CN100506378C - Low ethylbenzene by product aromatics alkyl transferring and dealkylation catalyst - Google Patents
Low ethylbenzene by product aromatics alkyl transferring and dealkylation catalyst Download PDFInfo
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- CN100506378C CN100506378C CNB2006100299555A CN200610029955A CN100506378C CN 100506378 C CN100506378 C CN 100506378C CN B2006100299555 A CNB2006100299555 A CN B2006100299555A CN 200610029955 A CN200610029955 A CN 200610029955A CN 100506378 C CN100506378 C CN 100506378C
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Abstract
The present invention relates to an aromatic transalkylation and an dealkylation catalyst with a low by-product of ethylbenzene and mainly solves the problems in the prior art that in the reaction products, a high by-product content of the ethylbenzene causes that a target product selectivity of xylene which is the product of mixed carbon eight is lower, and the xylene has no selectivity towards dealkylation of aromatic side chain alkyl. The present invention solves the problem well by a technical proposal that the catalyst consists of 40 to 90 portions of zeolite, the SiO2/Al2O3 molar ratio of which is 12 to 70, 10 to 60 portions of binder and 0.5 to 12 portions of compound metal-oxide, which are accounted by weight portions. The catalyst can be used for the industrial productions of a transfer of a heavy aromatic hydrocarbon of carbon-nine or above with toluene alkyl and the dealkylation, which reduce the by-product of ethylbenzene and increase the xylene products.
Description
Technical field
The present invention relates to a kind of aromatic hydrocarbons transalkylation and dealkylation catalyst of low ethyl benzene accessory substance, particularly about being raw material or being raw material with carbon nine and above heavy arene thereof separately with carbon nine and above heavy arene thereof and toluene, carry out transalkylation and dealkylation, thereby can reduce the catalyst of ethylbenzene by-products content increasing production of xylol product in side reaction and the product.
Background technology
Paraxylene in the dimethylbenzene is one of main basic organic of petrochemical industry, in numerous chemical production field such as chemical fibre, synthetic resin, agricultural chemicals, medicine, plastics purposes is widely arranged.For increasing production of xylol, utilize toluene disproportionation or toluene and carbon nine and above heavy aromatics (C thereof
9 +A) disproportionation and transalkylation reaction generate benzene and C
8A reaches the purpose of effective volume increase paraxylene by increasing production of xylol.
People are usually C9 aromatic (C
9A), carbon ten and above heavy aromatics (C thereof
10 +A) be referred to as heavy aromatics.Petroleum Aromatics is mainly derived from the byproduct that light oil cracking is produced ethylene unit; The aromatic hydrocarbons that the oil plant catalytic reforming is produced; The byproduct of toluene disproportionation and transalkylation unit.Along with increasing of heavy arene amount, the comprehensive utilization of heavy arene becomes the problem that people are concerned about, wherein C
9The processing and utilization of A has ripe method, is widely used as the raw material of toluene disproportionation and transalkylation reaction, is used for making benzene and C
8A.Aromatic Hydrocarbon United Plant of producing 22.5 ten thousand tons of paraxylene per year according to estimates, because the difference of feedstock oil, the difference of process, the annual C that produces
10 +A is 1～30,000 ton, and this is a kind of resource of preciousness, and present Aromatic Hydrocarbon United Plant does not also have suitable processing and utilizes method to this.
Along with the development of catalyst technology, can adopt the carbon ten heavy arene (C that sneak into certain content in the reaction raw materials at present
10A) method improves the yield of purpose product, pursues under high conversion, the high-speed deficiency that product yield is on the low side, but C in fact to remedy
10Have only about 20～30% to be utilized among the A, and about 80～70% C
10A discharges at the bottom of the heavy aromatics Tata.
As a kind of important research project of rationally utilizing the heavy arene resource, heavy arene is produced dimethylbenzene by transalkylation and dealkylation lighting highly selective and also more and more has been subjected to people's attention.Heavy aromatic hydrocarbon light is by the hydro-dealkylation reaction, finally generates benzene, toluene and dimethylbenzene.Yet because heavy arene mainly is to produce light aromatic hydrocarbons by pyrolysismethod and catalytic dealkylation method at present, pyrolysismethod takes off alkyl and causes the hydrogen consumption to increase, and the side chain alkyl-methyl of aromatic hydrocarbons, the alkyl that takes off of ethyl are not had selectivity, causes raw material toluene, C
9 +The Main Ingredients and Appearance trimethylbenzene of A and ethyl methyl benzene and product dimethylbenzene demethylation are serious, the methyl conservation rate is low, dimethylbenzene selective is poor thereby make, more than cause raw material toluene, trimethylbenzene, ethyl methyl benzene are not utilized effectively, the yield of purpose product dimethylbenzene is lower, owing to optionally do not take off ethyl, make product C simultaneously
8Ethyl-benzene level is higher among the A, gives mixed C
8The further separating dimethyl benzene technology of A is brought difficulty, and these all make the technical-economic index of xylene production relatively poor, and commercialization is restricted.
In the public clear 51-29131 patent of spy, use MoO
3-NiO/Al
2O
3(weight consists of 13%Wo, 5%Ni) is catalyst, with C
9A～C
10A (benzene 0.81%, toluene 0.26%, C
8A0.95%, C
10A15.23%) be raw material, under 6MPa and 550 ℃ of reaction conditions, during product is formed by weight percentage for containing benzene 9.74%, toluene 30.27%, dimethylbenzene 32.33% and non-aromatics 0.16%.
USP5,942,651 disclose a kind of with benzene or toluene and C
9 +The method of the light aromatic hydrocarbons of A transalkylation production, this method is loaded into two beds with two kinds of catalyst, perhaps be seated in the reactor of two polyphones, the described first kind of zeolite of this method mainly is selected from MCM-22, PSH-3, SSZ-25, ZSM-12 or β, second kind of zeolite is selected from ZSM-5, the amount of second kind of catalyst accounts for 1～20% of catalyst total amount, and best 10～15%.When reaction, raw material need be passed through first beds earlier, and the control weight space velocity is at 1.0～7.0 o'clock
-1, be preferably at 2.5～4.5 o'clock
-1, be 5.0～100.0 o'clock by the weight space velocity of second beds
-1, be preferably at 15.0～35.0 o'clock
-1, the purpose of this method is to make raw material pass through first catalyst with slower speed, generates intermediate products, then allowing these intermediate products pass through second catalyst with fast speeds, to generate more BTX.
Carbon nine and above heavy arene content thereof more only carry out transalkylation reaction by zeolite itself in raw material, the often very fast inactivation of catalyst.United States Patent (USP) 4723048 discloses a kind of toluene and alkylaromatic hydrocarbon disproportionation/transalkylation catalyst, load Ni or Pd, Ag, Sn, Pt or Ge on modenite.Mainly as hydrogenation metal, its activity is subjected to the control of Sn, Ge metal, to improve the performance of catalyst for nickel or palladium in this patent.
In the above-mentioned document, include toluene aromatic hydrocarbons in the fresh feed of use, the yield of purpose product dimethylbenzene is lower when perhaps having only heavy arene in the reaction feed, owing to optionally do not take off ethyl, makes product C simultaneously
8Ethyl-benzene level is higher among the A, gives mixed C
8The further separating dimethyl benzene technology of A is brought difficulty, technical-economic index and unreasonable problem such as feasible, thus limit its industrializing implementation.
Because heavy arene mainly is to produce light aromatic hydrocarbons by pyrolysismethod and catalytic dealkylation method at present, pyrolysismethod takes off alkyl and causes the hydrogen consumption to increase, and the side chain alkyl-methyl of aromatic hydrocarbons, the alkyl that takes off of ethyl are not had selectivity; At present the bibliographical information catalyst to the side chain alkyl-methyl of aromatic hydrocarbons, ethyl to take off the alkyl selectivity also lower, can not carry out high efficiency, highly selective takes off ethyl, cause ethylbenzene by-products content height in the product, to mix in carbon eight products dimethylbenzene target product selectivity lower, bring difficulty to technology, simultaneously because to raw material toluene, C
9 +The Main Ingredients and Appearance trimethylbenzene of A and ethyl methyl benzene and product dimethylbenzene demethylation are serious, thereby raw material toluene, trimethylbenzene, ethyl methyl benzene are not utilized effectively, and these all make the technical-economic index of xylene production relatively poor.
Summary of the invention
Technical problem to be solved by this invention is to exist in the product ethylbenzene by-products content height to cause in the prior art to mix in carbon eight products dimethylbenzene target product selectivity lower, to the not problem optionally of alkyl of taking off of aromatic hydrocarbons side chain alkyl, provide a kind of aromatic hydrocarbons transalkylation and dealkylation catalyst of new low ethyl benzene accessory substance.This catalyst is used for being raw material or being raw material with carbon nine and above heavy arene thereof separately with carbon nine and above heavy arene thereof and toluene, when carrying out transalkylation and dealkylation, can realizes that high efficiency, highly selective take off ethyl, make product C
8Ethyl-benzene level is lower among the A, has product dimethylbenzene selective height, mixed C
8The further separating dimethyl benzene of A is easy, xylene loss is less, to greatest extent the characteristics of increasing production of xylol target product.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of aromatic hydrocarbons transalkylation of low ethyl benzene accessory substance and dealkylation catalyst comprise following component in parts by weight:
1) SiO
2/ Al
2O
3Mol ratio is 40～90 parts of 12～70 h-type zeolites;
2) oxide of molybdenum is 0.002～8 part;
3) be selected from 0.005～8 part of oxide at least a in palladium or the nickel;
4) 0.02～8 part of at least a oxide in chosen from Fe, bismuth, tin, platinum, cerium, magnesium or the titanium;
5) binding agent is 10～60 parts.
In the technique scheme, the h-type zeolite preferred version is selected from least two kinds among β zeolite, modenite or the ZSM-5; They are the mixed crystal of the synthetic different zeolites of the mechanical impurity, direct crystallization of different zeolites or direct crystallization synthetic method and the mixture that combines of mechanical mixture method.In parts by weight, the oxide consumption preferable range of molybdenum is 0.1～6 part; Being selected from oxide consumption preferable range at least a in palladium or the nickel is 0.05～5 part; Oxide consumption preferable range at least a in chosen from Fe, bismuth, tin, platinum, cerium, magnesium or the titanium is 0.1～6 part; The binding agent preferred version is for being selected from aluminium oxide, silica or bentonite.
The Preparation of catalysts method is through dipping or ion-exchange or mixing or mediate extrusion, after 400～570 ℃ of roastings make by h-type zeolite, aluminium oxide and employed slaine among the present invention.
Catalyst of the present invention uses fixed bed reactors to carry out reactivity worth and investigates.25 millimeters of reactor inside diameter φ, 1200 millimeters of length, stainless steel.Adopt electrical heating, temperature is controlled automatically.5 millimeters beades of reactor bottom filling φ are as supporter, filling catalyst 20 grams in the reactor, and 5 millimeters beades of top filling φ are made for the usefulness of raw material preheating and vaporization.Fresh C in the raw material
9 +A and raw material toluene mix with hydrogen, from top to bottom by beds, transalkylation and/or dealkylation take place, and generate more rudimentary aromatic hydrocarbons such as dimethylbenzene, benzene, and alkane such as a small amount of methane, ethane, propane, butane.The weight content of carbon ten and above heavy arene thereof can be preferably 4～10 weight % up to 3～18 weight % in the reaction raw materials.
Raw material C
9 +A derives from the petrochemical industry Aromatic Hydrocarbon United Plant, and test data is calculated as follows.
Catalyst of the present invention, owing in catalyst, adopt at least two kinds of composite zeolites that are selected among β zeolite, modenite or the ZSM-5 as the catalytic activity main body, at least three kinds of composite metal oxides have been added simultaneously as the catalytic activity auxiliary agent, this catalyst is used for being raw material or being raw material with carbon nine and above heavy arene thereof separately with carbon nine and above heavy arene thereof and toluene, when carrying out transalkylation and dealkylation production dimethylbenzene target product, can realize that high efficiency, highly selective take off ethyl, make product C
8Ethyl-benzene level is lower among the A, has the high characteristics of product dimethylbenzene selective, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 25 gram and the Na of molecular proportion 22
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 46 gram and the Na of molecular proportion 22
2O content is less than the Al of 0.1% (weight)
2O
340 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; Powder behind the dipping adds the dilute nitric acid solution of nickel nitrate, cerous nitrate again, fully mediates evenly, carries out extruded moulding, catalyst A is made in 500 ℃ of roastings.
[embodiment 2]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 35 gram and the Na of molecular proportion 23
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 24 gram and the Na of molecular proportion 26
2O content is less than the Al of 0.1% (weight)
2O
336 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; Powder behind the dipping adds a certain amount of dilute nitric acid solution, bismuth nitrate, ferric nitrate and palladium bichloride, fully mediates evenly, carries out extruded moulding, catalyst B is made in 500 ℃ of roastings.
[embodiment 3]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3The ammonium type modenite of molecular proportion 21 and 14 gram Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 60 gram and the Na of molecular proportion 31
2O content is less than the Al of 0.1% (weight)
2O
339 grams evenly mix, and are made into the aqueous solution with ammonium molybdate and flood; Add a certain amount of dilute nitric acid solution, cobalt acetate, chlorination four ammonia platinum, stannous chloride and nickel nitrate then, fully mediate evenly, carry out extruded moulding, catalyst C is made in 500 ℃ of roastings.
[embodiment 4]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 22 grams of molecular proportion 20, Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 54 gram and the Na of molecular proportion 22
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 zeolite 10 gram and the Na of molecular proportion 49
2O content is less than the Al of 0.1% (weight)
2O
340 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; The catalyst D that powder behind the dipping adds a certain amount of dilute nitric acid solution, ferric nitrate, bismuth nitrate and palladium nitrate, carries out extruded moulding, different metal content is made in 500 ℃ of roastings.
[embodiment 5]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3The ammonium type modenite of molecular proportion 25/ZSM-5 mixed crystal zeolite (modenite/ZSM-5 (weight)=1:2) 20 grams, Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 39 gram and the Na of molecular proportion 26
2O content is less than the Al of 0.1% (weight)
2O
338 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; Add a certain amount of dilute nitric acid solution, nickel nitrate, bismuth nitrate, cerous nitrate, titanium tetrachloride then, fully mediate evenly, carry out the catalyst E that extruded moulding, 500 ℃ of roastings are made different metal content.
[embodiment 6]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 19 grams of molecular proportion 23, Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 47 gram and the Na of molecular proportion 25
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 zeolite 17 gram and the Na of molecular proportion 33
2O content evenly mixes less than acid-treated bentonite 23 grams of 0.1% (weight), is made into the aqueous solution with ammonium molybdate and floods; Add a certain amount of dilute nitric acid solution, nickel nitrate, bismuth nitrate, cerous nitrate and ferric nitrate then, fully mediate evenly, carry out extruded moulding, 500 ℃ of roastings, make the catalyst F of different metal content.
[embodiment 7]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 13 grams of molecular proportion 20, Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 59 gram and the Na of molecular proportion 22
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 zeolite 22 gram and the Na of molecular proportion 27
2O content is less than the Al of 0.1% (weight)
2O
323 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; Add a certain amount of dilute nitric acid solution, titanium tetrachloride, bismuth nitrate and palladium nitrate solution then, fully mediate evenly, carry out extruded moulding, catalyst G is made in 500 ℃ of roastings.
[embodiment 8]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 7 grams of molecular proportion 15, Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 28 gram and the Na of molecular proportion 24
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 zeolite 32 gram and the Na of molecular proportion 36
2O content is less than the Al of 0.1% (weight)
2O
355 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; Add a certain amount of dilute nitric acid solution, chlorination four ammonia platinum, stannous chloride and palladium nitrate solution solution then, fully mediate evenly, carry out extruded moulding, catalyst H is made in 500 ℃ of roastings.
[embodiment 9]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 38 gram and the Na of molecular proportion 22
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 zeolite 25 gram and the Na of molecular proportion 76
2O content is less than the Al of 0.1% (weight)
2O
361 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; Add a certain amount of dilute nitric acid solution, nickel nitrate, bismuth nitrate and cerous nitrate solution then, fully mediate evenly, carry out extruded moulding, 500 ℃ of roastings, make catalyst I.
[embodiment 10]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite 42 gram and the Na of molecular proportion 18
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 zeolite 26 gram and the Na of molecular proportion 26
2O content is less than the Al of 0.1% (weight)
2O
330 grams evenly mix, and are made into the aqueous solution with ammonium molybdate and flood; Add a certain amount of dilute nitric acid solution, nickel nitrate, cerous nitrate, magnesium nitrate and bismuth nitrate solution then, fully mediate evenly, carry out extruded moulding, catalyst J is made in 500 ℃ of roastings.
[embodiment 11]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type modenite 51 gram and the Na of molecular proportion 23
2O content is less than 0.10% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 zeolite 16 gram and the Na of molecular proportion 45
2O content (contains SiO by weight percentage, less than the Ludox of 0.1% (weight)
230%) 60 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; After the oven dry of powder behind the dipping, fully mediate evenly with the dilute nitric acid solution of palladium nitrate, bismuth nitrate, stannous chloride and titanium tetrachloride again, carry out extruded moulding, catalyst K is made in 500 ℃ of roastings.
[embodiment 12]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type β zeolite/ZSM-54 mixed crystal zeolite (β zeolite/ZSM-5 (weight)=7: 2) 48 gram and Na of molecular proportion 24
2O content is less than the Al of 0.1% (weight)
2O
330 grams evenly mix, and are made into the aqueous solution with ammonium molybdate then and flood; Add a certain amount of nickel nitrate solution then and carry out incipient impregnation, fully mediate with the dilute nitric acid solution of cerous nitrate again after the oven dry, carry out extruded moulding, 500 ℃ of roastings, make the catalyst L that contains three kinds of metals.
The catalyst that makes with embodiment 1～12 carries out disproportionation and the active investigation of transalkylation reaction on the fixed bed reaction evaluating apparatus.Loaded catalyst is 40 grams, and weight space velocity is 2.5 hours
-1, 390 ℃ of reaction temperatures, reaction pressure 3.0MPa, hydrogen/hydrocarbon molecule be than 4.0, the raw material weight percentage composition: toluene is 45.5%, C
9 +A is 54.5% (C wherein
10 +A is 6.2, indane 0.9), C in the raw material
9The A weight percent consists of: propyl benzene 3.5%, first and second benzene 35.1%, trimethylbenzene 63.4%, C
10 +The A weight percent consists of: diethylbenzene 2.3%, dimethyl ethylbenzene 27.0%, methyl propyl benzene 2.3%, durene 27.8%, methyl naphthalene 14.5%, dimethylnaphthalene 11.2%, other 12.9%, the concrete evaluation result such as the table 1 of catalyst.
The reaction evaluating result of the catalyst that table 1 is made (unit: weight is in oxide)
| Embodiment | Catalyst | Zeolite | Binding agent | M 1 /％ | M 2 /％ | M 3 /％ | Ethyl-benzene level/% | Ethyl removes ratio/% | Dimethylbenzene selective/% among the C8A |
| 1 | A | β/MOR | Aluminium oxide | Mo/3.2 | Ni/2.2 | Ce/2.2 | 0.14 | 93.7 | 99.5 |
| 2 | B | β/MOR | Aluminium oxide | Mo/1.2 | Ni/1.5 Pd/0.2 | Bi/1.3 Fe/1.4 | 0.25 | 90.6 | 99.1 |
| 3 | C | β/MOR | Aluminium oxide | Mo/3.7 | Ni/1.5 | Sn/2.0 Pt/0.1 | 0.12 | 94.4 | 99.6 |
| 4 | D | β/MOR/ZSM-5 | Aluminium oxide | Mo/3.5 | Pd/0.3 | Bi/1.9 Fe/0.3 | 0.09 | 95.1 | 99.6 |
| 5 | E | β/MOR+ZSM-5 | Aluminium oxide | Mo/2.6 | Ni/1.2 | Bi/1.3 Ti/2.2 Ce/1.9 | 0.22 | 90.9 | 99.2 |
| 6 | F | β/MOR/ZSM-5 | Bentonite | Mo/1.3 | Ni/1.8 | Bi/2.0 Fe/2.3 Ce/4.0 | 0.18 | 91.8 | 99.3 |
| 7 | G | β/MOR/ZSM-5 | Aluminium oxide | Mo/3.4 | Pd/0.1 | Bi/2.4 Ti/0.4 | 0.19 | 91.2 | 99.3 |
| 8 | H | β/MOR/ZSM-5 | Aluminium oxide | Mo/3.1 | Pd/0.2 | Sn/1.8 Pt/0.2 | 0.13 | 94.4 | 99.7 |
| 9 | I | MOR/ZSM-5 | Aluminium oxide | Mo/0.4 | Ni/1.1 | Bi/2.7 Ce/1.9 | 0.18 | 92.0 | 99.4 |
| 10 | J | β/ZSM-5 | Aluminium oxide | Mo/2.1 | Ni/1.6 | Bi/2.0 Ce/2.8 Mg/2.1 | 0.17 | 92.9 | 99.5 |
| 11 | K | MOR/ZSM-5 | Silica | Mo/2.5 | Pd/0.1 | Bi/1.0 Sn/1.9 Ti/1.0 | 0.19 | 91.8 | 99.3 |
| 12 | L | β+ZSM-5 | Aluminium oxide | Mo/4.1 | Ni/1.7 | Ce/3.5 | 0.13 | 94.3 | 99.6 |
* MOR is a modenite.
Evaluation result shows, the present invention makes is selected from the β zeolite, at least two kinds of zeolites among modenite or the ZSM-5 and at least three kinds are selected from molybdenum, nickel, palladium, iron, bismuth, tin, platinum, cerium, the catalyst that magnesium or titanium oxide are made, this catalyst is by adopting the β zeolite, at least two kinds of composite zeolites among modenite or the ZSM-5 are as the catalytic activity main body, the composition metal that has added at least three kinds simultaneously is as the method for catalytic activity auxiliary agent, can regulate the control catalytic performance effectively, be raw material with carbon nine and above heavy arene thereof and toluene or be under the condition of raw material with carbon nine and above heavy arene thereof separately, by transalkylation and dealkylation, and realization high efficiency, highly selective takes off ethyl, makes product C
8Ethyl-benzene level is lower among the A, suppresses the demethylation side reaction simultaneously, thereby has high target product dimethylbenzene selective.
The invention is not restricted to above embodiment, those skilled in the art can make various changes and distortion according to the present invention, only otherwise break away from aim of the present invention, all should belong to scope of the present invention.
Claims (4)
1, a kind of aromatic hydrocarbons transalkylation of low ethyl benzene accessory substance and dealkylation catalyst comprise following component in parts by weight:
1) SiO
2/ Al
2O
3Mol ratio is 40～90 parts of 12～70 h-type zeolites, and wherein h-type zeolite is selected among β zeolite, modenite or the ZSM-5 at least two kinds;
2) oxide of molybdenum is 0.1～6 part;
3) be selected from 0.05～5 part of oxide at least a in palladium or the nickel;
4) 0.1～8 part of at least a oxide in chosen from Fe, bismuth, tin, platinum, cerium, magnesium or the titanium;
5) binding agent is 10～60 parts.
2,, it is characterized in that in oxide consumption at least a in parts by weight chosen from Fe, bismuth, tin, platinum, cerium, magnesium or the titanium be 0.1～6 part according to the aromatic hydrocarbons transalkylation and the dealkylation catalyst of the described low ethyl benzene accessory substance of claim 1.
3,, it is characterized in that binding agent is selected from, aluminium oxide, silica or bentonite according to the aromatic hydrocarbons transalkylation and the dealkylation catalyst of the described low ethyl benzene accessory substance of claim 1.
4, according to the aromatic hydrocarbons transalkylation and the dealkylation catalyst of the described low ethyl benzene accessory substance of claim 1, it is characterized in that h-type zeolite is selected from least two kinds of zeolites among β zeolite, modenite or the ZSM-5, they are the mixed crystal of the synthetic different zeolites of the mechanical impurity, direct crystallization of different zeolites or direct crystallization synthetic method and the mixture that combines of mechanical mixture method.
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|---|---|---|---|
| CNB2006100299555A CN100506378C (en) | 2006-08-11 | 2006-08-11 | Low ethylbenzene by product aromatics alkyl transferring and dealkylation catalyst |
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|---|---|---|---|
| CNB2006100299555A CN100506378C (en) | 2006-08-11 | 2006-08-11 | Low ethylbenzene by product aromatics alkyl transferring and dealkylation catalyst |
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| Publication Number | Publication Date |
|---|---|
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| CN100506378C true CN100506378C (en) | 2009-07-01 |
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| 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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| CN103285912B (en) * | 2012-03-01 | 2015-09-23 | 中国石油天然气股份有限公司 | Preparation method of ethylbenzene dealkylation catalyst in carbon octaaromatic hydrocarbon |
| EP2834004B1 (en) * | 2012-04-02 | 2020-12-23 | Saudi Arabian Oil Company | Multimetal zeolites based catalyst for transalkylation of heavy reformate to produce xylenes and petrochemical feedstocks |
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| EP3539652A1 (en) | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Method of heavy reformate conversion into btx over metal-impregnated zsm-5+mesoporous mordenite zeolite composite catalyst |
| EP3539650B1 (en) | 2018-03-14 | 2021-03-31 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| EP3785797B1 (en) | 2018-03-14 | 2024-04-24 | Saudi Arabian Oil Company | Heavy reformate conversion into xylenes using composite zeolite catalysts |
| CN112808301B (en) * | 2021-01-04 | 2022-01-11 | 大连理工大学 | Composite catalyst and method for catalyzing formaldehyde to be completely oxidized and eliminated by composite catalyst |
| WO2022223012A1 (en) * | 2021-04-23 | 2022-10-27 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbons |
| GB202107524D0 (en) * | 2021-05-27 | 2021-07-14 | Johnson Matthey Plc | Adsorbent materials |
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| 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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