CN102219630B - Method for producing ethylene by virtue of dehydration of ethanol - Google Patents

Method for producing ethylene by virtue of dehydration of ethanol Download PDF

Info

Publication number
CN102219630B
CN102219630B CN2010101477749A CN201010147774A CN102219630B CN 102219630 B CN102219630 B CN 102219630B CN 2010101477749 A CN2010101477749 A CN 2010101477749A CN 201010147774 A CN201010147774 A CN 201010147774A CN 102219630 B CN102219630 B CN 102219630B
Authority
CN
China
Prior art keywords
parts
catalyzer
hours
ethanol
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.)
Active
Application number
CN2010101477749A
Other languages
Chinese (zh)
Other versions
CN102219630A (en
Inventor
徐菁
金萍
李亚男
金照生
杨为民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN2010101477749A priority Critical patent/CN102219630B/en
Publication of CN102219630A publication Critical patent/CN102219630A/en
Application granted granted Critical
Publication of CN102219630B publication Critical patent/CN102219630B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a method for producing ethylene by virtue of dehydration of ethanol, and the method is mainly used for solving the problem that the selectivity of ethylene is low in the prior art. The method comprises the following steps: based on a 5-100wt% ethanol aqueous solution serving as a raw material, contacting the reaction raw material with a catalyst so as to generate ethylene at the reaction temperature of 250-500 DEG C at the volume space velocity of 0.1-25 h<-1>, wherein the catalyst comprises the following components in parts by weight: a) 1-99 parts of SiO2 and b) 1-99 parts of Al2O3 surface coating. By using the technical scheme, the problem that the selectivity of ethylene is low in the prior art is well solved. The method can be used in industrial production for preparing ethylene by virtue of dehydration of ethanol.

Description

The method of producing ethylene by ethanol dehydration
Technical field
The present invention relates to a kind of method of producing ethylene by ethanol dehydration.
Background technology
Ethene, molecular formula C 2H 4, be very important petrochemical material.Producing ethylene from dehydration of ethanol was once the route of a widely used acquisition ethene, and the history of more than 200 year has been arranged, and at 19th-century, was once main ethylene production route.Flourish due to the twentieth century petrochemical complex, cracking ethylene preparation is more economical, and this route is eliminated gradually.But, in some occasion, as the ethanol wide material sources, under the situation such as the ethene consumption is less, ethanol dehydration is still being used.
More and more face exhausted danger along with a large amount of uses of petroleum resources, oil price day by day soaring, the competitive edge of cracking legal system ethene route is more and more less.The producing ethylene from dehydration of ethanol route becomes again competitive technological line.The particularly exploitation of new alcohol production technology, ethanol as processed as synthetic gas, the biological legal system ethanol of Mierocrystalline cellulose etc.
The producing ethylene from dehydration of ethanol reaction is stronger thermo-negative reaction, producing ethylene from dehydration of ethanol is industrial hotbed and two kinds of techniques of adiabatic reactor such as at present, the isothermal bed reaction technique generally adopts shell and tube reactor, and catalyst loading is in tubulation, and between pipe, medium provides reaction needed heat.Adiabatic reactor technique adopts the multi-stage type reactor, the mode of intersegmental heat supply.On hotbed and adiabatic reactor reaction process, its characteristics are respectively arranged, isothermal bed process energy consumption is relatively low, but yield is a little less than adiabatic reactor technique.
Aluminum oxide, load phosphoric acid, pure aluminium silicate etc. can be arranged for the catalyzer of producing ethylene from dehydration of ethanol, and what studies have reported that has molecular sieve, heteropolyacid etc., an industrial aluminium oxide catalyst that mainly still adopts.In order to improve the catalytic performance of aluminium oxide catalyst, it has been carried out to a lot of improvement, such as the aluminum oxide that adds second component.
Document US4207424 discloses a kind of with Al 2O 3For carrier, by adopting the organosilicon vapour deposition process, prepare SiO 2-Al 2O 3The method of the catalyzer of the corresponding alkene of dehydration of alcohols system, alcohol comprises fatty alcohol, aromatic alcohol, cyclic alcohol etc.Mainly enumerated the situation of methyl phenyl carbinol dehydration in embodiment, only has the reaction that an embodiment is ethanol dehydration, the variation of only having compared ethylene content in the product of silanization front and back, 350 ℃ of temperature of reaction, after silanization, ethylene content is brought up to 24wt% from 19wt%, has improved 26.3%, has the problem that ethylene selectivity is lower.
[γ-the Al such as Li Ying 2O 3The experimental study of producing ethylene from dehydration of ethanol on catalyzer, Beijing University of Chemical Technology's journal, 2007,34 (5): 449-452] adopt the alumina granules ethanol dehydration catalyzer of 0.3～1 millimeter, temperature of reaction is more than 420 ℃, and ethanol conversion just can reach 99%.
Document EP0498573 discloses a kind of γ-Al 2O 3Catalyzer, at 0.5 hour -1, 400 ℃, under 18 kilograms of pressure conditions, ethanol conversion 83%, ethylene selectivity 94%.There is equally the shortcoming that ethylene selectivity is lower.
Summary of the invention
Technical problem to be solved by this invention is the problem that exists ethylene selectivity low in conventional art, and a kind of method of new producing ethylene by ethanol dehydration is provided.The method has the advantages that ethylene selectivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing ethylene by ethanol dehydration, the aqueous ethanolic solution that the weight percent concentration of take is 5～100% is raw material, in temperature of reaction, is 250～500 ℃, with respect to the volume space velocity of ethanol, is 0.1～25 hour -1Under condition, reaction raw materials contacts with catalyzer and generates ethene; Wherein catalyzer used, in parts by weight, comprises following component:
A) SiO of 1～99 part 2Kernel;
B) Al of 1～99 part 2O 3Top coat.
In technique scheme, in parts by weight, SiO 2The consumption preferable range of kernel is 50～98 parts, and more preferably scheme is 70～95 parts; Al 2O 3The consumption preferable range of top coat is 2～50 parts, and more preferably scheme is 5～30 parts.The temperature of reaction preferable range is 300～450 ℃, with respect to the volume space velocity preferable range of ethanol, is 0.5～15 hour -1.
In the present invention, the preparation method of catalyzer can adopt pickling process, coprecipitation method, chemical deposition, chemiadsorption, physical mixed method, and preferred method is pickling process.Pickling process, be about to be selected from least one carrier in silica gel, silicon-dioxide or White Carbon black, with the aluminum compound dipping be dissolved in solvent, carries out surface treatment, and then drying, roasting obtain described catalyzer; Wherein the consumption of aluminum compound is vehicle weight 1～99%, described aluminum compound is selected from least one in aluminum nitrate, Tai-Ace S 150, three aluminum ethylates, aluminum isopropylate or isobutanol aluminum, and described solvent is selected from least one in water, normal hexane, benzene, toluene, ethanol, acetone, ether or dme.Wherein, the dipping temperature preferable range is 5～100 ℃, and the dipping time preferable range is 1～50 hour; The drying temperature preferable range is 80～150 ℃, and time of drying, preferable range was 4～20 hours; The maturing temperature preferable range is 500～700 ℃, and the roasting time preferable range is 3～20 hours.Dipping, drying, roasting process can carry out repeatedly, to obtain desired Al 2O 3Content.
SiO 2And Al 2O 3During Individual existence, acidity is all very weak, but shows very strong acidity after mutually combining.This is had to two kinds of explanations, the firstth, SiO 2-Al 2O 3On surface, first aluminum ion is only linked by oxo bridge by the silicon of three positive tetravalences, and the side outside surface lacks a coordination silicon.This mal-distribution of silicon causes aluminum ion to have strong electrophilic characteristic.When the close this aluminum ion of water molecules, the negativity hydroxyl of water molecules is attracted by aluminum ion, and result is isolated a proton, has formed B acid, and three-fold coordination aluminium originally plays L acid effect.The second is Al 3+To Si in the silicon oxide skeleton 4+Isomorphous substitution, make to replace point and unnecessary negative charge occurred, therefore play the H of trim electrical function +Become B acid.Slough with the form of water if acid hydroxy group is heated, form three-fold coordination aluminium, this aluminium becomes the L acid site.As follows.
Figure GSA00000085480200031
So employing the inventive method, can make reaction carry out at 300～450 ℃ of lower temperature, avoids the polymerization of ethene, and the selectivity of ethene can be reached more than 98%, than pure alumina catalyzer, improved 3～5%, obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
30 gram aluminum nitrates are dissolved in 25 gram deionized waters, get silica-gel carrier 20 grams, the above-mentioned solution of dipping under 20 ℃ of conditions, take out 120 ℃ and dry 5 hours after 3 hours, put 600 ℃ of roastings of retort furnace 4 hours, cooling rear taking-up obtains catalyst A through double-steeping, oven dry, roasting again.Al in catalyzer 2O 3The parts by weight of top coat are 22.5 parts, SiO 2The kernel parts by weight are 77.5 parts.
[embodiment 2]
20 gram Tai-Ace S 150 are dissolved in 100 gram deionized waters, get silica supports 20 grams, the above-mentioned solution of dipping under 50 ℃ of conditions, take out 100 ℃ and dry 6 hours after 4 hours, put 500 ℃ of roastings of retort furnace 5 hours, cooling rear taking-up obtains catalyst B through double-steeping, oven dry, roasting again.Al in catalyzer 2O 3The parts by weight of top coat are 25.2 parts, SiO 2The kernel parts by weight are 74.8 parts
[embodiment 3]
12 gram aluminum nitrates are dissolved in 20 gram deionized waters, get White Carbon black carrier 15 grams, the above-mentioned solution of dipping under 70 ℃ of conditions, take out 110 ℃ and dry 4 hours after 2 hours, put 650 ℃ of roastings of retort furnace 4 hours, obtains catalyzer C.Al in catalyzer 2O 3The parts by weight of top coat are 13.0 parts, SiO 2The kernel parts by weight are 87.0 parts.
[embodiment 4]
15 gram Tai-Ace S 150 are dissolved in 100 gram deionized waters, get silica-gel carrier 15 grams, the above-mentioned solution of dipping under 40 ℃ of conditions, take out latter 120 ℃ in 2 hours and dry 4 hours, puts 700 ℃ of roastings of retort furnace 5 hours, obtains catalyzer D.Al in catalyzer 2O 3The parts by weight of top coat are 12.3 parts, SiO 2The kernel parts by weight are 87.7 parts.
[embodiment 5]
Get silica-gel carrier 20 grams, be placed under the 10 ℃ of conditions of solution that formed by 10 gram three aluminum ethylates and 30 gram dehydrated alcohols, flood 5 hours, take out latter 140 ℃ and dry 5 hours, then put 600 ℃ of roastings of retort furnace 4 hours, obtain catalyzer E.Al in catalyzer 2O 3The parts by weight of top coat are 8.5 parts, SiO 2The kernel parts by weight are 91.5 parts.
[embodiment 6]
Get silica-gel carrier 20 grams, be placed under the 15 ℃ of conditions of solution that formed by 20 gram aluminum isopropylates and 50 gram benzene, flood 10 hours, take out latter 110 ℃ and dry 6 hours, then put 700 ℃ of roastings of retort furnace 4 hours, obtain catalyzer F.Al in catalyzer 2O 3The parts by weight of top coat are 15.6 parts, SiO 2The kernel parts by weight are 84.4 parts.
[embodiment 7]
Get silica-gel carrier 15 grams, be placed under the 25 ℃ of conditions of solution that formed by 20 gram isobutanol aluminums and 30 gram ether, flood 20 hours, take out latter 120 ℃ and dry 8 hours, then put 550 ℃ of roastings of retort furnace 8 hours, obtain catalyzer G.Al in catalyzer 2O 3The parts by weight of top coat are 18.2 parts, SiO 2The kernel parts by weight are 81.8 parts.
[embodiment 8]
Get silica-gel carrier 25 grams, be placed under the 20 ℃ of conditions of solution that formed by 20 gram aluminum isopropylates and 40 gram dme, flood 8 hours, take out latter 110 ℃ and dry 10 hours, put 700 ℃ of roastings of retort furnace 4 hours, cooling rear taking-up obtains catalyzer H through double-steeping, oven dry, roasting more again.Al in catalyzer 2O 3The parts by weight of top coat are 27.7 parts, SiO 2The kernel parts by weight are 72.3 parts.
[Comparative Examples 1]
Weighing pseudo-boehmite 300 grams, sesbania powder 15 grams are mediated 20 minutes in kneader, add 200 milliliters of 5% salpeter solutions, then mediate 25 minutes, extruded moulding then, and 120 ℃ of dryings 12 hours, 550 ℃ of roastings 10 hours, obtain catalyst I.Al in catalyzer 2O 3Parts by weight be 100 parts.
[Comparative Examples 2]
Weighing silica gel 200 grams are dried 12 hours in 120 ℃, and 550 ℃ of roastings 10 hours, obtain catalyzer J.SiO in catalyzer 2Parts by weight be 100 parts
[embodiment 9～16]
Catalyst A～H prepared by [embodiment 1～8] carries out catalytic performance test.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters stainless steels of Φ), and the catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation, and gas phase adopts HP6890 gas-chromatography (3398 workstation), Al 2O 3Pillar, hydrogen flame detector; Liquid phase adopts HP4890, Plot Q kapillary pillar.Reaction conditions and reaction result are in Table 1.
[Comparative Examples 3～6]
By each Step By Condition of [embodiment 9], catalyst I～J prepared by [Comparative Examples 1～2] carries out catalytic performance test.Reaction conditions and reaction result are in Table 1.
Table 1
Embodiment Catalyzer Raw material Temperature, ℃ Air speed, hour -1 Ethanol conversion, % Ethylene selectivity, %
Embodiment 9 A 95% ethanol 360 12 99.35 99.23
Embodiment 10 B 10% ethanol 310 1 98.14 98.07
Embodiment 11 C 80% ethanol 420 15 100.00 99.57
Embodiment 12 D 20% ethanol 330 2 99.51 99.35
Embodiment 13 E 35% ethanol 350 5 99.79 99.42
Embodiment 14 F 75% ethanol 370 8 99.84 99.58
Embodiment 15 G 45% ethanol 330 5 99.38 99.29
Embodiment 16 H 50% ethanol 340 10 99.49 99.61
Comparative Examples 3 I 95% ethanol 360 12 98.66 96.90
Comparative Examples 4 I 10% ethanol 310 1 80.50 56.87
Comparative Examples 5* J 95% ethanol 360 12 - -
Comparative Examples 6* J 10% ethanol 310 1 - -
* in these two Comparative Examples, do not react.

Claims (2)

1. the method for a producing ethylene by ethanol dehydration, the aqueous ethanolic solution that the weight percent concentration of take is 80% is raw material, in temperature of reaction, is 420 ℃, with respect to the volume space velocity of ethanol, is 15 hours -1Under condition, reaction raw materials contacts with catalyzer C and generates ethene; Reaction is carried out on fixed-bed tube reactor, and described reactor is of a size of 25 * 500 millimeters of Φ, and described reactor is stainless steel, and catalyzer C loading capacity is 10 milliliters; Reaction product is analyzed respectively after gas-liquid separation, and gas phase adopts the HP6890 gas-chromatography, adopts 3398 workstations, Al 2O 3Pillar, hydrogen flame detector; Liquid phase adopts HP4890, Plot Q kapillary pillar; Reaction result is ethanol conversion 100.00%, ethylene selectivity 99.57%; Wherein said catalyzer C preparation method is as follows:
12 gram aluminum nitrates are dissolved in 20 gram deionized waters, get White Carbon black carrier 15 grams, the above-mentioned solution of dipping under 70 ℃ of conditions, take out 110 ℃ and dry 4 hours after 2 hours, put 650 ℃ of roastings of retort furnace 4 hours, obtains catalyzer C; Al in catalyzer 2O 3The parts by weight of top coat are 13.0 parts, SiO 2The kernel parts by weight are 87.0 parts.
2. the method for a producing ethylene by ethanol dehydration, the aqueous ethanolic solution that the weight percent concentration of take is 50% is raw material, in temperature of reaction, is 340 ℃, with respect to the volume space velocity of ethanol, is 10 hours -1Under condition, reaction raw materials contacts with catalyzer H and generates ethene; Reaction is carried out on fixed-bed tube reactor, and described reactor is of a size of 25 * 500 millimeters of Φ, and described reactor is stainless steel, and catalyzer H loading capacity is 10 milliliters; Reaction product is analyzed respectively after gas-liquid separation, and gas phase adopts the HP6890 gas-chromatography, adopts 3398 workstations, Al 2O 3Pillar, hydrogen flame detector; Liquid phase adopts HP4890, Plot Q kapillary pillar; Reaction result is ethanol conversion 99.49%, ethylene selectivity 99.61%; Wherein said catalyzer H preparation method is as follows:
Get silica-gel carrier 25 grams, be placed under the 20 ℃ of conditions of solution that formed by 20 gram aluminum isopropylates and 40 gram dme, flood 8 hours, take out latter 110 ℃ and dry 10 hours, put 700 ℃ of roastings of retort furnace 4 hours, cooling rear taking-up obtains catalyzer H through double-steeping, oven dry, roasting more again; Al in catalyzer 2O 3The parts by weight of top coat are 27.7 parts, SiO 2The kernel parts by weight are 72.3 parts.
CN2010101477749A 2010-04-15 2010-04-15 Method for producing ethylene by virtue of dehydration of ethanol Active CN102219630B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010101477749A CN102219630B (en) 2010-04-15 2010-04-15 Method for producing ethylene by virtue of dehydration of ethanol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010101477749A CN102219630B (en) 2010-04-15 2010-04-15 Method for producing ethylene by virtue of dehydration of ethanol

Publications (2)

Publication Number Publication Date
CN102219630A CN102219630A (en) 2011-10-19
CN102219630B true CN102219630B (en) 2013-12-04

Family

ID=44776365

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010101477749A Active CN102219630B (en) 2010-04-15 2010-04-15 Method for producing ethylene by virtue of dehydration of ethanol

Country Status (1)

Country Link
CN (1) CN102219630B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN2014DN06848A (en) * 2012-01-20 2015-05-22 Mitsui Chemicals Inc
CN106831308B (en) * 2015-12-03 2020-01-03 中国石油化工股份有限公司 Method for preparing n-pentene from n-pentanol

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101274286A (en) * 2007-03-28 2008-10-01 湖南大学 Catalyst used in reaction process of producing ethylene from dehydration of ethanol

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101274286A (en) * 2007-03-28 2008-10-01 湖南大学 Catalyst used in reaction process of producing ethylene from dehydration of ethanol

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Bei Cheng et al..Facile fabrication of SiO2/Al2O3 composite microspheres with a simple electrostatic attraction strategy.《Materials Research Bulletin》.2007,第43卷(第3期),摘要、第714页.
Facile fabrication of SiO2/Al2O3 composite microspheres with a simple electrostatic attraction strategy;Bei Cheng et al.;《Materials Research Bulletin》;20070405;第43卷(第3期);第714页 *

Also Published As

Publication number Publication date
CN102219630A (en) 2011-10-19

Similar Documents

Publication Publication Date Title
CN109701629B (en) Combined catalyst for preparing low-carbon olefin and use method thereof
CN102372562B (en) Method for producing ethene by ethanol dehydration
CN102219630B (en) Method for producing ethylene by virtue of dehydration of ethanol
CN105312044B (en) C6~C10 dehydration of alcohols prepares the catalyst of corresponding carbon number
CN103058809B (en) Method for preparing low-carbon alkenes by low-carbon alkane dehydrogenation
CN109678174B (en) Hierarchical pore ZSM-5 molecular sieve, and preparation method and application thereof
CN102190543B (en) Method for preparing ethylene by dehydrating ethanol
CN102218307B (en) Catalyst for ethanol dehydration and preparation method
CN103664452B (en) Method for producing ethylene by dehydration of alcohol
CN102049313A (en) Preparation method of load catalyst
CN102372561B (en) Method for preparing ethylene by using ethanol
CN102649670B (en) Method for preparing ethylene through dehydration of ethanol
CN103058808A (en) Method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation
CN101768040A (en) Method for preparing propylene from butylene and ethylene
CN112642455B (en) Aluminum nitride supported metal oxide catalyst for synthesizing guaiacol and preparation method and application thereof
CN104557404B (en) Method for preparing isobutene through dehydrogenation of iso-butane
CN104230624B (en) Vanadium-based catalyst for light alkane dehydrogenation to produce alkene and preparation method and process thereof
CN103030501A (en) Method for producing propylene
CN115477568B (en) Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropolyacid
CN106316742B (en) The method for producing C 4 olefin
CN104689853B (en) A kind of preparation method and application for being used to prepare the catalyst of iso-amylene
CN103121900B (en) Method for preparing ethylene by dehydrating ethanol
CN104151120B (en) The method of preparing ethylene by dehydrating ethanol
CN103787841B (en) A kind of method of synthesizing tertiary amyl ethyl ether
CN103055953A (en) Low-carbon alkane dehydrogenation catalyst carrier and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant