CN105272794B - The method of alcohol production ethene - Google Patents
The method of alcohol production ethene Download PDFInfo
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- CN105272794B CN105272794B CN201410354570.0A CN201410354570A CN105272794B CN 105272794 B CN105272794 B CN 105272794B CN 201410354570 A CN201410354570 A CN 201410354570A CN 105272794 B CN105272794 B CN 105272794B
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- 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
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Abstract
The present invention relates to a kind of method of alcohol production ethene, mainly solve the presence of the problem of catalyst activity is low in the prior art.The present invention, as raw material, is 200~500 DEG C in reaction temperature by using the ethanol water for being 5~100% using weight percent concentration, and the liquid volume air speed of ethanol is 0.1~25 hour‑1Under the conditions of, reaction raw materials contact generation ethene with catalyst；Catalyst wherein used is in terms of parts by weight, including following components：A) 1~99 part of the molecular sieves of MCM 48；B) 1~99 part of Al2O3；And the molecular sieves of MCM 48 and Al2O3The technical scheme that number amounts to 100 parts preferably solves the problem, available in the industrial production of preparation of bio-ethylene.
Description
Technical field
The present invention relates to a kind of method of alcohol production ethene.
Background technology
Ethene, molecular formula C2H4, it is very important petrochemical material.Producing ethylene from dehydration of ethanol was once one and widely used
Acquisition ethene route, had the history of more than 200 years, be once main ethylene production route in 19th-century.Due to
Twentieth century petrochemical industry flourish, cracking ethylene preparation is more economical, and this route is gradually eliminated.But, in some occasions,
Such as ethanol wide material sources, under the situation such as ethene consumption figure is smaller, ethanol dehydration is still being used.
The danger of exhaustion is increasingly faced with a large amount of uses of petroleum resources, increasingly riseing for oil price is cracked
The competitive advantage of legal system ethene route is less and less.Producing ethylene from dehydration of ethanol route turns into competitive technology path again.It is special
It is not the exploitation of new alcohol production technology, such as synthesis gas ethanol, cellulose biology legal system ethanol etc..
Alumina catalyst is the catalyst of industrial producing ethylene from dehydration of ethanol application relative maturity at present, last century 80
The code name of age U.S. Halcon company's development is best for Syndol catalyst performance, but the catalyst will to reaction condition
Ask harsh, reaction temperature is high, ethanol raw material concentration requirement is high, causes overall high energy consumption.Therefore, performance is more excellent urges for exploitation
Agent, the ethanol of low concentration is efficiently converted into the long life catalytic agent of ethene, it has also become biomass is by ethanol intermediate
The key of ethene processed.Using zeolite catalysis producing ethylene from dehydration of ethanol, reaction temperature is although relatively low, but catalyst stability not
It is good, and unrealized industrialized production.
[Beijing University of Chemical Technology's journal, 2007,34 (5) such as Li Ying：449-452] using 0.3~1 millimeter of particulate oxidation
Aluminium ethanol dehydration catalyst, reaction temperature is more than 420 DEG C, and ethanol conversion can be only achieved 99%.There is catalyst activity low
Shortcoming.
Li Shulian etc. describes a kind of alumina having mesoporous structure catalyst in patent [CN101643228A, 2010], but
The catalyst is in 365 DEG C of reaction temperature, air speed 3.15 hours-1, under the conditions of concentration of alcohol 95% (v/v), ethanol conversion is only
80% or so, ethylene selectivity is only 70% or so.Have the shortcomings that catalyst activity is low.
Document US4207424 discloses one kind with Al2O3For carrier, SiO is prepared by using organosilicon vapour deposition process2-
Al2O3The method of the catalyst of the corresponding alkene of dehydration of alcohols system, alcohol includes fatty alcohol, aromatic alcohol, cyclic alcohol etc..Mainly arranged in embodiment
The situation of α benzyl carbinols dehydration is lifted, only one of which embodiment is the reaction of ethanol dehydration, only compared before and after silanization in product
The change of ethylene contents, 350 DEG C of reaction temperature, after silanization, ethylene contents bring up to 24wt% from 19wt%, improve
26.3%, there is the problem of catalyst activity is low.
Document EP0498573 discloses a kind of γ-Al2O3Catalyst, at 0.5 hour-1, 400 DEG C, 18 kilograms of pressure conditions
Under, ethanol conversion 83%, ethylene selectivity 94%.Equally exist the problem of catalyst activity is low.
In summary, the catalyst used in conventional art, haves the shortcomings that catalyst activity is low.
The content of the invention
The technical problems to be solved by the invention are there is the problem of catalyst activity is low in conventional art there is provided a kind of new
Producing ethylene with ethyl alcohol method.This method has the characteristics of catalyst activity is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：The method of alcohol production ethene, with weight
The ethanol water that percent concentration is 5~100% is raw material, is 200~500 DEG C, the liquid volume of ethanol in reaction temperature
Air speed is 0.1~25 hour-1Under the conditions of, reaction raw materials contact generation ethene with catalyst；Catalyst wherein used is with weight
Number meter, including following components：
A) 1~99 part of MCM-48 molecular sieves；
B) 1~99 part of Al2O3；
And MCM-48 molecular sieves and Al2O3Number amounts to 100 parts.
In above-mentioned technical proposal, it is preferable that in terms of parts by weight, the consumption of MCM-48 molecular sieves is 1~50 part, more preferably
Ground, the consumption of MCM-48 molecular sieves is 2~20 parts.
In above-mentioned technical proposal, it is preferable that reaction temperature be 200~450 DEG C, it is highly preferred that reaction temperature be 250~
450℃。
In above-mentioned technical proposal, it is preferable that the liquid volume air speed of ethanol is 0.5~20 hour-1, it is highly preferred that ethanol
Liquid volume air speed be 0.5~15 hour-1。
Catalyst can be prepared via a method which in the present invention：Cetyl trimethylammonium bromide (abbreviation CTMAB) is molten
In deionized water after stirring and dissolving, ethanol is added, stirs, adds ammoniacal liquor, stir, add positive silicic acid second
Ester, methyl silicate, Ludox wherein at least one silicon source, stir at room temperature, add boehmite, stirring 1~20
Hour, room temperature~120 DEG C crystallization 0.5~5 day is filtered, and is dried, and roasting produces the catalyst；Silicon source is with SiO2Meter, SiO2：
Ethanol：CTMAB：H2O：The mol ratio of ammonia is 1：(10~50)：(0.05~1)：(100~500)：(5~15).It is highly preferred that
SiO2：Ethanol：CTMAB：H2O：The mol ratio of ammonia is 1：(15~45)：(0.1~0.8)：(110~400)：(7~12).
Using the inventive method, reaction can be made to be carried out at 300~450 DEG C relatively low of temperature, reduce reaction temperature, profit
In that can lower consumption, while the selectivity of ethene can reach more than 98%, 3~5% are improved than pure alumina catalyst, is achieved
Preferable technique effect.
Brief description of the drawings
Fig. 1 is【Embodiment 1】The small angle XRD of the catalyst of synthesis.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
5 grams of CTMAB are dissolved in 191 gram-ion water after stirring and dissolving, 55 grams of absolute ethyl alcohols are added, stirred 0.5 hour,
The ammoniacal liquor that 25 milliliters of concentration are 26w% is added, is stirred 0.5 hour, is added 10 milliliters of tetraethyl orthosilicates, stir at room temperature
0.5 hour, 10 grams of boehmites are added, are stirred 5 hours, room temperature crystallization 2 days, filtering, 120 DEG C of drying, 550 DEG C of roastings 5 are small
When, obtain catalyst A.MCM-48 parts by weight are 28 parts, Al in catalyst2O3Parts by weight are 72 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
【Embodiment 2】
5 grams of CTMAB are dissolved in 190 gram-ion water after stirring and dissolving, 70 gram of 95% ethanol is added, stirred 0.5 hour,
The ammoniacal liquor that 40 milliliters of concentration are 26w% is added, is stirred 0.5 hour, is added 15 milliliters of methyl silicates, stir at room temperature
0.5 hour, add 30 grams of boehmites, stir 5 hours, 50 DEG C of crystallization 2 days, filtering, 120 DEG C of drying, 550 DEG C of roastings 5 are small
When, obtain catalyst B.MCM-48 parts by weight are 17 parts, Al in catalyst2O3Parts by weight are 83 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
【Embodiment 3】
5 grams of CTMAB are dissolved in 190 gram-ion water after stirring and dissolving, 70 grams of absolute ethyl alcohols are added, stirred 0.5 hour,
The ammoniacal liquor that 40 milliliters of concentration are 26w% is added, stirs 0.5 hour, adds 15 grams of Ludox, is stirred 0.5 hour at room temperature,
Add 300 grams of boehmites, stir 5 hours, 100 DEG C of crystallization 4 days, filtering, 120 DEG C of drying, 550 DEG C are calcined 5 hours, obtain
Catalyst C.MCM-48 parts by weight are 2.8 parts, Al in catalyst2O3Parts by weight are 97.2 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
【Embodiment 4】
10 grams of CTMAB are dissolved in 185 gram-ion water after stirring and dissolving, 65 grams of absolute ethyl alcohols are added, stirring 0.5 is small
When, the ammoniacal liquor that 70 milliliters of concentration are 26w% is added, is stirred 0.5 hour, is added 40 milliliters of tetraethyl orthosilicates, stir at room temperature
Mix 0.5 hour, add 300 grams of boehmites, stir 5 hours, 80 DEG C of crystallization 4 days, filtering, 120 DEG C of drying, 550 DEG C of roastings 5
Hour, obtain catalyst D.MCM-48 parts by weight are 5 parts, Al in catalyst2O3Parts by weight are 95 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
【Embodiment 5】
6 grams of CTMAB are dissolved in 190 gram-ion water after stirring and dissolving, 80 absolute ethyl alcohols are added, stirred 0.5 hour, then
The ammoniacal liquor that 45 milliliters of concentration are 26w% is added, is stirred 0.5 hour, is added 15 milliliters of methyl silicates, 0.5 is stirred at room temperature
Hour, add 40 grams of boehmites, stir 5 hours, 50 DEG C of crystallization 2 days, filtering, 120 DEG C of drying, 550 DEG C are calcined 5 hours,
Obtain catalyst E.MCM-48 parts by weight are 13 parts, Al in catalyst2O3Parts by weight are 87 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
【Embodiment 6】
4 grams of CTMAB are dissolved in 190 gram-ion water after stirring and dissolving, 70 absolute ethyl alcohols are added, stirred 0.5 hour, then
The ammoniacal liquor that 50 milliliters of concentration are 26w% is added, stirs 0.5 hour, adds 15 gram of 40% Ludox, 0.5 is stirred at room temperature small
When, add 50 grams of boehmites, stir 5 hours, 50 DEG C of crystallization 2 days, filtering, 120 DEG C of drying, 550 DEG C are calcined 5 hours, obtain
To catalyst F.MCM-48 parts by weight are 17 parts, Al in catalyst2O3Parts by weight are 83 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
【Embodiment 7】
8 grams of CTMAB are dissolved in 190 gram-ion water after stirring and dissolving, 70 absolute ethyl alcohols are added, stirred 0.5 hour, then
The ammoniacal liquor that 80 milliliters of concentration are 26w% is added, is stirred 0.5 hour, is added 30 milliliters of tetraethyl orthosilicates, 0.5 is stirred at room temperature
Hour, add 55 grams of boehmites, stir 5 hours, 80 DEG C of crystallization 2 days, filtering, 120 DEG C of drying, 550 DEG C are calcined 5 hours,
Obtain catalyst G.MCM-48 parts by weight are 26 parts, Al in catalyst2O3Parts by weight are 74 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
【Comparative example 1】
Weigh 300 grams of boehmite, 120 DEG C of drying 12 hours, 550 DEG C of roastings 10 hours obtain catalyst H.Catalysis
Al in agent2O3Parts by weight be 100 parts.
Press【Embodiment 1】Each Step By Condition, the catalyst H of preparation is subjected to catalytic performance test.Reaction condition and
Reaction result is shown in Table 1.
【Comparative example 2】
Press【Embodiment 2】Each Step By Condition, the catalyst H of preparation is subjected to catalytic performance test.Reaction condition and
Reaction result is shown in Table 1.
【Comparative example 3】
Weigh MCM-48 to dry 12 hours in through 120 DEG C for totally 200 grams, 550 DEG C of roastings are used for catalyst in 10 hours, are expressed as
Catalyst I.
Press【Embodiment 1】Each Step By Condition, the catalyst I of preparation is subjected to catalytic performance test.Reaction condition and
Reaction result is shown in Table 1.
【Comparative example 4】
Press【Embodiment 2】Each Step By Condition, the catalyst I of preparation is subjected to catalytic performance test.Reaction condition and
Reaction result is shown in Table 1.
【Comparative example 5】
In addition to not using the template CTMAB for synthesizing MCM-48, other steps with【Embodiment 1】It is identical.Tool
Body is：
191 gram-ion water are taken, 55 grams of absolute ethyl alcohols are added, stirred 0.5 hour, it is 26w%'s to add 25 milliliters of concentration
Ammoniacal liquor, stirs 0.5 hour, adds 10 milliliters of tetraethyl orthosilicates, stirs 0.5 hour at room temperature, adds 10 grams of boehmites,
Stirring 5 hours, room temperature is placed 2 days, filtering, 120 DEG C of drying, and 550 DEG C are calcined 5 hours, obtain catalyst J.SiO in catalyst2
Parts by weight are 28 parts, Al2O3Parts by weight are 72 parts.
The performance evaluation of catalyst is carried out on fixed-bed tube reactor (25 × 500 millimeters of stainless steels of Ф), catalyst
Useful load is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation.Reaction condition and reaction result are shown in Table 1.
Table 1
* in the two comparative examples, do not react.
Claims (6)
1. the method for alcohol production ethene, using weight percent concentration be 5~100% ethanol water as raw material, in reaction
Temperature is 200~500 DEG C, and the liquid volume air speed of ethanol is 0.1~25 hour-1Under the conditions of, reaction raw materials are contacted with catalyst
Generate ethene；Catalyst wherein used is in terms of parts by weight, including following components：
A) 2~20 parts of MCM-48 molecular sieves；
B) 1~99 part of Al2O3；
And MCM-48 molecular sieves and Al2O3Number amounts to 100 parts；
The catalyst is prepared via a method which：Cetyl trimethylammonium bromide is dissolved in stirring and dissolving in deionized water
Afterwards, add ethanol, stir, add ammoniacal liquor, stir, add tetraethyl orthosilicate, methyl silicate, Ludox its
At least one of silicon source, stir at room temperature, add boehmite, stir 1~20 hour, room temperature~120 DEG C crystallization 0.5
~5 days, filter, drying after roasting, produces the catalyst；Silicon source is with SiO2Meter, SiO2：Ethanol：CTMAB：H2O：Ammonia rubs
You are than being 1：(10~50)：(0.05~1)：(100~500)：(5~15).
2. the method for alcohol production ethene according to claim 1, it is characterised in that reaction temperature is 200~450 DEG C.
3. the method for alcohol production ethene according to claim 2, it is characterised in that reaction temperature is 250~450 DEG C.
4. the method for alcohol production ethene according to claim 1, it is characterised in that the liquid volume air speed of ethanol is 0.5~
20 hours-1。
5. the method for alcohol production ethene according to claim 4, it is characterised in that the liquid volume air speed of ethanol is 0.5~
15 hours-1。
6. the method for alcohol production ethene according to claim 1, it is characterised in that SiO2：Ethanol：CTMAB：H2O：Ammonia rubs
You are than being 1：(15~45)：(0.1~0.8)：(110~400)：(7~12).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372561A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing ethylene by using ethanol |
| 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 |
| CN102875300A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethene by catalytic dehydration of ethanol |
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2014
- 2014-07-24 CN CN201410354570.0A patent/CN105272794B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372561A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing ethylene by using ethanol |
| 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 |
| CN102875300A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethene by catalytic dehydration of ethanol |
Non-Patent Citations (2)
| Title |
|---|
| erent aluminium sources and by some hydrothermal methods.《Microporous and Mesoporous Materials》.2006,第92卷第270–285页. * |
| M.M.L. Ribeiro Carrott等.Comparative study of Al-MCM materials prepared at room temperature with diff * |
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