CN101485993A - Novel nano molecular sieve catalyst for benzene alkylation as well as preparation method and application - Google Patents
Novel nano molecular sieve catalyst for benzene alkylation as well as preparation method and application Download PDFInfo
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- CN101485993A CN101485993A CNA2008100328148A CN200810032814A CN101485993A CN 101485993 A CN101485993 A CN 101485993A CN A2008100328148 A CNA2008100328148 A CN A2008100328148A CN 200810032814 A CN200810032814 A CN 200810032814A CN 101485993 A CN101485993 A CN 101485993A
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Abstract
The invention discloses a modified nanometer molecular sieve catalyst for preparing ethyl benzene from benzene alkylation. The catalyst has proper nanometer aperture and nanometer grain size, wherein the aperture and grain size of the molecular sieve are between 0.1 and 100nm, and the mol ratio of SiO2 to Al2O3 of the zeolite molecular sieve is 30-500; and the molecular sieve is loaded with 0 to 10 percent (weight) of alkaline earth oxides and 0 to 10 percent(weight)of rare earth oxides. Sodium silicate, sodium aluminate, sodium hydroxide and water are stirred to form an even gel and further form the catalyst with proper nanometer aperture and nanometer grain size, and high conversion rate of the catalytic reaction is achieved; simultaneously, the alkaline earth oxides and the rare earth oxides are modified so as to adjust the distribution of acid strength in the catalyst and further reduce the deactivation rate of the zeolite catalyst and improve the selectivity of the catalyst. In the application of the benzene alkylation, tests show that the selectivity of the ethyl benzene is more than 99 percent, the conversion rate of the ethylene is 99 percent, the content of the xylene in the finished product of ethyl benzene is less than 100ppm, and the catalyst has the advantages of high reaction activity, good selectivity and good stability, and can be used for industrial production.
Description
Technical field
The present invention relates to a kind of modified nano molecular sieve catalyst and preparation method and application, particularly relate to modified nano molecular sieve catalyst, its preparation method and the application in benzene alkylation thereof of a kind of benzene alkylation to prepare ethylbenzene under the ethene existence condition.
Background technology
Ethylbenzene is a kind of important Organic Chemicals, of many uses, be to produce cinnamic raw material, the polystyrene and various copolymer A BS, the AS that produce by styrene, can also be used to produce ion exchange resin, unsaturated polyester resin and agricultural emulsifier, coating etc. are with a wide range of applications in fields such as automobile, household electrical appliances, light industrys, styrene occupies the 3rd of world's polyolefin monomer output, development in recent years is comparatively rapid, and market has driven the sustainable growth of ethylbenzene output to cinnamic thriving demand.Therefore, open up the new source of all raw materials in the ethylbenzene production, the new and more cheap approach of seeking ethylbenzene production has great importance.
Cinnamic material ethylbenzene mainly was to use AlCl by ethene and benzene alkylation explained hereafter gained in the past
3The liquid-phase catalysis reaction method is produced.AlCl
3Method and homogeneous phase AlCl
3The method exploitation is early used many ethylbenzene-AlCl
3Complex compound be the main technique of producing ethylbenzene in the past the eighties in 20th century, but they exists corrosive medium strong as catalyst, and are very strict to ingredient requirement, and catalyst amount is big, and problems such as height are all compared in energy consumption, material consumption.Produce the technology appearance of ethylbenzene since molecular sieve catalytic after, they are eliminated just gradually.
Mobil-Badger invention in 1978 has been used since the molecular sieve catalyst gas-phase reaction method, and benzene alkylation technology develops rapidly.Since the nineties in 20th century, the production of ethylbenzene begins from traditional AlCl
3For the Friedel-Crafts benzene-alkylation technology of catalyst changes to molecular sieve catalytic technology.Molecular sieve has very strong application in a lot of fields, as dehydration, and deoxidation etc., and in Catalyst Production, also be the most basic a kind of type, as ZSM-5, ZSM-11 etc., molecular sieve can be produced polytype catalyst through after the modification.
In order to adapt to the requirement of fixed bed, improve the stability of ZSM-5 aromatisation, people improve catalyst from the following aspects.
In order to reduce the carbon deposit of catalyst, patent CN200510136597.3 discloses a kind of modified molecular sieve catalyst that is used for the alkene aromatization, is made up of molecular sieve and bonding agent, and wherein bonding agent accounts for the 20-80% of catalyst weight, on fixed bed reactors, 350 ℃, 0.5MPa, 2h
-1Contact catalyst under the weight space velocity condition, olefin conversion are 99%.
Patent CN1058284C then discloses the rare earth modified HZSM-5 alkene aromatized catalyst of a kind of usefulness, catalyst is carried out high-temperature water vapor handle, and at 520-550 ℃, weight space velocity is 0.6-1.5h
-1Condition under, aromatics yield is 300-450 hour greater than 40% one way life-span.
Disclosing a kind of among the CN1051166A is raw material with the plant catalytic cracking dry gas that contains low-concentration ethane, does not need refining in advance and directly reacts the technology of producing ethylbenzene with benzene.Used rare ethylene raw only need not contain free water, H
2S content＜6000mg/m
3Its reaction condition is: 300～450 ℃, 0.4～2.5MPa, weight ethylene air speed 0.4～2.5 hour
-1, benzene and ethylene molar ratio be 3～12.Used catalyst is the disclosed a kind of Pentasil type Si-Al zeolite catalyst of CN1031072A, is to be that 40～100 Pentasil type zeolite is the primary activity component with 30～70% silica alumina ratio, is aided with 70～30% Al
2O
3Carrier constitutes, and wherein contains the La of 0.3～6% mishmetal or 0.2～3% and 0.05～0.2% S.This zeolite catalyst is seated in the multistage reactor bed, and rare ethylene raw segmentation injecting reactor is with the control reaction temperature rising.Alkylation reaction and dealkylation reaction carry out in same reactor in the flow process.This process can make conversion of ethylene reach more than 95%, and ethene generates the selectivity of ethylbenzene more than 99%.
Summary of the invention
The object of the present invention is to provide the new modified nano molecular sieve catalyst of a kind of benzene alkylation.
Another object of the present invention provides a kind of above-mentioned Preparation of catalysts method.
Another purpose of the present invention is that above-mentioned catalyst is used in preparation ethylbenzene.
For realizing the object of the invention, nano molecular sieve catalyst provided by the invention is a kind of catalyst for reaction that is used for fixing of high stability, the even gel that under agitation forms by sodium metasilicate, sodium aluminate, NaOH and water, formation has the catalyst of suitable nano aperture and nano particle size, obtains the catalytic reaction high conversion; Simultaneously, can adjust the distribution of the acid strength of catalyst, thereby can reduce the deactivation rate of zeolite catalyst and improve selection of catalysts by alkaline earth oxide and rare-earth oxide modification.
Zeolite molecular sieve catalyst provided by the invention has suitable nano aperture and nano particle size, wherein the aperture of zeolite molecular sieve and granularity between 0.1-100nm, SiO
2/ Al
2O
3Mol ratio is 30-500; Support the alkaline earth oxide of 0-10% (weight) and the rare-earth oxide of 0-10% (weight) on the molecular sieve.
Described molecular sieve catalyst, molecular sieve are one or more in ZSM-5, ZSM-11, the ZSM-22 molecular sieve.
Described molecular sieve catalyst, SiO
2/ Al
2O
3The mol ratio preferable range is 40-200.
Described alkaline earth oxide is beryllium oxide, magnesia, calcium oxide or barium monoxide, preferred magnesia.
Described rare-earth oxide is a kind of or its mixture in lanthana, samarium oxide and the cerium oxide, preferred lanthana.
The preparation method of nano molecular sieve catalyst provided by the invention comprises the following steps:
(1) will be according to the Al that contains of certain raw material proportioning
2O
31.0-1.3mol/L sodium aluminate solution, aqueous slkali, organic amine solution and water add and mix in the glue still, under agitation solution in the still is preheating to about 28-32 ℃, add a certain amount of SiO of containing again
2Concentration is that the waterglass of 2.5-3.0mol/L drops in the still apace, continues to stir, and makes into even gel;
(2) step (1) gained reactant mixture is added in the synthesis reaction vessel, under agitation heat to 170-190 ℃, stop then stirring, and keep this temperature, make it crystallization under static state;
(3) partial mother liquid of the still middle and upper part after step (2) crystallization is introduced in the mother liquor container, the product of bottom is put into storage tank, further reclaims mother liquor after the sedimentation; Spending deionised water is 9-10 to pH, and centrifugal filtration is 110 ℃ of dryings also, obtains having the zeolite of suitable nano particle size and nano aperture;
(4) with step (3) gained zeolite and Al
2O
3Proportionally roasting behind the 65/35 mixing extruded moulding;
(5) step (4) gained zeolite is carried out ion-exchange at the finite concentration ammonium salt solution, more than dry 12h under 100-120 ℃, 530-580 ℃ of roasting 4-6h gets Hydrogen nano molecular sieve zeolite catalyst then;
(6) step (5) gained nano molecular sieve catalyst is joined respectively in the solution that contains rare-earth salts, the alkaline-earth metal salt solution, at 60-100 ℃, the pH value is 3-6, carries out ion-exchange treatment 0.5-2h; Filter, washing, dry, obtain modified nano molecular sieve catalyst.
Described preparation method, whether also available microscopic examination crystallization is complete.
Described preparation method, described aqueous slkali is NaOH, KOH or NH
3H
2O, concentration is 0.05-0.3mol/L.
Described preparation method, the preferred 70-90 of temperature in the step (6) ℃; The preferred 4-5 of pH value; Preferred 1-1.5 of ion-exchange treatment time hour.
It is the preparation of the ethylbenzene of raw material that molecular sieve catalyst of the present invention is used for benzene and ethene, and reaction condition is temperature 320-450 ℃, pressure 0.5-2.0Mpa, weight ethylene air speed 0.5-2.0h
-1, benzene and ethylene molecule are than being 3-12.
Employed benzene feedstock is industrial purified petroleum benzin, also can be benzene and ethene and benzene-alkylation mixture of products, and reacting used unstripped gas is the plant catalytic cracking dry gas that contains low-concentration ethane.Catalysis drying gas contains ethene 10-60%, contains H
2S100-5000ppm contains CO
x1.0-5.0v% contains oxygen 0.1-1.5v%, and moisture is 1000-4000ppm.
Compare with prior art, catalyst characteristics provided by the invention are to have suitable nano aperture and nano particle size, have more high catalytic activity and catalytic efficiency than other catalyst; In catalysis drying gas and the reaction of benzene system ethylo benzene, use, experimental result shows the selectivity of ethylbenzene greater than 99%, and the conversion ratio of ethene is 99%, and xylene content is less than 100ppm in the finished product ethylbenzene, have the reactivity height, selectivity is excellent and the advantage of good stability, can be used in the industrial production.
Specific implementation method
Below further describe the present invention with embodiment because these embodiment represent an example of the present invention, the present invention is not limited among these embodiment.
[embodiment 1]
To contain Al
2O
31.0mol/L sodium aluminate solution 50ml, contain Na
2O 3mol/L sodium hydroxide solution 150ml and water 300ml add in the mixed glue still, under agitation solution in the still are preheating to about 30 ℃, will contain SiO again
22.5mol/L waterglass 600ml drops in the still apace, continues to stir about 30min, makes into even gel.
After crystallization begins, need 5h left and right sides crystallization complete approximately, product is sunken to the reactor bottom, adds water in storage tank, and stirs, and filter, and to wash filtrate pH value is 9-10.110 ℃ of dryings, obtain silica alumina ratio and be 30 ZSM-5 type zeolite.
[embodiment 2]
To contain Al
2O
31.0mol/L sodium aluminate solution 15ml, contain Na
2O 3mol/L sodium hydroxide solution 150ml and water 300ml add in the mixed glue still, under agitation solution in the still are preheating to about 30 ℃, will contain SiO again
22.5mol/L waterglass 900ml drops in the still apace, continues to stir about 30min, makes into even gel.
After crystallization begins, need 5h left and right sides crystallization complete approximately, product is sunken to the reactor bottom, adds water in storage tank, and stirs, and filter, and to wash filtrate pH value is 9-10.110 ℃ of dryings, obtain silica alumina ratio and be 150 ZSM-5 type zeolite.
[embodiment 3]
To contain Al
2O
31.0mol/L sodium aluminate solution 10ml, contain Na
2O 3mol/L sodium hydroxide solution 150ml and water 300ml add in the mixed glue still, under agitation solution in the still are preheating to about 30 ℃, will contain SiO again
23.0mol/L waterglass 1000ml drops in the still apace, continues to stir about 30min, makes into even gel.
After crystallization begins, need 5h left and right sides crystallization complete approximately, product is sunken to the reactor bottom, adds water in storage tank, and stirs, and filter, and to wash filtrate pH value is 9-10.110 ℃ of dryings, obtain silica alumina ratio and be 300 ZSM-5 type zeolite.
[embodiment 4]
To contain Al
2O
31.0mol/L sodium aluminate solution 9ml, contain Na
2O 3mol/L sodium hydroxide solution 150ml and water 300ml add in the mixed glue still, under agitation solution in the still are preheating to about 30 ℃, will contain SiO again
23.0mol/L waterglass 1500ml drops in the still apace, continues to stir about 30min, makes into even gel.
After crystallization begins, need 5h left and right sides crystallization complete approximately, product is sunken to the reactor bottom, adds water in storage tank, and stirs, and filter, and to wash filtrate pH value is 9-10.110 ℃ of dryings, obtain silica alumina ratio and be 500 ZSM-5 type zeolite.
[embodiment 5]
The zeolite powder and the gibbsite of the drying of embodiment 1 gained are mixed, mediate extrusion.The consumption of gibbsite is so that Al
2O
3With the zeolite weight ratio be 35/65, be extruded into the bar that diameter is 2mm, more than 110 ℃ of dry 12h, then in air 550 ℃ roasting 4-6 hour, the sample of gained is used 1N NH at 90 ℃
4NO
3Solution carries out ion-exchange, dries by the fire 16h down at 110 ℃ then, and 550 ℃ of roasting 4h obtain hydrogen zeolite catalyst.
[embodiment 6]
With the La (NO of embodiment 5 gained catalyst 4g in 6% (weight)
3)
3Dipping, drying among the solution 14g then at 500 ℃ of roasting 10h, get the lanthana that catalyst contains 7.8% (weight).
[embodiment 7]
With the Mg (NO of embodiment 5 gained catalyst 4g in 4% (weight)
3)
2With 4% (weight) La (NO
3)
3The 16g mixed solution in flood, drying, at 500 ℃ of roasting 10h, the gained catalyst contains the lanthana of the magnesia and 5.7% (weight) of 3.8% (weight).
[embodiment 8-10]
Embodiment 8-10 is to use the embodiment of above-mentioned Preparation of Catalyst ethylbenzene, and raw material is the benzene of 1:1 (mol ratio): ethene, catalyst are the prepared catalyst of embodiment 5-7, and the catalyst use amount is 5g.Concrete experimentation is as follows:
Test is carried out on the fixed bed reactors of continuous-flow, and the reaction procatalyst is at N
2Be warmed up to 500 ℃ in the atmosphere, activation 2h is cooled to 400 ℃ of reaction temperatures then, and fresh benzene is gone into the constant temperature vaporizer by the micro-sampling infusion, and ethylene gas is with mass space velocity (WHSV) 0.5-2.0h
-1Enter gaseous mass meter control flow behind drying jar, filter, the pressure maintaining valve, with enter into preheater after benzene mixes and heat after enter the alkylation reaction device again.Experiment condition is: 420 ℃ of temperature, pressure 0.5MPa, total air speed 1.5h
-1Experimental result is listed in table 1.
The experimental result of table 1 embodiment 8-10
| The embodiment sequence number | The catalyst source | Conversion of ethylene % | Ethylbenzene selectivity % | Xylene content ppm in the ethylbenzene |
| 8 | Embodiment 5 | 98.4 | 98.2 | 98 |
| 9 | Embodiment 6 | 99.0 | 98.8 | 92 |
| 10 | Embodiment 7 | 99.3 | 99.1 | 85 |
[embodiment 11-13]
Embodiment 11-13 is embodiment of preparation ethylbenzene, and raw material is the benzene of 8:1 (mol ratio): ethene is raw material, and catalyst is the prepared catalyst of embodiment 5,6 and 7, and the catalyst use amount is 5g.Experimentation is with embodiment 8-10.Experiment condition is: 420 ℃ of temperature, pressure 1.6MPa, total air speed 2.0h
-1Experimental result is listed in table 2.
The experimental result of table 2 embodiment 11-13
| The embodiment sequence number | The catalyst source | Conversion of ethylene % | Ethylbenzene selectivity % | Xylene content ppm in the ethylbenzene |
| 11 | Embodiment 5 | 98.6 | 98.3 | 95 |
| 12 | Embodiment 6 | 99.2 | 98.9 | 90 |
| 13 | Embodiment 7 | 99.5 | 99.3 | 81 |
Claims (13)
1. a zeolite molecular sieve catalyst is characterised in that to have suitable nano aperture and nano particle size, wherein zeolite molecules mesh size and granularity between 0.1-100nm, SiO
2/ Al
2O
3Mol ratio is 30-500; Support the alkaline earth oxide of 0-10% (weight) and the rare-earth oxide of 0-10% (weight) on the molecular sieve.
2. according to the described molecular sieve catalyst of claim 1, it is characterized in that described molecular sieve is one or more in ZSM-5, ZSM-11, the ZSM-22 molecular sieve.
3. according to the described molecular sieve catalyst of claim 1, it is characterized in that SiO
2/ Al
2O
3Mol ratio is 40-200.
4. according to the described molecular sieve catalyst of claim 1, it is characterized in that described alkaline earth oxide is one or more in beryllium oxide, magnesia, calcium oxide or the barium monoxide.
5. according to the described molecular sieve catalyst of claim 4, it is characterized in that described alkaline earth oxide is a magnesia.
6. according to the described molecular sieve catalyst of claim 1, it is characterized in that described rare-earth oxide is a kind of or its mixture in lanthana, samarium oxide and the cerium oxide.
7. according to the described molecular sieve catalyst of claim 6, it is characterized in that described rare-earth oxide is a lanthana.
8. the preparation method of the described molecular sieve catalyst of claim 1 comprises the following steps:
(1) will be according to the Al that contains of certain raw material proportioning
2O
31.0-1.3mol/L sodium aluminate solution, aqueous slkali, organic amine solution and water add and mix in the glue still, under agitation solution in the still is preheating between 28-32 ℃, add a certain amount of SiO of containing again
2Concentration is that the waterglass of 2.5-3.0mol/L drops in the still apace, continues to stir, and makes into even gel;
(2) step (1) gained reactant mixture is added in the synthesis reaction vessel, under agitation heat to 170-190 ℃, stop then stirring, and keep this temperature, make it crystallization under static state;
(3) crystallization fully after, the partial mother liquid of still middle and upper part is introduced in the mother liquor container, the product of bottom is put into storage tank, further reclaims mother liquor after the sedimentation; Spending deionised water is 9-10 to pH, and centrifugal filtration and 100-120 ℃ drying obtains having the zeolite of suitable nano particle size and nano aperture;
(4) with step (3) gained zeolite and Al
2O
3Proportionally roasting behind the 65/35 mixing extruded moulding;
(5) step (4) gained zeolite is carried out ion-exchange in ammonium salt solution, then at 100-120 ℃ down more than the dry 12h, 530-580 ℃ roasting 4-6 hour, Hydrogen nano molecular sieve zeolite catalyst;
(6) step (5) gained nano molecular sieve catalyst is joined respectively in the solution of the solution that contains rare-earth salts, alkali salt, at 60-100 ℃, the pH value is 3-6, carries out ion-exchange treatment 0.5-2 hour; Filter, washing, dry, obtain modified nano molecular sieve catalyst.
9. according to the described preparation method of claim 8, it is characterized in that described aqueous slkali is NaOH, KOH or NH
3H
2O, concentration is 0.05-0.3mol/L.
10. according to the described preparation method of claim 8, it is characterized in that temperature is 70-90 ℃ in the described step (6).
11., it is characterized in that pH value is 4-5 in the described step (6) according to the described preparation method of claim 8.
12., it is characterized in that the ion-exchange treatment time in the described step (6) is 1-1.5 hour according to the described preparation method of claim 8.
13. it is the preparation of the ethylbenzene of raw material that the described molecular sieve catalyst of claim 1 is used for benzene and ethene, reaction condition is temperature 320-450 ℃, pressure 0.5-2.0Mpa, and weight ethylene air speed 0.5-2.0h-1, benzene and ethylene molecule are than being 3-12.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872899A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102875315A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102875316A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by alkylation of dry gas and benzene |
| CN102872900A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene |
| CN106281433A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | Oil refinery dry gas produces the method for gasoline mediation component |
| CN107008488A (en) * | 2017-05-24 | 2017-08-04 | 兰州理工大学 | Preparation method for benzene and the catalyst of methanol alkylation |
| CN114057531A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Synthetic method of ethylbenzene |
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2008
- 2008-01-18 CN CNA2008100328148A patent/CN101485993A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872899A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102875315A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102875316A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by alkylation of dry gas and benzene |
| CN102872900A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene |
| CN102875316B (en) * | 2011-07-11 | 2014-07-23 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by alkylation of dry gas and benzene |
| CN102875315B (en) * | 2011-07-11 | 2015-12-09 | 中国石油化工股份有限公司 | The method of ethanol and benzene producing ethyl benzene through alkylation in gas phase |
| CN106281433A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | Oil refinery dry gas produces the method for gasoline mediation component |
| CN106281433B (en) * | 2015-06-12 | 2018-02-13 | 中国石油化工股份有限公司 | The method of oil refinery dry gas production gasoline mediation component |
| CN107008488A (en) * | 2017-05-24 | 2017-08-04 | 兰州理工大学 | Preparation method for benzene and the catalyst of methanol alkylation |
| CN114057531A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Synthetic method of ethylbenzene |
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