CN1052666C - Zeolite catalyst for synthesizing cumine and method for preparing cumin by using said catalyst - Google Patents
Zeolite catalyst for synthesizing cumine and method for preparing cumin by using said catalyst Download PDFInfo
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Abstract
The present invention discloses a catalyst used for synthesizing cumene, which comprises zeolite and an optional inorganic oxide adhesive. The zeolite has the following properties: (1). the amount of Bronsted acid measured by a 2, 6-dimethyl pyridine adsorption method at 200 DEG C is larger than 0.50 mmol/g; (2) the mole ratio of the Bronsted acid to Lewis acid is 2.5:1.2; (3) the amount of strong Bronsted acid measured by a 2, 6-dimethyl pyridine adsorption method at 400 DEG C is larger than 0.08 mmol/g.
Description
The present invention relates to synthesizing iso-propylbenzene with zeolite catalyst and use the method for this Preparation of Catalyst isopropylbenzene.
The commercial run of preparation isopropylbenzene mainly contains two kinds at present, and the first is used Friedal-Crafts type catalyst, and this class catalyst has alchlor, boron trifluoride, hydrofluoric acid, liquid phosphoric acid, sulfuric acid etc.These materials have serious corrosivity to process equipment, cause many operational problems and be difficult to usually to dispose with environmentally acceptable mode; It two is solid phosphoric acid methods, though solved equipment corrosion and problem of environmental pollution, because of it can not carry out the transfering alkylation reaction, causes the total recovery of isopropylbenzene lower.
It is the hot subject of this area that searching is used for the synthetic non-aggressive solid catalyst of isopropylbenzene always.For this reason, people have developed various types of zeolite catalysts.
U.S.Pat.No.4,469,908 disclose a kind of aromatic hydrocarbons and the alkylation that the alkylating agent of 1 to 5 carbon atom is arranged, and wherein reactant contacts in the presence of HZSM-12 preferably with liquid form.Reaction is carried out under from about 0.1MPa to about 20MPa at 100 ℃ to 300 ℃ and pressure.From this patent specification Table X V, can find out, only could obtain greater than 90% isopropylbenzene selectivity with greater than the conversion ratio of 10% benzene down and greater than 125Psig (absolute pressure is under the 0.85MPa) at 200 ℃.
U.S.Pat.NO 5,081, and 323 disclose a kind of alkylation of aromatic hydrocarbons or the method for transfering alkylation, by aromatic hydrocarbons and C
2～C
4Olefin alkylation or with the transfering alkylation of many alkylaromatic hydrocarbons, under Partial Liquid Phase condition at least, contact in the presence of a kind of catalyst that contains the β zeolite.Though this patent claims that alkylated reaction can be at 100～600 °F, best 250～450 and 50～1000Psig carry out, and alkylated reaction pressure is 600Psig (absolute pressure is 4.2MPa) in an embodiment.
EP 0 629 599A1 disclose and a kind ofly with propylene benzene alkylation have been prepared the method for isopropylbenzene, and catalyst system therefor is a β zeolite of introducing a certain amount of suitable alkali metal, alkaline-earth metal or metal cation through ion-exchange.The alkylated reaction temperature is 150 ℃ to 300 ℃, and preferred 150 ℃ to 200 ℃, pressure is 1.0 to 5.0MPa, preferred 2.5 to 3.5MPa.
EP 0521 554A2 discloses a kind of alkylating aromatic hydrocarbon catalyst, comprises the Y zeolite of handling with a kind of phosphorus compound modification.The alkylated reaction temperature is 100 to 300 ℃, and preferred 110 to 200 ℃, pressure is 1.0 to 5.0MPa, and preferred 3.0 to 4.0MPa.
Also have a large amount of the friendship to offer as U.S.Pat.NO 5,145,817; 4,891,458; 5,030,785; 5,118,896; 5,198,595; EP 0 432 814A1; 0 308 097Al; 0 272 830 A2 etc. have described alkylating aromatic hydrocarbon and the transfering alkylation method of using various zeolite catalysts, and these zeolite catalysts can modification makes by zeolite is carried out various specially treateds such as ion-exchange, roasting and steam treatment.
Because the vapour phase alkylated reaction is difficult to overcome rapid inactivation of zeolite catalyst and the many problems of accessory substance, present most of alkylating aromatic hydrocarbons or many alkylaromatic hydrocarbons transfering alkylation method adopt liquid phase method, are in liquid phase for making reactant, must adopt higher pressure.Thereby development can carry out the alkylation of aromatic hydrocarbons under temperate condition or the high performance catalyst of many alkylaromatic hydrocarbons transfering alkylation is the key point of this area always.
Therefore, one of purpose of the present invention provides a kind of zeolite catalyst of synthesizing iso-propylbenzene, comprises that (A) has the zeolite of following performance:
1) descend with 2 at 200 ℃, the Bronsted of 6-lutidines determination of adsorption method acid amount is greater than 0.50 (mM/gram);
2) Bronsted acid is 2.5～12 with the mol ratio of Lewis acid; With
3) under 400 ℃, with 2, the strong Bronsted acid amount of 6-lutidines determination of adsorption method is greater than 0.08 (mM/gram); With
(B) inorganic oxide adhesive of choosing any one kind of them.
Another object of the present invention provides a kind of method with benzene and propylene reaction synthesizing iso-propylbenzene, comprises that it is under 0.1～1.0MPa condition with pressure that benzene and propylene are 60～150 ℃ in temperature, contacts on above-mentioned catalyst.
The 3rd purpose of the present invention provides a kind of method with benzene and diisopropylbenzene (DIPB) reaction synthesizing iso-propylbenzene, comprises that it is under 0.5～3.0MPa condition with pressure that benzene and diisopropylbenzene (DIPB) are 150～250 ℃ in temperature, contacts on above-mentioned catalyst.
As everyone knows, the acid on the zeolite comprises Bronsted acid (hereinafter to be referred as B acid) and Lewis acid (hereinafter to be referred as L acid).The total acid content of zeolite (or claiming the acid centre number) has material impact to the alkylation of benzene and the transfering alkylation reaction of polyalkylbenzene.B acid amount (or B acid site number) and B acid strength also have material impact to the alkylation of benzene and the transfering alkylation reaction of polyalkylbenzene.Reaction usually occurs on the B acid site of medium above intensity, and the B acid site is many more, and catalyst activity is high more, but L acid is not then had such clear regularity.
The present invention finds for making zeolite catalyst good activity is arranged, and it is with 2, and the B of 6-lutidines absorption method (below in detail measurement will be described in detail) acid amount should be greater than 0.5 (mM/gram).
The present invention finds that the activity of zeolite catalyst is also relevant with the ratio of L acid with B acid.For benzene and propylene synthesizing iso-propylbenzene, the B/L mol ratio of zeolite catalyst is usually between 2.5～12, between preferred 2.5～8, more preferably between 2.5～4.
The present invention also invents, and the catalytic activity of zeolite catalyst also distributes relevant with the B acid strength.Have only its activity of modified zeolite of moderate strength extremely low, along with after the B acid strength increases to certain value, reactivity just increases considerably.But zeolite catalyst B acid strength also has adverse effect to life of catalyst and activity too by force.
As everyone knows, the acid of zeolite is measured available absorption method or temperature programmed desorption method (TPD) is measured.Acid strength distribution available programs desorption by heating method is measured, and the high more expression acid strength of desorption temperature is strong more, and the acid amount of the big more expression respective strengths of desorption peaks area is many more.
Because pyridine can be adsorbed in the B acid, also can be adsorbed in the L acid, therefore available pyridine adsorption method is measured the zeolite total acid content.Because 2, the 6-lutidines only is adsorbed in the B acid, and therefore available similarly 2, the adsorbance of 6-lutidines is calculated B acid amount.The difference of total acid content and B acid amount is L acid amount (referring to Benesi, H.A., J.Catal.28 176 (1973)).
By pyridine or 2,6-lutidines degree desorption by heating method also can correspondingly be measured total acid content or B acid amount.
The present invention uses 200 ℃ of following pyridine adsorption methods to measure total acid content, measures the total acid intensity distributions with pyridine degree desorption by heating method.With 200 ℃ down 2,6-lutidines determination of adsorption method B acid amount, with 2,6-lutidines temperature programmed desorption method is measured the B acid strength and is distributed, and with 400 ℃ down 2, the strong B of 6-lutidines determination of adsorption method is sour to be measured.
Describe these assay methods below in detail.
30 milligrams of zeolites of 60～80 purposes are packed in the pipe, handled 1 hour, be cooled to 200 ℃ then with 550 ℃ helium (He), extremely saturated with Pulse Chromatographic method absorption pyridine well known in the art, use helium purge half an hour again.Under the flow velocity of the carrier gas (He) of 30 ml/min, be warming up to 700 ℃ with 20 ℃/minute heating rates, the curve that changes with temperature with gas-chromatography record pyridine desorption rate is the TPD curve.By the corresponding peak of certain desorption temperature that this curve is represented, can find out that acid strength distributes, promptly desorption temperature is high more, and acidity is strong more, and peak area is big more, and the corresponding acid amount of expression is many more.Can calculate total acid content by whole peak areas, this value with can verify mutually with pyridine adsorption method measured value.Calculating formula is as follows:
Total acid content (mM/gram)=
B acid amount and intensity distributions assay method thereof are the same, just change pyridine into 2, and the 6-lutidines gets final product.Calculate B acid amount by being similar to top formula, by 2, the TPD curve of 6-lutidines can find out that the B acid strength distributes.
Above-mentioned 2, only there are two desorption peaks of 300～400 ℃ and 500～650 ℃, the B acid site of corresponding two kinds of intensity on the TPD curve of 6-lutidines.Therefore, available 2, the 6-lutidines is similar to the saturated extent of adsorption of said method under 400 ℃ and calculates strong B acid amount.Such determination of adsorption method value can relatively and mutually be verified with above-mentioned TPD curve calculation value.
The B acid that modified zeolite of the present invention is measured by above-mentioned measuring method is measured greater than 0.5 (mM/gram), and B/L is 2.5～12, and strong B acid amount is greater than 0.08 (mM/gram).
The present invention finds that the higher modified zeolite of reactivity has the B acid site of tangible two kinds of varying strengths.The desorption temperature in moderate strength B acid site is 300～400 ℃, and the desorption temperature in strong B acid site is 500～650 ℃, and superpower B acid is greater than more than 650 ℃ desorption peaks being arranged.Only between 300～400 ℃, there is the zeolite activity of desorption peaks lower.
For making zeolite have characteristic as mentioned above, can handle zeolite by in following three kinds of conventional treatment methods one or more.
I type processing method: with finite concentration, the ammonium salt aqueous solution of preferred 0.5N-5N and/or hydrochloric acid were handled zeolite 1-6 hour in room temperature to boiling, be washed till no chlorion with deionized water, and the filtration back is dry down in 120 ℃, at 400～600 ℃ of following roasting 2-6 hours, this process can repeat 2-5 time then.Wherein said ammonium salt can be ammonium chloride or ammonium nitrate.
II type processing method: with finite concentration, the inorganic salt solution of preferred 0.5N-4N was handled zeolite 1～6 hour under boiling, be washed till no chlorion with deionized water, and is dry down in 120 ℃ after filtering, at 400～600 ℃ of following roasting 2-6 hours, this process can repeat 2-5 time then.
Above-mentioned inorganic acid salt comprises chloride, nitrate or sulfate etc.Metal ion comprises metal ions such as magnesium, zinc, copper, calcium or rare earth in the inorganic salts.
III type processing method: magnesium nitrate or magnesium chloride brine with the phosphoric acid and 5%～15% (weight) of 0.1～1% (weight) were handled zeolite 1～6 hour in room temperature to boiling, and it is dry down in 120 ℃ to filter the back.Can repeat 2-5 time 400～600 ℃ of following roasting 3-6 hour these processes then.
Be used for zeolite of the present invention and can be general Si-Al zeolite, be preferably the Y zeolite, β zeolite or overstable gamma zeolite, used zeolite pore is about 6～12 , is preferably 6～9 .Carrying out before above-mentioned three kinds of processing, earlier with zeolite 450～550 ℃ of following roastings 3 hours.
Do not wish to be bound by any theory, it is believed that I type processing method hocketing by ammonium salt aqueous solution and/or hydrochloric acid exchange and roasting, can improve the B acid amount of zeolite and the intensity distributions of change B acid, can make B acid amount greater than 0.5 (mM/gram), and make zeolite that 2 between 500～650 ℃ be arranged, 6-lutidines desorption peaks.II type processing method is mainly used to change the B/L value.III type processing method can be eliminated superpower B acid, makes zeolite not have more than 650 ℃ 2,6-lutidines desorption peaks.
For non-H type zeolite, generally carry out the I type earlier and handle like this, carry out II type and/or III type then and handle, and, also can directly carry out II type and/or III type and handle for H type zeolite.In a word, by using in above-mentioned three kinds of processing methods one or more, make the B acid amount of zeolite, B/L value and strong B acid are measured within the required range.
When the zeolite after above-mentioned processing was used as alkylating aromatic hydrocarbon and many alkyl aromatic hydrocarbons transfering alkylation catalyst, active high selectivity was good, and the life-span is long.When being used for benzene and propylene synthesizing iso-propylbenzene, can under relatively mild condition, carry out.For example the alkylated reaction of benzene and propylene can carry out under 80～140 ℃ and 0.1～0.4MPa.When benzene and propylene mol ratio are 2: 1～10: 1, the weight hourly space velocity of benzene is 0.8-2hr
-1Preferred 0.8～1.6hr
-1The time, third rare absorptivity can reach 100%, and the benzene conversion ratio can reach more than 10%, and the isopropylbenzene selectivity reaches more than 90%; The reaction of the transfering alkylation of benzene and diisopropylbenzene (DIPB) can be carried out under 150～250 ℃ and 0.5～3.0MPa.When benzene and diisopropylbenzene (DIPB) mol ratio are 2: 1～16: 1, the WHSV of benzene and diisopropylbenzene (DIPB) raw material is 0.8～2.0hr
-1Preferred 0.8～1.4hr
-1The time, the diisopropylbenzene (DIPB) conversion ratio can reach more than 30%.So just alleviated the problem of serious, the rapid inactivation of existing zeolite catalyst carbon deposit.
The conversion alkylated reaction of the alkylated reaction of benzene and propylene and benzene and diisopropylbenzene (DIPB) can be operated with continuous, semicontinuous and intermittent mode.
Various types of reactors can be used in the method for the present invention.When using intermittent mode, catalyst and aroamtic hydrocarbon raw material are put in the reactor or autoclave of stirring, be heated to reaction temperature, add propylene or diisopropylbenzene (DIPB) raw material then.Reaction temperature is by the heat-transfer fluid in reactor jacket circulation or the condenser that is used for removing reaction heat is housed keeps.The large-scale industry method can be used fixed bed reactors, or fluidized-bed reactor.These reactors all are well-known to those skilled in the art.
Zeolite can directly be used as catalyst after handling with the present invention, but preferably with zeolite powder and first machine oxide adhesive such as aluminium oxide, silica, silica/alumina or natural clay mix and with the mixture moulding.Final catalyst can contain the zeolite of 1～99% (weight).Usually zeolite content is between 10～90% (weight), and preferred adhesive is an aluminium oxide.Mixture can be with method moulding well known in the art.Shape is normally cylindrical, spherical or annular.
Further explain the present invention with non-limiting example below.
Used zeolite is commodity in the following example, and wherein embodiment 2 raw materials used zeolites are bought from naphthology research institute of China Petroleum Chemicals Corporation.The raw materials used zeolite of all the other embodiment is all bought from catalyst subsidiary factory of Fushun No.3 Petroleum Factory.
Wherein the β zeolite has following characteristic:
Na
2O％≤2.0％
Si/Al (mol ratio)=15-30
Degree of crystallinity 〉=70%
Aperture 5.9～6
Specific area 〉=400m
2/ g
The Y zeolite has following characteristic
Na
2O(％)≤11％
Si/Al (mole) 〉=5.0
Degree of crystallinity 〉=90%
Aperture=8～9 embodiment 1
With 50 gram H type β zeolites, carry out following processing:
What (1) under agitation add 500ml 1N transfers to the solder(ing)acid of PH=1-2 with hydrochloric acid, keeps boiling 6 hours;
(2) cooled and filtered goes out zeolite, is washed till no chlorion with deionized water;
(3) dry filter cake and porphyrize down at 120 ℃;
Calcined 3 hours down for (4) 550 ℃;
(5) the above zeolite of handling is stirring and the exchange down 6 hours of gently boiling with 500ml 0.1% (weight) phosphoric acid and 10% (weight) magnesium nitrate aqueous solution;
(6) repeat above-mentioned steps (2)～(4)
(7) above step (1)-(6) are repeated 2 times
(8) measure total acid content, B acid amount, strong B acid amount and B acid strength by top described method and distribute, the results are shown in subordinate list 1.Embodiment 2
With 50 gram H type β zeolites, carry out following processing:
(1) under stirring and boiling condition, handled zeolite 6 hours with 500ml 1N aqueous ammonium chloride solution;
(2) with embodiment 1 step (2)～(4)
(3) above step repeats 4 times;
(4) with embodiment 1 step (8) embodiment 3
With 50 gram H type β zeolites, carry out following processing:
(1) under stirring and boiling condition, handled zeolite 6 hours with 500ml magnesium chloride brine (containing the 20ml concentrated hydrochloric acid);
(2) with embodiment 1 step (2)～(4);
(3) above step repeats 2 times;
(4) with step (8) among the embodiment 1.Embodiment 4
With 50 gram y-type zeolites, carry out following processing:
(1) with (1) among the embodiment 2,
(2) under stirring and the boiling condition, handled zeolite 6 hours with the lanthanum nitrate aqueous solution of 500ml 1N again;
(3) leach zeolite after the cooling, dry filter cake and porphyrize down for 120 ℃;
(4) 550 ℃ of following roastings 3 hours;
(5) above process repeats 2 times;
(6) with (8) among the embodiment 1.Embodiment 5:
With 50 gram y-type zeolites, carry out following processing:
(1) aqueous ammonium chloride solution with 500ml 2N was handled zeolite 6 hours under stirring and boiling condition;
(2) with embodiment 1 step (2)～(4);
(3) under stirring and boiling condition, use the magnesium nitrate aqueous solution of the phosphoric acid and 10% (weight) of 500ml 0.5% (weight) to handle 6 hours;
(4) repeating step (2)
(5) repeat above step (3)～(4) 2 times;
(6) with embodiment 1 (8) embodiment 6
With 50 gram ultrastables, carry out following processing:
(1) under stirring and boiling condition, handled zeolite 6 hours with the magnesium nitrate aqueous solution (containing the 2ml concentrated hydrochloric acid) of 500ml 1N;
(2) with step (2)～(4) of embodiment 1
(3) repeat 2 times above step (1)-(2)
(4) with (8) embodiment 7 among the embodiment 1
With the super y-type zeolite that claims of 50 grams, carry out following processing:
(1) under stirring and boiling condition, handled zeolite 4 hours with 500ml 1N copper nitrate aqueous solution;
(2) with step (3)～(4) among the embodiment 4
(3) with (8) embodiment 8 among the embodiment 1
50 gram Y zeolites are carried out following processing:
1) under stirring and seething with excitement, handled 6 hours with the aqueous ammonium chloride solution of 500ml 2N;
2) with (2) among the embodiment 1～(4)
3) with (8) among the embodiment 1.Comparative example 1
With 50 gram y-type zeolites, carry out following processing:
(1) under stirring and boiling condition, handled zeolite 6 hours with the aqueous ammonium nitrate solution of 500ml 0.2N;
(2) cooled and filtered goes out zeolite, dries filter cake and porphyrize down for 120 ℃;
(3) under stirring and boiling condition, handled zeolite 6 hours with the aqueous ammonium nitrate solution of 500ml 2N;
(4) with above-mentioned step (2);
(5) 550 ℃ of following roastings 3 hours;
(6) with (8) among the embodiment 1.
Comparative example 2
With 50 gram y-type zeolites, carry out following processing:
(1) with (1) in the comparative example 1～(2);
(2) under stirring and boiling condition, handled zeolite 6 hours with the calcium chloride water of 500ml 1N;
(3) with (2) among the embodiment 1～(4);
(4) with (8) among the embodiment 1.
Comparative example 3
With 500 gram y-type zeolites, carry out following processing:
(1) under stirring and boiling condition, handled zeolite 6 hours with the aqueous ammonium chloride solution of 500ml 1N;
(2) with (2) among the embodiment 1～(4);
(3) with (8) among the embodiment 1.
Comparative example 4
50 gram H type β zeolites are carried out following processing:
1) calcined 2 hours down at 450 ℃;
2) under agitation in the zeolite after calcining, add the aqueous ammonium chloride solution of 500ml 0.1N, reflux and handled 6 hours down;
3) with (2) among the embodiment 1～(4); With
4) with (8) among the embodiment 1.The alkylated reaction of embodiment 9 benzene and propylene
The zeolite of embodiment 1～7 and comparative example 1-4 is estimated in semicontinuous bubbling stirring isothermal reactor (four neck flasks of strap clamp cover).In reactor, add 100 milliliters of benzene and 2.55 grams, 80～100 purpose zeolites.Under agitation use the water bath with thermostatic control reactor heating, reaction temperature is controlled at 75 ± 1 ℃.Feed propylene then and pick up counting, the propylene flow is 2 milliliters/second, sample analysis in the time of 90 minutes.The AL injection of taking out is equipped with distilled water in vitro in advance,, gets supernatant liquor and carry out chromatography through the centrifugation catalyst.The alkylation properties of the zeolite conversion ratio X of benzene
B, the selectivity S that reaches isopropylbenzene represents, the results are shown in table 1.The transfering alkylation reaction of embodiment 10 benzene and diisopropylbenzene (DIPB)
Press carry out the evaluation of transfering alkylation reactivity in the stirred reactor intermittence in 0.1 rising in the zeolite after embodiment 1～8 and comparative example 1～4 processing.In reactor, add 35ml benzene and 30ml diisopropylbenzene (DIPB), and add the zeolite after 1.70g handles.Reacted 2 hours down with 1.8MPa in 200 ℃, utilize the chromatography reactant liquor.Conversion ratio X with diisopropylbenzene (DIPB)
DRepresent the transfering alkylation reactivity.The results are shown in table 1.The life test of embodiment 12 zeolite catalysts
The catalyst that is used for present embodiment is the φ 3 * 3mm cylindrical particle that is made as adhesive by the aluminium oxide of handling zeolite and 15% (weight) by embodiment 1.Fixed bed reactors are internal diameter 219mm, and two sections is the straight tube of 2000mm respectively, the 120 kilograms of above-mentioned catalyst of packing into.Reaction temperature is 130 ℃, and pressure is 0.35MPa, and benzene and propylene mol ratio are 6: l, the weight space velocity of benzene 1.35 hours
-1, benzene and propylene from bottom to top and stream flow through reaction tube.After carrying out 3600 hours, propylene conversion is 100%, the conversion ratio 14.75% of benzene, and the isopropylbenzene selectivity is 93.64%.
Table 1
| Embodiment number | Zeolite | B acid amount (mM/gram) | The amount (mM/gram) of strong B | B/L | T(℃) | X B(％) | S(％) | X D(％) | The alkylation life-span (hour) |
| 12345678 Comparative Examples 1234 | The super steady Y Y Y Y Y β of the super steady Y of β β β Y Y | 0.55 0.54 0.52 0.50 0.51 0.53 0.52 0.51 0.37 0.60 0.68 0.35 | 0.13 0.12 0.12 0.18 0.18 0.12 0.10 0.31 0.07 - 0.08 - | 3.3 3.8 3.4 2.9 3.1 4.0 2.6 2.7 4.2 2.9 2.4 1.9 | 500 515 505 550 565 530 520 580 520 380 525 670 | 21.3 21.1 18.1 11.7 12.6 11.3 10.2 - 3.05 2.05 2.72 4.10 | 94.5 94.1 94.7 95.0 90.7 90.4 92.0 - 100 100 100 100 | 35.0 32.9 30.5 30.8 45.0 32.1 30.8 46.0 8.5 13.2 5.1 - | ＞3000 * 20 ** |
T:2, the highest desorption peaks temperature of 6-lutidines.
*: the experiment of in embodiment 11, carrying out.
*: record on the continuous fixed bed reactors of filling 20 gram catalyst, reaction condition is: 100 ℃ of temperature, benzene: propylene=4: 1, benzene weight space velocity 1hr
-1
Claims (7)
1. zeolite catalyst that is used for synthesizing iso-propylbenzene comprises (A) a kind of zeolite with following performance:
1) descend with 2 at 200 ℃, the Bronsted of 6-lutidines determination of adsorption method acid amount is greater than 0.50 (mM/gram);
2) Bronsted acid is 2.5～12 with the mol ratio of Lewis acid;
3) under 400 ℃, with 2, the strong Bronsted of 6-lutidines determination of adsorption method acid amount greater than 0.08 (mM/gram) and
(B) Ren Xuan a kind of inorganic oxide adhesive.
2. according to the catalyst of claim 1, it is characterized in that described zeolite is y-type zeolite, overstable gamma zeolite or β zeolite.
3. according to the catalyst of claim 1, the aperture that it is characterized in that described zeolite is 6～12 dusts.
4. one kind is reacted into the method for isopropylbenzene with benzene and propylene, comprises that benzene and propylene are 60～150 ℃ in temperature, and pressure is 0.1～1.0MPa, and the mol ratio of benzene and propylene is 2: 1～10: 1, and the WHSV of benzene is 0.8～1.6hr
-1, contact in the presence of the catalyst of claim 1.
5. according to the method for claim 4, wherein temperature is 80～130 ℃, and pressure is 0.1～0.5MPa.
6. method by benzene and Transalkylation of Di-isopropyl Benzene prepared in reaction isopropylbenzene, comprise that benzene and diisopropylbenzene (DIPB) are under 150～250 ℃ in temperature, pressure is under 0.5～3.0MPa, and benzene and diisopropylbenzene (DIPB) mol ratio are 2: 1～16: 1, and the WHSH of benzene and diisopropylbenzene (DIPB) raw material is 0.8～1.3hr
-1, contact in the presence of the catalyst of claim 1.
7. according to the method for claim 6, wherein reaction temperature is 180～220 ℃, and pressure is 0.8～2.5MPa.
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| CN95120165A CN1052666C (en) | 1994-12-26 | 1995-12-25 | Zeolite catalyst for synthesizing cumine and method for preparing cumin by using said catalyst |
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| CN94119501.5 | 1994-12-26 | ||
| CN94119501A CN1125641A (en) | 1994-12-26 | 1994-12-26 | Catalyzer for isopropyl benzene synthetic zeolite |
| CN95120165A CN1052666C (en) | 1994-12-26 | 1995-12-25 | Zeolite catalyst for synthesizing cumine and method for preparing cumin by using said catalyst |
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|---|---|---|---|---|
| CN85102764A (en) * | 1985-04-01 | 1986-08-13 | 大连工学院 | Zeolite catalyst modified by rare earth preparation and application |
| EP0272830A2 (en) * | 1986-12-19 | 1988-06-29 | Union Oil Company Of California | Alkylation catalysts and processes |
| CN1005385B (en) * | 1986-12-06 | 1989-10-11 | 中国石油化工总公司石油化工科学研究院 | Y-type molecular sieve cracking catalyst containing rare earths oxidate |
| EP0432814A1 (en) * | 1989-11-16 | 1991-06-19 | ENIRICERCHE S.p.A. | Process for alkylating benzene |
| US5081323A (en) * | 1987-12-17 | 1992-01-14 | Chevron Research And Technology Company | Liquid phase alkylation or transalkylation process using zeolite beta |
| EP0521554A2 (en) * | 1991-07-01 | 1993-01-07 | Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica | Process for alkylation of aromatic compounds using a catalyst |
-
1995
- 1995-12-25 CN CN95120165A patent/CN1052666C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102764A (en) * | 1985-04-01 | 1986-08-13 | 大连工学院 | Zeolite catalyst modified by rare earth preparation and application |
| CN1005385B (en) * | 1986-12-06 | 1989-10-11 | 中国石油化工总公司石油化工科学研究院 | Y-type molecular sieve cracking catalyst containing rare earths oxidate |
| EP0272830A2 (en) * | 1986-12-19 | 1988-06-29 | Union Oil Company Of California | Alkylation catalysts and processes |
| US5081323A (en) * | 1987-12-17 | 1992-01-14 | Chevron Research And Technology Company | Liquid phase alkylation or transalkylation process using zeolite beta |
| EP0432814A1 (en) * | 1989-11-16 | 1991-06-19 | ENIRICERCHE S.p.A. | Process for alkylating benzene |
| EP0521554A2 (en) * | 1991-07-01 | 1993-01-07 | Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica | Process for alkylation of aromatic compounds using a catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1134317A (en) | 1996-10-30 |
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