3]
[comparative example 3] is used for the SiO of Si modification is described
2/ Al
2o
3be that the ZSM-5 molecular sieve of 150 is as the preparation of active constituent catalyst.
By 5 grams of tetraethoxys and the mixing of 5 grams of hexanaphthenes, add 10 grams of Hydrogen ZSM-5 molecular sieves, in 170 DEG C of crystallization 6 hours in crystallizing kettle.After crystallization terminates, chilling, sample in 120 DEG C of dried overnight, then 550 DEG C of roastings 5 hours.Repeating said process more once, obtain the molecular sieve of Si modification, is 28% of molecular sieve through silicon dioxide layer of weighing.Get 10 grams of these molecular sieves, 6 grams of silicon sol, 0.1 gram of sesbania powder and 2 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[embodiment 1]
The TPAOH of 25 gram 25%, 130 grams of tetraethoxys, 787 grams of water mixing are made into shell liquid, and stir 4 hours, in shell liquid, each component molar is than being H
2o/SiO
2=70, R/SiO
2=0.05.By 5 grams of SiO
2/ Al
2o
3be 150 Hydrogen ZSM-5 molecular sieve add in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 DEG C of crystallization 8 hours.After crystallization terminates, chilling, filtration, wash, be drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.13:1, and its XRD analysis result conforms to data in literature.
By 2.5 grams of tetraethoxys and the mixing of 2.5 grams of hexanaphthenes, add the core-shell molecular sieve of above-mentioned non-roasting, in 170 DEG C of crystallization 6 hours in crystallizing kettle.After crystallization terminates, chilling, sample, in 120 DEG C of dried overnight, then 550 DEG C of roastings 5 hours, obtains the molecular sieve of Si modification.Be 14% of core-shell molecular sieve weight through silicon dioxide layer of weighing.
Get the molecular sieve of 5 grams of above-mentioned Si modification, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[embodiment 2]
The TPAOH of 25 gram 25%, 130 grams of tetraethoxys, 787 grams of water mixing are made into shell liquid, and stir 4 hours, in shell liquid, each component molar is than being H
2o/SiO
2=70, R/SiO
2=0.05.By 5 grams of SiO
2/ Al
2o
3be 150 Hydrogen ZSM-5 molecular sieve add in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 DEG C of crystallization 8 hours.After crystallization terminates, chilling, filtration, wash, be drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.13:1, and its XRD analysis result conforms to data in literature.
By 1.3 grams of tetraethoxys and the mixing of 3.7 grams of hexanaphthenes, add the core-shell molecular sieve of above-mentioned non-roasting, in 170 DEG C of crystallization 6 hours in crystallizing kettle.After crystallization terminates, chilling, sample, in 120 DEG C of dried overnight, then 550 DEG C of roastings 5 hours, obtains the molecular sieve of Si modification.Be 7% of core-shell molecular sieve weight through silicon dioxide layer of weighing.
Get the molecular sieve of 5 grams of above-mentioned Si modification, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[embodiment 3]
The TPAOH of 25 gram 25%, 103 grams of tetraethoxys, 787 grams of water mixing are made into shell liquid, and stir 4 hours, in shell liquid, each component molar is than being H
2o/SiO
2=89, R/SiO
2=0.06.By 5 grams of SiO
2/ Al
2o
3be 150 Hydrogen ZSM-5 molecular sieve add in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 DEG C of crystallization 8 hours.After crystallization terminates, chilling, filtration, wash, be drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.16:1, and its XRD analysis result conforms to data in literature.
By 3.7 grams of tetraethoxys and the mixing of 1.3 grams of hexanaphthenes, add the core-shell molecular sieve of above-mentioned non-roasting, in 170 DEG C of crystallization 6 hours in crystallizing kettle.After crystallization terminates, chilling, sample, in 120 DEG C of dried overnight, then 550 DEG C of roastings 5 hours, obtains the molecular sieve of Si modification.Be 21% of core-shell molecular sieve weight through silicon dioxide layer of weighing.
Get the molecular sieve of 5 grams of above-mentioned Si modification, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[embodiment 4]
The TPAOH of 35 gram 25%, 45 grams of tetraethoxys, 272 grams of water mixing are made into shell liquid, and stir 4 hours, in shell liquid, each component molar is than being H
2o/SiO
2=70, R/SiO
2=0.2.By 5 grams of good for ion-exchange SiO
2/ Al
2o
3be 150 Hydrogen ZSM-5 molecular sieve add in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 DEG C of crystallization 8 hours.At the end of crystallization, chilling, filters, and washing, is drying to obtain core-shell molecular sieve.The weight ratio of core/shell is 0.38:1, and its XRD analysis result conforms to data in literature.
By 2.5 grams of tetraethoxys and the mixing of 2.5 grams of hexanaphthenes, add the core-shell molecular sieve of above-mentioned non-roasting, in 170 DEG C of crystallization 6 hours in crystallizing kettle.After crystallization terminates, chilling, sample, in 120 DEG C of dried overnight, then 550 DEG C of roastings 5 hours, obtains the molecular sieve of Si modification.Be 14% of core-shell molecular sieve weight through silicon dioxide layer of weighing.
Get the molecular sieve of 5 grams of above-mentioned Si modification, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[embodiment 5]
The TPAOH of 25 gram 25%, 103 grams of tetraethoxys, 787 grams of water mixing are made into shell liquid, and stir 4 hours, in shell liquid, each component molar is than being H
2o/SiO
2=89, R/SiO
2=0.06.By 5 grams of good for ion-exchange SiO
2/ Al
2o
3be 150 Hydrogen ZSM-5 molecular sieve add in shell liquid, stir 30 minutes, add in crystallizing kettle in 180 DEG C of crystallization 8 hours.At the end of crystallization, chilling, filters, and washing, is drying to obtain core-shell molecular sieve H.The weight ratio of core/shell is 0.16:1, and its XRD analysis result conforms to data in literature.
By 2.5 grams of tetraethoxys and the mixing of 2.5 grams of hexanaphthenes, add the core-shell molecular sieve of above-mentioned non-roasting, in 170 DEG C of crystallization 6 hours in crystallizing kettle.After crystallization terminates, chilling, sample, in 120 DEG C of dried overnight, then 550 DEG C of roastings 5 hours, obtains the molecular sieve of Si modification.Be 14% of core-shell molecular sieve weight through silicon dioxide layer of weighing.
Get the molecular sieve of 5 grams of above-mentioned Si modification, 3 grams of silicon sol, 0.05 gram of sesbania powder and 1 ml waters, mixing is mediated, extruded moulding, 550 DEG C of roastings 5 hours.
[embodiment 6]
It is carry out in fixed-bed reactor that toluene and methanol alkylation react.Get 2 grams of catalyzer, reaction raw materials mol ratio is toluene: methyl alcohol=6:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 3, and feed liquid weight space velocity is 3 hours
-1, temperature of reaction 380 DEG C.Charging 4 hours sampling analysis record toluene conversion and Selectivity for paraxylene, as shown in table 1.
Table 1
| Embodiment | Selectivity for paraxylene % | Toluene conversion % | Loss of catalyst activity % |
| Comparative example 1 | 23.7 | 13.4 | - |
| Comparative example 2 | 62.7 | 12.3 | 8.2 |
| Comparative example 3 | 90.4 | 6.2 | 53.4 |
| Embodiment 1 | 96.7 | 11.7 | 12.6 |
| Embodiment 2 | 93.1 | 12.3 | 8.2 |
| Embodiment 3 | 92.6 | 12.1 | 9.7 |
| Embodiment 4 | 90.3 | 12.7 | 5.2 |
| Embodiment 5 | 92.5 | 11.2 | 16.4 |
[embodiment 7]
Get catalyzer prepared by 2 grams [embodiments 1], reaction raw materials mol ratio is toluene: methyl alcohol=2:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 5, and feed liquid weight space velocity is 3 hours
-1, temperature of reaction 380 DEG C.It is 30.7% that charging 4 hours sampling analysis record toluene conversion, and Selectivity for paraxylene 92.9%, loss of catalyst activity is 14.3%.
[embodiment 8]
Get catalyzer prepared by 2 grams [embodiments 2], reaction raw materials mol ratio is toluene: methyl alcohol=2:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 5, and feed liquid weight space velocity is 3 hours
-1, temperature of reaction 420 DEG C.It is 36.7% that charging 4 hours sampling analysis record toluene conversion, and Selectivity for paraxylene 90.9%, loss of catalyst activity is 12.9%.
[embodiment 9]
Get catalyzer prepared by 2 grams [embodiments 3], reaction raw materials mol ratio is toluene: methyl alcohol=1:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 3, and feed liquid weight space velocity is 3 hours
-1, temperature of reaction 450 DEG C.It is 75.2% that charging 4 hours sampling analysis record toluene conversion, and Selectivity for paraxylene 90.1%, loss of catalyst activity is 13.7%.
[embodiment 10]
Get catalyzer prepared by 2 grams [embodiments 4], reaction raw materials mol ratio is toluene: methyl alcohol=1:1, and nitrogen is carrier gas, and the mol ratio of nitrogen and methanol toluene total amount is 3, and feed liquid weight space velocity is 2 hours
-1, temperature of reaction 350 DEG C.It is 68.7% that charging 4 hours sampling analysis record toluene conversion, and Selectivity for paraxylene 93.4%, loss of catalyst activity is 17.2%.
Claims (9)
1. a method for alkylation of toluene methanol, with toluene and methyl alcohol for raw material, with to the gas of reaction in inertia for carrier gas, be 300 ~ 500 DEG C in temperature of reaction, reaction pressure is 0 ~ 1 MPa, and air speed is 1 ~ 10 hour
-1, the mol ratio of toluene and methyl alcohol is (10:1) ~ (1:3), and the mol ratio of carrier gas and methylbenzene methanol total amount is under the condition of (1:1) ~ (5:1), reaction raw materials and catalyst exposure, generates dimethylbenzene and water; Catalyzer wherein used, comprises following component with weight parts:
A) core-shell molecular sieve of Si modification of 5 ~ 95 parts;
B) binding agent of 5 ~ 95 parts;
Wherein, the nuclear phase of the core-shell molecular sieve of described Si modification is ZSM-5 molecular sieve, and shell is Silicalite-1 molecular sieve, is coated with silicon dioxide layer outside shell; Wherein, the weight ratio of core/shell is (0.01 ~ 3): 1; Silicon dioxide layer is 1 ~ 30% of core-shell molecular sieve weight.
2. the method for alkylation of toluene methanol according to claim 1, is characterized in that in the core-shell molecular sieve of Si modification, nuclear phase ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2o
3be 10 ~ 350, the weight ratio of core/shell is (0.02 ~ 2): 1, and silicon dioxide layer is 2 ~ 25% of core-shell molecular sieve weight.
3. the method for alkylation of toluene methanol according to claim 2, is characterized in that in the core-shell molecular sieve of Si modification, nuclear phase ZSM-5 molecular sieve silica alumina ratio SiO
2/ Al
2o
3be 20 ~ 300, the weight ratio of core/shell is (0.03 ~ 1.5): 1, and silicon dioxide layer is 3 ~ 22% of core-shell molecular sieve weight.
4. the method for alkylation of toluene methanol according to claim 1, is characterized in that described binding agent is selected from least one in silicon sol or silicon oxide.
5. the method for alkylation of toluene methanol according to claim 1, is characterized in that temperature of reaction is 320 ~ 480 DEG C.
6. the method for alkylation of toluene methanol according to claim 5, is characterized in that temperature of reaction is 350 ~ 450 DEG C.
7. the method for alkylation of toluene methanol according to claim 1, is characterized in that the mol ratio of toluene and methyl alcohol in raw material is for (8:1) ~ (1:2).
8. the method for alkylation of toluene methanol according to claim 7, is characterized in that the mol ratio of toluene and methyl alcohol in raw material is for (6:1) ~ (1:1).
9. the method for alkylation of toluene methanol according to claim 1, is characterized in that carrier gas is nitrogen.
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