CN103896706B - A kind of method utilizing Dextrose production propylene - Google Patents

A kind of method utilizing Dextrose production propylene Download PDF

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Publication number
CN103896706B
CN103896706B CN201210570625.2A CN201210570625A CN103896706B CN 103896706 B CN103896706 B CN 103896706B CN 201210570625 A CN201210570625 A CN 201210570625A CN 103896706 B CN103896706 B CN 103896706B
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propylene
reaction
alkali
catalyzer
glucose
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CN103896706A (en
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董兴隆
黄为
袁丹华
徐云鹏
刘中民
李铭芝
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a kind of novel method utilizing Dextrose production propylene.Method of the present invention utilize glucose in the basic conditions after pyrolysis through the process of catalyst bed reaction preparing propone.Method choice of the present invention is high, and process is simple, is easy to control, has very high economic worth and prospects for commercial application.

Description

A kind of method utilizing Dextrose production propylene
Technical field
The invention belongs to a kind of novel method utilizing Dextrose production propylene, the method is applicable to utilizing glucose alkalescence catalytic pyrolysis preparing to get propylene.
Background technology
Propylene is a kind of important industrial chemicals.What propylene consumption was maximum is produces polypropylene, in addition propylene can acrylonitrile production, Virahol, phenol and acetone, butanols and octanol, vinylformic acid and lipid thereof and propylene oxide processed and propylene glycol, epoxy chloropropane and synthetic glycerine etc.
Current propylene is produced primarily of fossil energy route.Along with the environmental problem that the day by day exhausted of oil equal energy source and fossil energy are brought, reproducible biomass energy receives to be paid close attention to widely.
Chinese patent CN101747135A proposes a kind of method of producing low-carbon alkene by catalytic pyrolysis of biomass, contact in riser tube or fluidized-bed reactor with the catalyzer containing five-ring supersiliceous zeolite with the raw material of hydrocarbon ils by biomass material or containing biomass, carry out being obtained by reacting product liquid and the gaseous product containing ethene, propylene under cracking condition.Chinese patent CN102531816A proposes a kind of method of preparing low-carbon alkene by catalytic cracking of micro algae, the preatreating reactors and the catalytic cracking reaction device that the flowing material carrying micro-algae raw material are passed through series connection carry out catalytic pyrolysis, obtain the low-carbon alkene comprising ethene, propylene and butylene, biomass wherein mainly refer to lipid acid.Chinese patent CN101747134A proposes a kind of method of producing low-carbon alkene by catalytically cracking biomass, and by biomass material or the raw material and the cracking catalyst contact reacts that contain biomass and hydrocarbon ils, biomass wherein mainly refer to lipid acid.
Glucose is the widest and of paramount importance a kind of monose of distributed in nature, is a kind of very important biomass energy.The utilization of current glucose mainly uses the method for biological fermentation to produce various chemical, and the production concentration of biological fermentation is low, and the energy that enriching and purifying needs is very large, and the cycle used of fermenting is very long.Utilize the technology of Dextrose production propylene and report less.
Therefore the novel method researching and developing the waste propylene that a kind of utilization is easy to get is needed.
Summary of the invention
For overcoming the problems of the prior art, the object of this invention is to provide a kind of novel method utilizing Dextrose production propylene.The present invention unexpectedly utilizes glucose in the basic conditions can preparing propone through catalyst bed reaction after pyrolysis.
Therefore, the invention provides and a kind ofly utilize the method for Dextrose production propylene (below sometimes referred to as " method of the present invention "), said method comprising the steps of: by glucose feed and excessive alkali (namely, alkali is greater than 1 with the mol ratio of glucose feed) mix after load tubular reactor epimere, catalyzer is placed in reactor hypomere, after catalyst activation, by reaction raw materials at 140 DEG C ~ 700 DEG C, preferably 300 DEG C ~ 700 DEG C heating 0.1hr ~ 2hr, preferred 1hr ~ 2hr, collect the gaseous product be obtained by reacting, described gaseous product comprises propylene.
In the method for the invention, glucose feed, alkali and catalyzer all can add in solid form, such as, directly with commercially available raw material form, or after suitable pulverizing or grinding plant process, make powder or particle form interpolation.If with powder or particle form charging, then its granularity is unrestricted, as long as be convenient to reactor charging and mutually mix.
In the method for the invention, alkali can be the mixture of a kind of in the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide or any two kinds.
In a preferred embodiment of method of the present invention, basic metal can be sodium, preferably uses its oxyhydroxide, i.e. sodium hydroxide.
In a preferred embodiment of method of the present invention, alkaline-earth metal can be calcium, preferably uses its oxide compound, i.e. calcium oxide.
In the further preferred embodiment of method of the present invention, alkali is the mixture of calcium oxide and sodium hydroxide, and the mol ratio of preferential oxidation calcium and sodium hydroxide is 1: 1 ~ 1: 5.
In the preferred embodiment of method of the present invention, catalyzer can be Al 2o 3, silicon oxide, molecular sieve (such as, ZSM-5 molecular sieve) etc., preferred Al 2o 3.The activation temperature of catalyzer and soak time can be determined according to the suitableeest conventional activation temperature of selected catalyzer and time.
In the preferred embodiment of method of the present invention, the activation temperature of catalyzer can be 180 DEG C ~ 550 DEG C, and preferably 250 DEG C ~ 550 DEG C, soak time can be selected in the scope of 0.5hr ~ 4hr.
In the present invention, the use of reactor is unrestricted, can to use in this area conventional tubular reactor, and such as, vertical tubular reactor, as long as this reactor is suitable for collecting gaseous product, and is suitable for catalyzer and raw material fully mixes.
Beneficial effect of the present invention:
1. method of the present invention opens a new route by Dextrose production propylene.
2. method choice of the present invention is high, and process is simple, is easy to control, has very high economic worth and prospects for commercial application.
Embodiment
Further describe technical scheme of the present invention and effect by the following examples, it should be appreciated by those skilled in the art that following embodiment is only for illustration of the present invention, does not really want to limit the scope of the invention.
Embodiment 1
By 10g glucose and 5g calcium oxide, 5g sodium hydroxide mixes, and is placed in tubular reactor, temperature of reaction 450 DEG C is set after 550 DEG C, aluminum oxide activation 4hr, by heating raw materials to 700 DEG C, reaction 1hr, collect the gas be obtained by reacting, gas total recovery 12.0%, the wherein yield 3.1% of propylene.
Embodiment 2
10g glucose is mixed with 10g calcium oxide, is placed in tubular reactor, after 450 DEG C, aluminum oxide activation 3hr, set temperature of reaction 450 DEG C, by heating raw materials to 500 DEG C, reaction 1hr, collects the gas be obtained by reacting, gas total recovery 10.5%, the wherein yield 2.6% of propylene.
Embodiment 3
10g glucose is mixed with 10g sodium hydroxide, is placed in tubular reactor, after 180 DEG C, aluminum oxide activation 4hr, set temperature of reaction 450 DEG C, by heating raw materials to 140 DEG C, reaction 1hr, collects the gas be obtained by reacting, gas total recovery 16.5%, the wherein yield 1.2% of propylene.
Embodiment 4
By 10g glucose and 5g calcium oxide, 5g sodium hydroxide mixes, be placed in tubular reactor, temperature of reaction 550 DEG C is set after 550 DEG C, aluminum oxide activation 0.5hr, by heating raw materials to 700 DEG C, reaction 1hr, collects the gas be obtained by reacting, gas total recovery 30.1%, the wherein yield 4.2% of propylene.
Embodiment 5
By 10g glucose and 5g calcium oxide, 5g sodium hydroxide mixes, and is placed in tubular reactor, temperature of reaction 250 DEG C is set after 350 DEG C, aluminum oxide activation 2hr, by heating raw materials to 500 DEG C, reaction 1hr, collect the gas be obtained by reacting, gas total recovery 10.1%, the wherein yield 1.7% of propylene.
Embodiment 6
By 10g glucose and 5g calcium oxide, 5g sodium hydroxide mixes, be placed in tubular reactor, temperature of reaction 450 DEG C is set after ZSM-5 molecular sieve 550 DEG C activation 2hr, by heating raw materials to 200 DEG C, reaction 1hr, collects the gas be obtained by reacting, gas total recovery 4.1%, the wherein yield 0.4% of propylene.
Embodiment 7
By 10g glucose and 5g calcium oxide, 5g sodium hydroxide mixes, be placed in tubular reactor, temperature of reaction 450 DEG C is set after 500 DEG C, aluminum oxide activation 2hr, by heating raw materials to 550 DEG C, reaction 0.1hr, collects the gas be obtained by reacting, gas total recovery 5.0%, the wherein yield 1.2% of propylene.
Embodiment 8
By 10g glucose and 5g calcium oxide, 5g sodium hydroxide mixes, and is placed in tubular reactor, temperature of reaction 450 DEG C is set after 550 DEG C, aluminum oxide activation 2hr, by heating raw materials to 550 DEG C, reaction 2hr, collect the gas be obtained by reacting, gas total recovery 12.7%, the wherein yield 3.5% of propylene.
Embodiment 9
By 10g glucose and 5g calcium oxide, 5g sodium hydroxide mixes, be placed in tubular reactor, temperature of reaction 450 DEG C is set after ZSM-5 molecular sieve 550 DEG C activation 2hr, by heating raw materials to 300 DEG C, reaction 1hr, collects the gas be obtained by reacting, gas total recovery 5.1%, the wherein yield 0.5% of propylene.

Claims (10)

1. one kind utilizes the method for Dextrose production propylene, said method comprising the steps of: after glucose feed being mixed with excessive alkali, load tubular reactor epimere, catalyzer is placed in reactor hypomere, after catalyst activation, by the heating temperatures 0.1hr ~ 2hr of reaction raw materials at 140 DEG C ~ 700 DEG C, collect the gaseous product be obtained by reacting, described gaseous product comprises propylene, and wherein glucose feed and excessive alkali refer to that the mol ratio of alkali and glucose feed is greater than 1.
2. method according to claim 1, is characterized in that described alkali is the mixture of a kind of in the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide or any two kinds.
3. method according to claim 2, is characterized in that described basic metal is sodium.
4. method according to claim 2, is characterized in that described alkaline-earth metal is calcium.
5. method according to claim 1, is characterized in that described alkali is the mixture of calcium oxide and sodium hydroxide.
6. method according to claim 5, is characterized in that the mol ratio of calcium oxide and sodium hydroxide is 1:1 ~ 1:5.
7. the method according to any one of claim 1-6, is characterized in that described catalyzer is for being selected from Al 2o 3, one in silicon oxide and molecular sieve.
8. the method according to any one of claim 1-6, is characterized in that described catalyzer is Al 2o 3.
9. the method according to any one of claim 1-6, is characterized in that the activation temperature of described catalyzer is 180 DEG C ~ 550 DEG C.
10. the method according to any one of claim 1-6, is characterized in that described temperature of reaction is 300 DEG C ~ 700 DEG C.
CN201210570625.2A 2012-12-25 2012-12-25 A kind of method utilizing Dextrose production propylene Expired - Fee Related CN103896706B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070191212A1 (en) * 2004-02-28 2007-08-16 Basf Aktiengesellschaft Supported catalyst with a defined pore distribution in the mesopore range
CN101747135A (en) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 Method for producing low-carbon alkene by catalytic pyrolysis of biomass
CN102015969A (en) * 2008-03-04 2011-04-13 马萨诸塞大学 Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds
CN102531816A (en) * 2010-12-28 2012-07-04 中国科学院大连化学物理研究所 Method for preparing low carbon olefin by catalytic pyrolysis of microalgae

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070191212A1 (en) * 2004-02-28 2007-08-16 Basf Aktiengesellschaft Supported catalyst with a defined pore distribution in the mesopore range
CN102015969A (en) * 2008-03-04 2011-04-13 马萨诸塞大学 Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds
CN101747135A (en) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 Method for producing low-carbon alkene by catalytic pyrolysis of biomass
CN102531816A (en) * 2010-12-28 2012-07-04 中国科学院大连化学物理研究所 Method for preparing low carbon olefin by catalytic pyrolysis of microalgae

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