CN101898152A - Toluene disproportionation and alkyl transfer catalyst and preparation method thereof - Google Patents
Toluene disproportionation and alkyl transfer catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a toluene disproportionation and alkyl transfer catalyst. A catalyst carrier consists of a hydrogen Y/Beta/ZSM-12 composite molecular sieve and an inorganic refractory oxide and carries an active metal ingredient, the hydrogen Y/Beta/ZSM-12 composite molecular sieve content of the catalyst is 10 to 90 percent, the active metal ingredient comprises bismuth, and the weight content of the bismuth in the catalyst is 0.1 to 10.0 percent based on oxide. A preparation method for the catalyst comprises an immersion method or a kneading method. The toluene disproportionation and alkyl transfer catalyst takes the hydrogen Y/Beta/ZSM-12 composite molecular sieve as the main body and carries the metal component by adopting the conventional immersion method or the conventional kneading method, and the composite molecular sieve does not need special treatment, so the preparation method is simple and the cost of the catalyst is low. The catalyst for toluene disproportionation and alkyl transfer reaction has high toluene conversion rate and B+C8A selectivity and good stability.
Description
Technical field
The present invention relates to a kind of catalyst for toluene disproportionation and transalkylation and preparation method thereof, particularly about a kind of catalyst for toluene disproportionation and transalkylation that adopts the composite molecular screen preparation and preparation method thereof.
Background technology
Toluene disproportionation and transalkylation technology are one of most important technical process in the large-scale Aromatic Hydrocarbon United Plant, its objective is direct purposes is less, superfluous relatively toluene and C
9Aromatic hydrocarbons changes into of many uses but under-supply benzene and dimethylbenzene, to meet the need of market.In the modernized aromatic hydrocarbons integrated complex of chemical fibre type, the toluene disproportionation device has critical role, and the benzene and the dimethylbenzene of its contribution account for 50%～70% of whole aromatic hydrocarbons integrated complex's benzene and dimethylbenzene total amount.
Toluene disproportionation and aromatic hydrocarbons transalkylation use molecular sieve catalyst usually, industrialized at present catalyst uses modenite, Beta molecular sieve and ZSM-5 molecular sieve mostly, in order to improve the serviceability of catalyst, need carry out special modification to molecular sieve usually and handle.As the Tatoray technology of Uop Inc. in industrialization in 1969, this process using mordenite catalyst.The ZSM-5 zeolite catalyst of the first generation MSTDP process using high selectivity of Mobil company, and the HZSM-5 zeolite catalyst of PxMax process using silica gel of new generation modification.Shanghai Petroleum Chemical Engineering Institute of state petrochemical industry limited company carries out catalyst for toluene disproportionation and transalkylation and complete set technology exploitation since the seventies in last century, successively succeeded in developing the catalyst for toluene disproportionation and transalkylation that 3 big series, 7 trades mark have independent intellectual property right, the domestic market occupation rate reaches 100%, and find a good sale in countries such as Iran and Byelorussia, this catalyst series all is based on modenite.
Chinese patent CN1201716A discloses a kind of catalyst for toluene disproportionation and transalkylation, and it adopts Si
2O
3/ Al
2O
3(mol ratio) is the high silicon h-mordenite of 15-35, the oxide of load bismuth and at least a oxide that is selected from silver, copper, zirconium, strontium, lanthanum, rhenium.This catalyst toluene conversion is about 45%, B+C
8A (benzene and dimethylbenzene) selectivity is about 95%.
Chinese patent CN1721069A discloses a kind of catalyst for toluene disproportionation and transalkylation, it adopts H-high silicon mordenite, H-Beta zeolite and H-ZSM-5 zeolite, load IA and/or IIA family metal or its oxide and at least a metal or the oxide that is selected from bismuth, molybdenum, silver, copper, zirconium, lanthanum or rhenium, its toluene conversion about 45%, C
8The A selectivity is about 70%～75%.
In sum, existing catalyst for toluene disproportionation and transalkylation adopts modenite, Beta molecular sieve or ZSM-5 molecular sieve mostly, one or more necessary metal components of load or molecular sieve need special modification to handle simultaneously, and the report of employing composite molecular screen seldom, composite molecular screen often has some unique advantages, is widely used in recent years in the various catalytic reaction processes.
Summary of the invention
The invention provides a kind of catalyst for toluene disproportionation and transalkylation and preparation method thereof, when this catalyst is used toluene disproportionation and transalkylation, have higher toluene conversion and higher B+C
8The A selectivity, and have good stable.
Catalyst for toluene disproportionation and transalkylation carrier provided by the invention is made up of Hydrogen Y/Beta/ZSM-12 composite molecular screen and inorganic refractory oxide, and supported active metal component, Hydrogen Y/Beta/ZSM-12 composite molecular screen content is 10wt%～90wt% in the catalyst, preferred 30wt%～80wt%.The content of inorganic refractory oxide in catalyst is 5wt%～85wt% in the catalyst, is preferably 20wt%～70wt%.Active metal component comprises bismuth, and bismuth is 0.1wt%～10.0wt% in the weight content of oxide in catalyst, is preferably 0.2wt%～5.0wt%.Active metal component can also comprise one or more in molybdenum, silver, zirconium, strontium, lanthanum, copper and the rhenium, in one or more weight contents in catalyst in oxide molybdenum, silver, zirconium, strontium, lanthanum, copper and the rhenium is 0.1wt%～10.0wt%, is preferably 0.1wt%～5.0wt%.
Inorganic refractory oxide can be selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay in the catalyst of the present invention.
Catalyst for toluene disproportionation and transalkylation preparation method of the present invention adopts conventional infusion process or kneading method.Infusion process comprises following content: behind Hydrogen Y/Beta/ZSM-12 composite molecular screen and inorganic refractory oxide and kneading and compactings such as peptization acid and extrusion aid, drying and roasting obtain carrier, adopt conventional infusion process carried metal component, baking temperature is room temperature～300 ℃, be preferably 100 ℃～150 ℃, be 1～48 hour drying time; Sintering temperature can be 400 ℃～800 ℃, is preferably 500 ℃～700 ℃, and roasting time can be 0.5～24 hour, is preferably 2～8 hours.
Kneading method comprises following content: after the salt or solution kneading and compacting with Hydrogen Y/Beta/ZSM-12 composite molecular screen, inorganic refractory oxide, peptization acid, extrusion aid and active metal component, drying and roasting obtain catalyst, baking temperature is room temperature～300 ℃, be preferably 100 ℃～150 ℃, be 1～48 hour drying time; Sintering temperature can be 400 ℃～800 ℃, is preferably 500 ℃～700 ℃, and roasting time can be 0.5～24 hour, is preferably 2～8 hours.
Inorganic refractory oxide can be selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay, is preferably aluminium oxide and/or silica, most preferably is aluminium oxide.Its precursor can be selected from boehmite, boehmite, diaspore, gibbsite and visit in the aluminium stone one or more, is preferably boehmite; Peptization is sour as nitric acid, hydrochloric acid, acetic acid, citric acid etc., preferred nitric acid; Extrusion aid is the material that helps extruded moulding, as graphite, starch, cellulose, sesbania powder etc., and preferred sesbania powder.
The preparation process of Hydrogen Y/Beta/ZSM-12 composite molecular screen is first preparation Y/Beta/ZSM-12 composite molecular screen, adopts then that the method for roasting obtains Hydrogen Y/Beta/ZSM-12 composite molecular screen after the ammonium ion exchange of this area routine.Ammonium ion exchange generally adopts ammonium nitrate solution to flood composite molecular screen down at 30～90 ℃, preferably floods 2～6 times.The silica alumina ratio of Hydrogen Y/Beta/ZSM-12 composite molecular screen (mol ratio of silica and aluminium oxide) is 5～30, preferred 10～15; Specific area is 600m
2/ g～800m
2/ g, pore volume 0.30cm
3/ g～0.40cm
3/ g.
Y/Beta/ZSM-12 composite molecular screen preparation process is as follows: the Y zeolite powder is added contain in the solution of NaOH (NaOH) and tetraethylammonium bromide (TEABr), selectivity adds ammoniacal liquor, add the silicon source, stirring obtains the reaction mixture gel system, and the mol ratio of reaction mixture gel system mixture is: 0.90-1.15Na
2O: 8.0-15.0SiO
2: 0.8-2.0TEABr: 0-8.0NH
4OH: Al
2O
3: 80-102H
2O, reactant mixture in 130-160 ℃ of following crystallization 5-10 days, obtain the Y/Beta/ZSM-12 composite molecular screen in confined conditions.
Among the Y/Beta/ZSM-12 composite molecular screen preparation method of the present invention, utilize Y zeolite to add suitable component and prepare gel rubber system as the aluminium source, react under certain condition then and obtain final Y/Beta/ZSM-12 composite molecular screen, a kind of detailed process is as follows: take by weighing a certain amount of NaOH and TEABr earlier, add a certain amount of distilled water then, use magnetic stirrer, NaOH and TEABr are dissolved fully, then the high-Si Y-type molecular sieve powder is added in the solution, add certain amount of ammonia water after stirring again, stir a period of time, add the silicon source then, stirring obtains white synthesis reaction mixture gel rubber system.With the mol ratio of final synthesis reaction mixture of preparation be: 0.90-1.15Na
2O: 8.0-15.0SiO
2: 0.8-2.0TEABr: 0-8.0NH
4OH: Al
2O
3: 80-102H
2The O reactant mixture stirs into even white jelly, in the stainless steel cauldron of packing into, in 130-160 ℃ of following crystallization 5-10 days.
The crystalline phase that contains Y, Beta, three kinds of zeolite molecular sieves of ZSM-12 in the composite molecular screen that above-mentioned Y/Beta/ZSM-12 composite molecular screen preparation method obtains simultaneously.And the relative scale of Y zeolite and Beta and ZSM-12 can be come modulation by regulating synthesis condition, specifically can be regulated on demand by those skilled in the art.
In the composite molecular screen building-up process, described Y zeolite silica alumina ratio is 4.8-5.2 (a silica molecule mol ratio), can be selected from the synthetic sodium type Y molecular sieve of industry.The silicon source is active silica or Ludox.
Catalyst for toluene disproportionation and transalkylation of the present invention is based on Hydrogen Y/Beta/ZSM-12 composite molecular screen, adopt conventional infusion process or kneading method carried metal component, composite molecular screen does not need specially treated, the preparation method is simple, catalyst is with low cost, catalyst of the present invention is used for toluene disproportionation and transalkylation reaction, has higher toluene conversion and B+C
8The A selectivity has good anti-impurity performance simultaneously, and catalyst stability is good.
Description of drawings
Fig. 1 is the XRD diffraction pattern of the synthetic composite molecular screen A of the embodiment of the invention 1.
Among the figure: indicate
It is Beta zeolite characteristic diffraction peak;
Indicate
It is ZSM-12 molecular sieve characteristic diffraction peak.
The specific embodiment
Further specify preparation process of the present invention below in conjunction with embodiment.Catalyst of the present invention adopts the 10mL fixed-bed micro-reactor to estimate, with toluene and 1,3, the 5-trimethylbenzene is a raw material, toluene and 1,3,5-trimethylbenzene mass ratio is 3: 2, and loaded catalyst is 5g (40～60 order), before the charging catalyst is activated two hours, activation condition is: 450 ℃ of temperature, pressure 2.8MPa.Appreciation condition is: mass space velocity 2.0h
-1, pressure 2.8MPa, NH
2/ N
Hydrocarbon=4: 1 (hydrogen hydrocarbon mol ratio), 440 ℃ of reaction temperatures, product are carried out quantitative analysis on the HP589 gas chromatograph.Analysis condition: capillary column HP-1 (OV-101, non-polar column), internal diameter 0.20mm, long 50m, shunting weight ratio 200: 1, temperature programming, FID detects.
Synthetic and the processing of embodiment 1 Y/Beta/ZSM-12 composite molecular screen
(1) the Y/Beta/ZSM-12 composite molecular screen is synthetic
Feed molar proportioning: 1.07Na
2O: 8.7SiO
2: 1.5TEABr: 0.8NH
4OH: Al
2O
3: 100H
2O.Taking by weighing 5.4g NaOH and 100gTEABr is dissolved in the 365ml deionized water, add 144gY type molecular sieve then while stirring, wait to add the 10ml concentrated ammonia liquor again after mixing, stir half an hour, add the 195ml Ludox again, move on in the closed stainless steel reactor behind the stirring 2h.140 ℃ of following crystallization 7 days, obtain Y/Beta/ZSM-12 composite molecular screen product A.
Feed molar proportioning: 1.07Na
2O: 9.0SiO
2: 1.5TEABr: 3.25NH
4OH: Al
2O
3: 100H
2O.Taking by weighing 5.4g NaOH and 100gTEABr is dissolved in the 325ml deionized water, add 144gY type molecular sieve then while stirring, wait to add the 40ml concentrated ammonia liquor again after mixing, stir half an hour, add the 205ml Ludox again, move on in the closed stainless steel reactor behind the stirring 2h.140 ℃ of following crystallization 7 days, obtain Y/Beta/ZSM-12 composite molecular screen product B.
Feed molar proportioning: 1.04Na
2O: 8.4SiO
2: 1.3TEABr: 0.7NH
4OH: Al
2O
3: 87H
2O.Taking by weighing 5.4g NaOH and 100gTEABr is dissolved in the 355ml deionized water, add 165gY type molecular sieve then while stirring, wait to add the 10ml concentrated ammonia liquor again after mixing, stir half an hour, add the 205ml Ludox again, move on in the closed stainless steel reactor behind the stirring 2h.135 ℃ of following crystallization 7 days, obtain Y/Beta/ZSM-12 composite molecular screen product C.
The main character of the composite molecular screen of table 1 embodiment 1 preparation
(2) processing of Y/Beta/ZSM-12 molecular sieve
Getting Y/Beta/ZSM-12 composite molecular screen A, B and C 200 grams that step (1) makes respectively, is that 50% ammonium nitrate solution exchanges each 2 hours 3 times at 80 ℃ with 400 gram mass concentration.110 ℃ of dryings 6 hours, 550 ℃ of roastings 4 hours make Hydrogen Y/Beta/ZSM-12 composite molecular screen A, Hydrogen Y/Beta/ZSM-12 composite molecular screen B, Hydrogen Y/Beta/ZSM-12 composite molecular screen C.
The preparation of embodiment 2 carriers
Get Hydrogen Y/Beta/ZSM-12 composite molecular screen A 45 grams that embodiment 1 makes, SB powder 145.8 grams, sesbania powder 3.75 grams, mix, add 70ml deionized water and 3.75ml red fuming nitric acid (RFNA) (66.5wt%) fully mixed pinching on roller then, make it to become the paste plastic, on banded extruder, extrude the cylinder bar of diameter 1.5mm, 110 ℃ of dryings 8 hours, 550 ℃ of roastings obtained carrier D1 in 4 hours in air atmosphere then.
Get Hydrogen Y/Beta/ZSM-12 composite molecular screen B 75 grams of embodiment 1 preparation, SB powder 104.2 grams, sesbania powder 3.75 grams, mix, add 85ml deionized water and 3.75ml red fuming nitric acid (RFNA) (66.5wt%) fully mixed pinching on roller then, make it to become the paste plastic, on banded extruder, extrude the cylinder bar of diameter 1.5mm, 110 ℃ of dryings 8 hours, 550 ℃ of roastings obtained carrier D2 in 4 hours in air atmosphere then.
Get Hydrogen Y/Beta/ZSM-12 composite molecular screen C 105 grams of embodiment 1 preparation, SB powder 62.5 grams, sesbania powder 3.75 grams, mix, add 100ml deionized water and 3.75ml red fuming nitric acid (RFNA) (66.5wt%) fully mixed pinching on roller then, make it to become the paste plastic, on banded extruder, extrude the cylinder bar of diameter 1.5mm, 110 ℃ of dryings 8 hours, 550 ℃ of roastings obtained carrier D3 in 4 hours in air atmosphere then.
Get Hydrogen Y/Beta/ZSM-12 composite molecular screen A 120 grams of embodiment 1 preparation, SB powder 41.7 grams, sesbania powder 3.75 grams, mix, add 110ml deionized water and 3.75ml red fuming nitric acid (RFNA) (66.5wt%) fully mixed pinching on roller then, make it to become the paste plastic, on banded extruder, extrude the cylinder bar of diameter 1.5mm, 110 ℃ of dryings 8 hours, 550 ℃ of roastings obtained carrier D4 in 4 hours in air atmosphere then.
Embodiment 3
Get among the embodiment 2 the carrier D1 of preparation, impregnated in the aqueous solution of bismuth nitrate 24 hours, 110 ℃ of dryings are 6 hours then, obtain containing Bi in 4 hours in 540 ℃ of roastings
2O
30.2% (weight) catalyst E1.Catalyst is formed and evaluation result sees Table 2.
Embodiment 4
Get among the embodiment 2 the carrier D2 of preparation, impregnated in the aqueous solution of bismuth nitrate 24 hours, 110 ℃ of dryings are 6 hours then, obtain containing Bi in 4 hours in 540 ℃ of roastings
2O
32.0% (weight) catalyst E2.Catalyst is formed and evaluation result sees Table 2.
Get among the embodiment 2 the carrier D3 of preparation, impregnated in the aqueous solution of bismuth nitrate 24 hours, 110 ℃ of dryings are 6 hours then, obtain containing Bi in 4 hours in 540 ℃ of roastings
2O
33.0% (weight) catalyst E3.Catalyst is formed and evaluation result sees Table 2.
Embodiment 6
Get among the embodiment 2 the carrier D4 of preparation, impregnated in the aqueous solution of bismuth nitrate 24 hours, 110 ℃ of dryings are 6 hours then, obtain containing Bi in 4 hours in 540 ℃ of roastings
2O
35.0% (weight) catalyst E4.Catalyst is formed and evaluation result sees Table 2.
Embodiment 7
Get among the embodiment 2 the carrier D3 of preparation, impregnated in the various aqueous solution of different metal content 24 hours, 110 ℃ of dryings are 6 hours then, obtain a series of catalyst E5～E11 in 4 hours in 540 ℃ of roastings.Catalyst is formed and evaluation result sees Table 2.
Embodiment 8
Get the Hydrogen Y/Beta/ZSM-12 composite molecular screen A that embodiment 1 makes, the SB powder, the sesbania powder, mix, add the solution of preparing by deionized water and red fuming nitric acid (RFNA) (66.5wt%), citric acid, bismuth nitrate then, on roller, fully mix and pinch, make it to become the paste plastic, on banded extruder, extrude the cylinder bar of diameter 1.5mm, 110 ℃ of dryings 8 hours, 550 ℃ of roastings obtained catalyst E12 in 4 hours in air atmosphere then.Catalyst is formed and evaluation result sees Table 2.
Embodiment 9
Adopt the preparation method of embodiment 8, difference is Bi in the catalyst
2O
3The content difference, make catalyst E13.Catalyst is formed and evaluation result sees Table 2.
The catalyst E3 of embodiment 5 preparations adopts the enterprising line stabilization evaluation of midget plant, and under identical appreciation condition, steady running is after 500 hours, and toluene conversion and purpose product selectivity do not descend, and illustrate that catalyst of the present invention has good stable.
Comparative example 1
Make catalyst F1, F2, F3 according to Chinese patent CN1721069A embodiment 1,5,6.Catalyst is formed and evaluation result sees Table 2.
Claims (10)
1. catalyst for toluene disproportionation and transalkylation, it is characterized in that: described catalyst for toluene disproportionation and transalkylation carrier is made up of Hydrogen Y/Beta/ZSM-12 composite molecular screen and inorganic refractory oxide, and supported active metal component, Hydrogen Y/Beta/ZSM-12 composite molecular screen content is 10wt%～90wt% in the catalyst, the content of inorganic refractory oxide in catalyst is 5wt%～85wt% in the catalyst, active metal component comprises bismuth, and bismuth is 0.1wt%～10.0wt% in the weight content of oxide in catalyst.
2. according to the described catalyst of claim 1, it is characterized in that: in the catalyst for toluene disproportionation and transalkylation, Hydrogen Y/Beta/ZSM-12 composite molecular screen content is 30wt%～80wt%, and the active metal component bismuth is 0.2wt%～5.0wt% in the weight content of oxide in catalyst.
3. according to claim 1 or 2 described catalyst, it is characterized in that: active metal component also comprises one or more in molybdenum, silver, zirconium, strontium, lanthanum, copper and the rhenium, is 0.1wt%～10.0wt% in one or more weight contents in catalyst in oxide molybdenum, silver, zirconium, strontium, lanthanum, copper and the rhenium.
4. according to the described catalyst of claim 3, it is characterized in that: in one or more weight contents in catalyst in oxide molybdenum, silver, zirconium, strontium, lanthanum, copper and the rhenium is 0.1wt%～5.0wt%.
5. according to the described catalyst of claim 1, it is characterized in that: inorganic refractory oxide is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay.
6. the preparation method of the described catalyst for toluene disproportionation and transalkylation of claim 1 adopts the preparation of infusion process or kneading method; Infusion process comprises: behind Hydrogen Y/Beta/ZSM-12 composite molecular screen and inorganic refractory oxide and peptization acid and extrusion aid kneading and compacting, drying and roasting obtain carrier, adopt infusion process carried metal component, baking temperature is room temperature～300 ℃, be 1～48 hour drying time, sintering temperature is 400 ℃～800 ℃, and roasting time is 0.5～24 hour; Kneading method comprises following content: after the salt or solution kneading and compacting with Hydrogen Y/Beta/ZSM-12 composite molecular screen, inorganic refractory oxide, peptization acid, extrusion aid and active metal component, drying and roasting obtain catalyst, baking temperature is room temperature～300 ℃, be 1～48 hour drying time, sintering temperature is 400 ℃～800 ℃, and roasting time is 0.5～24 hour.
7. in accordance with the method for claim 6, it is characterized in that: the preparation process of Hydrogen Y/Beta/ZSM-12 composite molecular screen wherein is for preparing the Y/Beta/ZSM-12 composite molecular screen earlier, adopt then that the method for roasting obtains Hydrogen Y/Beta/ZSM-12 composite molecular screen after the ammonium ion exchange, ammonium ion exchange adopts ammonium nitrate solution at 30～90 ℃ of dipping composite molecular screens down.
8. in accordance with the method for claim 7, it is characterized in that: Y/Beta/ZSM-12 composite molecular screen preparation process wherein is as follows: the Y zeolite powder is added contain in the solution of NaOH and tetraethylammonium bromide, selectivity adds ammoniacal liquor, add the silicon source, stir and obtain the reaction mixture gel system, reactant mixture in 130-160 ℃ of following crystallization 5-10 days, obtains the Y/Beta/ZSM-12 composite molecular screen in confined conditions.
9. it is characterized in that in accordance with the method for claim 8: the mol ratio of reaction mixture gel system mixture is: 0.90-1.15Na
2O: 8.0-15.0SiO
2: 0.8-2.0TEABr: 0-8.0NH
4OH: Al
2O
3: 80-102H
2O, TEABr are tetraethylammonium bromide.
10. in accordance with the method for claim 8, it is characterized in that: the Y zeolite silica alumina ratio is 4.8-5.2, is selected from the synthetic sodium type Y molecular sieve of industry, and the silicon source is active silica or Ludox.
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| CN100352548C (en) * | 2004-10-29 | 2007-12-05 | 中国石油化工股份有限公司 | Method for preparing catalyst for toluene selective disproportionation |
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