CN105582982A - In situ pretreatment method of catalyst for selective alkylation of toluene and ethene - Google Patents
In situ pretreatment method of catalyst for selective alkylation of toluene and ethene Download PDFInfo
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Abstract
The invention discloses an in situ pretreatment method of a catalyst for selective alkylation of toluene and ethene. The method comprises the following steps: (1) an amorphous silica-aluminium carrier is filled in a reactor; (2) an aqueous solution containing an organic compound is added and contacts the amorphous silica-aluminium carrier for reaction, and oxygen containing gas is added for processing; (3) an aqueous solution of ammonium nitrate is added and contacts a catalyst precursor for reaction, and nitrogen is added for processing. The catalyst processed by the method has the characteristics of uniform distribution of molecular sieves on the surface of the catalyst, increased utilization rate of molecular sieves, high catalytic activity, high selectivity of PET, etc.; at the same time, production cost of the catalyst is greatly reduced, generation of waste water which is difficult to treat in the traditional molecular sieve synthesis process is avoided, and the method is good for environmental protection.
Description
Technical field
The present invention relates to the in-situ pretreatment method of a kind of toluene and ethylene selectivity alkylation catalyst, the inventive method is synthetic to methyl-ethyl benzene course of reaction for toluene and ethylene selectivity alkylation, compared with prior art, there is catalytic activity high and to the selective high of methyl-ethyl benzene.
Background technology
The raw materials for production of novel high polymer synthon p-methylstyrene to methyl-ethyl benzene (PET). Novel high polymer material-poly-p-methylstyrene is the external high performance plastics kind of exploitation in recent years, roughly the same polystyrene of the various performances of this polymer, keep good processing and forming, and be all better than existing polystyrene plastics (hot strength 48MPa at aspects such as proportion, heat resistance, anti-flammability, transparency and shrinkage factors, elastic modelling quantity 2210MPa, cantilever beam notched Izod impact strength 16J/m, 95 DEG C of heat distortion temperatures). In addition p-methylstyrene can with other monomer copolymerization (as styrene), can improve heat resistance and the anti-flammability of some polymer, can be in a large number for engineering plastics, the manufacture of the aspects such as phthalic resin coating, thereby in widespread attention.
At present, due to methyl-ethyl benzene monomer manufacturing cost is much higher than to styrene, thereby limit being widely used of poly-p-methylstyrene, be mainly used at present replacing polystyrene to make electrical accessorie and packaging needing heatproof high field to share, and for illuminating equipment etc. Conventionally first benzene alkylation with ethylene generates in product containing a certain amount of to methyl-ethyl benzene, and a small amount of benzene and the mixed xylenes of by-product, and wherein most of toluene does not transform (most of toluene recovery circulation) and uses; By rectifying obtain purity 90% left and right to methyl-ethyl benzene. Through further adsorbing separation or freezing and crystallizing purify to more than 98% methyl-ethyl benzene. In the product that methyl-ethyl benzene is generated through dehydrogenation, contain the p-methylstyrene of 50% left and right, then obtain the more than 99% polymerization single polymerization monomer p-methylstyrene of purity by rectifying. Can adopt and produce polymethylstyrene with the similar method of styrene polymerization or process for suspension polymerization or use as the comonomer of styrene etc.
Traditional Friede-Crafts catalyst, the thermodynamical equilibrium mixture containing three isomers of methyl-ethyl benzene that can only make, as the AlCl3 series catalysts of DOW company of the U.S., the system of being reacted with pure ethylene by toluene be called vinyltoluene product (containing PET approximately 38%, remaining be between position methyl-ethyl benzene). It is catalyst that USP4117024 adopts chemical modification high silica ZSM-5 type zeolite, when toluene reacts with pure ethylene, the content of the PET in product methyl-ethyl benzene isomers that obtains, reaches more than 90%, and ortho position methyl-ethyl benzene generation is significantly inhibited, its content can level off to zero. CN1047986A adopts the Pentasil type Si-Al zeolite catalyst that contains antimony (or phosphorus) and magnesium elements chemical modification processing, although can directly making raw material with the refinery tail-gas that contains the impurity such as hydrogen sulfide, water (containing ethene 10% ~ 20%), this zeolite catalyst reacts the process that is mainly contraposition methyl-ethyl benzene of producing with toluene, adopt antimony (or phosphorus) and magnesium elements modification can play to molecular sieve surface acidity the effect of neutralization and modulation, after antimony, phosphorus modification, make molecular sieve surface strong acid center reduce, weak acid center increases relatively, is conducive to form para-isomer. In addition, phosphorus can also make the effective dimensions in duct infall or aperture reduce. But this processing method can obviously reduce the activity of catalyst, even if reaction is carried out at very high temperature, conversion ratio is still lower, and P elements is easier to run off under reaction condition, is also a deficiency of this technology. So conversion of ethylene of this catalyst and selectively all lower to methyl-ethyl benzene.
MCM-22 molecular sieve has two kinds of independently many membered ring channels systems, and one is two-dimentional sinusoidal waveform, the ten-ring duct of intersection, and cross section is oval (0.45nm*0.51nm); Another kind is that cross section is the large cylindrical type supercage of twelve-ring, supercage internal freedom space is 0.71nm*0.71nm*1.82nm, these supercages be connected with the window (0.45*0.45nm) of ten-ring half twelve-ring supercage (0.71*0.71*0.91nm) [001] crystal outer surface form have religion large adsorption capacity pocket, two supercages are connected by hexagonal prismoid. Because MCM-22 zeolite crystal is thin slab construction, therefore it has larger outer surface MCM-22, therefore the reactions such as alkylation, aromatisation, toluene disproportionation is all had to excellent catalytic performance. And mostly adopt hydrothermal crystallization method about the synthetic method of MCM-22 molecular sieve, and be all generally under alkaline environment, organic amine is structure directing agent, at a certain temperature crystallization certain hour. What in this building-up process, meeting generation was a large amount of contains the industrial wastewater such as organic amine and alkali, is difficult to carry out harmless treatment, not only makes molecular sieve production cost greatly improve, and causes serious environmental pollution, and its use is limited greatly.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of toluene and ethylene selectivity alkylation catalyst in-situ pretreatment method, the method catalyst surface molecular sieve after treatment is evenly distributed, improve the utilization rate of molecular sieve, be conducive to the diffusion of product, compared with prior art, not only there is catalytic activity high and to the selective high of methyl-ethyl benzene, significantly reduce catalyst and become to produce cost simultaneously, avoid the generation of the unmanageable waste water of traditional synthesis of molecular sieve process, be conducive to environmental protection.
The in-situ pretreatment method of toluene of the present invention and ethylene selectivity alkylation catalyst, comprises with following content: (1) is by catalyst precarsor A(amorphous silicon alumina supporter) be loaded in reactor; (2) pass into the aqueous solution containing organic amine and halogenated hydrocarbons, with catalyst precarsor A haptoreaction, and then pass into oxygen-containing gas and process, obtain catalyst precarsor B; (3) pass into aqueous ammonium nitrate solution and catalyst precarsor B haptoreaction, then pass into nitrogen and process, obtain catalyst A 1; Wherein the described organic amine of step (2) is one or more in alcamines or arylamine class.
In the inventive method, the described catalyst precarsor A of step (1) has following character: the SiO of described amorphous silicon aluminium2And Al2O3Mol ratio be 5 ~ 200, be preferably 10 ~ 100, more preferably 20 ~ 50.
In the inventive method, the preparation method of catalyst precarsor A described in step (1) can be prepared according to prior art, general process is as follows: aluminum hydroxide solid elastomer powder, white carbon, sesbania powder are fully mixed, then add peptizing agent (sodium hydroxide solution), kneading is plastic paste, extruded moulding, drying, calcination process, obtain catalyst precarsor A. Concrete preparation condition can be determined according to the conventional knowledge in this area.
In the inventive method, the described alcamines of step (2) is selected from one or more in monoethanolamine, diethanol amine and triethanolamine, and arylamine class is selected from one or more in aniline, benzidine and phenylenediamine. Be preferably triethanolamine and aniline; Described halogenated hydrocarbons is the halogenated alkane containing 1 ~ 3 carbon atom, preferably CH3I、CH3CHCl2Or CHCl3In one or more, the concentration of halogenated hydrocarbons in the aqueous solution is 0.01 ~ 2mol/L, is preferably 0.1 ~ 1mol/L.
In the inventive method, the organic amine that step (2) is described and the mol ratio of halogenated hydrocarbons are 0.5 ~ 5, are preferably 1 ~ 3.
In the inventive method, the inlet amount of the described aqueous solution containing organic amine and halogenated hydrocarbons of step (2) is 0.1 ~ 10 with catalyst volume ratio, is preferably 0.5 ~ 5; Haptoreaction condition is: reaction pressure is 0.2 ~ 10MPa, is preferably 0.5 ~ 5MPa; Reaction temperature is 150 ~ 220 DEG C, is preferably 170 ~ 200 DEG C; Time is 12 ~ 100 hours, is preferably 24 ~ 72 hours.
In the inventive method, 400 ~ 600 DEG C of temperature that oxygen-containing gas processes that what step (2) was described pass into, processing time is 4 ~ 12 hours, gas agent volume ratio (entering the volume of gas and the admission space of catalyst ratio) 100 ~ 1000, wherein said oxygen-containing gas is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and the volume fraction of oxygen in gas phase is 5% ~ 50%.
In the inventive method, the described inlet amount of the aqueous solution and the volume ratio of catalyst containing ammonium nitrate of step (3) is 0.1:1 ~ 10:1, is preferably 1:1 ~ 5:1, and wherein the mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%; Haptoreaction condition is: reaction pressure is 0.2 ~ 10MPa, is preferably 0.5 ~ 5MPa; Reaction temperature is the boiling temperature lower than water under this pressure, is preferably 20 ~ 100 DEG C; Time is 1 ~ 24 hour, is preferably 2 ~ 12 hours.
In the inventive method, 100 DEG C ~ 300 DEG C of temperature that nitrogen processes that what step (3) was described pass into, gas agent volume ratio (entering the volume of gas and the admission space of catalyst ratio) 100 ~ 1000, the time is 4 ~ 12 hours.
In the inventive method, in step (3) afterwards, in reactor, directly pass into reaction mass, carry out toluene and ethylene selectivity alkylated reaction.
The pretreated catalyst that the inventive method obtains is applied to toluene and ethylene selectivity alkylated reaction, and general process conditions are as follows: toluene/ethylene molar ratio 1:1 ~ 10:1, reaction temperature is 350 ~ 450 DEG C, volume space velocity 1 ~ 10h-1, reaction pressure is 0.8 ~ 3MPa. Wherein said toluene and ethylene selectivity alkylation process are that toluene and ethylene selectivity alkylation are generated to the technical process to methyl-ethyl benzene.
The inventive method is by Kaolinite Preparation of Catalyst precursor (being mainly amorphous silicon aluminium surface), catalyst precarsor contacts with the organic amine halogenated hydrocarbons aqueous solution, under certain temperature and pressure, crystallization, forms for the molecular sieve (MCM-22) that is applicable to toluene and the needed special duct of ethylene selectivity alkylated reaction on catalyst precarsor surface. Main feature of the present invention is to form desired molecule sieve on the surface of catalyst precarsor, not only avoid the generation of the unmanageable waste water of synthesis of molecular sieve process, and can improve the utilization rate of molecular sieve, the method catalyst surface molecular sieve after treatment is evenly distributed, improve the utilization rate of molecular sieve, be conducive to the diffusion of product, improve reaction selectivity and activity, can significantly reduce catalyst and become to produce cost simultaneously, avoid the generation of the unmanageable waste water of traditional synthesis of molecular sieve process, be conducive to environmental protection.
Detailed description of the invention
Below by embodiment, technology of the present invention is described further, is limited to this scope but should not be construed as.
The key data relating in the present embodiment has the conversion ratio of ethene and selective to methyl-ethyl benzene, and concrete computational methods are as follows:
Conversion of ethylene=[enter the weight of weight-reactor outlet ethene of reactor ethene)/enter the weight of reactor ethene] × 100%
To methyl-ethyl benzene selective=(weight of the weight/reactor outlet methyl-ethyl benzene of reactor outlet to methyl-ethyl benzene) × 100%
Embodiment 1
(1) 600 grams of white carbons, 33 grams of (butt 76%) aluminium hydroxide (SB that German Condean company produces) and 20 grams of sesbania powder are fully mixed, then adding 380ml concentration is the sodium hydroxide solution of 0.1M, fully kneading, make it to become paste plastic, on banded extruder, extrude the cylindrical bars that diameter is 1.5mm, cylindrical bars at 100 DEG C dry 16 hours, then 550 DEG C of roastings 4 hours in air atmosphere, obtain catalyst precarsor A. SiO in this catalyst precarsor2And Al2O3Mol ratio be 41. Get 100ml catalyst, in pilot-plant reactor, carry out catalytically active assessment with being packed into after 100ml quartz sand dilution.
(2) be 2MPa at pressure, 180 DEG C of temperature, CH in treatment fluid3CHCl2Concentration is 0.2Mol/L, triethanolamine and CH3CHCl2Mol ratio is 2, feed volume air speed (volume of charging per hour and the ratio of catalyst) 2.0h-1, 36 hours processing times. Then stop into treatment fluid, pass into air with the speed of gas agent volume ratio (entering the volume of gas and the admission space of catalyst ratio) 800, improve temperature to 550 DEG C, the retention time is after 6 hours, to start nature cooling, obtains catalyst precarsor B.
(3) in the time that temperature is reduced to 60 DEG C, under normal pressure, start to pass into the aqueous solution containing ammonium nitrate in beds, feed volume air speed is 2.0h-1, keep stopping into water after 4 hours, pass into nitrogen with the speed of gas agent volume ratio (entering the volume of gas and the admission space of catalyst ratio) 500, improve temperature to 200 DEG C, the retention time is within 4 hours, to stop passing into nitrogen, obtains catalyst A 1.
(4) at pressure 2MPa, under the condition that temperature is 400 DEG C, taking volume space velocity as 6.0h-1Enter raw material (toluene/ethylene molar ratio 4), carry out evaluating catalyst, negate answers the product of 4 hours to analyze, and the reaction result in the selective alkylation of toluene and ethene is in table 1.
Embodiment 2
With embodiment 1, difference is CH in step (2) treatment fluid3CHCl2Concentration is 0.6, and aniline replaces triethanolamine, and volume space velocity is 4.0h-1, in 28 hours processing times, air-treatment temperature is 580 DEG C, the time is 4 hours. Evaluation result is in table 1.
Embodiment 3
With embodiment 1, difference is CH in step (2) treatment fluid3I replaces CH3CHCl2, triethanolamine and CH3The mol ratio of I is 3. Evaluation result is in table 1.
Embodiment 4
With embodiment 1, difference is in step (3) that containing the feed volume air speed of the aqueous solution of ammonium nitrate be 1.0h-1, flooding time 8 hours, temperature is 25 DEG C, nitrogen gas agent volume ratio is 300,260 DEG C of temperature, hour. Evaluation result is in table 1.
Embodiment 5
With embodiment 1, difference is in step (3) that containing the feed volume air speed of the aqueous solution of ammonium nitrate be 1.0h-1, flooding time 6 hours, temperature is 60 DEG C, nitrogen gas agent volume ratio is 500,200 DEG C of temperature, hour. Evaluation result is in table 1.
Comparative example 1
600 grams of white carbons, 33 grams of (butt 76%) aluminium hydroxide (SB that German Condean company produces) and 20 grams of sesbania powder are fully mixed, then adding 380ml concentration is the sodium hydroxide solution of 0.1M, fully kneading, make it to become paste plastic, on banded extruder, extrude the cylindrical bars that diameter is 1.5mm, cylindrical bars is dried 16 hours at 100 DEG C, and then in air atmosphere, 550 DEG C of roastings obtain catalyst precarsor, SiO in this catalyst precarsor for 4 hours2And Al2O3Mol ratio be 41. Appreciation condition is with embodiment 1, and evaluation result is in table 1.
Comparative example 2
100 grams of (butt 76%) aluminium hydroxides (SB that German Condean company produces), 24 grams of MCM-22 molecular sieves (Chinese patent CN1328960A) and 6 grams of sesbania powder are fully mixed, then adding 70ml concentration is the salpeter solution of 0.2M, fully kneading, make it to become paste plastic, on banded extruder, extrude the cylindrical bars that diameter is 1.5mm, cylindrical bars is dried 16 hours at 100 DEG C, then in air atmosphere, 550 DEG C of roastings obtain catalyst for 4 hours, appreciation condition is with embodiment 1, and evaluation result is in table 1.
The evaluation result of table 1 different catalysts.
From the results shown in Table 1, catalyst of the present invention is in the alkylated reaction of toluene and ethene, and generation selectively all reaches more than 93% methyl-ethyl benzene, apparently higher than the result of comparative example (67.0%).
Claims (13)
1. an in-situ pretreatment method for toluene and ethylene selectivity alkylation catalyst, is characterized in that comprising with following content: (1) is loaded into catalyst precarsor A in reactor; (2) pass into the aqueous solution containing organic amine and halogenated hydrocarbons, with catalyst precarsor A haptoreaction, and then pass into oxygen-containing gas and process, obtain catalyst precarsor B; (3) pass into aqueous ammonium nitrate solution and catalyst precarsor B haptoreaction, then pass into nitrogen and process, obtain catalyst A 1; Wherein the described catalyst precarsor A of step (1) is amorphous silicon alumina supporter; The described organic amine of step (2) is one or more in alcamines or arylamine class.
2. it is characterized in that in accordance with the method for claim 1: the SiO of the catalyst precarsor A described in step (1)2And Al2O3Mol ratio be 5 ~ 200.
3. it is characterized in that in accordance with the method for claim 1: the described organic amine of step (2) is triethanolamine and aniline.
4. in accordance with the method for claim 1, it is characterized in that: the described halogenated hydrocarbons of step (2) is the halogenated alkane containing 1 ~ 3 carbon atom, and the concentration of halogenated hydrocarbons in the aqueous solution is 0.01 ~ 2mol/L.
5. according to the method described in claim 1 or 4, it is characterized in that: the described halogenated hydrocarbons of step (2) is CH3I、CH3CHCl2Or CHCl3In one or more.
6. it is characterized in that in accordance with the method for claim 1: the organic amine that step (2) is described and the mol ratio of halogenated hydrocarbons are 0.5 ~ 5.
7. it is characterized in that in accordance with the method for claim 1: the inlet amount of the aqueous solution containing organic amine and halogenated hydrocarbons described in step (2) is 0.1 ~ 10 with catalyst volume ratio.
8. in accordance with the method for claim 1, it is characterized in that: the described haptoreaction condition of step (2) is: reaction pressure is 0.2 ~ 10MPa, and reaction temperature is 150 ~ 220 DEG C, and the time is 12 ~ 100 hours.
9. in accordance with the method for claim 1, it is characterized in that: 400 ~ 600 DEG C of temperature that oxygen-containing gas processes that what step (2) was described pass into, the processing time is 4 ~ 12 hours, enters the volume of gas and the admission space of catalyst ratio is 100 ~ 1000; Wherein said oxygen-containing gas is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and the volume fraction of oxygen in gas phase is 5% ~ 50%.
10. in accordance with the method for claim 1, it is characterized in that: the described inlet amount of the aqueous solution and the volume ratio of catalyst containing ammonium nitrate of step (3) is 0.1:1 ~ 10:1, and wherein the mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%; Haptoreaction condition is: reaction pressure is 0.2 ~ 10MPa, and reaction temperature is 20 ~ 100 DEG C, and the reaction time is 1 ~ 24 hour.
11. in accordance with the method for claim 1, it is characterized in that: 100 ~ 300 DEG C of temperature that nitrogen processes that what step (3) was described pass into, enter the volume of gas and the admission space of catalyst than 100 ~ 1000, and the time is 4 ~ 12 hours.
12. in accordance with the method for claim 1, it is characterized in that: in step (3) afterwards, in reactor, directly pass into reaction mass, carry out toluene and ethylene selectivity alkylated reaction.
The 13. pretreated catalyst that obtain are in accordance with the method for claim 1 applied to toluene and ethylene selectivity alkylated reaction, and process conditions are as follows: toluene/ethylene molar ratio 1:1 ~ 10:1, reaction temperature is 350 ~ 450 DEG C, volume space velocity 1 ~ 10h-1, reaction pressure is 0.8 ~ 3MPa.
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