CN103664452A - Method for producing ethylene by dehydration of alcohol - Google Patents

Method for producing ethylene by dehydration of alcohol Download PDF

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CN103664452A
CN103664452A CN201210325071.XA CN201210325071A CN103664452A CN 103664452 A CN103664452 A CN 103664452A CN 201210325071 A CN201210325071 A CN 201210325071A CN 103664452 A CN103664452 A CN 103664452A
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producing ethylene
ethanol
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reaction
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CN103664452B (en
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李亚男
金照生
徐菁
孙兰萍
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method of producing ethylene by dehydration of alcohol, which is used for solving a problem that a catalyst is low in activity in the prior art. In order to solve the problem, a following technical scheme is as follows: 5%-100% by weight alcohol aqueous liquor is taken as a material, the reaction material contacts with the catalyst to generate ethylene under conditions with a reaction temperature of 200 DEG C-500 DEG C and volume space velocity of 0.1 per hour-25 per hour relative to alcohol, wherein the used catalyst comprises the following components in parts by weight: (a), 1-99 parts of MCM (Molecular and Cellular Modeling)-41 molecular sieve and (b), 1-99 parts of Al2O3. And therefore, the method can be used for industrial production for preparing the ethylene by dehydration of alcohol.

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, as basic Organic Chemicals and the flagship product of petrochemical industry, is described as " mother of petrochemical complex ", mainly for the production of chemical such as polyethylene, ethylene oxide/ethylene glycol, ethylene dichloride, vinylbenzene, vinyl acetate between to for plastics.Along with the fast development of the ethene derivatives industries such as chemical industry, the energy, material, the demand of ethene is in continuous increase.Ethene is mainly derived from naphtha cracking at present.Because petroleum resources are non-renewable, gradually exhausted, thereby utilize reproducible biomass resource development bioenergy and biochemical industry to become inexorable trend current and even Economic development from now on.Ethanol can obtain through fermentation by plant amylum or wood fibre, and raw material sources are extensive, sufficient and renewable, can meet the needs of extensive biomass chemical industry development.Therefore, from producing ethylene from dehydration of ethanol, there is part or all of replacement and from oil, obtain the great potential of ethene.Producing ethylene by ethanol dehydration is traditional ethylene production route, continues to use this method always produce ethene in the country of some petroleum resources scarcities such as Brazil, India, Pakistan.
Along with a large amount of uses of petroleum resources, more and more face exhausted danger, oil price day by day soaring, the competitive edge of cracking legal system ethene route is more and more less.Producing ethylene from dehydration of ethanol route becomes again competitive technological line.The particularly exploitation of new alcohol production technology, ethanol as processed in synthetic gas, the development of the technology such as the biological legal system ethanol of Mierocrystalline cellulose, will greatly advance the large-scale application of producing ethylene with ethyl alcohol technology.
Alumina catalyst is the relatively ripe catalyzer of current industrial producing ethylene from dehydration of ethanol application, the catalyst performance that the code name of the U.S. Halcon company development eighties in last century is Syndol is best, it is harsh that but this catalyzer requires reaction conditions, temperature of reaction is high, ethanol raw material concentration requirement is high, causes whole energy consumption high.Therefore, the better catalyzer of exploitation performance, is converted into the ethanol of low concentration the long life catalytic agent of ethene efficiently, has become biomass by the key of system ethene in the middle of ethanol.Utilize zeolite catalysis producing ethylene from dehydration of ethanol, although temperature of reaction is lower, the stability of catalyzer is bad, and unrealized suitability for industrialized production.
Li Ying etc. [Beijing University of Chemical Technology's journal, 2007,34 (5): 449-452] adopt the alumina granules ethanol dehydration catalyzer of 0.3～1 millimeter, and temperature of reaction is more than 420 ℃, and ethanol conversion just can reach 99%.There is the shortcoming that catalyst activity is low.
Li Shulian etc. have introduced a kind of alumina having mesoporous structure catalyzer in patent [CN101643228A, 2010], but this catalyzer is 365 ℃ of temperature of reaction, air speed 3.15 hours -1, alcohol concn 95%(v/v) and under condition, ethanol conversion is only that 80% left and right, ethylene selectivity are only 70% left and right.There is the shortcoming that catalyst activity is low.
Document US4207424 discloses a kind of with Al 2o 3for carrier, by adopting organosilicon vapour deposition process to 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.In embodiment, mainly enumerated the situation of methyl phenyl carbinol dehydration, 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 catalyst activity is low.
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 problem that catalyst activity is low.
In sum,, there is the shortcoming that catalyst activity is low in the catalyzer adopting in conventional art.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the problem that catalyst activity is low, and a kind of method of new producing ethylene by ethanol dehydration is provided.The method has the advantages that catalyst activity 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 200 ~ 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) the MCM-41 molecular sieve of 1 ~ 99 part;
B) Al of 1 ~ 99 part 2o 3.
In technique scheme, in parts by weight, the consumption preferable range of MCM-41 molecular sieve is 1 ~ 50 part, and more preferably scheme is 2 ~ 20 parts; Al 2o 3consumption preferable range be 50 ~ 99 parts, more preferably scheme is 80 ~ 98 parts.Temperature of reaction preferable range is 200 ~ 450 ℃, and more preferably scope is 250 ~ 450 ℃; Volume space velocity preferable range with respect to ethanol is 0.5 ~ 20 hour -1, more preferably scope is 0.5 ~ 15 hour -1.
Catalyzer preferred version in the present invention can be prepared by the following method: silicon source, aluminium source, template, ammoniacal liquor and water are formed to mixture, and mixture is ℃ crystallization 0.5 ~ 5 day in room temperature ~ 120, after filtration, obtain MCM-41/Al after oven dry, roasting 2o 3; Wherein, SiO 2: Al 2o 3mass ratio be 1:1/99 ~ 99, SiO 2: CTMAB: ammoniacal liquor: H 2the mol ratio of O is 1:0.05 ~ 1:5 ~ 15:50 ~ 100.Wherein, described silicon source preferred version is at least one being selected from tetraethoxy, methyl silicate or silicon sol, and described aluminium source preferred version is for being selected from boehmite, and described template preferred version is for being selected from cetyl trimethylammonium bromide.
SiO 2and Al 2o 3during Individual existence, acidity is all very weak, but after mutually combining, shows very strong acidity.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 water molecules is during near this aluminum ion, 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 silicon oxide skeleton 4+isomorphous substitution, make to replace point and occurred unnecessary negative charge, therefore play the H of trim electrical function +become B acid.If acid hydroxy group is heated, with the form of water, slough, form three-fold coordination aluminium, this aluminium becomes L acid site.As follows.
Figure 299389DEST_PATH_IMAGE001
So employing the inventive method, can make reaction carry out at 300 ~ 450 ℃ of lower temperature, reduces temperature of reaction, be beneficial to and can lower consumption, the selectivity of ethene can reach more than 98% simultaneously, than pure alumina catalyzer, has improved 3 ~ 5%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the little angle XRD figure of [embodiment 3] synthetic catalyzer.
  
Below by embodiment, the present invention is further elaborated.
  
Embodiment
[embodiment 1]
4 grams of cetyl trimethylammonium bromides are dissolved in 104 grams of deionized waters, after stirring and dissolving, add 20 milliliters of tetraethoxys, stir 0.5 hour, add again 48 milliliters of ammoniacal liquor, under room temperature, stir 0.5 hour, then add 76 grams of boehmites, stir 5 hours, room temperature crystallization 2 days, filters 120 ℃ of oven dry, 550 ℃ of roastings 5 hours, obtain catalyst A.In catalyzer, MCM-41 parts by weight are 10 parts, Al 2o 3parts by weight are 90 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters of stainless steels of Ф), and catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction conditions and reaction result are in Table 1.
  
[embodiment 2]
6 grams of cetyl trimethylammonium bromides are dissolved in 104 grams of deionized waters, after stirring and dissolving, add 25 milliliters of methyl silicates, stir 0.5 hour, add again 50 milliliters of ammoniacal liquor, under room temperature, stir 0.5 hour, then add 48 grams of boehmites, stir 5 hours, 100 ℃ of crystallization 1 day, filter 120 ℃ of oven dry, 550 ℃ of roastings 5 hours, obtain catalyst B.In catalyzer, MCM-41 parts by weight are 16 parts, Al 2o 3parts by weight are 84 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters of stainless steels of Ф), and catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction conditions and reaction result are in Table 1.
  
[embodiment 3]
6 grams of cetyl trimethylammonium bromides are dissolved in 140 grams of deionized waters, after stirring and dissolving, add 30 milliliters of methyl silicates, stir 0.5 hour, add again 50 milliliters of ammoniacal liquor, under room temperature, stir 0.5 hour, then add 48 grams of boehmites, stir 5 hours, 80 ℃ of crystallization 2 days, filter 120 ℃ of oven dry, 550 ℃ of roastings 5 hours, obtain catalyzer C.In catalyzer, MCM-41 parts by weight are 30 parts, Al 2o 3parts by weight are 70 parts.In the little angle XRD diffractogram explanation catalyzer of synthetic catalyzer, really contain MCM-41 molecular sieve.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters of stainless steels of Ф), and catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction conditions and reaction result are in Table 1.
  
[embodiment 4]
2 grams of cetyl trimethylammonium bromides are dissolved in 60 grams of deionized waters, after stirring and dissolving, add 10 milliliters of tetraethoxys, stir 0.5 hour, add again 50 milliliters of ammoniacal liquor, under room temperature, stir 0.5 hour, then add 75 grams of boehmites, stir 5 hours, 80 ℃ of crystallization 1 day, filter 120 ℃ of oven dry, 550 ℃ of roastings 5 hours, obtain catalyzer D.In catalyzer, MCM-41 parts by weight are 5 parts, Al 2o 3parts by weight are 95 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters of stainless steels of Ф), and catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction conditions and reaction result are in Table 1.
  
[embodiment 5]
4 grams of cetyl trimethylammonium bromides are dissolved in 100 grams of deionized waters, after stirring and dissolving, add 13.4 gram of 40% silicon sol, stir 0.5 hour, add again 50 milliliters of ammoniacal liquor, under room temperature, stir 0.5 hour, then add 47 grams of boehmites, stir 5 hours, 110 ℃ of crystallization 1 day, filter 120 ℃ of oven dry, 550 ℃ of roastings 5 hours, obtain catalyzer E.In catalyzer, MCM-41 parts by weight are 16 parts, Al 2o 3parts by weight are 84 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters of stainless steels of Ф), and catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction conditions and reaction result are in Table 1.
  
[embodiment 6]
4 grams of cetyl trimethylammonium bromides are dissolved in 100 grams of deionized waters, after stirring and dissolving, add 15 gram of 40% silicon sol, stir 0.5 hour, add again 50 milliliters of ammoniacal liquor, under room temperature, stir 0.5 hour, then add 50 grams of boehmites, stir 5 hours, 110 ℃ of crystallization 1 day, filter 120 ℃ of oven dry, 550 ℃ of roastings 5 hours, obtain catalyzer F.In catalyzer, MCM-41 parts by weight are 17 parts, Al 2o 3parts by weight are 83 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters of stainless steels of Ф), and catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction conditions and reaction result are in Table 1.
  
[embodiment 7]
8 grams of cetyl trimethylammonium bromides are dissolved in 140 grams of deionized waters, after stirring and dissolving, add 30 milliliters of tetraethoxys, stir 0.5 hour, add again 76 milliliters of ammoniacal liquor, under room temperature, stir 0.5 hour, then add 55 grams of boehmites, stir 5 hours, 80 ℃ of crystallization 2 days, filter 120 ℃ of oven dry, 550 ℃ of roastings 5 hours, obtain catalyzer G.In catalyzer, MCM-41 parts by weight are 26 parts, Al 2o 3parts by weight are 74 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (25 * 500 millimeters of stainless steels of Ф), and catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction conditions and reaction result are in Table 1.
  
[comparative example 1]
Weigh 300 grams of pseudo-boehmites, 120 ℃ dry 12 hours, 550 ℃ of roastings 10 hours, obtain catalyzer H.Al in catalyzer 2o 3parts by weight be 100 parts.
Each Step By Condition by [embodiment 1], carries out catalytic performance test by the catalyzer F of preparation.Reaction conditions and reaction result are in Table 1.
  
[comparative example 2]
Each Step By Condition by [comparative example 1], carries out catalytic performance test by the catalyzer H of preparation.Reaction conditions and reaction result are in Table 1.
  
[comparative example 3]
Weigh MCM-41 totally 200 grams dry 12 hours in 120 ℃, 550 ℃ of roastings 10 hours, obtain catalyst I.SiO in catalyzer 2parts by weight be 100 parts.
Each Step By Condition by [embodiment 1], carries out catalytic performance test by the catalyst I of preparation.Reaction conditions and reaction result are in Table 1.
  
[comparative example 4]
Each Step By Condition by [comparative example 3], carries out catalytic performance test by the catalyst I of preparation.Reaction conditions and reaction result are in Table 1.
  
Table 1
Figure 842628DEST_PATH_IMAGE003
In these two comparative examples of note: *, do not react.

Claims (9)

1. a method for 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 200 ~ 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) the MCM-41 molecular sieve of 1 ~ 99 part;
B) Al of 1 ~ 99 part 2o 3.
2. the method for producing ethylene by ethanol dehydration according to claim 1, is characterized in that in parts by weight, and the consumption of MCM-41 molecular sieve is 1 ~ 50 part, Al 2o 3consumption be 50 ~ 99 parts.
3. the method for producing ethylene by ethanol dehydration according to claim 2, is characterized in that in parts by weight, and the consumption of MCM-41 molecular sieve is 2 ~ 20 parts, Al 2o 3consumption be 80 ~ 98 parts.
4. the method for producing ethylene by ethanol dehydration according to claim 1, is characterized in that temperature of reaction is 200 ~ 450 ℃.
5. the method for producing ethylene by ethanol dehydration according to claim 4, is characterized in that temperature of reaction is 250 ~ 450 ℃.
6. the method for producing ethylene by ethanol dehydration according to claim 1, is characterized in that the volume space velocity with respect to ethanol is 0.5 ~ 20 hour -1.
7. the method for producing ethylene by ethanol dehydration according to claim 6, is characterized in that the volume space velocity with respect to ethanol is 0.5 ~ 15 hour -1.
8. the method for producing ethylene by ethanol dehydration according to claim 1, it is characterized in that described catalyzer can be prepared by the following method: silicon source, aluminium source, template, ammoniacal liquor and water are formed to mixture, mixture is ℃ crystallization 0.5 ~ 5 day in room temperature ~ 120, after filtration, obtain MCM-41/Al after oven dry, roasting 2o 3; Wherein, SiO 2: Al 2o 3mass ratio be 1:1/99 ~ 99, SiO 2: CTMAB: ammoniacal liquor: H 2the mol ratio of O is 1:0.05 ~ 1:5 ~ 15:50 ~ 100.
9. the method for producing ethylene by ethanol dehydration according to claim 8, it is characterized in that described silicon source is selected from least one in tetraethoxy, methyl silicate or silicon sol, described aluminium source is selected from boehmite, and described template is selected from cetyl trimethylammonium bromide.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104084232A (en) * 2014-06-18 2014-10-08 浙江工业大学 Preparation method for catalyst used for deoxidation of biological fatty alcohol
CN105272795A (en) * 2014-07-24 2016-01-27 中国石油化工股份有限公司 Method for producing ethylene through ethanol dehydration
CN109835916A (en) * 2019-04-12 2019-06-04 浙江工业大学 A method of simply preparing high-specific surface area MCM-41

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1974812A1 (en) * 2006-01-21 2008-10-01 Tokyo Institute of Technology Catalysts and process for the production of olefins with the same
CN102372545A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Method for preparing olefin by alcohol dehydration
CN102372562A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Method for producing ethene by ethanol dehydration

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1974812A1 (en) * 2006-01-21 2008-10-01 Tokyo Institute of Technology Catalysts and process for the production of olefins with the same
CN102372545A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Method for preparing olefin by alcohol dehydration
CN102372562A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Method for producing ethene by ethanol dehydration

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张君涛等: "氨水介质中Al- MCM-41的合成与表征", 《西安石油大学学报（自然科学版）》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104084232A (en) * 2014-06-18 2014-10-08 浙江工业大学 Preparation method for catalyst used for deoxidation of biological fatty alcohol
CN104084232B (en) * 2014-06-18 2016-03-02 浙江工业大学 A kind of preparation method of catalyst of biological fatty alcohol deoxidation
CN105272795A (en) * 2014-07-24 2016-01-27 中国石油化工股份有限公司 Method for producing ethylene through ethanol dehydration
CN105272795B (en) * 2014-07-24 2017-07-14 中国石油化工股份有限公司 The method of producing ethylene from dehydration of ethanol
CN109835916A (en) * 2019-04-12 2019-06-04 浙江工业大学 A method of simply preparing high-specific surface area MCM-41

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