CN106582796A - Catalyst used for alkylation reaction of ethane and benzene - Google Patents
Catalyst used for alkylation reaction of ethane and benzene Download PDFInfo
- Publication number
- CN106582796A CN106582796A CN201510662113.2A CN201510662113A CN106582796A CN 106582796 A CN106582796 A CN 106582796A CN 201510662113 A CN201510662113 A CN 201510662113A CN 106582796 A CN106582796 A CN 106582796A
- Authority
- CN
- China
- Prior art keywords
- ethane
- catalyst
- benzene
- molecular sieve
- alkylation reaction
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a catalyst used for an alkylation reaction of ethane and benzene. The catalyst mainly solves the problem of low ethane conversion rate in the alkylation reaction of ethane and benzene in the presence of a molecular sieve supported Pt catalyst. The catalyst used for the alkylation reaction of ethane and benzene comprises Pt or its oxide, Zn oxide, at least one of oxides of group VIB or IIIA metals, and a molecular sieve. The catalyst well solves the technical problem, and can be used in the alkylation reaction of ethane and benzene.
Description
Technical field
The present invention relates to the catalyst of ethane and benzene alkylation reaction.
Background technology
Shale gas are a kind of important unconventional gas resources of rising in recent years, particularly since " the shale gas leather in the U.S.
After life ", shale gas develop appreciable impact and change the general layout of world energy sources chemical industry.China's shale gas resource
It is abundant, and a large amount of ethane of shale gas association, also containing low-carbon alkanes such as a large amount of ethane in natural gas, casing-head gas and refinery gas,
Low price.But ethane structure is highly stable, it is difficult to activate, it is difficult to directly apply as the raw material of industry.At present, changing
Learn and be mainly used to convert ethane to ethylene by steam cracking in industry, to carry out at a high temperature of 900 DEG C or more,
Power consumption is high.In a mild condition Efficient Conversion is always the focus of catalytic field research using ethane.In recent years, it is external
Document proposes a kind of new method utilized for low-carbon alkanes such as ethane, and ethane and benzene are alkylated into reaction, can be with
The alkylbenzenes such as synthesizing ethyl benzene at a lower temperature, diethyl benzene,toluene,xylene.Wherein, ethylbenzene is that current chemical industry is produced
The important commercialization derivant of benzene in industry, mainly for the production of styrene, is additionally operable to organic synthesiss and intermediate pharmaceutically,
Also can use as solvent.Ethylbenzene yield occupies sizable proportion in basic organic chemical industry, and Year's consumption is huge.
Styrene is the important foundation raw material of petrochemical industry, mainly for the production of styrene series resin and butadiene-styrene rubber, is additionally operable to
The industries such as pharmacy, dyestuff, pesticide and ore dressing.Cinnamic homopolymer polystyrene is five big general thermoplasticity synthesis trees
One of fat, is widely used in the fields such as injection-molded item, extruded product and foamed product.And ethylbenzene is the cinnamic key of production
Raw material, the styrene of the industrial overwhelming majority is obtained by ethylbenzene.Therefore, synthesized using ethane and the step alkylated reaction of benzene one
The alkylbenzenes such as ethylbenzene, it is possible to achieve shale gas are converted into the large petrochemicals in downstream, grind with very important
Study carefully meaning and using value.
At present, the external research for only having a small amount of document report alkylbenzene such as ethane and producing phenylethane from alkylation of benzene to react.Text
Offer Journal of the American Chemical Society, 1975,97:6807-6810 report earliest in superacid catalysis
Agent HF-SbF5On ethane and benzene alkylation reaction, the selectivity 76% of principal product ethylbenzene, but yield only be for about 1%.Text
Offer Catalysis Letters, 2001,73:The ZSM-5 molecular sieve catalyst of 175-180 Pt loads for reporting 6.8wt%
The alkylated reaction of upper ethane and benzene, in 500 DEG C of reaction temperature, the conversion ratio of benzene is 8.3%, in addition with ethylene and benzene
Ethylene synthesis, document does not clearly provide the selectivity of each product.Document Journal of Molecular Catalysis A:
Chemical,2008,279:128-132 are reported on the ZSM-5 molecular sieve catalyst of 1wt%Pt loads, benzene and ethane
Mol ratio is 1/9, and mass space velocity is 3.1h-1When, in the alkylbenzene that ethane and benzene alkylation reaction are generated, the selection of ethylbenzene
Property be 92.6%, the selectivity of toluene is 0.99%, and the selectivity of diethylbenzene is 2.3%, but ethane conversion is less than 2%.
In the document of report disclosed above, Pt/ZSM-5 molecular sieve catalysts are adopted as single Pt elements and are supported on ZSM-5
It is seasonable for the alkylation between ethane and benzene on molecular sieve, it is more than or equal to 1% in the parts by weight of precious metals pt element
In the case of, the conversion ratio of ethane and benzene is still relatively low.
The content of the invention
One of the technical problem to be solved is the alkylation that molecular sieve carried Pt catalyst is used between ethane and benzene
The low problem of the conversion ratio of benzene and ethane in answering, there is provided a kind of new ethane and benzene are alkylated the catalyst of reaction, should
Catalyst has the advantages that the high conversion rate of ethane and benzene.
The two of the technical problem to be solved are to provide the preparation side of catalyst described in one of above-mentioned technical problem
Method.
The three of the technical problem to be solved be to provide using one of above-mentioned technical problem catalyst ethane and
Alkylation reaction method between benzene.
To solve one of above-mentioned technical problem, technical scheme is as follows：The catalyst of ethane and benzene alkylation reaction,
Including following components：
(a) Pt or its oxide；
The oxide of (b) Zn；
At least one in (c) VIB or IIIA in metal-oxide；
(d) molecular sieve.
In above-mentioned technical proposal, Zn elements and Pt elements have and cooperate with facilitation.
In above-mentioned technical proposal, in terms of parts by weight, composition (a) is preferably 0.1～4 part, more preferably 0.2～2 part.
In above-mentioned technical proposal, in terms of parts by weight, composition (b) is preferably 0.1～4 part, more preferably 0.2～2 part.
In above-mentioned technical proposal, in terms of parts by weight, composition (c) is preferably 0.1～10 part, more preferably 0.3～5 part.
In above-mentioned technical proposal, in terms of parts by weight, composition (d) is preferably 80～100 parts.
In above-mentioned technical proposal, the vib metal oxide preferably is selected from Cr2O3Or Mo2O3In at least one.
In above-mentioned technical proposal, the IIIA metal-oxides preferably are selected from Ga2O3Or In2O3In at least one.
In above-mentioned technical proposal, vib metal element and IIIA metals are most preferably included simultaneously, now the vib metal unit
There is synergism, the synergism between such as but not limited to Cr and Ga between element and IIIA metallic elements.
In above-mentioned technical proposal, the molecular sieve is hydrogen type molecular sieve.
In above-mentioned technical proposal, the molecular sieve is ZSM-5, Beta molecular sieve, MCM-22, ZSM-35, HMOR
At least one in molecular sieve.The Si/Al mol ratios of molecular sieve are not particularly limited, and those skilled in the art can rationally select
Select.Such as but not limited to when using ZSM-5 molecular sieve, optional Si/Al mol ratios are 20～300.
In above-mentioned technical proposal, more preferably in parts by weight, composition includes the composition of the catalyst：
(a) 0.1～4 part of Pt or its oxide；
The oxide of (b) 0.1～4 part of Zn；
At least one in (c) 0.1～10 part of VIB or IIIA in metal-oxide；
(d) 80～100 parts of molecular sieves.
To solve the two of above-mentioned technical problem, technical scheme is as follows：In stating the technical scheme of one of technical problem
The preparation method of the catalyst, comprises the steps：
(1) by containing the compound at least one of metal, the compound containing Pt and the change containing Zn in the VIB or IIIA
Compound is scattered in solvent；
(2) dispersion for obtaining step (1) impregnates the molecular sieve；
(3) roasting.
In above-mentioned technical proposal, the described compound containing Pt, the compound containing Zn contain and VIB or IIIA metallic elements
Compound be not particularly limited, those skilled in the art can be able to be with reasonable selection, such as described compound containing Pt
But it is not limited to chloroplatinic acid, four ammino platinum nitrates, the compound containing Zn but is not limited to zinc nitrate, zinc chloride, zinc acetate
Deng the compound containing VIB or IIIA metallic elements, such as but not limited to nitrate, chloride etc..
The solvent that step (1) is adopted is not particularly limited, as long as the operation of dip loading can be realized, these solvents can
Be dissolving, or by adjust pH dissolving, or can be formed colloid or by adjust pH formed colloid that
A little solvents, can be single solvents, or mixed solvent.
In above-mentioned technical proposal, one skilled in the art will appreciate that may be inserted between step (2) and step (3) dry
Dry step is improving the intensity of catalyst.Dry condition is not particularly limited, and such as baking temperature is optional 60～120 DEG C,
Drying time optional 2～24h.
In above-mentioned technical proposal, the temperature of roasting is preferably 400～600 DEG C.
In above-mentioned technical proposal, the time of roasting is preferably 1～12h, more preferably 1～5h.
In above-mentioned technical proposal, Pt can be present in the form of an oxide in the commercial form of the catalyst, and Zn elements are with ZnO
In the form of, metallic element is present in the form of an oxide in VIB or IIIA, but using the oxygen front needed with reducing agent Pt
Compound is reduced to Pt metal；Or Pt elements can be in the form of Pt metal in the commercial form of the catalyst, Zn
In the form of ZnO, metallic element exists in the form of an oxide element in VIB or IIIA, now only in catalyst
Preparation process in after firing include reduction the step of.Those skilled in the art will know that rationally determining actual going back
Old terms, such as but not limited to：With pure hydrogen or hydrogen and inert gas mixture as reducing agent (such as but not limited to
Hydrogen-nitrogen gaseous mixture, hydrogen-helium mix gas etc.).
To solve the three of above-mentioned technical problem, technical scheme is as follows：Ethane and benzene are alkylated the side of reaction
Method, in the presence of catalyst any one of the technical scheme in one of above-mentioned technical problem, is entered with ethane and benzene as raw material
Row reaction obtains alkylate.
In above-mentioned technical proposal, reaction temperature is preferably 350～600 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 0～0.5MPa.
In above-mentioned technical proposal, raw materials quality air speed is preferably 1～15h-1。
In above-mentioned technical proposal, ethane is preferably (1～20) with the mol ratio of benzene in raw material:1.
The present invention introduces VIB or IIIA metallic elements in Pt-Zn/ZSM-5 catalyst, improves the conversion of ethane and benzene
Rate, especially has superior technique effect when VIB or IIIA metallic elements are contained simultaneously.For example work as employing
When Pt-Zn-Cr-Ga/ZSM-5 is catalyst, up to 9.8%, benzene high conversion rate can be used for the high conversion rate of ethane up to 28.3%
In the glycosylation reaction of ethane and benzene.
Below by embodiment, the invention will be further elaborated, but these embodiments are not that the scope of the present invention is entered
Row is limited.
Specific embodiment
【Embodiment 1】
1st, catalyst preparation
(molecular formula is H to weigh the chloroplatinic acid containing 0.5g Pt2PtCl6·6H2O zinc nitrate), equivalent to 0.7g ZnO (divides
Minor is Zn (NO3)2·6H2O), equivalent to 1.1g Cr2O3Chromic nitrate (molecular formula be Cr (NO3)3·9H2) and phase O
When in 0.8g Ga2O3Ganite (Fujisawa). (molecular formula be Ga (NO3)3·9H2O in) being added to 120mL deionized waters, stirring
It is all dissolved, form mixed solution；The Hydrogen ZSM-5 molecular sieve (Si/Al mol ratios are 46) of 96.9g is weighed,
In being then added to above-mentioned mixed solution, 3h is impregnated, 100 DEG C are dried 12h, 500 DEG C of roasting 2h.
Above-mentioned product tabletting is crushed to into 20～40 mesh, it is also to adopt hydrogen volume content for 5% hydrogen-nitrogen gaseous mixture
Former agent, reduction temperature is 340 DEG C, and the recovery time obtained catalyst for 1 hour, and catalysis composition is shown in Table 1.
2nd, evaluating catalyst
Ethane is carried out with benzene alkylation reaction on continuous fixed bed reactor, and Catalyst packing quality is 3.0g.Instead
Ying Qian, is then adjusted to reaction temperature by temperature of reactor, is passed through feed ethan and is reacted with benzene.Reaction condition is：
485 DEG C of reaction temperature, reaction pressure is 0.1MPa, and the mass space velocity of raw material is 5.5h-1, ethane is with the mol ratio of benzene
6.Reaction result is shown in Table 2.
【Embodiment 2】
1st, catalyst preparation
(molecular formula is H to weigh the chloroplatinic acid containing 0.5g Pt2PtCl6·6H2O zinc nitrate), equivalent to 0.7g ZnO (divides
Minor is Zn (NO3)2·6H2O) and equivalent to 1.9g Ga2O3Ganite (Fujisawa). (molecular formula be Ga (NO3)3·9H2O) add
To in 120mL deionized waters, stirring makes it all dissolve, and forms mixed solution；Weigh the Hydrogen ZSM-5 of 96.9g
Molecular sieve (Si/Al mol ratios are 46), in being then added to above-mentioned mixed solution, impregnates 3h, and 100 DEG C are dried 12h,
500 DEG C of roasting 2h.
Above-mentioned product tabletting is crushed to into 20～40 mesh, it is also to adopt hydrogen volume content for 5% hydrogen-nitrogen gaseous mixture
Former agent, reduction temperature is 340 DEG C, and the recovery time obtained catalyst for 1 hour, and catalysis composition is shown in Table 1.
2nd, evaluating catalyst
The catalyst ethane and benzene alkylation reaction performance are evaluated according to the same manner as in Example 1.Reaction result is shown in Table 2.
【Embodiment 3】
1st, catalyst preparation
(molecular formula is H to weigh the chloroplatinic acid containing 0.5g Pt2PtCl6·6H2O zinc nitrate), equivalent to 0.7g ZnO (divides
Minor is Zn (NO3)2·6H2O) and equivalent to 1.9g Cr2O3Chromic nitrate (molecular formula be Cr (NO3)3·9H2O) add
To in 120mL deionized waters, stirring makes it all dissolve, and forms mixed solution；Weigh the Hydrogen ZSM-5 of 96.9g
Molecular sieve (Si/Al mol ratios are 46), in being then added to above-mentioned mixed solution, impregnates 3h, and 100 DEG C are dried 12h,
500 DEG C of roasting 2h.
Above-mentioned product tabletting is crushed to into 20～40 mesh, it is also to adopt hydrogen volume content for 5% hydrogen-nitrogen gaseous mixture
Former agent, reduction temperature is 340 DEG C, and the recovery time obtained catalyst for 1 hour, and catalysis composition is shown in Table 1.
2nd, evaluating catalyst
The catalyst ethane and benzene alkylation reaction performance are evaluated according to the same manner as in Example 1.Reaction result is shown in Table 2.
【Embodiment 4】
1st, catalyst preparation
(molecular formula is H to weigh the chloroplatinic acid containing 0.5g Pt2PtCl6·6H2O zinc nitrate), equivalent to 0.7g ZnO (divides
Minor is Zn (NO3)2·6H2O), equivalent to 1.1g Cr2O3Chromic nitrate (molecular formula be Cr (NO3)3·9H2) and phase O
When in 0.8g In2O3Indium nitrate (molecular formula be In (NO3)3·5H2O in) being added to 120mL deionized waters, stirring
It is all dissolved, form mixed solution；The Hydrogen ZSM-5 molecular sieve (Si/Al mol ratios are 46) of 96.9g is weighed,
In being then added to above-mentioned mixed solution, 3h is impregnated, 100 DEG C are dried 12h, 500 DEG C of roasting 2h.
Above-mentioned product tabletting is crushed to into 20～40 mesh, it is also to adopt hydrogen volume content for 5% hydrogen-nitrogen gaseous mixture
Former agent, reduction temperature is 340 DEG C, and the recovery time obtained catalyst for 1 hour, and catalysis composition is shown in Table 1.
2nd, evaluating catalyst
The catalyst ethane and benzene alkylation reaction performance are evaluated according to the same manner as in Example 1.Reaction result is shown in Table 2.
【Embodiment 5】
1st, catalyst preparation
(molecular formula is H to weigh the chloroplatinic acid containing 0.5g Pt2PtCl6·6H2O zinc nitrate), equivalent to 0.7g ZnO (divides
Minor is Zn (NO3)2·6H2O), equivalent to 0.8g Cr2O3Ganite (Fujisawa). (molecular formula be Cr (NO3)3·9H2) and phase O
When in 0.8g In2O3Indium nitrate (molecular formula be In (NO3)3·5H2O in) being added to 120mL deionized waters, stirring
It is all dissolved, form mixed solution；The Hydrogen ZSM-5 molecular sieve (Si/Al mol ratios are 46) of 97.2g is weighed,
In being then added to above-mentioned mixed solution, 3h is impregnated, 100 DEG C are dried 12h, 500 DEG C of roasting 2h.
Above-mentioned product tabletting is crushed to into 20～40 mesh, it is also to adopt hydrogen volume content for 5% hydrogen-nitrogen gaseous mixture
Former agent, reduction temperature is 340 DEG C, and the recovery time obtained catalyst for 1 hour, and catalysis composition is shown in Table 1.
2nd, evaluating catalyst
The catalyst ethane and benzene alkylation reaction performance are evaluated according to the same manner as in Example 1.Reaction result is shown in Table 2.
【Comparative example 1】
1st, catalyst preparation
(molecular formula is H to weigh the chloroplatinic acid containing 1.2g Pt2PtCl6·6H2O), equivalent to 1.1g Cr2O3Chromic nitrate (point
Minor is Cr (NO3)3·9H2O) and equivalent to 0.8g Ga2O3Ganite (Fujisawa). (molecular formula be Ga (NO3)3·9H2O) add
To in 120mL deionized waters, stirring makes it all dissolve, and forms mixed solution；Weigh the Hydrogen ZSM-5 of 96.9g
Molecular sieve (Si/Al mol ratios are 46), in being then added to above-mentioned mixed solution, impregnates 3h, and 100 DEG C are dried 12h,
500 DEG C of roasting 2h.
Above-mentioned product tabletting is crushed to into 20～40 mesh, it is also to adopt hydrogen volume content for 5% hydrogen-nitrogen gaseous mixture
Former agent, reduction temperature is 340 DEG C, and the recovery time obtained catalyst for 1 hour, and catalysis composition is shown in Table 1.
2nd, evaluating catalyst
The catalyst ethane and benzene alkylation reaction performance are evaluated according to the same manner as in Example 1.Reaction result is shown in Table 2.
【Comparative example 2】
1st, catalyst preparation
(molecular formula is Zn (NO to weigh zinc nitrate equivalent to 1.2g ZnO3)2·6H2O), equivalent to 1.1g Cr2O3's
(molecular formula is Cr (NO to chromic nitrate3)3·9H2O) and equivalent to 0.8g Ga2O3Ganite (Fujisawa). (molecular formula is
Ga(NO3)3·9H2O in) being added to 120mL deionized waters, stirring makes it all dissolve, and forms mixed solution；Weigh
The Hydrogen ZSM-5 molecular sieve (Si/Al mol ratios are 46) of 96.9g, in being then added to above-mentioned mixed solution, impregnates 3h,
100 DEG C are dried 12h, 500 DEG C of roasting 2h.
Above-mentioned product tabletting is crushed to into 20～40 mesh, it is also to adopt hydrogen volume content for 5% hydrogen-nitrogen gaseous mixture
Former agent, reduction temperature is 340 DEG C, and the recovery time obtained catalyst for 1 hour, and catalysis composition is shown in Table 1.
2nd, evaluating catalyst
The catalyst ethane and benzene alkylation reaction performance are evaluated according to the same manner as in Example 1.Reaction result is shown in Table 2.
Compared with embodiment 2 and 3 by embodiment 1, Cr and Ga is showed in terms of ethane and benzene conversion ratio is improved
Go out to cooperate with facilitation.By embodiment 1 and comparative example 1 and 2, in terms of ethane and benzene conversion ratio is improved Pt and
Zn elements show to cooperate with facilitation.
The catalyst of table 1 constitutes (representing with weight percentage)
| Pt | ZnO | Cr2O3 | Ga2O3 | In2O3 | ZSM-5 | |
| Embodiment 1 | 0.5 | 0.7 | 1.1 | 0.8 | - | 96.9 |
| Embodiment 2 | 0.5 | 0.7 | - | 1.9 | - | 96.9 |
| Embodiment 3 | 0.5 | 0.7 | 1.9 | - | - | 96.9 |
| Embodiment 4 | 0.5 | 0.7 | 1.1 | 0.8 | 96.9 | |
| Embodiment 5 | 0.5 | 0.7 | - | 0.8 | 0.8 | 97.2 |
| Comparative example 1 | 1.2 | - | 1.1 | 0.8 | - | 96.9 |
| Comparative example 2 | - | 1.2 | 1.1 | 0.8 | - | 96.9 |
The evaluating catalyst result of table 2
Claims (9)
1. the catalyst of ethane and benzene alkylation reaction, including following components：
(a) Pt or its oxide；
The oxide of (b) Zn；
At least one in (c) VIB or IIIA in metal-oxide；
(d) molecular sieve.
2. catalyst according to claim 1, is characterized in that, in terms of parts by weight, composition (a) is 0.1～4
Part.
3. catalyst according to claim 1, is characterized in that, in terms of parts by weight, composition (b) is 0.1～4
Part.
4. catalyst according to claim 1, is characterized in that, in terms of parts by weight, composition (c) is 0.1～10
Part.
5. catalyst according to claim 1, is characterized in that, in terms of parts by weight, composition (d) is 80～100
Part.
6. catalyst according to claim 1, is characterized in that：The molecular sieve is hydrogen type molecular sieve.
7. catalyst according to claim 1, is characterized in that：The molecular sieve be ZSM-5, Beta molecular sieve,
At least one in MCM-22, ZSM-35, HMOR molecular sieve.
8. the preparation method of catalyst described in claim 1, comprises the steps：
(1) by containing the compound at least one of metal, the compound containing Pt and the change containing Zn in the VIB or IIIA
Compound is scattered in solvent；
(2) dispersion for obtaining step (1) impregnates the molecular sieve；
(3) roasting.
9. the method for ethane and benzene alkylation reaction, with ethane and benzene as raw material, any one of claim 1～8
Reaction in the presence of catalyst obtains the alkylbenzenes such as ethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510662113.2A CN106582796B (en) | 2015-10-14 | 2015-10-14 | The catalyst of ethane and benzene alkylation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510662113.2A CN106582796B (en) | 2015-10-14 | 2015-10-14 | The catalyst of ethane and benzene alkylation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582796A true CN106582796A (en) | 2017-04-26 |
| CN106582796B CN106582796B (en) | 2019-07-09 |
Family
ID=58553014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510662113.2A Active CN106582796B (en) | 2015-10-14 | 2015-10-14 | The catalyst of ethane and benzene alkylation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582796B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263480A (en) * | 1997-06-11 | 2000-08-16 | 戴姆勒-克莱斯勒股份公司 | Storage catalyst |
| CN1058476C (en) * | 1995-05-05 | 2000-11-15 | 陶氏化学公司 | Process of preparing ethylbenzene or substed. derivs. thereof |
| CN102451750A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Selective dealkylation catalyst for alkyl aromatic hydrocarbon |
| CN103962172A (en) * | 2014-04-30 | 2014-08-06 | 上海倍能化工技术有限公司 | Method for preparing high-carbon hydrocarbon by using low-carbon oxygen containing compound as well as catalyst and preparation method thereof |
-
2015
- 2015-10-14 CN CN201510662113.2A patent/CN106582796B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058476C (en) * | 1995-05-05 | 2000-11-15 | 陶氏化学公司 | Process of preparing ethylbenzene or substed. derivs. thereof |
| CN1263480A (en) * | 1997-06-11 | 2000-08-16 | 戴姆勒-克莱斯勒股份公司 | Storage catalyst |
| CN102451750A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Selective dealkylation catalyst for alkyl aromatic hydrocarbon |
| CN103962172A (en) * | 2014-04-30 | 2014-08-06 | 上海倍能化工技术有限公司 | Method for preparing high-carbon hydrocarbon by using low-carbon oxygen containing compound as well as catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582796B (en) | 2019-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106268923B (en) | A kind of preparation method and application of bifunctional catalyst | |
| CN107970988B (en) | Catalyst for synthesizing aromatic hydrocarbon and preparation method thereof | |
| WO2018010358A1 (en) | Method for preparing styrene from side-chain alkylation of methylbenzene and synthesis gas | |
| CN104722305A (en) | Catalyst applicable to synthesis of methanol by multi-component mixed gas as well as preparation method and application of methanol catalyst | |
| CN104399520A (en) | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst | |
| US20220144748A1 (en) | Method for producing methyl acetate by means of carbonylation of dimethyl ether | |
| CN105732288A (en) | Selective hydrogenation method of carbon four-fraction | |
| CN106582791B (en) | Catalyst for benzene and ethane ethylbenzene | |
| CN107282090B (en) | The catalyst that ethane is reacted with benzene | |
| TWI549749B (en) | A catalyst composition for preparing o-phenylphenol and a process for preparing o-phenylphenol using the catalyst composition | |
| CN106316766A (en) | Aromatization method | |
| CN105732255A (en) | Selective hydrogenation method for alkyne | |
| CN106582796A (en) | Catalyst used for alkylation reaction of ethane and benzene | |
| CN107282100B (en) | The catalyst of ethane alkylated reaction | |
| CN106582792B (en) | The catalyst of benzene and ethane alkylated reaction | |
| CN106582795A (en) | Catalyst for alkylation reaction of ethane and benzene | |
| CN102309978B (en) | Ethyl benzene dealkylation catalyst and preparation method and application thereof | |
| CN107282098B (en) | The catalyst reacted for ethane with benzene | |
| CN106966849A (en) | A kind of method for improving oxygenatedchemicals aromatisation yield | |
| CN107282089B (en) | Catalyst for alkylation of benzene and ethane | |
| CN106582790B (en) | The catalyst reacted is alkylated with ethane for benzene | |
| CN104549432B (en) | The synthetic method of aromatic hydrocarbons methylation catalyst and dimethylbenzene | |
| CN107304368A (en) | A kind of method for synthesizing high density aviation fuel | |
| CN102806101A (en) | Catalyst for preparing ethylene by conversion of ethanol and preparation method of catalyst | |
| CN106256811B (en) | The composition that the method and this method for synthesizing aromatic hydrocarbons obtain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |