CN85101896A - In being the catalyzer on basis, crystal silicon-aluminate zeolite adds the process that the molybdenum thing improves the hydrocarbon conversion - Google Patents
In being the catalyzer on basis, crystal silicon-aluminate zeolite adds the process that the molybdenum thing improves the hydrocarbon conversion Download PDFInfo
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Abstract
Based on hydro-dealkylation, the process that transforms alkyl aromatics ties up under the conversion condition, with the alkyl aromatic hydrocarbon feed be loaded with molybdate compound, intermediate pore size, crystal silicon-aluminate zeolite and contact for basic catalyzer.
Description
What the present invention said is the catalyzer that constitutes with the crystal aluminosilicate molecular sieve, transforms the process, particularly isomeric xylenes and the method that transforms ethylbenzene of the arene compound of alkyl replacement.In this method, mainly transform ethylbenzene by hydro-dealkylation.
Generally, in the industrial production of p-Xylol, use and contain C
8The raw material of aromatic hydrocarbons (p-Xylol, o-Xylol, m-xylene and ethylbenzene).Generally remove p-Xylol by crystallization or absorption from this raw material, remaining mixture contacts with catalyzer, and isomery o-Xylol and m-xylene are the mixture that contains near the p-Xylol of thermodynamics concentration.Isomery mixture be recycled to the device that removes of p-Xylol.In this process, remove the byproduct that comprises fuel gas (as ethane), benzene, toluene and heavy aromatics by several covering devices resemble the diethylbenzene.Because boiling point is approaching, to remove ethylbenzene be difficult in distillation from dimethylbenzene, it is desirable to hydro-dealkylation or disproportionation/ethyl and shift and transform the aromatic hydrocarbon of ethylbenzene for other.The former mainly produces ethane and benzene; The latter mainly produces benzene, diethylbenzene and dimethyl ethyl benzene.The xylene isomerization catalyst of industrial practicality usually transforms ethylbenzene.
Have been found that the crystal aluminosilicate molecular sieve that comprises base matter as catalyzer, mainly the approach that shifts by disproportionation/ethyl transforms ethylbenzene.Sometimes the method with hydro-dealkylation transforms more ethylbenzene, and the method that shifts than disproportionation/ethyl is favourable, and this depends on the composition from the economic worth of each byproduct of p-Xylol production equipment and aromatic hydrocarbon raw material.Based on the catalyzer of aluminosilicate molecular sieves, under certain conditions, it is very favorable transforming alkyl aromatics (as ethylbenzene) by hydro-dealkylation.
United States Patent (USP) 4,400,573 describe with the silicon metal borate molecular sieve that is loaded with the molybdenum thing is basic catalyzer, transforms alkyl aromatics by hydro-dealkylation.
The summary of invention
Based on hydro-dealkylation, the process that transforms alkyl aromatics ties up under the conversion condition, with the alkyl aromatic hydrocarbon feed be loaded with molybdate compound, intermediate pore size, crystal silicon-aluminate zeolite and contact for basic catalyzer.
The concise and to the point description of invention
Have been found that with a kind of aluminosilicate molecular sieves of having improved and to transform the method for alkyl aromatic compound by hydro-dealkylation as catalyzer.This catalyzer is to be loaded with aluminosilicate zeolite molybdate compound, suitable.Generally, these catalyzer show and are beneficial to the catalysis characteristics that hydro-dealkylation transforms alkyl aromatics.
It is in the presence of hydrogen that hydro-dealkylation transforms alkyl aromatics, from the aromatic proton groups that ruptures, produces an alkane and an aromatic hydrocarbon usually.Therefore, by hydro-dealkylation, ethylbenzene is converted into ethane and benzene.The suitable alkyl aromatics that is used for the present invention is to have two but most preferably less than the groups of 6 carbon atoms, be connected the compound that aromatic hydrocarbon is fastened.The example of this compound comprises: ethylbenzene, propylbenzene, ethyltoluene, diethylbenzene, butylbenzene, ethyl naphthalene and the like or the like.
It is considered herein that suitable crystal silicon-aluminate zeolite is to have internal orifice dimension less than about 6.0 dusts but greater than the intermediate pore size of about 4.5 dusts in this technology.The example of this intermediate pore size zeolite comprises ferrierite, ZSM-5 and ZSM-11.The example that is used for intermediate pore size zeolite of the present invention also has heulandite, clinoptilolite and dachiardite.
The molecular sieve that is called " ferrierite " is naturally occurring material and synthetic material by chemical constitution and the difference of X ray wave spectrum.For example, common ferrierite is that the alkaline mixt by the oxide compound of sodium aluminate of crystallization and silicon produces, and does not use the organic formwork compound.Such ferrierite is described in D.W. mine-laying gram (D.W.Breck) " zeolite molecular sieve " that John Willie and Shan Shi shown in 1974, is enrolled in this article by reference.United States Patent (USP) 4,000,248 disclose with the positive methylpyrrole of hydroxide as sieve crystalline organic formwork compound, the method for producing the ferrierite molecular sieve.United States Patent (USP) 4,016,245 and 4,107,195 and 4,046,859 disclose and to use from 1, tetrahydropyrrole or butanediamine, or organometallic 2-(hydroxyalkyl) organic formwork that obtains in the trialkyl aluminium compound, constitute similar ferrierite.United States Patent (USP) 4,323,481 preparations of describing ferrierite are with 2, the 4-diacetylmethane is as the structure direction agent.Breck describes these zeolites and is differentiated and be heulandite, clinoptilolite and dachiardite.
Label is that the aluminosilicate molecular sieves of ZSM-5 is described in United States Patent (USP) 3,702, in 886 and 4,139,600.Such aluminosilicate molecular sieves is to use such as the organic formwork of tetraalkylammonium salt, primary alkyl amine and Alkylenediamine to make, as United States Patent (USP) 4,139, and 600 and 4,151, described in 189.Label is that the aluminosilicate molecular sieves of ZSM-11 is described in United States Patent (USP) 3,709, in 979.
The SiO of the aluminosilicate molecular sieves of label ZSM-5
2/ Al
2O
3Ratio has different arrangements.Between 5 and 100, be described in United States Patent (USP) 3,702, in 886, between 5 and 500, be described in United States Patent (USP) 4,139, in 600.Typical scope is between 35 and 100.
Add in the catalyzer of the present invention suitable molybdenum thing and be describe in the present invention, can be loaded in the molybdenum thing on the molecular sieve component.Generally, though molybdenum carbonyl can be used for the gas phase switching technology, water-soluble molybdenum compound suits for dipping.The specific examples of water-soluble molybdenum compound comprises: Ammonium Heptamolybdate, molybdenum hydroxide, molybdic oxide, two molybdenum oxybromides, tetrachloro molybdenum oxide, two molybdenum oxychlorides, oxychlorination molybdic acid, difluoro molybdenum dioxide, molybdic acid, molybdenum arsenic acid, molybdenum silicic acid and permolybdic acid ammonium.The molybdenum thing that the present invention preferentially selects for use is Ammonium Heptamolybdate ((NH
3)
6Mo
7O
244H
2O).
When the conversion ethylbenzene was other hydrocarbon product, best hydrocarbon conversion process was the process of the used isomeric xylenes mixture of the present invention.In this process, contain the mixture of dimethylbenzene (lacking p-Xylol usually) and ethylbenzene, with crystal aluminosilicate be in basis, the adding base matter and the catalyzer that floods with the molybdenum thing contacts.Xylol based on o-Xylol and m-xylene tautomerizes to the mixture that contains p-Xylol.Isomery mixture preferably near the thermodynamic(al)equilibrium mixture of dimethylbenzene, it contains the 23.5 heavy % p-Xylol of having an appointment, about 23.8 heavy % o-Xylols and about 52.7 heavy % m-xylenes.Simultaneous with xylene isomerization is the hydrocarbon product that ethylbenzene is converted into other, as phenylethane, diethylbenzene and ethyltoluene.
More particularly, process of the present invention is used for the liquid phase or the gas phase isomerization of p-Xylol, and the xylol that takes place along with the conversion of ethylbenzene is to the isomerization of p-Xylol.The operational condition that the isomerization of dimethylbenzene raw material and ethylbenzene transform mainly comprises: about 95～540 ℃ of temperature, hydrogen are about 0.5～20 to the mol ratio of hydrocarbon, about 0.01～90 unit weight raw material of weight-space velocity (WHSV) per hour the per unit weight catalyzer (time
-1) and about 0～1000 pound/inch of pressure
2(gauge pressure).Advantageous conditions comprises: about 250～480 ℃ of temperature, hydrogen are about 1～12 to the mol ratio of hydrocarbon, about 1～20 o'clock of WHSV
-1, and about 0～500 pound/inch of pressure
2(gauge pressure).Xylene isomerization and ethylbenzene transform best condition and comprise: about 295～440 ℃ of temperature, hydrogen are about 2～8 to the mol ratio of hydrocarbon, about 1～10 o'clock of WHSV
-1, and about 0～300 pound/inch of pressure
2(gauge pressure).Generally, the raw material that enters this process contains 75～85 heavy % dimethylbenzene of having an appointment, about 10～15 heavy % ethylbenzenes, about 0.2～1.0 heavy % alkane and naphthenic hydrocarbon and about 0.5～5 heavy %C
+ 9Aromatic hydrocarbon.
Just as described above, the present invention is the most useful in xylene isomerization-ethylbenzene conversion process obviously, and this invention also can be used for other hydrocarbon conversion process, and wherein, the hydro-dealkylation of alkyl aromatics is attracting.
In the used process of the present invention, the main method that ethylbenzene transforms is considered to hydro-dealkylation.In this method, ethylbenzene is converted into benzene and ethane in the presence of hydrogen, as following represented:
Ethylbenzene hydrogen phenylethane
Transform used in the process of ethylbenzene, be described in the catalyzer of crystal aluminosilicate herein and do not have the molybdenum thing for the basis.It is believed that disproportionation/transalkylation is between two ethylbenzene molecules, or main method for transformation between ethylbenzene molecule and the dimethylbenzene molecule, as following represented:
Ethylbenzene benzene diethylbenzene
Ethylbenzene dimethylphenyl phenyl ethyl dimethylbenzene
Be used for xylene isomerization/ethylbenzene conversion process, based on crystal aluminosilicate, be added in the binding agent and, transform ethylbenzene mainly takes off ethyl by hydrogenation approach with the catalyzer of molybdenum thing dipping.Generally, about 40～90% ethylbenzenes that transformed take off ethyl by hydrogenation and transform, and remaining the transfer by disproportionation/ethyl transforms.At a specific silico-aluminate is in the catalyzer on basis, and the numerical value that hydrogenation takes off ethylated spirit depends on or depend in part on the quantity and the type of the catalytic activity thing that is loaded on the catalyzer.
Used isomerization catalyst system is the catalyst system on the crystal aluminosilicate molecular sieve basis of intermediate pore size among the present invention, as described above.
Generally, molybdenum-containing material matter can be loaded on the aluminosilicate structure by dipping or other suitable contact method.Before the catalytic activity compound was loaded on the aluminosilicate structure, silico-aluminate may be in the Hydrogen, and is general, by one or many and ammonium ion (generally using ammonium acetate) exchange, then produces with roasting by dry, as described above.
Initial positively charged ion (normally sodium ion) in crystal aluminosilicate, by with other cationic ion-exchange, can be replaced whole or in part.Other positively charged ion comprises: other metal ion and their amine complex, alkyl phosphate ion, ammonium ion, hydrogen ion and their mixture.In this technology, ion exchange technique is well-known.The general cationic aqueous solution is exchanged one or many down at about 25～100 ℃.
Generally, the water soluble salt of molybdenum-containing material is immersed on the used crystal aluminosilicate of the present invention, the dipping of catalyst activity compound on silico-aluminate or component, binding the crystal silicon aluminate is suspended in the matrix of upholder, and distribute and to spread all in matrix and produce suitable catalyzer, base matter is the porous resemble aluminium, refractory inorganic oxide.Ion-exchange and dipping can be used in combination.The existence of sodium ion is deleterious to activity of such catalysts usually in component.
Be stated from the quantity of the molybdenum-containing material matter on the aluminosilicate catalyst component, can be from changing less than 1 heavy %～about, 30 heavy %, generally between about 0.05～25 heavy %, depend on that process gives fixed purposes.The molybdenum that transforms preferably about 0.5～10 heavy % for ethylbenzene is loaded on the component of the present invention.Best quantity can be determined by routine test.
In this technology, known other catalytic activity thing can be stated from the component that zeolite of the present invention is the basis with dipping and switching technology.The example of this catalytic activity thing comprises: the metal ion or the compound of the metal ion of hydrogen and I B II B, III A, IV B, V B, VI B, VII B and each family of VIII B or compound and manganese, vanadium, chromium, uranium, and uncommon earth elements.
Though tungsten is not best for effect of the present invention, thinks to be equal to molybdenum.
Used in the present invention crystal aluminosilicate can be used as pure substance and adds in catalyzer or the sorbent material, also may be combined in or joins in various tackiness agents or the base matter, depends on that process gives fixed purposes.Can be used to bonding silico-aluminate as the organic or inorganic thing, crystal aluminosilicate can combine with active or inactive material, synthetic or naturally occurring zeolite.Well-known material has: silicon, sial, aluminium, aluminium colloidal sol, hydrated aluminum, such as the clay of wilkinite or china clay or in this technology well-known other tackiness agent.Generally, silico-aluminate adds in the base matter by the mixture that mixes with the colloidal sol of base matter and gel produces.And the solia particle of silico-aluminate and base matter can physically mix.Generally, practical shape can be suppressed or be extruded to such silico-aluminate component.The content of crystal aluminosilicate can change up to any point of 100 heavy % from percentum of total composition.Catalyst component can contain the silico-aluminate of 0.01～100 heavy %, and best be to contain about 2～65 heavy %.
Contain the crystal aluminosilicate among the present invention and the catalyst component of suitable base matter, can in the water-sol of base matter or gel, form by adding levigated crystal aluminosilicate and molybdate compound.The mixture that produces generally by adding resemble the ammonium material and blending and gel fully.The gel that produces can be dry and roasting form crystal aluminosilicate and contain molybdenum compound and be distributed to component in the carrier substance.
Example I-comparison test A
According to United States Patent (USP) 3,702, the sample of the HZSM-5 aluminosilicate zeolite that contains aluminium 1.88 heavy % of 866 preparations.
The preparation of ZSM-5 aluminosilicate zeolite sample is: 15.02 gram sodium aluminates and 30.25 gram sodium hydroxide, be dissolved in the 1000 gram distilled water, and add 62.02 gram organic formworks again.Lai Duoshi (Ladox) HS-40 of 452.1 grams are joined in this solution along with the stirring of fierceness, and continued high degree of agitation about 15 minutes.Produce curdy, gelatinous mixture, place a crystallisation vessel crystallization stirring, sealing 3 days.The crystallisate that produces reclaims after filtration, wash fully with distilled water, and in force ventilated loft drier, drying is 4 hours under 165 ℃.Dry thing carries out the program roasting by following program.(a) to be less than or equal to 100 ℃ of speed hourly, from 165～540 ℃ of linear elevated temperatures, (b) kept 12 hours down at 540 ℃, and (c) under maximum 100 ℃ of speed hourly, from 540～120 ℃ of reduction temperature.Sample is by ultimate analysis and X-ray diffraction spectroscopic analysis.
A part is the zeolite of preparation so, with being dissolved in sodium acetate in 1 liter of distilled water, that double zeolite weight, 95 ℃ of down each exchanges two hours.Filter molecular sieve then, with about 200 milliliters distilled water wash, and device for drying and filtering.Repeat this step, exchange with about 2 liters of distilled water washs for the second time.Washed molecular sieve is following dry about 3 hours at 165 ℃.Dry molecular sieve carries out the program roasting by following program: (a) to be less than or equal to 100 ℃ of speed hourly, from 165～540 ℃ of linear elevated temperatures, (b) kept 12 hours down at 540 ℃, and (c) under maximum 100 ℃ of speed hourly, from 540～120 ℃ of reduction temperature.Catalyzer prepares in PHF-aluminium by exchange and baked zeolite above disperseing, and PHF-aluminium is the aluminium water-sol that initial acetate was stablized, and contains 9% the solid of having an appointment.40.03 gram exchange and baked molecular sieve add 65.81 gram distilled water, water is full of sieve aperture.Wet sieve then adds the aluminium water-sol of 607.6 grams and mixes fully.Along with the adding of 60 milliliters of concentrated ammonium hydroxides, mixture is by gel (solidification).The gel that produces in forcing air drying cabinet, 165 ℃ dry 4 hours down, use as described above, the program except that 540 ℃ of temperature maintenance 4 hours program roasting to 540 ℃ then.
This material of a part (40.02 gram) floods with the 102.22 gram Ammonium Heptamolybdate aqueous solution (0.02M), has provided the molybdenum of 3 heavy % on catalyzer.Impregnated catalyzer was with 540 ℃ program roasting roasting once more in described above 4 hours.Baked solid grinds and sieves 18～40 orders (U.S. sieve system).
5.00 the HZSM-5 crystal aluminosilicate that gram prepares above is contained in the tubular reactor of 0.5 inch internal diameter, at 319 ℃ and 180 pounds/inch for the catalyst sample on basis
2Under (gauge pressure), with 0.755 standard foot
3The hydrogen in/time gives to be handled 2 hours, then under about 0.75 Grams Per Minute, was once passing through on the basis of no recirculation C
8Raw material is introduced reactor.Liquid efflunent is analyzed with gas chromatography.What the sample (comparison test A) that floods from the sample (routine I) and the nothing of test dipping molybdenum drew the results are shown in the table 1.Data show, form contrast with the sample that does not have dipping, and the catalyzer of routine I shows that the conversion of ethylbenzene is mainly taken off ethyl by hydrogenation.
Hydrogenation takes off the amount of the ethylbenzene that ethyl transforms, and is to calculate on the basis of the transalkylation approach of following supposition:
Ethylbenzene+dimethylbenzene → dimethyl ethyl benzene+benzene
(ethyl transfer)
Ethylbenzene+dimethylbenzene → ethyltoluene+toluene
(Methyl transporters)
2 ethylbenzenes → diethylbenzene+benzene
(disproportionation)
On the basis of these approach, the mol of the ethylbenzene that the percentage ratio that takes off the ethylbenzene that ethyl transformed by hydrogenation has equaled to react deducts the mol summation of the ethylbenzene that has transformed by the transalkylation approach, whole mol divided by the ethylbenzene that has reacted, and multiply by 100.
The table I
ZSM-5 comparison test A example I
Condition
Molybdenum (heavy %) 03
Temperature (℃) 319 319
Pressure (pound/inch
2Gauge pressure) 180 180
Hydrogen/hydrocarbon (mol ratio) 2.03 1.98
Space velocity (WHSV) (time
-1) 9.0 9.0
Form heavy % raw material raw material
Alkane and naphthenic hydrocarbon 1.38 1.42 1.38 1.43
Benzene 0.0 1.65 0.0 1.90
Toluene 1.02 3.27 1.02 2.96
Ethylbenzene 15.55 11.62 15.52 11.98
P-Xylol 8.16 17.36 8.14 17.68
M-xylene 48.15 39.53 48.11 39.98
O-Xylol 20.29 16.33 20.31 16.35
Ethyltoluene 1.22 2.15 1.23 1.74
Three methyl Benzene 0.51 1.06 0.52 1.03
Diethylbenzene 1.66 2.56 1.69 2.17
Dimethyl ethyl benzene 1.95 2.91 1.97 2.60
Tetramethyl-benzene 0.12 0.16 0.11 0.19
The result
Ethyl transforms (%) 25.2 22.9
P-Xylol approaches balance (%) 99.1 100.6
Ethylbenzene transform by
Hydrogenation takes off ethylization (%) 23.7 51.7
Disproportionation (%) 36.1 21.4
Methyl transporters (%) 20.9 12.8
Ethyl shifts (%) 19.3 14.1
Example II-comparison test B
By United States Patent (USP) 4,323,481 methods of describing, with 2, the 4-diacetylmethane is as the sample of the ferrierite of organic structure directing agent preparation.
25.02 a ferrierite of gram is pressed described in routine I, floods with Ammonium Heptamolybdate.The raw material (comparison test B) of the sample (routine II) of dipping and nothing dipping is tested, described in routine I.The presentation of results that provides in the table II forms contrast with comparison test B, has flooded the catalyzer of molybdenum, mainly takes off to ethylize by hydrogenation to transform ethylbenzene.
The table II
Ferrierite comparison test B example II
Condition
Molybdenum (heavy %) 03
Temperature (℃) 359 360
Pressure (pound/inch
2, gauge pressure) 180 180
Hydrogen/hydrocarbon (mol ratio) 2.04 2.04
Air speed (WHSV) (time
-1) 6.06 6.01
Form (heavy %) raw material raw material
Alkane and naphthenic hydrocarbon 1.40 1.37 1.45 1.39
Benzene 0.0 1.80 0.0 2.55
Toluene 1.03 2.01 1.05 2.04
Ethylbenzene 15.54 12.19 15.56 12.45
P-Xylol 8.16 17.56 8.16 18.02
M-xylene 48.19 39.90 48.19 40.66
O-Xylol 20.28 17.62 20.25 17.88
Ethyltoluene 1.22 1.37 1.20 0.96
Three methyl Benzene 0.50 0.66 0.50 0.70
Diethylbenzene 1.66 2.66 1.64 1.30
Dimethyl ethyl benzene 1.94 2.77 1.91 2.01
Tetramethyl-benzene 0.07 0.09 0.09 0.04
The result
Ethylbenzene transforms (%) 21.6 20.0
P-Xylol approaches balance (%) 97.9 99.0
Ethylbenzene transform by
Hydrogenation takes off ethylization (%) 29.4 97.3
Disproportionation (%) 47.0 0.0
Methyl transporters (%) 4.1 0.0
Ethyl shifts (%) 19.4 2.7
Comparison test C-F
The conversion test of finishing according to the method for describing in the routine I is with mordenite (ZeolonH) and zeolite Y and molybdenum dipping and does not have the sample of dipping to carry out.Mordenite and zeolite Y both are considered to large pore zeolite.The presentation of results that provides in table III and the IV uses this large pore zeolite in the test of conversion/selectivity, the effect of molybdenum dipping is actually very little.
The table III
Mordenite comparison test C comparison test D
Condition
Molybdenum (heavy %) 03
Temperature (℃) 359 360
Pressure (pound/inch
2Gauge pressure) 180 180
Hydrogen/hydrocarbon (mol ratio) 1.98 2.00
Air speed (WHSV) (time
-1) 5.98 6.02
Form (heavy %) raw material
Alkane and naphthenic hydrocarbon 1.45 1.28 1.31
Benzene 0.0 0.51 1.43
Toluene 1.04 1.89 5.43
Ethylbenzene 15.55 14.69 12.16
P-Xylol 8.16 11.56 15.87
M-xylene 18.19 44.07 36.31
O-Xylol 20.26 19.07 15.04
Ethyltoluene 1.21 1.50 2.84
Three methyl Benzene 0.50 1.24 4.25
Diethylbenzene 1.65 1.74 1.88
Trimethylammonium ethylbenzene 1.92 2.33 3.28
Tetramethyl-benzene 0.07 0.11 0.23
The result
Ethylbenzene transforms (%) 5.52 21.8
P-Xylol approaches balance (%) 37.0 99.5
Ethylbenzene transform by
Hydrogenation takes off ethylization (%) 14.5 15.1
Disproportionation (%) 17.9 10.8
Methyl transporters (%) 29.9 42.5
Ethyl shifts (%) 37.8 31.6
The table IV
Zeolite Y comparison test E comparison test F
Condition
Molybdenum (heavy %) 03
Temperature (℃) 372 372
Pressure (pound/inch
2Gauge pressure) 180 180
Hydrogen/hydrocarbon (mol ratio) 1.96 2.01
Air speed (WHSV) (time
-1) 6.08 6.06
Form (heavy %) raw material
Alkane and naphthenic hydrocarbon 1.45 1.40 2.10
Benzene 0.0 1.12 1.25
Toluene 1.04 4.89 5.85
Ethylbenzene 15.55 13.59 13.35
P-Xylol 8.17 11.54 11.94
M-xylene 48.19 38.88 36.73
O-Xylol 20.26 16.72 15.72
Ethyltoluene 1.21 2.11 2.25
Three methyl Benzene 0.50 4.67 5.74
Diethylbenzene 1.64 1.50 1.33
Dimethyl ethyl benzene 1.91 3.26 3.36
Tetramethyl-benzene 0.08 0.32 0.37
The result
Ethylbenzene transforms (%) 12.6 14.2
Dimethylbenzene approaches balance (%) 50.4 60.8
Ethylbenzene transform by
Hydrogenation takes off ethylization (%) 4.7 5.8
Disproportionation (%) 0.0 0.0
Methyl transporters (%) 40.7 42.0
Ethyl shifts (%) 54.6 52.2
Claims (12)
1, based on hydro-dealkylation, the process that transforms alkyl aromatics ties up under the conversion condition, the alkyl aromatic hydrocarbon feed with add base matter in, intermediate pore size, crystal silicon-aluminate zeolite contacts for basic catalyst component.On catalyst component, be loaded with the containing metal compound that constitutes by molybdate compound basically.
2, in the process of claim 1, the alkyl aromatic hydrocarbon feed contains ethylbenzene and dimethylbenzene.
3, in the process of claim 1, aluminosilicate zeolite is that the catalyzer on basis adds in the base matter of aluminium.
4, in the process of claim 1, aluminosilicate zeolite is ZSM-5.
5, in the process of claim 1, aluminosilicate zeolite is a ferrierite.
6, in the process of claim 1, the molybdenum thing of about 0.05～25 heavy % is loaded on the catalyst component of zeolite for the basis.
7, in the process of claim 1, conversion condition comprises: about 95～540 ℃ of temperature, hydrogen are about 0.5～20 to the mol ratio of hydrocarbon, about 0.01～90 o'clock of weight-space velocity
-1, and about 0～1000 pound/inch of pressure
2(gauge pressure).
8, in the process of claim 1, the molybdenum thing is Ammonium Heptamolybdate or molybdenum carbonyl.
9, based on hydro-dealkylation, isomeric xylenes and the process that transforms ethylbenzene tie up under the conversion condition, the hydrocarbon feed that contains dimethylbenzene and ethylbenzene with add base matter in, intermediate pore size, crystal silicon-aluminate zeolite contacts for basic catalyst component.On catalyst component, be loaded with the metallic compound that constitutes by molybdate compound basically.
10, in the process of claim 9, aluminosilicate zeolite is ZSM-5.
11, in the process of claim 9, the molybdenum of about 0.5～10 heavy % is loaded on the catalyst component of zeolite for the basis.
12, in the process of claim 9, conversion condition comprises: about 95～540 ℃ of temperature, hydrogen are about 0.5～20 to the mol ratio of hydrocarbon, about 0.01～90 o'clock of weight-space velocity
-1, and about 0～1000 pound/inch of pressure
2(gauge pressure).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101896A CN1012169B (en) | 1983-10-17 | 1985-04-01 | Modification of hydrocarbon conversion processes over crystalline aluminosilicate zeolite-based catalysts by incorporation of a molybdenum compound |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54248383A | 1983-10-17 | 1983-10-17 | |
| CN85101896A CN1012169B (en) | 1983-10-17 | 1985-04-01 | Modification of hydrocarbon conversion processes over crystalline aluminosilicate zeolite-based catalysts by incorporation of a molybdenum compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101896A true CN85101896A (en) | 1987-01-17 |
| CN1012169B CN1012169B (en) | 1991-03-27 |
Family
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|---|---|---|---|
| CN85101896A Expired CN1012169B (en) | 1983-10-17 | 1985-04-01 | Modification of hydrocarbon conversion processes over crystalline aluminosilicate zeolite-based catalysts by incorporation of a molybdenum compound |
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| Country | Link |
|---|---|
| CN (1) | CN1012169B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361959A (en) * | 2009-03-27 | 2012-02-22 | 吉坤日矿日石能源株式会社 | Method for producing aromatic hydrocarbons |
| CN108530249A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of benzene and isopropylbenzene production n-proplbenzene |
-
1985
- 1985-04-01 CN CN85101896A patent/CN1012169B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361959A (en) * | 2009-03-27 | 2012-02-22 | 吉坤日矿日石能源株式会社 | Method for producing aromatic hydrocarbons |
| CN102361959B (en) * | 2009-03-27 | 2014-07-30 | 吉坤日矿日石能源株式会社 | Method for producing aromatic hydrocarbons |
| US9243192B2 (en) | 2009-03-27 | 2016-01-26 | Jx Nippon Oil & Energy Corporation | Method for producing aromatic hydrocarbons |
| CN108530249A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of benzene and isopropylbenzene production n-proplbenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1012169B (en) | 1991-03-27 |
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