CN101954294A - Alkylating catalyst for synthesizing p-isopropyltoluene by methylbenzene and propylene and preparation method thereof - Google Patents
Alkylating catalyst for synthesizing p-isopropyltoluene by methylbenzene and propylene and preparation method thereof Download PDFInfo
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- CN101954294A CN101954294A CN2010102918429A CN201010291842A CN101954294A CN 101954294 A CN101954294 A CN 101954294A CN 2010102918429 A CN2010102918429 A CN 2010102918429A CN 201010291842 A CN201010291842 A CN 201010291842A CN 101954294 A CN101954294 A CN 101954294A
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to an alkylating catalyst for synthesizing p-isopropyltoluene by methylbenzene and propylene and a preparation method thereof. The catalyst comprises the following components in parts by weight: 50-95 parts of one or a mixture of two of SAPO-5 or SAPO-11 zeolite subjected to liquid-phase silicon deposition surface modification, 0.3-10 parts of metal oxide of at least one of lanthanum, cerium, calcium, zinc and magnesium and the balance of oxide binding agent, wherein the total weight part is 100 parts. The technical scheme better solves the problems. The reaction conditions for synthesizing the p-isopropyltoluene are as follows: the reaction temperature is 340-460 DEG C, the pressure is 0-3.0MPa, the benzene/alkene ratio is 2.0-10.0 and the space velocity is 0.5-8h<-1>. The prepared catalyst is applied to a methylbenzene alkylating process for synthesizing the p-isopropyltoluene by the methylbenzene and the propylene, and has better catalysis reaction effect.
Description
Technical field
The present invention relates to alkylation catalyst of the synthetic p-Methylisopropylbenzene of a kind of toluene and propylene and preparation method thereof, the catalyst that obtains can be applied in the Chemical Manufacture of synthetic p-Methylisopropylbenzene, particularly can high selectivity catalysis synthetic contraposition cymene, and between avoiding, ortho position cymene production of by-products.
Background technology
The chemicals p-Methylisopropylbenzene, be commonly called as p-cymene (being cymene), it is a kind of broad-spectrum chemical products, it is the synthetic middle important intermediate of resin, is widely used in essence and flavoring agent, field of medicaments simultaneously, also can be used as the intermediate of multiple organic synthesis product.Isopropyl toluene (IPT) mainly is to be that raw material is synthetic by alkylated reaction under the acidic catalyst effect with toluene and propylene; Industrial production technology is divided into Monsanto/LumInus Crast method (aluminum trichloride catalyst) and UOP-Hercules method (phosphoric acid/kieselguhr catalyst) by the catalyst difference of using; Wherein the pollution problem of aluminum trichloride catalyst is serious, and the phosphoric acid/kieselguhr catalyst easily runs off, poor stability, both common shortcomings that exists are the selectivity lower (being lower than 50 %) of target product contraposition IPT isomers (cymene) in the product, position IPT isomers is a lot of between the accessory substance neighbour, must could get product by product being carried out the adsorbing separation purification, the energy consumption material consumption of production process is higher, and present production technology can cause cost too high or product is impure.The key that overcomes these drawbacks is the novel preparation with high selectivity alkylation catalyst.This important function for of research has caused the extensive interest of each company and scientific research institution, and obtained certain progress, if can obtain further success, to produce dramatic change to the production technology of p-Methylisopropylbenzene, and to energy savings, simplified apparatus reduces production costs, and increasing economic efficiency all has very important meaning.
In recent years, the researcher has carried out the exploration work of many novel solid acid catalysts, use composite oxides, imvite and various zeolite catalyst to study, though bigger progress is arranged, but the para-selectivity great majority still are lower than 80 %, and toluene conversion is on the low side, and catalyst performance awaits further raising, could satisfy the needs of practical application.
Mobil patent US 4197413 has announced a kind of synthetic method of paracresol, has wherein related to a kind of ZSM-5, ZSM-11, ZSM-23 or ZSM-12 molecular sieve allcylation catalyst, and selects the shape selectivity through B, P, Mg, Sb modification to obtain catalysis; Toluene and propylene are by the synthetic contraposition cymene of alkylated reaction (the further oxidation of contraposition cymene, decomposition can be produced paracresol) under above-mentioned molecular sieve catalyst effect, this catalyst activity is higher, propylene conversion is greater than 95%, and the contraposition selectivity of product has surpassed the thermodynamical equilibrium CONCENTRATION DISTRIBUTION of contraposition cymene, a position cymene, ortho position cymene product, reached 60%, but its para-selectivity is still lower for industrial application requirements, awaits further improvement.
Domestic scholars (Tang Xianghai, Zhu Ruizhi, Yang Shujiang etc., Nankai University's journal, 1998,31 (4): 68-72) studied to mordenite molecular sieve employing MgO, CaO, NiO, TiO
2, Fe
2O
3, P
2O
5, SiO
2, F and La
2O
3Behind the modified load, be used for the catalytic performance of toluene and propylene alkylated reaction.The result shows that the catalyst contraposition methyl isopropyl benzene selective of acquisition is higher, but toluene conversion is on the low side, and catalyst stability is treated in further raising.
The technology of above bibliographical information has all promoted the selectivity of p-Methylisopropylbenzene and the conversion ratio of toluene preferably, but overall selectivity is still lower.Can not satisfy the demand of actual production, limit its industrial applications.As fully visible, the satisfactory method that does not also have the p-Methylisopropylbenzene of the synthetic high concentration of acquisition for a long time, want high selectivity to obtain the product of contraposition, a kind of good shape-selective catalyst must be arranged, acid site intensity is suitable in duct size, grain size and the hole of requirement zeolite catalyst, with and the acidity of outer surface be inhibited, just can make the alkylation of toluene reaction break the thermodynamical equilibrium CONCENTRATION DISTRIBUTION of contraposition cymene, a position cymene, ortho position cymene product, mainly generate the contraposition cymene.
Summary of the invention
The object of the present invention is to provide alkylation catalyst of the synthetic p-Methylisopropylbenzene of a kind of toluene and propylene and preparation method thereof.
The SAPO phosphate aluminium molecular sieve is by A1O
4, PO
4And SiO
4Tetrahedron constitutes the skeleton structure of three-dimensional non-neutral, its pore size can from 3 to 13, substantially cross over the four corner of micropore Si-Al molecular sieve hole size, had certain ion-exchange capacity and middle strong acidity, and had good heat endurance and hydrothermal stability.Since 1984 the report since, SAPO molecular sieve water heat synthetic method than mature and reliable (Lok, B. M., Messina, C. A., Lyle, P.R. et al, US 4440871,1984; Barthomed, D. N. ASI Ser., 1994,444:375-380; Maistriau, L., Gebelica, Z., Derouane, E.G., Vogt, E.T.C., J. Vanoene, Zeolites, 1991,11:253; Hartmann, M., Kevan, L., J. Phys. Chem., 1996,100 (11): 4606-4611).Think that by theory analysis and test determination aperture and the acidity of SAPO-5 and SAPO-11 is suitable for as toluene and propylene alkylation catalyst in the SAPO molecular sieve.
The alkylation catalyst of the synthetic p-Methylisopropylbenzene of toluene that the present invention proposes and propylene, this catalyst comprises following component:
(1) the Si:Al:P mol ratio is 1:(6-9): a kind of or two kinds of mixtures are 50 ~ 95 parts in the SAPO-5 of (5-8) or the SAPO-11 zeolite, and two kinds of zeolites mix by 1/10 –, 1/1 weight rate, and zeolite must be handled through the modification of liquid-phase silicone deposition surface after the moulding;
(2) be selected from 0.3 ~ 10 part of at least a metal oxide in lanthanum, cerium, calcium, zinc, the magnesium metal;
(3) all the other are adhesive oxides, and its gross weight umber satisfies 100 parts.
Among the present invention, adhesive oxides is selected from aluminium oxide or silica.
Among the present invention, the methyl-silicone oil that the liquid-phase silicone deposition surface modification of zeolite is selected commodity for use in handling is as modifier, and the deposition of silica is 3%～15%.
The form selected methylation Preparation of catalysts method of the synthetic p-Methylisopropylbenzene of toluene that the present invention proposes and propylene, concrete steps are as follows: by h-type zeolite and adhesive oxides mixed-forming, or granulation or extrusion modling, after the moulding 120-130 ℃ dry 2 hours down, in 520～540 ℃ of following air roasting 2.8-3.2 hour then; In the liquid-phase silicone deposition surface modification of zeolite is handled, adopt the n-heptane solution of 10～20wt% methyl-silicone oil that zeolite is carried out the 1:1 incipient impregnation, and handle modification through 120 ℃ of dryings, 500～540 ℃ of roasting air atmospheres; The carrying method of metal oxide adopt moulding and after the modification of liquid-phase silicone deposition surface the zeolite method of impregnating metal nitrate solution again, the dipping back 110-130 ℃ dry 4 hours down, then 480～540 ℃ of following roastings 2 hours, promptly get required product.Wherein, the n-heptane solution of the methyl-silicone oil of 10-20 wt% refers to the percentage that methyl-silicone oil accounts for methyl-silicone oil and normal heptane gross weight.
Catalyst of the present invention uses fixed bed reactors to carry out catalytic perfomance and investigates.15 millimeters of reactor inside diameter, length 400mm, stainless steel.Adopt electrical heating, temperature is controlled automatically.The bead that it is 2mm that reactor bottom is filled one section diameter is as support, catalyst filling 10 ml in the reactor, and the bead that 2mm is filled on top plays the effect of preheating and vaporization raw material.Toluene in the raw material and propylene gas are passed through beds from top to bottom after mixing, and taking place, alkylated reaction generates p-Methylisopropylbenzene, other a spot of side reaction product mainly is adjacent cymene, m-Methylisopropylbenzene, dimethyl benzene and trimethylbenzene etc.The reaction condition that adopts is: 340～460 ℃ of reaction temperatures; Pressure 0.2 MPa～3.0 MPa; Benzene/alkene is than 2.0 ~ 10.0; Air speed 0.5 ~ 8 h
-1
Experimental data result adopts following formula to calculate.
×100%
The Si:Al:P mol ratio that has adopted middle strong acidity in Preparation of Catalyst of the present invention is the SAPO-5 of 1:6 ~ 9:5 ~ 8, at least a in the SAPO-11 zeolite as active component, used the method for liquid-phase silicone deposition surface modification simultaneously, passivation its do not have the surface acidity of shape selective catalysis function, improve the selectivity of molecular sieve carrier, and do not influenced the acidity in its inner duct; Further added simultaneously at least a metal that is selected from rare earth metal, the alkaline-earth metal as the catalytic activity auxiliary agent.Above-mentioned technology of preparing makes in the technology of this catalyst with toluene and the synthetic p-Methylisopropylbenzene of propylene alkylation, can satisfy the high selectivity of toluene and propylene alkylated reaction and the requirement of conversion ratio, and the lower toluene loss late of maintenance, obtain actual preferably catalytic reaction result, had the value of commercial Application.
It is not high to the invention solves in the prior art toluene conversion, and the selectivity of p-Methylisopropylbenzene is lower, the problem that side reactions such as disproportionated reaction and isomerization reaction are serious, thus improve the effect of alkylation of toluene reaction, greatly suppress the generation of side reaction simultaneously.The invention provides a kind of Preparation of catalysts method, this catalyst is used for the synthetic p-Methylisopropylbenzene reaction of toluene and propylene alkylation, has the conversion ratio height, contraposition product selectivity height, characteristics such as side reaction is few, and catalyst stability is good.
The specific embodiment
Below the present invention is further illustrated by the following example.
Embodiment 1:
Adopting the Si:Al:P mol ratio is SAPO-11 molecular sieve 48 grams and 16 gram Al of 1:8:7
2O
3Mix, add field mountain valley with clumps of trees and bamboo powder 1.5 grams again and mix, add the rare nitric acid of a certain amount of 3 % then and fully mediate evenly as adhesive, carry out extruded moulding, after 120 ℃ of dryings, the catalyst I is made in 540 ℃ of roastings.
Embodiment 2:
Adopt the SAPO-11 molecular sieve after example 1 described method makes moulding, the molecular sieve that makes is flooded with the 12% methyl-silicone oil n-heptane solution that contains that configures, leave standstill behind the dipping, thorough to solvent evaporates, catalyst II is made 510 ℃ of following roastings in dry back, and the siliceous deposits amount is 5.1%.
Embodiment 3:
The SAPO-11 molecular sieve that adopts example 1 described method to make floods in the magnesium nitrate aqueous solution of 6.2% concentration with the molecular sieve that makes, behind the dipping, and the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 500 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst III, and its magnesium-supported amount is 3.7%.
Embodiment 4:
The siliceous deposits modification SAPO-11 molecular sieve that adopts example 2 described methods to make, the molecular sieve that usefulness makes floods the metal with catalyst III equivalent in the calcium nitrate aqueous solution of 6.0% concentration, behind the dipping, the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 540 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst IV, and its calcium load capacity is 3.6%.
Embodiment 5:
The siliceous deposits modification SAPO-11 molecular sieve that adopts example 2 described methods to make floods in the lanthanum nitrate aqueous solution of 5.2% concentration with the molecular sieve that makes, behind the dipping, and the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 530 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst V, and the load capacity of its lanthanum is 3.5%.
Embodiment 6:
The SAPO-11 molecular sieve that adopts example 2 described methods to make floods in the zinc nitrate aqueous solution of the lanthanum nitrate of 3.0% concentration and 2.0% concentration with the molecular sieve that makes, behind the dipping, and the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 540 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst VI, and the load capacity of its lanthanum, zinc is respectively 2.6% and 1.4%.
Embodiment 7:
Adopting the Si:Al:P mol ratio is that 1:9:8 SAPO-5 molecular screen primary powder replaces the SAPO-11 molecular screen primary powder, make the siliceous deposits modification SAPO-5 molecular sieve of moulding according to example 1 and example 2 described method programs and condition, in the cerous nitrate aqueous solution of 5.5% concentration, flood again, behind the dipping, the remaining maceration extract of elimination.Drying is 3 hours under 110 ℃, then 520 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst VII, and its cerium load capacity is 3.6%.
Embodiment 8:
Adopting the Si:Al:P mol ratio is that 1:7:6 SAPO-5 molecular screen primary powder replaces the SAPO-11 molecular screen primary powder, silicon dioxide gel replaces aluminium oxide as bonding agent, make the siliceous deposits modification SAPO-5 molecular sieve of moulding according to example 1 and example 2 described method programs and condition, in the lanthanum nitrate aqueous solution of 5.0% concentration, flood again, behind the dipping, the remaining maceration extract of elimination.Drying is 3 hours under 130 ℃, then 540 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst VIII, and its lanthanum load capacity is 3.5%.
Embodiment 9:
On fixed bed reactors, investigate its alkylation activity and selectivity with catalyst I, II, III, IV, and side reaction mainly is the degree (representing with total selection rate) of isomerization and disproportionated reaction.Reaction condition adopts: 390 ℃ of temperature; Pressure 1.2MPa; Benzene/alkene is than 4.0; Air speed 3.0 h
-1Evaluation result is as shown in the table.
| Catalyst | Toluene conversion/% | Selection rate/the % of p-Methylisopropylbenzene | Overall selectivity/the % of p-Methylisopropylbenzene |
| I | 24.2 | 47.6 | 41.9 |
| II | 22.8 | 80.7 | 66.5 |
| III | 19.8 | 81.1 | 71.6 |
| IV | 20.2 | 98.3 | 91.5. |
As can be seen the SAPO-11 molecular sieve after the siliceous deposits modification with compare without the catalyst of siliceous deposits modification, because the acidity of having regulated bore size and catalyst outer surface, brought into play the zeolite cavity stopping effect, make that great effect has been played in position and the generation of ortho position product and the generation of minimizing side reaction between the height of cymene suppresses near the diffusion velocity of p-Methylisopropylbenzene in the hole, the p-Methylisopropylbenzene selectivity obviously improves; Supported magnesium oxide modification SAPO-11 molecular sieve also can play similar raising p-Methylisopropylbenzene selectivity effect.P-Methylisopropylbenzene selectivity and the overall selectivity of SAPO-11 molecular sieve catalyst further improve after the further modification of magnesia but handle through siliceous deposits earlier again, have reached the index request of industrial production application.
Embodiment 10:
On fixed bed reactors, investigate catalyst V under the same reaction conditions, the reactivity of VI, evaluation result is as shown in the table.
| Catalyst | Toluene conversion/% | Selection rate/the % of p-Methylisopropylbenzene | Overall selectivity/the % of p-Methylisopropylbenzene |
| V | 19.8 | 98.0 | 91.2 |
| VI | 20.2 | 98.1 | 90.9. |
The above results replaces supported magnesium oxide modification SAPO-11 molecular sieve also can play similar effects with lanthanum oxide-carrying as can be seen; Simultaneously, the SAPO-11 molecular sieve catalyst has still kept higher p-Methylisopropylbenzene selectivity after lanthana and the common modification of magnesia, and the product overall selectivity is also higher.
Embodiment 11:
On fixed bed reactors, investigate catalyst V II under the same reaction conditions, VIII, reactivity, evaluation result is as shown in the table.
| Catalyst | Toluene conversion/% | Selection rate/the % of p-Methylisopropylbenzene | Overall selectivity/the % of p-Methylisopropylbenzene |
| VII | 20.1 | 98.4 | 91.5 |
| VIII | 20.7 | 98.7 | 91.0. |
The above results adopts the SAPO-5 molecular sieve to replace the SAPO-11 molecular sieve as can be seen, the SAPO-5 molecular sieve catalyst that makes moulding according to same catalyst preparation method program and condition also can play similar catalytic effect, and higher p-Methylisopropylbenzene selectivity and product overall selectivity are arranged equally.
Embodiment 12:
Adopting the Si:Al:P mol ratio is that 1:9:8 SAPO-5 molecular sieve molecular sieve 45 grams and Si:Al:P mol ratio are after SAPO-11 molecular sieve 4.5 grams of 1:8:7 mix, to restrain Al with 15 again
2O
3Mix, add field mountain valley with clumps of trees and bamboo powder 1.6 grams again and mix, add the rare nitric acid of a certain amount of 3 % then and fully mediate evenly, carry out extruded moulding as adhesive, after 120 ℃ of dryings, 540 ℃ of roastings make the SAPO-5/ SAPO-11 molecular sieve after the moulding, and the molecular sieve that makes is carried out forvacuum, flood with the 16% methyl-silicone oil n-heptane solution that contains that configures then, leave standstill behind the dipping, thorough to solvent evaporates, catalyst II is made 520 ℃ of following roastings in dry back, and the siliceous deposits amount is 8.1%.Again the mixed molecular sieve after the above-mentioned processing is flooded in the magnesium nitrate aqueous solution of 6.6% concentration, behind the dipping, the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 540 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as catalyst I X, and its magnesium-supported amount is 4.5%.
Embodiment 13:
Adopt the Si:Al:P mol ratio be 1:9:8 SAPO-5 molecular sieve molecular sieve 22 grams and Si:Al:P mol ratio be the SAPO-11 molecular sieve 20 of 1:8:7 restrain mix after, mix with 16 gram silicon dioxide gels again, adding field mountain valley with clumps of trees and bamboo powder 1.9 grams again mixes, adding the rare nitric acid of a certain amount of 3 % then fully mediates evenly as adhesive, carry out extruded moulding, after 120 ℃ of dryings, 520 ℃ of roastings make the SAPO-5/ SAPO-11 molecular sieve after the moulding, the molecular sieve that makes is carried out forvacuum, flood with the 20% methyl-silicone oil n-heptane solution that contains that configures then, leave standstill behind the dipping, thorough to solvent evaporates, catalyst II is made 510 ℃ of following roastings in dry back, and the siliceous deposits amount is 13.5%.Again the mixed molecular sieve after the above-mentioned processing is flooded in the calcium nitrate aqueous solution of the lanthanum nitrate of 4.0% concentration and 3.0% concentration, behind the dipping, the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 540 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst VI, and the load capacity of its lanthanum, calcium is respectively 3.2% and 2.5%.
Investigate the modification mixed molecular sieve catalyst IX of above-mentioned acquisition, alkylation activity and the selectivity of catalyst X on fixed bed reactors, reaction condition is 400 ℃ of temperature; Pressure 2.0MPa; Benzene/alkene is than 5.0; Air speed 6.0 h
-1, evaluation result is as shown in the table.
| Catalyst | Toluene conversion/% | Selection rate/the % of p-Methylisopropylbenzene | Overall selectivity/the % of p-Methylisopropylbenzene |
| IX | 19.1 | 98.7 | 91.5 |
| X | 18.9 | 98.6 | 91.0. |
The above results adopts Hydrogen mixed molecular sieve SAPO-5/ SAPO-11 molecular sieve to replace the alkylation catalyst of SAPO-5 or the preparation of SAPO-11 molecular sieve still to have the selectivity of high reactivity and product p-Methylisopropylbenzene as can be seen.
Claims (3)
1. the alkylation catalyst of the synthetic p-Methylisopropylbenzene of toluene and propylene is characterized in that this catalyst comprises following component:
(1) the Si:Al:P mol ratio is 1:(6-9): a kind of or two kinds of mixture 50-95 parts in the SAPO-5 of (5-8) or the SAPO-11 zeolite, two kinds of zeolites mix by 1/10 –, 1/1 weight rate, and zeolite must be handled through the modification of liquid-phase silicone deposition surface after the moulding;
(2) be selected from least a metal oxide 0.3-10 part in lanthanum, cerium, calcium, zinc, the magnesium metal;
(3) all the other are adhesive oxides, and its gross weight umber satisfies 100 parts.
2. the alkylation catalyst of the synthetic p-Methylisopropylbenzene of toluene according to claim 1 and propylene is characterized in that described adhesive oxides adopts aluminium oxide or silica.
3. the preparation method of the alkylation catalyst of the synthetic p-Methylisopropylbenzene of toluene as claimed in claim 1 and propylene, it is characterized in that concrete steps are as follows: by h-type zeolite and adhesive oxides mixed-forming, or granulation or extrusion modling, after the moulding 120-130 ℃ dry 2 hours down, in 520～540 ℃ of following air roasting 2.8-3.2 hour then; In the liquid-phase silicone deposition surface modification of zeolite is handled, adopt the n-heptane solution of 10～20wt% methyl-silicone oil that zeolite is carried out the 1:1 incipient impregnation, and handle modification through 120 ℃ of dryings, 500～540 ℃ of roasting air atmospheres; The carrying method of metal oxide adopt moulding and after the modification of liquid-phase silicone deposition surface the zeolite method of impregnating metal nitrate solution again, the dipping back 110-130 ℃ dry 4 hours down, then 480～540 ℃ of following roastings 2 hours, promptly get required product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102397792A (en) * | 2011-11-25 | 2012-04-04 | 同济大学 | Molecular sieve based catalyst for synthetizing p-diethylbenzene by ethylbenzene and ethylene |
| WO2013127044A1 (en) * | 2012-03-01 | 2013-09-06 | 中国石油天然气股份有限公司 | Ethylbenzene of carbon eight aromatic hydrocarbon dealkylation catalyst |
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| CN1110628A (en) * | 1994-04-18 | 1995-10-25 | 大连理工大学 | Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance |
| EP0943594A1 (en) * | 1998-02-24 | 1999-09-22 | Fina Technology, Inc. | Aromatic alkylation process |
| US6943131B1 (en) * | 2004-03-02 | 2005-09-13 | Saudi Basic Industries Corporation | Selective zeolite catalyst modification |
| US20080009406A1 (en) * | 2005-05-05 | 2008-01-10 | Ghosh Ashim K | Method of Hydrothermal Treatment of Phosphorus-Modified Zeolite Catalyts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1110628A (en) * | 1994-04-18 | 1995-10-25 | 大连理工大学 | Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance |
| EP0943594A1 (en) * | 1998-02-24 | 1999-09-22 | Fina Technology, Inc. | Aromatic alkylation process |
| US6943131B1 (en) * | 2004-03-02 | 2005-09-13 | Saudi Basic Industries Corporation | Selective zeolite catalyst modification |
| US20080009406A1 (en) * | 2005-05-05 | 2008-01-10 | Ghosh Ashim K | Method of Hydrothermal Treatment of Phosphorus-Modified Zeolite Catalyts |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102397792A (en) * | 2011-11-25 | 2012-04-04 | 同济大学 | Molecular sieve based catalyst for synthetizing p-diethylbenzene by ethylbenzene and ethylene |
| WO2013127044A1 (en) * | 2012-03-01 | 2013-09-06 | 中国石油天然气股份有限公司 | Ethylbenzene of carbon eight aromatic hydrocarbon dealkylation catalyst |
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