CN105709815A - Methylbenzene-ethylene selective alkylation catalyst, and preparation method thereof - Google Patents
Methylbenzene-ethylene selective alkylation catalyst, and preparation method thereof Download PDFInfo
- Publication number
- CN105709815A CN105709815A CN201410716665.2A CN201410716665A CN105709815A CN 105709815 A CN105709815 A CN 105709815A CN 201410716665 A CN201410716665 A CN 201410716665A CN 105709815 A CN105709815 A CN 105709815A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- organic substance
- accordance
- toluene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a methylbenzene-ethylene selective alkylation catalyst, and a preparation method thereof. According to the preparation method, small crystal grain MWW-type molecular sieve is coated with an organic matter, an obtained product is uniformly mixed with a precursor of a high temperature resistant indifferent oxide, and an obtained mixture is subjected to moulding, drying, and roasting so as to obtain the methylbenzene-ethylene selective alkylation catalyst. The methylbenzene-ethylene selective alkylation catalyst is especially suitable to be applied to synthesis of para-methyl ethylbenzene via methylbenzene-ethylene selective alkylation. Compared with the prior art, the methylbenzene-ethylene selective alkylation catalyst possesses following advantages: molecular sieve using amount of the methylbenzene-ethylene selective alkylation catalyst is reduced greatly, so that catalyst production cost is reduced greatly, and discharge of wastewater difficult to process in molecular sieve synthesis process is avoided; and catalytic activity and para-methyl ethylbenzene selectivity are high.
Description
Technical field
The present invention relates to a kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof.This catalyst synthesizes in methyl-ethyl benzene course of reaction with ethylene selectivity alkylation for toluene.
Background technology
It is 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 high performance plastics kind abroad developed in recent years, the various performances of this polymer are similar to polystyrene, keep good molding processibility, and it is superior to existing polystyrene plastics (hot strength 48MPa in proportion, thermostability, anti-flammability, transparency and shrinkage factor etc., elastic modelling quantity 2210MPa, Izod notched impact strength 16J/m, heat distortion temperature 95 DEG C).In addition p-methylstyrene with other monomer copolymerization (such as styrene), can improve thermostability and the anti-flammability of some polymer, can be largely used to the manufacture of the aspect such as engineering plastics, phthalic resin coating, thus in widespread attention.
MCM-22 molecular sieve has polynary ring channel systems two kinds independent, and one is two dimension sinusoidal wave form, the ten-ring duct of intersection, and cross section is oval (0.45nm*0.51nm)；Another kind is cross section is the large-scale cylindrical supercage of twelve-ring, supercage free internal space is 0.71nm*0.71nm*1.82nm, these supercages half twelve-ring supercage (0.71*0.71*0.91nm) that is connected with the window of ten-ring (0.45*0.45nm) is formed at [001] crystal outer surface and has pocket teach big absorbability, and two supercages are connected by hexagonal prismoid.Due to the slab construction that MCM-22 zeolite crystal is thin, therefore it has bigger outer surface, and therefore the reactions such as alkylation, aromatisation, toluene disproportionation all have the catalytic performance of excellence.
At present, owing to methyl-ethyl benzene monomer manufacturing cost is much higher than styrene, thus limiting widely using of poly-p-methylstyrene, existing it is mainly used in replacing polystyrene to make electrical accessorie and packaging needing heatproof high field to share, and for illuminating equipment etc..Containing a certain amount of to methyl-ethyl benzene in usual first benzene alkylation with ethylene generation product, and a small amount of benzene of by-product and mixed xylenes, wherein most toluene does not convert (major part toluene recovery recycle), by rectification obtain purity about 90% to methyl-ethyl benzene.More than 98% is purified to methyl-ethyl benzene through further adsorbing separation or freezing and crystallizing.To methyl-ethyl benzene in the product that dehydrogenation generates containing the p-methylstyrene of about 50%, obtain the polymerization single polymerization monomer p-methylstyrene of purity more than 99% again through rectification.The method similar with styrene polymerization or process for suspension polymerization can be adopted to produce polymethylstyrene or the comonomer as styrene etc. uses.
Traditional Friede-Crafts catalyst, can only prepare the thermodynamical equilibrium mixture containing three isomers of methyl-ethyl benzene, such as the AlCl of DOW company of the U.S.3Series catalysts, by toluene and pure ethylene react prepare be called vinyltoluene product (containing PET about 38%, remaining be between position methyl-ethyl benzene).USP4117024 adopts chemical modification high silica ZSM-5 type zeolite to be catalyst, when toluene reacts with pure ethylene, in obtained product methyl-ethyl benzene isomer, the content of PET, reaches more than 90%, and making the generation of ortho methyl group ethylbenzene be significantly inhibited, its content can level off to zero.CN1047986A adopts the Pentasil type Si-Al zeolite catalyst processed containing antimony (or phosphorus) and magnesium elements chemical modification, react with toluene and produce, although this zeolite catalyst directly can make raw material with the refinery tail-gas (containing ethylene 10% ~ 20%) containing the impurity such as hydrogen sulfide, water, the process being mainly para-position methyl-ethyl benzene, adopt antimony (or phosphorus) and the modified effect that molecular sieve surface acidity can be played neutralization and modulation of magnesium elements, molecular sieve surface strong acid center is made to reduce after antimony, P Modification, weak acid center increases relatively, advantageously forms para-isomer.It addition, the effective dimensions that phosphorus can also make duct infall or aperture reduces.But this processing method can substantially reduce the activity of catalyst, even if reaction carries out at very high temperatures, conversion ratio is still relatively low, and, P elements is easier to run off at reaction conditions, is also a deficiency of this technology.So the conversion of ethylene of this catalyst and methyl-ethyl benzene selectivity is all relatively low.
CN1103607A provides ethylene and toluene reaction in a kind of catalytic cracked dry gas and produces the shape selective catalysis agent to methyl-ethyl benzene.This catalyst is a kind of Pentasil type catalyst containing rare earth, molecular sieve carries out the dipping such as aluminum and magnesium and modifiies, and the amount of its oxide modifier is not less than 0.25%.This processing method can substantially reduce the activity of catalyst, even if reaction carries out at very high temperatures, conversion ratio is still relatively low.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof.The method can avoid the active center of catalyst to be capped, and improves the activity of catalyst and isomerisation selectivity and stability.
The preparation method of the toluene of the present invention and ethylene selectivity alkylation catalyst, including:
(1) MWW type molecular sieve is embedded in Organic substance, obtains the molecular sieve of Organic substance embedding；
(2) molecular sieve of Organic substance embedding step (1) obtained is mixed homogeneously with the precursor of high temperature resistant indifferent oxide, through molding, and dry and roasting, obtain toluene and ethylene selectivity alkylation catalyst.
Step (1) described MWW type molecular sieve preferably employs little crystal grain MWW type molecular sieve, and average grain diameter is 0.1 ~ 1.0 micron, it is preferred to 0.2 ~ 0.8 micron, SiO2/Al2O3Mol ratio is 20 ~ 80, it is preferred to 30 ~ 60.Described MWW type molecular sieve can be selected from various MWW structure molecular screens in prior art, including one or more in MCM-22, SSZ-25, MCM-36, MCM-49 and MCM-56, it is preferred to one or more in MCM-22 and MCM-49 molecular sieve.Described MWW type molecular sieve mass content in the catalyst is 1.0% ~ 20.0%, it is preferred to 2.0% ~ 15.0%, more preferably 2.0% ~ 10.0%.Described high temperature resistant indifferent oxide can be selected from one or more in aluminium oxide, silicon oxide, calcium oxide, zinc oxide, magnesium oxide etc., it is preferred to aluminium oxide is or/and silicon oxide.The precursor of described high temperature resistant indifferent oxide refers to the hydroxide that this oxide is corresponding.
Organic species described in step (1) can be selected from one or more in starch and polyvinyl alcohol, and the degree of polymerization of described polyvinyl alcohol is 1500 ~ 2500, and alcoholysis degree is more than 85%, it is preferred to 90% ~ 99%.Described starch is water soluble starch, and its molecular weight is 20000 ~ 100000, and described starch sedimentation is one or more in corn starch, tapioca and potato starch, it is preferred to corn starch.The process that step (1) can adopt by the method for Organic substance embedding molecular sieve is as follows: mixed with water by Organic substance, MWW type molecular sieve is suspended in wherein, then pelletize is carried out, molecular sieve is made to be embedded in Organic substance, wherein prilling process can be vacuum spray drying method, boiling granulation method, centrifugal granulation or extrusion-spherozation etc., it is preferred to vacuum spray drying method.In vacuum spray drying method, vacuum is generally 0.01 ~ 0.05MPa, and baking temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 24 hour, carries out vacuum spray drying by suspension obtained above, forms small dry granule.In the molecular sieve of the Organic substance embedding of step (1) gained, the mass ratio of Organic substance and molecular sieve is 20:1 ~ 1:1, it is preferred to 10:1 ~ 5:1.The particle diameter of the molecular sieve of the Organic substance embedding of step (1) gained is 10 ~ 100 microns.
Molding described in step (2), it is possible to select according to practical application, such as spherical, strip or other abnormity granules, it is preferred to strip.Drying condition described in step (2) is: baking temperature 80 ~ 150 DEG C, 5 ~ 20 hours drying times, and described roasting is to carry out in oxygenous atmosphere, and the condition of roasting is: sintering temperature 400 ~ 650 DEG C, roasting time 5 ~ 20 hours.Purpose is by Organic substance at high temperature oxidation removal, discharges duct and the reaction channel of needs.
Toluene of the present invention and ethylene selectivity alkylation process are that with ethylene selectivity alkylation, toluene is generated the technical process to methyl-ethyl benzene.The process conditions adopted are generally as follows: toluene/ethylene molar ratio 1:1 ~ 10:1, reaction temperature is 350 DEG C ~ 450 DEG C, volume space velocity 1 ~ 10h during liquid-1, reaction pressure is 0.8MPa ~ 3MPa.
The toluene of the present invention and ethylene selectivity alkylation catalyst are to adopt first to be embedded by molecular sieve Organic substance, then it is mixed with catalyst with high temperature resistant inert inorganic oxide again, molecular sieve distribution so can be made more uniform, can also make the more active center distribution of catalyst in pore passage structure, the active center that so can avoid catalyst is capped, when reactant is by catalyst duct, directly contact with the catalytic active species in its duct and react efficiently, again owing to active particle is little, orifice throat length is short, product can quickly diffuse out, avoid deep reaction, improve the selectivity of target product.Compared with prior art, the inventive method is in toluene and ethylene selectivity alkylation process, not only there is catalysis activity height and to methyl-ethyl benzene selectivity high, and Catalyst Production cost significantly declines, avoid the feature of the discharge of intractable waste water in sieve synthesis procedure simultaneously.
Detailed description of the invention
By the examples below the technology of the present invention is described further, but should not be construed as being limited to this scope.In the present invention, wt% is mass fraction.
In the present invention, the grain size of molecular sieve adopts SEM(scanning electron microscope) mode measure, silica alumina ratio is to adopt chemical analysis to record.
The little crystal grain MCM-22 that this experiment uses is that the method that reference literature (petrochemical industry the 33rd phase in 2004) is reported is synthetically derived, and its average grain diameter is 0.6 micron.
The key data related in the present embodiment has the conversion ratio of ethylene and the selectivity to methyl-ethyl benzene, and concrete computational methods are as follows:
Conversion of ethylene=[weight of (entering the weight of the weight-reactor outlet ethylene of reactor ethylene)/enter reactor ethylene] × 100%
To methyl-ethyl benzene selectivity=(reactor outlet weight to the weight/reactor outlet methyl-ethyl benzene of methyl-ethyl benzene) × 100%
Embodiment 1
Catalyst one preparation process of the present invention is as follows:
(1) being dissolved in 300 grams of water by 90 grams of water solublity corn starchs (molecular weight is 35000), (particle diameter is 0.6 micron, SiO then to add 10 grams of MCM-22 molecular sieves under room temperature2/Al2O3Mol ratio is 35), it is sufficiently stirred for uniformly suspension, through vacuum spray drying (vacuum 0.03MPa, baking temperature is 60 DEG C, and drying time is 5h), obtains the molecular sieve of the starch embedding that average particulate diameter is 80 microns.
(3) take the molecular sieve of starch embedding prepared by 25 grams of steps (2) and 118 grams of (butt 76wt%) aluminium hydroxide and SB powder is sufficiently mixed, it is subsequently adding the salpeter solution that 85mL concentration is 0.1mol/L, abundant kneading, make paste plastic, on banded extruder, forming diameter is the cylindrical bars of 1.5mm, this cylindrical bars dries 16 hours at 100 DEG C, and then in air atmosphere, 550 DEG C of roastings obtain catalyst of the present invention in 4 hours.Catalyst forms, in mass fraction, MCM-22:2.5%, aluminium oxide: surplus.
Take 10mL catalyst, be packed in the miniature flow reactor of fixing bed after diluting with 10mL quartz sand and carry out catalytically active assessment.Process conditions are as follows: toluene/ethylene molar ratio 4, and reaction temperature is 400 DEG C, and reaction pressure is 2.0MPa, volume space velocity 5h during with liquid-1Entering raw material, carry out evaluating catalyst, negate and answer the product of 4 hours to be analyzed, the reaction result in the selective alkylation of toluene and ethylene is in Table 1.
Embodiment 2
Catalyst one embodiment of the present invention is with embodiment 1, and being different in that in each step, content of material has adjusted, and MCM-49(particle diameter is 0.8 micron, SiO2/Al2O3Mol ratio is 40) replace MCM-22 molecular sieve, obtain catalyst composition, in mass fraction, MCM-49:3.0%, aluminium oxide: surplus.Evaluation result is in Table 1.
Embodiment 3
Catalyst one embodiment of the present invention is with embodiment 1, and being different in that in each step, content of material has adjusted, and the mass ratio of starch and molecular sieve is 5:1, is prepared into the molecular sieve of the starch embedding that average particulate diameter is 50 microns.Obtain catalyst composition, in mass fraction, MCM-22:10%, aluminium oxide: surplus.Evaluation result is in Table 1.
Embodiment 4
Catalyst one embodiment of the present invention is with embodiment 1, it is different in that in step (1) and replaces chloroplatinic acid with Palladous chloride., and content of material has adjusted in each step, the mass ratio of starch and molecular sieve is 10:1, it is prepared into the molecular sieve of the starch embedding that average particulate diameter is 100 microns, obtain catalyst composition, in mass fraction, MCM-22:5.0%, aluminium oxide: surplus.Evaluation result is in Table 1.
Embodiment 5
Catalyst one embodiment of the present invention is with embodiment 1, it is different in that in step (1) and is additionally added Palladous chloride., and content of material has adjusted in each step, the mass ratio of starch and molecular sieve is, 2:1, is prepared into the molecular sieve of the starch embedding that average particulate diameter is 70 microns, obtains catalyst composition, in mass fraction, Pd:0.15%, MCM-22:5.5%, aluminium oxide: surplus.Evaluation result is in Table 1.
Embodiment 6
Catalyst one embodiment of the present invention is with embodiment 1, it is different in that (degree of polymerization is 1800 to step (2) middle polyvinyl alcohol, alcoholysis degree is 98%) replace water soluble starch, in each step, content of material has adjusted, the mass ratio of polyvinyl alcohol and molecular sieve is 5:1, is prepared into the molecular sieve of the polyvinyl alcohol embedding that average particulate diameter is 50 microns, obtains catalyst composition, in mass fraction, MCM-22:8%, aluminium oxide: surplus.Evaluation result is in Table 1.
Embodiment 7
Catalyst one embodiment of the present invention is with embodiment 1, it is different in that in step (3) and replaces aluminium hydroxide with silica gel, in each step, content of material has adjusted, the mass ratio of starch and molecular sieve is 8:1, it is prepared into the molecular sieve of the starch embedding that average particulate diameter is 80 microns, obtain catalyst to form in mass fraction, MCM-22:1.0%, silicon oxide: surplus.Evaluation result is in Table 1.
Comparative example 1
Aluminium hydroxide and SB powder, MCM-22 molecular sieve and sesbania powder are sufficiently mixed, it is subsequently adding the salpeter solution that appropriate concentration is 0.1mol/L, abundant kneading, making paste plastic, extruding diameter on banded extruder is the cylindrical bars of 1.5mm, and cylindrical bars dries 16 hours at 100 DEG C, then in air atmosphere, 550 DEG C of roastings obtain catalyst in 4 hours, prepare catalyst composition, in mass fraction, MCM-22:65%, aluminium oxide: surplus.Appreciation condition is with embodiment 1, and evaluation result is in Table 1.
Comparative example 2
The preparation method of this comparative example catalyst with comparative example 1, be different in that obtained catalyst form with embodiment 1, in mass fraction, namely MCM-22:2.5%, aluminium oxide: surplus.Appreciation condition is with embodiment 1, and evaluation result is in Table 1.
Comparative example 3
The preparation method of this comparative example catalyst, with comparative example 1, is different in that obtained catalyst forms with embodiment 2, in mass fraction, MCM-49:3.0%, aluminium oxide: surplus.Appreciation condition is with embodiment 1, and evaluation result is in Table 1.
The evaluation result of table 1 different catalysts
| Embodiment is numbered | Conversion of ethylene, % | To methyl-ethyl benzene selectivity, % |
| Embodiment 1 | 97.8 | 93.8 |
| Embodiment 2 | 98.8 | 95.3 |
| Embodiment 3 | 97.9 | 96.1 |
| Embodiment 4 | 98.1 | 95.8 |
| Embodiment 5 | 97.6 | 93.4 |
| Embodiment 6 | 97.9 | 95.7 |
| Embodiment 7 | 98.2 | 96.1 |
| Comparative example 1 | 96.5 | 77.5 |
| Comparative example 2 | 75.1 | 35.6 |
| Comparative example 3 | 65.3 | 30.9 |
From the results shown in Table 1, catalyst of the present invention, in the alkylated reaction of toluene and ethylene, generates the selectivity to methyl-ethyl benzene and all reaches more than 93%, hence it is evident that higher than the result of comparative example.
Claims (16)
1. a preparation method for toluene and ethylene selectivity alkylation catalyst, including:
(1) MWW type molecular sieve is embedded in Organic substance, obtains the molecular sieve of Organic substance embedding；
(2) molecular sieve of Organic substance embedding step (1) obtained is mixed homogeneously with the precursor of high temperature resistant indifferent oxide, through molding, and dry and roasting, obtain toluene and ethylene selectivity alkylation catalyst.
2. in accordance with the method for claim 1, it is characterised in that described MWW type molecular sieve adopts little crystal grain MWW type molecular sieve, and average grain diameter is 0.1 ~ 1.0 micron, it is preferred to 0.2 ~ 0.8 micron.
3. the method described in claim 1 or 2, it is characterised in that the SiO of described MWW type molecular sieve2/Al2O3Mol ratio is 20 ~ 80, it is preferred to 30 ~ 60.
4. the method described in claim 1 or 2, it is characterised in that one or more in MCM-22, SSZ-25, MCM-36, MCM-49 and MCM-56 of described MWW type molecular screening, it is preferred to one or more in MCM-22 and MCM-49 molecular sieve.
5. in accordance with the method for claim 1, it is characterised in that described MWW type molecular sieve mass content in the catalyst is 1.0% ~ 20.0%, it is preferred to 2.0% ~ 15.0%.
6. in accordance with the method for claim 1, it is characterised in that described high temperature resistant indifferent oxide selected from aluminium oxide or/and silicon oxide.
7. in accordance with the method for claim 1, it is characterized in that one or more in starch and polyvinyl alcohol of Organic substance described in step (1), the degree of polymerization of described polyvinyl alcohol is 1500 ~ 2500, alcoholysis degree is more than 85%, described starch is water soluble starch, and its molecular weight is 20000 ~ 100000.
8. in accordance with the method for claim 7, it is characterised in that described starch is one or more in corn starch, tapioca and potato starch.
9. in accordance with the method for claim 1, it is characterized in that the process that the method for step (1) Organic substance embedding molecular sieve adopts is as follows: mixed with water by Organic substance, MWW type molecular sieve is suspended in wherein, then pelletize is carried out, making molecular sieve be embedded in Organic substance, wherein prilling process is vacuum spray drying method, boiling granulation method, centrifugal granulation or extrusion-spherozation.
10. in accordance with the method for claim 9, it is characterised in that step (1) prilling process is vacuum spray drying method, vacuum is 0.01 ~ 0.05MPa, and baking temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 24 hour.
11. in accordance with the method for claim 1, it is characterised in that in the molecular sieve of the Organic substance embedding of step (1) gained, Organic substance is 20:1 ~ 1:1 with the mass ratio of molecular sieve, it is preferred to 10:1 ~ 5:1.
12. in accordance with the method for claim 1, it is characterised in that the particle diameter of the molecular sieve of the Organic substance embedding of step (1) gained is 10 ~ 100 microns.
13. in accordance with the method for claim 1, it is characterized in that the drying condition described in step (2) is: baking temperature 80 ~ 150 DEG C, 5 ~ 20 hours drying times, described roasting is to carry out in oxygenous atmosphere, the condition of roasting is: sintering temperature 400 ~ 650 DEG C, roasting time 5 ~ 20 hours.
14. a toluene and ethylene selectivity alkylation catalyst, it is characterised in that adopt the arbitrary described method of claim 1 ~ 13 to prepare.
15. a toluene and ethylene selectivity alkylation, it is characterised in that adopt the catalyst described in claim 14.
16. the method described in claims 14 or 15, it is characterized in that described toluene and ethylene selectivity alkylation process are that with ethylene selectivity alkylation, toluene is generated the technical process to methyl-ethyl benzene, its reaction condition is as follows: toluene/ethylene molar ratio 1:1 ~ 10:1, reaction temperature is 350 DEG C ~ 450 DEG C, volume space velocity 1 ~ 10h during liquid-1, reaction pressure is 0.8MPa ~ 3MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410716665.2A CN105709815B (en) | 2014-12-02 | 2014-12-02 | A kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410716665.2A CN105709815B (en) | 2014-12-02 | 2014-12-02 | A kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105709815A true CN105709815A (en) | 2016-06-29 |
| CN105709815B CN105709815B (en) | 2018-06-19 |
Family
ID=56146136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410716665.2A Active CN105709815B (en) | 2014-12-02 | 2014-12-02 | A kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105709815B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101563159A (en) * | 2006-12-21 | 2009-10-21 | 埃克森美孚化学专利公司 | A catalyst composition, the method of manufacturing, and the process of use thereof in aromatics alkylation |
| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| US20130225888A1 (en) * | 2006-09-05 | 2013-08-29 | Fina Technology, Inc. | Process for the Reduction of Alkylation Catalyst Deactivation |
| CN103301889A (en) * | 2012-03-15 | 2013-09-18 | 山西腾茂科技有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN103801385A (en) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition |
-
2014
- 2014-12-02 CN CN201410716665.2A patent/CN105709815B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130225888A1 (en) * | 2006-09-05 | 2013-08-29 | Fina Technology, Inc. | Process for the Reduction of Alkylation Catalyst Deactivation |
| US20140005454A1 (en) * | 2006-09-05 | 2014-01-02 | Fina Technology, Inc. | Process for the Reduction of Alkylation Catalyst Deactivation Utilizing Low Silica to Alumina Ratio Catalyst |
| CN101563159A (en) * | 2006-12-21 | 2009-10-21 | 埃克森美孚化学专利公司 | A catalyst composition, the method of manufacturing, and the process of use thereof in aromatics alkylation |
| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| CN103301889A (en) * | 2012-03-15 | 2013-09-18 | 山西腾茂科技有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN103801385A (en) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105709815B (en) | 2018-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2607633C2 (en) | Moulded catalyst for converting methanol into aromatic hydrocarbons and method of producing said catalyst | |
| CN103561867B (en) | Manufacture the improved method being used for that methanol is changed into the zeolite based catalysts of alkene | |
| CN103561866A (en) | Process for manufacture of a zeolite based catalyst for the conversion of methanol to olefins | |
| CN105381814A (en) | Catalyst used in alkylation reaction of ethylbenzene and ethanol and preparation method thereof | |
| CN111672532A (en) | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof | |
| TW201305088A (en) | The addition of a base to enhance product yield in alkylation reactions | |
| CN103041846B (en) | Alkylated catalyst containing modified ZSM-11 zeolite and application of alkylated catalyst | |
| CN103028435A (en) | Catalyst for preparing propylene through conversion of methanol and preparation method of catalyst | |
| CN105709815A (en) | Methylbenzene-ethylene selective alkylation catalyst, and preparation method thereof | |
| CN103041845B (en) | Catalyst composition containing modified ZSM-11 zeolite and application of catalyst composition | |
| WO2004108282A2 (en) | Selective para-xylene production via methylation of toluene with methanol in the presence of modified hzsm-5 catalyst | |
| CN104148108A (en) | Catalyst used for alkylation reaction, preparation method and application method thereof | |
| CN105582982B (en) | A kind of in-situ pretreatment method of toluene and ethylene selectivity alkylation catalyst | |
| CN105712830B (en) | A kind of preparation method of isobutene | |
| CN102875316B (en) | Method for preparing ethylbenzene by alkylation of dry gas and benzene | |
| CN102909052B (en) | Mordenite-containing catalyst, and preparation method and application thereof | |
| CN102649086B (en) | Catalyst used in preparation of ethylene through ethanol dehydration | |
| CN102909051B (en) | Catalyst containing modified mordenite, and preparation method and applications thereof | |
| JP7360551B2 (en) | Catalyst and manufacturing method for producing vinyl chloride by decomposition of 1,2-dichloroethane | |
| CN112142549B (en) | Synthesis method of methyl isopropyl benzene | |
| CN1047106C (en) | Zeolite catalyst for producing p-methyl-ethyl benzene with ethylene and toluene | |
| CN104549485B (en) | The method that catalyst of naphtha catalytic cracking production propylene and preparation method thereof and naphtha catalytic cracking produce propylene | |
| RU2458739C1 (en) | Method of encapsulating titanium silicate in polymer matrix | |
| CN113185378B (en) | Method for preparing divinylbenzene by taking ethanol and ethylbenzene as raw materials | |
| CN114057538B (en) | Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |