CN101279885B - Method for iquid-phase alkylation of benzene and N-butene - Google Patents
Method for iquid-phase alkylation of benzene and N-butene Download PDFInfo
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- CN101279885B CN101279885B CN2007100390619A CN200710039061A CN101279885B CN 101279885 B CN101279885 B CN 101279885B CN 2007100390619 A CN2007100390619 A CN 2007100390619A CN 200710039061 A CN200710039061 A CN 200710039061A CN 101279885 B CN101279885 B CN 101279885B
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- benzene
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Abstract
The invention relates to a method for the liquid phase alkylation between benzene and normal butene, which mainly solves the problems of strong corrosivity to the equipment and serious pollution by the catalyst and complex post-treatment of the prior art. The invention properly solves the problems by adopting the technical proposals that: the active constituents of the adopted catalyst have the following mole relation: (1/n)Al2O3: SiO2: (m/n)R, wherein, n is between 5 and 250, m is between 0.01 and 20, R is at least one of the C1-8 alkyl or C2-10 alkenyl; an Si<29>NMR solid nuclear magnetic spectrum comprises at least one Si<29> nuclear magnetic resonance spectral peak between -80 and +50ppm; and an X-ray diffraction pattern has the d-distance maximum value at the lengths of 12.4+-0.2, 11.0+-0.3, 9.3+-0.3, 6.8+-0.2, 6.1+-0.2, 5.5+-0.2, 4.4+-0.2, 4.0+-0.2 and 3.4+-0.1 angstroms, and the method of preparation better solves the above problems and can be used for the industrial production of butylbenzene.
Description
Technical field
The present invention relates to the method for a kind of benzene and n-butene liquid-phase alkylation.
Background technology
Butylbenzene can be used as solvent, also can be used as chemical intermediate.The 2-butylbenzene can be used as the raw material of synthesizing phenol and methylethylketone.When synthesizing phenol and methylethylketone, the 2-butylbenzene at first is oxidized to the peroxidation butylbenzene, and the peroxidation butylbenzene is decomposed into phenol and methylethylketone in the presence of acid catalyst then.
It is catalyzer that EP0395360A1 has described the employing liquid aluminum trichloride, is raw material with n-butene and benzene, and 20～70 ℃ of temperature of reaction, catalyzer aluminum chloride consumption is to react Synthetic 2-butylbenzene under 0.3～5% condition of benzene weight.Yet the catalyzer aluminum chloride that this method adopts is strong, seriously polluted to equipment corrosion, and by-product Isobuytel Benzene, dibutyl benzene and tributyl benzene, so aftertreatment is numerous and diverse.It is catalyzer that document Applied Catalysis A:General 153 (1997) has introduced with the Beta zeolite, with butanols and the synthetic butylbenzene of benzene reaction.
Summary of the invention
The catalyzer that uses in the technical problem conventional art to be solved by this invention exists the problem that equipment corrosion is strong, seriously polluted and aftertreatment is numerous and diverse, and a kind of new benzene and the method for n-butene liquid-phase alkylation are provided.This method has does not have corrosion to equipment, environmentally safe, selectivity height, aftertreatment characteristic of simple.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of benzene and n-butene liquid-phase alkylation, with benzene and n-butene is reaction raw materials, in temperature of reaction is 50～250 ℃, reaction pressure is 0.5～3.0MPa, benzene/n-butene mol ratio is 0.5～10, n-butene weight space velocity 0.1～10 hour
-1Under the condition, reaction raw materials contacts with catalyzer, and used catalyzer comprises following component by weight percentage:
A) 50～80% organic silicon micro-pore zeolite;
B) 20～50% binding agent;
Wherein said organic silicon micro-pore zeolite comprises the composition of following molar relationship: (l/n) Al
2O
3: SiO
2: (m/n) R, n=5 in the formula～250, m=0.01～20, R is that carbonatoms is that 1～8 alkyl or carbonatoms are at least a in 2～10 the alkane thiazolinyl; The Si of described organic silicon micro-pore zeolite
29NMR solid state nmr collection of illustrative plates-80～+ include a Si at least between the 50ppm
29The nuclear magnetic resonance spectrum peak; The X-ray diffracting spectrum of described organic silicon micro-pore zeolite is 12.4 ± 0.2, and there is d-spacing maximum value at 11.0 ± 0.3,9.3 ± 0.3,6.8 ± 0.2,6.1 ± 0.2,5.5 ± 0.2,4.4 ± 0.2,4.0 ± 0.2 and 3.4 ± 0.1 dust places.
In the technique scheme, the preferable range of n is 10～100, and the preferable range of m is 0.05～20.Described alkyl preferred version is for being selected from methyl or ethyl.Described alkane thiazolinyl preferred version is a vinyl.The binding agent preferred version is to be selected from least a in aluminum oxide, titanium oxide, zinc oxide or the zirconium white.The temperature of reaction preferable range is 100～200 ℃ ℃; The reaction pressure preferable range is 1.0～2.5MPa; N-butene weight space velocity preferable range is 0.2～5.0 hour
-1Benzene/n-butene mol ratio preferable range is 1.0～6.0.
The synthetic method of the organic silicon micro-pore zeolite among the present invention is as follows:
A) organosilicon source, inorganic silicon source, aluminium source, alkali, organic amine template and water are mixed, with the SiO in the inorganic silicon source
2Be benchmark, reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=5～250, organosilicon source/SiO
2=0.001～1, OH
-/ SiO
2=0.01～5.0, H
2O/SiO
2=5～100, organic amine/SiO
2=0.01～2.0;
B) be under 90～200 ℃ of conditions with above-mentioned reaction mixture in the crystallization temperature, react after 1～100 hour and take out, make organic silicon micro-pore zeolite through washing, drying.
Wherein, inorganic silicon source preferred version is to be selected from least a in silicon sol, solid oxidation silicon, silica gel, silicon ester, diatomite or the water glass.Organosilicon source preferred version is to be selected from least a in halosilanes, silazane or the organoalkoxysilane; Wherein the halosilanes preferred version is to be selected from least a in trimethylchlorosilane, dimethyldichlorosilane(DMCS), chlorotriethyl silane, diethyl dichlorosilane, dimethyl chloride bromo-silicane, dimethyl ethyl chlorosilane, dimethylbutyl chlorosilane, 3,5-dimethylphenyl chlorosilane, dimethyl isopropyl chloride silane, dimethyl tertiary butyl chloride silane, dimethyl stearyl chlorosilane, methyl phenyl vinyl chlorosilane, vinyl trichloro silane or the diphenyl dichlorosilane; The silazane preferred version is to be selected from least a in hexamethyldisilazane, heptamethyldisilazane, tetramethyl-disilazane, divinyl tetramethyl-disilazane or the phenylbenzene tetramethyl-disilazane; Organoalkoxysilane is selected from least a in trimethylethoxysilane, dimethyldiethoxysilane, trimethylammonium methoxy silane, dimethyldimethoxysil,ne, trimethoxy-benzene base silane or the phenylbenzene diethoxy silane.Aluminium source preferred version is to be selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, aluminum oxide, kaolin or the polynite.Alkali is mineral alkali, and preferred version is to be selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.The organic amine preferred version is to be selected from least a in quadrol, hexanediamine, hexahydroaniline, hexamethylene imine, heptamethylene imines, pyridine, hexahydropyridine, butylamine, hexylamine, octylame, quinamine, amino dodecane, cetylamine or the stearylamine.
Reaction mixture is with the SiO in the inorganic silicon source
2Be benchmark, with the molar ratio computing preferable range be: SiO
2/ Al
2O
3=10～100, organosilicon source/SiO
2=0.005～0.5, OH
-/ SiO
2=0.05～1.0, H
2O/SiO
2=10～80, organic amine/SiO
2=0.05～1.0.Crystallization temperature preferable range is 100～180 ℃, and crystallization time preferable range is 2～60 hours.Preferred version is a reaction mixture in ageing 2～100 hours under 10～80 ℃ of conditions earlier before the crystallization when synthetic.
The Preparation of catalysts method of using in the inventive method is as follows:
Above-mentioned synthetic organic silicon micro-pore zeolite and binding agent is mixed, and zeolite content is 50～80 (weight) %.Add kneaded and formed, the oven dry of 5 (weight) % dilute nitric acid solution then, roasting to 500 in air～600 ℃ obtain finished catalyst.
In the inventive method, have special diffraction peak and special Si owing to adopt
29The organic silicon micro-pore zeolite at nuclear magnetic resonance spectrum peak is made the catalyst activity main body, when being used for benzene and n-butene liquid phase alkylation reaction, equipment is not had corrosion, non-environmental-pollution, the n-butene transformation efficiency can reach 98% simultaneously, and the butyl selectivity reaches as high as 97%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With sodium aluminate (Al
2O
342.0 weight %) 6.1 grams are dissolved in the 288 gram water, add sodium hydroxide 1.0 grams and make it dissolving, under condition of stirring, add hexahydropyridine 34.0 grams then, add solid oxidation silicon 60 grams again, trimethylchlorosilane 5.5 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝40
NaOH/SiO
2＝0.025
Trimethylchlorosilane/SiO
2=0.05,
Hexahydropyridine/SiO
2=0.50
H
2O/SiO
2＝16
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 135 ℃ of crystallization 50 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 42.1.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at 15.1ppm.Its X-ray diffraction data see Table 1.
Table 1
Get the dried powdered sample of 50 grams, 530 ℃ of roastings 5 hours then with the ammonium nitrate exchange of 1M 3 times, are filtered, drying.Afterwards,, and add that 5 (weight) % nitric acid is mediated, extruded moulding is the bar of 1.6 * 2 millimeters of φ with 20 gram aluminum oxide thorough mixing, 120 ℃ of dryings 12 hours, 550 ℃ of roastings 6 hours are prepared into the catalyzer that needs.
[embodiment 2]
Aluminum oxide 3.0 grams are dissolved in the 450 gram water, add sodium hydroxide 16.0 grams and make it dissolving, under condition of stirring, add hexamethylene imine 34.7 grams then, add solid oxidation silicon 60 grams again, dimethyldiethoxysilane 5.9 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝30
NaOH/SiO
2＝0.2
Dimethyldiethoxysilane/SiO
2=0.04,
Hexamethylene imine/SiO
2=0.35
H
2O/SiO
2＝25
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 145 ℃ of crystallization 70 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 30.1.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at-18.9ppm.Its X-ray diffraction data see Table 2.
Table 2
Get the dried powdered sample of 50 grams, use the nitric acid of 1M to exchange filtration, drying 3 times.Afterwards,, and add that 5 (weight) % nitric acid is mediated, extruded moulding is the bar of 1.6 * 2 millimeters of φ with 20 gram aluminum oxide thorough mixing, 120 ℃ of dryings 12 hours, 550 ℃ of roastings 6 hours are prepared into the catalyzer that needs.
[embodiment 3]
With sodium aluminate (Al
2O
342.0 weight %) 3.5 grams are dissolved in the 540 gram water, add sodium hydroxide 8.0 grams and make it dissolving, under condition of stirring, add hexamethylene imine 30 grams then, add solid oxidation silicon 60 grams again, hexamethyldisiloxane 8.0 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝70
NaOH/SiO
2＝0.2
Hexamethyldisiloxane/SiO
2=0.05,
Hexamethylene imine/SiO
2=0.3
H
2O/SiO
2＝30
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 135 ℃ of crystallization 35 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 68.5.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at 16.8ppm, and its X-ray diffraction data see Table in 3.
Table 3
Get the dried powdered sample of 50 grams, use the ammonium nitrate of 1M to exchange filtration, drying 4 times.Afterwards,, and add that 5 (weight) % nitric acid is mediated, extruded moulding is the bar of 1.6 * 2 millimeters of φ with 20 gram aluminum oxide thorough mixing, 120 ℃ of dryings 12 hours, 520 ℃ of roastings 6 hours are prepared into the catalyzer that needs.
[embodiment 4]
Catalyzer 5.0 grams of getting [embodiment 1] preparation are seated in the fixed-bed reactor, feed the mixture of n-butene and benzene.Reaction conditions is: n-butene weight space velocity=5.0 hour
-1, benzene and n-butene mol ratio are 1.5,150 ℃ of temperature of reaction, reaction pressure 1.5MPa.Successive reaction 24 hours, reaction result is: n-butene transformation efficiency 99%, butyl selectivity 96%.
[embodiment 5]
Catalyzer 5.0 grams of getting [embodiment 2] preparation are seated in the fixed-bed reactor, feed the mixture of n-butene and benzene.Reaction conditions is: n-butene weight space velocity=0.3 hour
-1, benzene and n-butene mol ratio are 5.0,120 ℃ of temperature of reaction, reaction pressure 2.0MPa.Successive reaction 24 hours, reaction result is: n-butene transformation efficiency 99%, butyl selectivity 97%.
[embodiment 6]
Catalyzer 5.0 grams of getting above-mentioned [embodiment 3] preparation are seated in the fixed-bed reactor, feed the mixture of n-butene and benzene.Reaction conditions is: n-butene weight space velocity=3.0 hour
-1, benzene and n-butene mol ratio are 2.5,180 ℃ of temperature of reaction, reaction pressure 1.9MPa.Successive reaction 24 hours, reaction result is: n-butene transformation efficiency 99%, butyl selectivity 95%.
[embodiment 7]
Catalyzer 5.0 grams of getting [embodiment 2] preparation are seated in the fixed-bed reactor, feed the mixture of n-butene and benzene.Reaction conditions is: n-butene weight space velocity=1.0 hour
-1, benzene and n-butene mol ratio are 4.0,100 ℃ of temperature of reaction, reaction pressure 2.0MPa.Successive reaction 24 hours, reaction result is: n-butene transformation efficiency 99%, butyl selectivity 97%.
Claims (8)
1. the method for benzene and n-butene liquid-phase alkylation is a reaction raw materials with benzene and n-butene, is 50～250 ℃ in temperature of reaction, and reaction pressure is 0.5～3.0MPa, and benzene/n-butene mol ratio is 0.5～10, n-butene weight space velocity 0.1～10 hour
-1Under the condition, reaction raw materials contacts with catalyzer, and used catalyzer comprises following component by weight percentage:
A) 50～80% organic silicon micro-pore zeolite;
B) 20～50% binding agent;
It is characterized in that described organic silicon micro-pore zeolite comprises the composition of following molar relationship: (l/n) Al
2O
3: SiO
2: (m/n) R, n=5 in the formula～250, m=0.01～20, R is that carbonatoms is that 1～8 alkyl or carbonatoms are at least a in 2～10 the alkane thiazolinyl; The Si of described organic silicon micro-pore zeolite
29NMR solid state nmr collection of illustrative plates-80～+ include a Si at least between the 50ppm
29The nuclear magnetic resonance spectrum peak; The X-ray diffracting spectrum of described organic silicon micro-pore zeolite is 12.4 ± 0.2, and there is d-spacing maximum value at 11.0 ± 0.3,9.3 ± 0.3,6.8 ± 0.2,6.1 ± 0.2,5.5 ± 0.2,4.4 ± 0.2,4.0 ± 0.2 and 3.4 ± 0.1 dust places.
2. according to the method for described benzene of claim 1 and n-butene liquid-phase alkylation, it is characterized in that n=10～100, m=0.05～20.
3. according to the method for described benzene of claim 2 and n-butene liquid-phase alkylation, it is characterized in that described alkyl is methyl or ethyl, described alkane thiazolinyl is a vinyl.
4. according to the method for described benzene of claim 1 and n-butene liquid-phase alkylation, it is characterized in that binding agent is selected from least a in aluminum oxide, titanium oxide, zinc oxide or the zirconium white.
5. according to the method for described benzene of claim 1 and n-butene liquid-phase alkylation, it is characterized in that temperature of reaction is 100～200 ℃.
6. according to the method for described benzene of claim 1 and n-butene liquid-phase alkylation, it is characterized in that reaction pressure is 1.0～2.5MPa.
7. according to the method for described benzene of claim 1 and n-butene liquid-phase alkylation, it is characterized in that the n-butene weight space velocity is 0.2～5.0 hour
-1
8. according to the method for described benzene of claim 1 and n-butene liquid-phase alkylation, it is characterized in that benzene/n-butene mol ratio is 1.0～6.0.
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| CN105085133A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Method for producing diisopropyl naphthalene |
| CN108569945B (en) * | 2017-03-14 | 2021-05-11 | 中国石油化工股份有限公司 | Process for producing linear alkylbenzene |
| CN108569944B (en) * | 2017-03-14 | 2021-03-30 | 中国石油化工股份有限公司 | Process for producing branched alkylbenzene |
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