CN105582982B - A kind of in-situ pretreatment method of toluene and ethylene selectivity alkylation catalyst - Google Patents
A kind of in-situ pretreatment method of toluene and ethylene selectivity alkylation catalyst Download PDFInfo
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Abstract
The invention discloses the in-situ pretreatment methods of a kind of toluene and ethylene selectivity alkylation catalyst, including following content：（1）Amorphous silicon alumina supporter is loaded into reactor；（2）It is passed through the aqueous solution containing organic compound, with amorphous silicon alumina supporter haptoreaction, oxygen-containing gas is then passed through again and is handled；（3）It is passed through aqueous ammonium nitrate solution and catalyst precarsor haptoreaction, nitrogen is then passed to and is handled；The method of the present invention treated photocatalyst surface element sieve is evenly distributed, it improves the utilization rate of molecular sieve, have the characteristics that catalytic activity height and to methyl-ethyl benzene high selectivity, catalyst is considerably reduced simultaneously into production cost, the generation for avoiding the intractable waste water of conventional synthesis molecular sieve process, is good for the environment.
Description
Technical field
The present invention relates to the in-situ pretreatment method of a kind of toluene and ethylene selectivity alkylation catalyst, the method for the present invention
It is combined to for toluene and ethylene selectivity alkyl in methyl-ethyl benzene reaction process, compared with prior art, there is catalysis to live
Property it is high and the features such as to methyl-ethyl benzene high selectivity.
Background technology
To methyl-ethyl benzene（PET）It is the raw materials for production of novel high polymer synthon p-methylstyrene.Novel high polymer
The poly- p-methylstyrene of material-is the external high performance plastics kind developed in recent years, the similar polyphenyl of the various performances of the polymer
Ethylene keeps good molding processibility, and is superior to now in proportion, heat resistance, anti-flammability, transparency and shrinking percentage etc.
Some polystyrene plastics（Tensile strength 48MPa, elasticity modulus 2210MPa, Izod notched impact strength 16J/m, thermal deformation
95 DEG C of temperature）.In addition p-methylstyrene can be copolymerized with other monomers（Such as styrene）, the heat resistance of certain polymer can be improved
And anti-flammability, it can be largely used to engineering plastics, the manufacture of phthalic resin coating etc., thus it is in widespread attention.
Currently, due to being much higher than styrene to methyl-ethyl benzene monomer manufacturing cost, it is poly- to methylbenzene second to limit
Alkene is widely used, and is currently used primarily in and makees electrical accessorie and packaging instead of polystyrene, be used in combination needing heatproof high field to share
In illuminating equipment etc..Usual first benzene alkylation with ethylene generates in product containing a certain amount of to methyl-ethyl benzene, and by-product is a small amount of
Benzene and mixed xylenes, wherein most toluene do not convert（Most of toluene recovery cycle）It uses；It is obtained by rectifying pure
Degree 90% or so to methyl-ethyl benzene.98% or more is purified to methyl-ethyl benzene through further adsorbing separation or freezing and crystallizing.To first
Contain 50% or so p-methylstyrene in the product that base ethylbenzene is generated through dehydrogenation, then the poly- of 99 % or more of purity is obtained by rectifying
Close monomer p-methylstyrene.The method similar with styrene polymerization or process for suspension polymerization production polymethylstyrene can be used
Or the comonomer as styrene etc. uses.
The thermodynamical equilibrium of traditional Friede-Crafts catalyst, three isomers containing methyl-ethyl benzene that can only be made is mixed
Object is closed, such as the AlCl3 series catalysts of DOW companies of the U.S., react the referred to as production of vinyltoluene made with pure ethylene by toluene
Product（Containing PET about 38%, remaining is meta position methyl-ethyl benzene）.USP4117024 uses chemical modification high silica ZSM-5 type zeolite for catalysis
Agent, when toluene is reacted with pure ethylene, the content of PET, reaches 90% or more in obtained reaction product methyl-ethyl benzene isomers, with
And the generation of ortho methyl group ethylbenzene is made to be significantly inhibited, content can level off to zero.CN1047986A, which is used, contains antimony（Or phosphorus）
And the Pentasil type Si-Al zeolite catalyst of magnesium elements chemical modification processing, although this zeolite catalyst can be directly with containing
There is the refinery tail-gas of the impurity such as hydrogen sulfide, water（Containing ethylene 10% ~ 20%）Make raw material and react to produce with toluene predominantly to align first
The process of base ethylbenzene, using antimony（Or phosphorus）And magnesium elements modification can play the role of molecular sieve surface acidity neutralization and modulation,
Reduce molecular sieve surface strong acid center after antimony, P Modification, weak acid center relative increase advantageously forms para-isomer.Separately
Outside, phosphorus can also be such that the effective dimensions in duct infall or aperture reduces.But this processing method can be substantially reduced catalyst
Activity, even if reaction carry out at very high temperatures, conversion ratio is still relatively low, moreover, P elements are easier at reaction conditions
One deficiency of loss and the technology.So the conversion of ethylene of the catalyst and to methyl-ethyl benzene selectivity it is all relatively low.
MCM-22 molecular sieves are there are two types of independent polynary ring channel systems, one is two-dimentional sinusoidal waveform, the ten of intersection
Membered ring channel, section are ellipse（0.45nm*0.51nm）；Another kind is the large cylindrical type supercage that section is twelve-ring,
Supercage free internal space is 0.71nm*0.71nm*1.82nm, the window of these supercages and ten-ring（0.45*0.45nm）Phase
Even half twelve-ring supercage（0.71*0.71*0.91nm）The mouth for having and teaching big adsorption capacity is formed in [001] crystal outer surface
Bag, two supercages are connected by hexagonal prismoid.Since MCM-22 zeolite crystals are thin slab construction, it possesses larger
Outer surface MCM-22, therefore all there is excellent catalytic performance to reactions such as alkylation, aromatisation, toluene disproportionations.And about
The synthetic method of MCM-22 molecular sieves mostly uses greatly hydrothermal crystallization method, and typically under alkaline environment, organic amine is led for structure
To agent, crystallization certain time at a certain temperature.It will produce in this building-up process largely containing works such as organic amine and alkali
Industry waste water not only greatly improves molecular sieve production cost it is difficult to carry out harmless treatment, but also causes serious environment dirty
Dye, makes its use greatly be limited.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of original position of toluene and ethylene selectivity alkylation catalyst
Preprocess method, this method treated photocatalyst surface element sieve are evenly distributed, improve the utilization rate of molecular sieve, be conducive to produce
The diffusion of object not only has the characteristics that catalytic activity is high and to methyl-ethyl benzene high selectivity, while substantially compared with prior art
Degree reduces catalyst into production cost, avoids the generation of the intractable waste water of conventional synthesis molecular sieve process, is conducive to ring
It protects.
The in-situ pretreatment method of the toluene and ethylene selectivity alkylation catalyst of the present invention, including with following content：
（1）By catalyst precarsor A（Amorphous silicon alumina supporter）It is loaded into reactor；（2）It is passed through water-soluble containing organic amine and halogenated hydrocarbons
Then liquid is passed through oxygen-containing gas and is handled, obtain catalyst precarsor B again with catalyst precarsor A haptoreactions；（3）It is passed through nitre
Sour aqueous ammonium and catalyst precarsor B haptoreactions, then pass to nitrogen and are handled, obtain catalyst A1；Wherein step（2）
The organic amine is one or more of alcamines or arylamine class.
In the method for the present invention, step（1）The catalyst precarsor A has following property：The amorphous silicon aluminium
SiO2And Al2O3Molar ratio be 5 ~ 200, preferably 10 ~ 100, more preferably 20 ~ 50.
In the method for the present invention, step（1）The preparation method of the catalyst precarsor A can according to prior art preparation, one
As process it is as follows：Aluminum hydroxide solid elastomer powder, white carbon, sesbania powder are sufficiently mixed, peptizing agent is then added（Sodium hydroxide is molten
Liquid）, kneading is plastic paste, and extruded moulding obtains catalyst precarsor A through drying, calcination process.Specific preparation condition
It can be determined according to this field Conventional wisdom.
In the method for the present invention, step（2）The one kind of the alcamines in monoethanolamine, diethanol amine and triethanolamine
Or it is several, arylamine class is selected from one or more of aniline, benzidine and phenylenediamine.Preferably triethanolamine and aniline；It is described
Halogenated hydrocarbons is the halogenated alkane containing 1 ~ 3 carbon atom, preferably CH3I、CH3CHCl2Or CHCl3One or more of, halogenated hydrocarbons
A concentration of 0.01 ~ 2 mol/L, preferably 0.1 ~ 1mol/L in aqueous solution.
In the method for the present invention, step（2）The molar ratio of the organic amine and halogenated hydrocarbons is 0.5 ~ 5, preferably 1 ~ 3.
In the method for the present invention, step（2）The inlet amount and caltalyst of the aqueous solution containing organic amine and halogenated hydrocarbons
Product is than being 0.1 ~ 10, preferably 0.5 ~ 5；Haptoreaction condition is：Reaction pressure is 0.2 ~ 10MPa, preferably 0.5 ~ 5MPa；Instead
It is 150 ~ 220 DEG C, preferably 170 ~ 200 DEG C to answer temperature；Time is 12 ~ 100 hours, preferably 24 ~ 72 hours.
In the method for the present invention, step（2）It is described to be passed through 400 ~ 600 DEG C of the temperature that oxygen-containing gas is handled, when processing
Between be 4 ~ 12 hours, gas agent volume ratio（Into the volume of gas and the admission space ratio of catalyst）100 ~ 1000, wherein described
Oxygen-containing gas be air, the mixture of oxygen and nitrogen or the mixture of oxygen and inert gas in one kind, oxygen is in gas
Volume fraction in phase is 5% ~ 50%.
In the method for the present invention, step（3）The inlet amount of the aqueous solution containing ammonium nitrate and the volume ratio of catalyst are
0.1:1~10:1, preferably 1:1~5:1, the wherein mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%；Haptoreaction item
Part is：Reaction pressure is 0.2 ~ 10MPa, preferably 0.5 ~ 5MPa；Reaction temperature is the boiling temperature less than water at this pressure,
Preferably 20 ~ 100 DEG C；Time is 1 ~ 24 hour, preferably 2 ~ 12 hours.
In the method for the present invention, step（3）Described is passed through 100 DEG C ~ 300 DEG C of the temperature that nitrogen is handled, gas agent volume
Than（Into the volume of gas and the admission space ratio of catalyst）100 ~ 1000, the time is 4 ~ 12 hours.
In step in the method for the present invention（3）Later, it is passed directly into reaction mass into reactor, carries out toluene and is selected with ethylene
Selecting property alkylated reaction.
The pretreated catalyst that the method for the present invention obtains is applied to toluene and ethylene selectivity alkylated reaction, general
Process conditions are as follows：Toluene/ethylene molar ratio 1:1~10:1, reaction temperature is 350 ~ 450 DEG C, 1 ~ 10h of volume space velocity-1, reaction
Pressure is 0.8 ~ 3MPa.Wherein the toluene is to be alkylated toluene and ethylene selectivity with ethylene selectivity alkylation process
Generate the technical process to methyl-ethyl benzene.
The method of the present invention is by preparing catalyst precarsor（Mainly amorphous silicon aluminium surface）, catalyst precarsor and organic amine
Halogenated hydrocarbons aqueous solution contact, under certain temperature and pressure, crystallization, catalyst precursor surface formed for be suitble to toluene with
The molecular sieve in the required special duct of ethylene selectivity alkylated reaction（MCM-22）.The present invention's is mainly characterized by being catalyzed
The surface of agent precursor forms required molecular sieve, not only avoids the generation of the intractable waste water of synthesis of molecular sieve process, Er Qieke
To improve the utilization rate of molecular sieve, treated that photocatalyst surface element sieve is evenly distributed for this method, improves the utilization of molecular sieve
Rate is conducive to the diffusion of product, improves reaction selectivity and activity, while can considerably reduce catalyst into production cost, keeps away
The generation for having exempted from the intractable waste water of conventional synthesis molecular sieve process, is good for the environment.
Specific implementation mode
The technology of the present invention is described further below by embodiment, but should not be construed as being limited to this range.
Key data involved in the present embodiment has the conversion ratio of ethylene and the selectivity to methyl-ethyl benzene, specific to calculate
Method is as follows：
Conversion of ethylene=[into the weight of weight-reactor outlet ethylene of reactor ethylene）/ into the weight of reactor ethylene
Amount] × 100%
Selective to methyl-ethyl benzene=（Weight of the reactor outlet to weight/reactor outlet methyl-ethyl benzene of methyl-ethyl benzene
Amount）×100%
Embodiment 1
（1）By 600 grams of white carbons, 33 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）With 20 grams
Sesbania powder is sufficiently mixed, and the sodium hydroxide solution of a concentration of 0.1M of 380ml is then added, and abundant kneading makes cream
Shape plastic squeezes out the cylindrical bars of a diameter of 1.5mm on banded extruder, and cylindrical bars are 16 hours dry at 100 DEG C, then in sky
It is roasted 4 hours for 550 DEG C in gas atmosphere, obtains catalyst precarsor A.SiO in the catalyst precarsor2And Al2O3Molar ratio be 41.
100ml catalyst is taken, is packed into pilot-plant reactor after being diluted with 100ml quartz sands and carries out catalytically active assessment.
（2）It is 2MPa, 180 DEG C of temperature, CH in treatment fluid in pressure3CHCl2A concentration of 0.2 Mol/L, triethanolamine with
CH3CHCl2Molar ratio is 2, feed volume air speed（The ratio of the volume and catalyst that feed per hour）2.0h-1, processing time
36 hours.Then stop into treatment fluid, with gas agent volume ratio（Into the volume of gas and the admission space ratio of catalyst）800
Speed is passed through air, improves temperature to 550 DEG C, the retention time is to start Temperature fall after 6 hours, obtains catalyst precarsor B.
（3）When temperature is reduced to 60 DEG C, start to be passed through the aqueous solution containing ammonium nitrate into catalyst bed under normal pressure, into
Material volume space velocity is 2.0h-1, stop water inlet after being kept for 4 hours, with gas agent volume ratio（Into the volume of gas and the dress of catalyst
Fill out volume ratio）500 speed is passed through nitrogen, improves temperature to 200 DEG C, the retention time is to stop within 4 hours being passed through nitrogen, is urged
Agent A1.
（4）It is 6.0h with volume space velocity under conditions of pressure 2MPa, 400 DEG C of temperature-1Into raw material（First benzene ethylene
Molar ratio 4）, evaluating catalyst is carried out, negates and 4 hours products is answered to be analyzed, in the selective alkylation of toluene and ethylene
Reaction result be shown in Table 1.
Embodiment 2
With embodiment 1, the difference is that step（2）CH in treatment fluid3CHCl2A concentration of 0.6, aniline replaces three ethyl alcohol
Amine, volume space velocity are 4.0 h-1, 28 hours processing times, air-treatment temperature is 580 DEG C, and the time is 4 hours.Evaluation result is shown in
Table 1.
Embodiment 3
With embodiment 1, the difference is that step（2）CH in treatment fluid3I replaces CH3CHCl2, triethanolamine and CH3I's
Molar ratio is 3.Evaluation results are shown in Table 1.
Embodiment 4
With embodiment 1, the difference is that step（3）In the aqueous solution containing ammonium nitrate feed volume air speed be 1.0 h-1, flooding time 8 hours, temperature is 25 DEG C, and nitrogen gas agent volume ratio is 300,260 DEG C of temperature, hour.Evaluation results are shown in Table 1.
Embodiment 5
With embodiment 1, the difference is that step（3）In the aqueous solution containing ammonium nitrate feed volume air speed be 1.0 h-1, flooding time 6 hours, temperature is 60 DEG C, and nitrogen gas agent volume ratio is 500,200 DEG C of temperature, hour.Evaluation results are shown in Table 1.
Comparative example 1
By 600 grams of white carbons, 33 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）With 20 grams of fields
Cyanines powder is sufficiently mixed, and the sodium hydroxide solution of a concentration of 0.1M of 380ml is then added, and abundant kneading makes paste
Plastic squeezes out the cylindrical bars of a diameter of 1.5mm on banded extruder, and cylindrical bars are 16 hours dry at 100 DEG C, then in air
550 DEG C of roastings obtain catalyst precarsor in 4 hours in atmosphere, SiO in the catalyst precarsor2And Al2O3Molar ratio be 41.Evaluation
Condition is with embodiment 1, and evaluation results are shown in Table 1.
Comparative example 2
By 100 grams（Butt 76%）Aluminium hydroxide（The SB of German Condean companies production）, 24 grams of MCM-22 molecular sieves（In
State patent CN1328960A）It is sufficiently mixed with 6 grams of sesbania powders, the salpeter solution of a concentration of 0.2M of 70ml is then added, fills
Divide kneading, make paste plastic, the cylindrical bars of a diameter of 1.5mm are squeezed out on banded extruder, cylindrical bars are done at 100 DEG C
Dry 16 hours, then 550 DEG C of roastings obtained catalyst in 4 hours in air atmosphere, and evaluation condition is the same as embodiment 1, evaluation result
It is shown in Table 1.
The evaluation result of 1 different catalysts of table.
From the results shown in Table 1, catalyst of the present invention generates in the alkylated reaction of toluene and ethylene to methyl
The selectivity of ethylbenzene all reaches 93% or more, hence it is evident that is higher than comparative example（67.0%）Result.
Claims (10)
1. the in-situ pretreatment method of a kind of toluene and ethylene selectivity alkylation catalyst, it is characterised in that including with following interior
Hold：（1）Catalyst precarsor A is loaded into reactor；（2）It is passed through the aqueous solution containing organic amine and halogenated hydrocarbons, before catalyst
Then body A haptoreactions are passed through oxygen-containing gas and are handled, obtain catalyst precarsor B again；（3）Be passed through aqueous ammonium nitrate solution with
Catalyst precarsor B haptoreactions, then pass to nitrogen and are handled, and obtain catalyst A1；Wherein step（1）The catalyst
Precursor A is amorphous silicon alumina supporter；Step（2）The organic amine is one or more of alcamines or arylamine class；Step
（2）The halogenated hydrocarbons is the halogenated alkane containing 1 ~ 3 carbon atom, a concentration of 0.01 ~ 2mol/L of halogenated hydrocarbons in aqueous solution；Step
Suddenly（2）The inlet amount of the aqueous solution containing organic amine and halogenated hydrocarbons is 0.1 ~ 10 with catalyst volume ratio；Step（2）It is described
Haptoreaction condition be：Reaction pressure is 0.2 ~ 10MPa, and reaction temperature is 150 ~ 220 DEG C, and the time is 12 ~ 100 hours.
2. according to the method for claim 1, it is characterised in that：Step（1）The SiO of the catalyst precarsor A2And Al2O3
Molar ratio be 5 ~ 200.
3. according to the method for claim 1, it is characterised in that：Step（2）The organic amine is triethanolamine and aniline.
4. according to the method for claim 1, it is characterised in that：Step（2）The halogenated hydrocarbons is CH3I、CH3CHCl2Or
CHCl3One or more of.
5. according to the method for claim 1, it is characterised in that：Step（2）The molar ratio of the organic amine and halogenated hydrocarbons
It is 0.5 ~ 5.
6. according to the method for claim 1, it is characterised in that：Step（2）Described is passed through what oxygen-containing gas was handled
400 ~ 600 DEG C of temperature, processing time be 4 ~ 12 hours, into gas volume and catalyst admission space ratio be 100 ~
1000；Wherein the oxygen-containing gas is in air, the mixture of oxygen and nitrogen or the mixture of oxygen and inert gas
One kind, the volume fraction of oxygen in the gas phase are 5% ~ 50%.
7. according to the method for claim 1, it is characterised in that：Step（3）The inlet amount of the aqueous solution containing ammonium nitrate
Volume ratio with catalyst is 0.1:1~10:1, the wherein mass percent concentration of aqueous ammonium nitrate solution is 16% ~ 50%；Contact is anti-
The condition is answered to be：Reaction pressure is 0.2 ~ 10MPa, and reaction temperature is 20 ~ 100 DEG C, and the reaction time is 1 ~ 24 hour.
8. according to the method for claim 1, it is characterised in that：Step（3）The temperature for being passed through nitrogen and being handled
100 ~ 300 DEG C, into the volume of gas and the admission space of catalyst than 100 ~ 1000, the time is 4 ~ 12 hours.
9. according to the method for claim 1, it is characterised in that：In step（3）Later, reaction is passed directly into reactor
Material carries out toluene and ethylene selectivity alkylated reaction.
10. the pretreated catalyst obtained according to the method for claim 1 is applied to toluene and ethylene selectivity alkyl
Change reaction, 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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| US7663011B2 (en) * | 1999-09-07 | 2010-02-16 | Lummus Technology Inc. | Mesoporous material with active metals |
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| CN101134171A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Method of producing C8 arene isomerization catalyst |
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