CN105272795A - Method for producing ethylene through ethanol dehydration - Google Patents
Method for producing ethylene through ethanol dehydration Download PDFInfo
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- CN105272795A CN105272795A CN201410355415.0A CN201410355415A CN105272795A CN 105272795 A CN105272795 A CN 105272795A CN 201410355415 A CN201410355415 A CN 201410355415A CN 105272795 A CN105272795 A CN 105272795A
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- ethanol
- dehydration
- producing ethylene
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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
- 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
Abstract
The present invention relates to a method for producing ethylene through ethanol dehydration. A purpose of the present invention is mainly to solve the problem of low catalyst activity in the prior ar. According to the present invention, the technical scheme comprises that an ethanol aqueous solution with a weight percentage concentration of 5-100% is adopted as a raw material, and the reaction raw material contacts a catalyst at a reaction temperature of 200-500 DEG C at an ethanol liquid hourly space velocity of 0.1-25 h<-1> to generate the ethylene, wherein the catalyst comprise, by weight, a) 1-99 parts of a HMS molecular sieve; and b) 1-99 parts of Al2O3. With the technical scheme of the present invention, the problem in the prior art is well solved, and the method can be used for ethylene preparation through ethanol dehydration in the industrial production.
Description
Technical field
The present invention relates to a kind of method of producing ethylene from dehydration of ethanol.
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, had had the history of more than 200 year, was once main ethylene production route at 19th-century.Flourish due to twentieth century petrochemical complex, cracking ethylene preparation is more economical, and this route is eliminated gradually.But in some occasion, as ethanol wide material sources, under the situations such as ethene consumption is less, ethanol dehydration is still in use.
More and more face exhausted danger along with a large amount of use of petroleum resources, 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 exploitation of particularly new alcohol production technology, as synthetic gas ethanol, the biological legal system ethanol of Mierocrystalline cellulose etc.
Alumina catalyst is the catalyzer of current industrial producing ethylene from dehydration of ethanol application relative maturity, the code name that the eighties in last century, U.S. Halcon company developed is that the catalyst performance of Syndol is best, but this catalyzer requires harsh to reaction conditions, temperature of reaction is high, ethanol raw material concentration requirement is high, causes overall energy consumption high.Therefore, the catalyzer that exploitation performance is more excellent, is converted into the long life catalytic agent of ethene efficiently, has become the key of biomass by ethanol intermediate ethene by the ethanol of low concentration.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 DEG C, and ethanol conversion just can reach 99%.There is the shortcoming that catalyst activity is low.
Li Shulian etc. describe a kind of alumina having mesoporous structure catalyzer in patent [CN101643228A, 2010], but this catalyzer is temperature of reaction 365 DEG C, air speed 3.15 hours
-1, under alcohol concn 95% (v/v) condition, ethanol conversion is only about 80%, ethylene selectivity is only about 70%.There is the shortcoming that catalyst activity is low.
Document US4207424 discloses a kind of with Al
2o
3for carrier, prepare SiO by adopting organosilicon vapour deposition process
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.The situation of α phenylethyl alcohol dehydration is mainly listed in embodiment, an embodiment is only had to be the reaction of ethanol dehydration, only compare the change of ethylene content in product before and after silanization, temperature of reaction 350 DEG C, after silanization, ethylene content brings up to 24wt% from 19wt%, improves 26.3%, there is the problem that catalyst activity is low.
Document EP0498573 discloses a kind of γ-Al
2o
3catalyzer, at 0.5 hour
-1, 400 DEG C, under 18 kilograms of pressure conditions, ethanol conversion 83%, ethylene selectivity 94%.There is the problem that catalyst activity is low equally.
In sum, there is the shortcoming that catalyst activity is low in the catalyzer adopted in conventional art.
Summary of the invention
Technical problem to be solved by this invention there is the low problem of catalyst activity in conventional art, provides a kind of method of new producing ethylene with ethyl alcohol.The method has the feature of good catalyst activity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for producing ethylene from dehydration of ethanol, take weight percent concentration as the aqueous ethanolic solution of 5 ~ 100% be raw material, be 200 ~ 500 DEG C in temperature of reaction, the liquid volume air speed of ethanol is 0.1 ~ 25 hour
-1under condition, reaction raw materials and catalyst exposure generate ethene; Catalyzer wherein used, with weight parts, comprises following component:
A) the HMS molecular sieve of 1 ~ 99 part;
B) Al of 1 ~ 99 part
2o
3;
And HMS molecular sieve and Al
2o
3number amounts to 100 parts.
In technique scheme, preferably, with weight parts, the consumption of HMS molecular sieve is 1 ~ 50 part, and more preferably, the consumption of HMS molecular sieve is 2 ~ 20 parts.
In technique scheme, preferably, temperature of reaction is 200 ~ 450 DEG C, and more preferably, temperature of reaction is 250 ~ 450 DEG C.
In technique scheme, preferably, the liquid volume air speed of ethanol is 0.5 ~ 20 hour
-1, more preferably, the liquid volume air speed of ethanol is 0.5 ~ 15 hour
-1.
In the present invention, catalyzer is prepared by following method: to be dissolved in by cetylamine (be called for short HAD) in deionized water and ethanol after stirring and dissolving, add tetraethoxy, methyl silicate wherein at least one silicon source again, stirred at ambient temperature is even, add boehmite again, stir 1 ~ 20 hour, room temperature ~ 120 DEG C crystallization 0.5 ~ 5 day, filter, dry, roasting, obtains described catalyzer; Silicon source is with SiO
2meter, SiO
2: ethanol: HAD:H
2o mol ratio is 1:(1 ~ 15): (0.1 ~ 1): (10 ~ 100).More preferably, SiO
2: ethanol: HAD:H
2the mol ratio of O is 1:(2 ~ 11): (0.3 ~ 0.8): (15 ~ 80).
Adopt the inventive method, reaction can be made to carry out at lower temperature 300 ~ 450 DEG C, reduce temperature of reaction, be beneficial to and can lower consumption, the selectivity of ethene can reach more than 98% simultaneously, improves 3 ~ 5%, achieve good technique effect than pure alumina catalyzer.
Accompanying drawing explanation
The little angle XRD figure of the catalyzer that Fig. 1 synthesizes for [embodiment 4].
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
7.23 grams of HAD to be dissolved in 63 grams of deionized waters and 32.2 grams of dehydrated alcohols after stirring and dissolving, add 20.8 grams of tetraethoxys again, stirred at ambient temperature 0.5 hour, add 30 grams of boehmites again, stir 5 hours, 90 DEG C of crystallization 3 days, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyst A.In catalyzer, HMS parts by weight are 22 parts, Al
2o
3parts by weight are 78 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (Ф 25 × 500 millimeters of stainless steels), 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]
8 grams of HAD are dissolved in 60 grams of deionized waters and 40 grams of dehydrated alcohols after stirring and dissolving, then add 30 grams of tetraethoxys, stirred at ambient temperature 0.5 hour, then add 80 grams of boehmites, stir 5 hours, room temperature crystallization 5 days, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyst B.In catalyzer, HMS parts by weight are 13 parts, Al
2o
3parts by weight are 87 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (Ф 25 × 500 millimeters of stainless steels), 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]
7.23 grams of HAD are dissolved in 63 grams of deionized waters and 50 grams of dehydrated alcohols after stirring and dissolving, then add 15 grams of methyl silicates, stirred at ambient temperature 0.5 hour, then add 200 grams of boehmites, stir 5 hours, 120 DEG C of crystallization 3 days, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyzer C.In catalyzer, HMS parts by weight are 3 parts, Al
2o
3parts by weight are 97 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (Ф 25 × 500 millimeters of stainless steels), 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]
7.23 grams of HAD are dissolved in 63 grams of deionized waters and 100 grams of dehydrated alcohols after stirring and dissolving, then add 40 grams of methyl silicates, stirred at ambient temperature 0.5 hour, then add 100 grams of boehmites, stir 5 hours, 50 DEG C of crystallization 3 days, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyzer D.In catalyzer, HMS parts by weight are 15 parts, Al
2o
3parts by weight are 85 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (Ф 25 × 500 millimeters of stainless steels), 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]
7.23 grams of HAD are dissolved in 63 grams of deionized waters and 100 grams of dehydrated alcohols after stirring and dissolving, then add 40 grams of tetraethoxys, stirred at ambient temperature 0.5 hour, then add 180 grams of boehmites, stir 5 hours, room temperature crystallization 3 days, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyzer E.In catalyzer, HMS parts by weight are 8 parts, Al
2o
3parts by weight are 92 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (Ф 25 × 500 millimeters of stainless steels), 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]
7.5 grams of HAD are dissolved in 63 grams of deionized waters and 150 grams of dehydrated alcohols after stirring and dissolving, then add 40 grams of tetraethoxys, stirred at ambient temperature 0.5 hour, then add 90 grams of boehmites, stir 5 hours, 120 DEG C of crystallization 3 days, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyzer F.In catalyzer, HMS 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 (Ф 25 × 500 millimeters of stainless steels), 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 HAD are dissolved in 63 grams of deionized waters and 200 grams of dehydrated alcohols after stirring and dissolving, then add 15 grams of methyl silicates, stirred at ambient temperature 0.5 hour, then add 100 grams of boehmites, stir 5 hours, 120 DEG C of crystallization 1 day, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyzer G.In catalyzer, HMS parts by weight are 6 parts, Al
2o
3parts by weight are 94 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (Ф 25 × 500 millimeters of stainless steels), 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 pseudo-boehmite 300 grams, 120 DEG C of dryings 12 hours, 550 DEG C of roastings 10 hours, obtain catalyzer H.Al in catalyzer
2o
3parts by weight be 100 parts.
By each Step By Condition of [embodiment 1], the catalyzer H of preparation is carried out catalytic performance test.Reaction conditions and reaction result are in table 1.
[comparative example 2]
By each Step By Condition of [embodiment 2], the catalyzer H of preparation is carried out catalytic performance test.Reaction conditions and reaction result are in table 1.
[comparative example 3]
Weigh HMS totally 200 grams dry 12 hours in 120 DEG C, 550 DEG C of roastings 10 hours, obtain catalyst I.SiO in catalyzer
2parts by weight be 100 parts.
By each Step By Condition of [embodiment 1], the catalyst I of preparation is carried out catalytic performance test.Reaction conditions and reaction result are in table 1.
[comparative example 4]
By each Step By Condition of [embodiment 2], the catalyst I of preparation is carried out catalytic performance test.Reaction conditions and reaction result are in table 1.
[comparative example 5]
Except not adopting the template HAD for the synthesis of HMS, other steps are identical with [embodiment 1].Be specially:
After being uniformly mixed in 63 grams of deionized waters and 32.2 grams of dehydrated alcohols, then add 20.8 grams of tetraethoxys, stirred at ambient temperature 0.5 hour, then add 30 grams of boehmites, stir 5 hours, 90 DEG C of crystallization 3 days, filter, 120 DEG C of oven dry, 550 DEG C of roastings 5 hours, obtain catalyzer J.In catalyzer, HMS parts by weight are 22 parts, Al
2o
3parts by weight are 78 parts.
The performance evaluation of catalyzer is carried out on fixed-bed tube reactor (Ф 25 × 500 millimeters of stainless steels), 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.
Table 1
*, in these two comparative examples, do not react.
Claims (9)
1. the method for producing ethylene from dehydration of ethanol take weight percent concentration as the aqueous ethanolic solution of 5 ~ 100% is raw material, is 200 ~ 500 DEG C in temperature of reaction, and the liquid volume air speed of ethanol is 0.1 ~ 25 hour
-1under condition, reaction raw materials and catalyst exposure generate ethene; Catalyzer wherein used, with weight parts, comprises following component:
A) the HMS molecular sieve of 1 ~ 99 part;
B) Al of 1 ~ 99 part
2o
3;
And HMS molecular sieve and Al
2o
3number amounts to 100 parts.
2. the method for producing ethylene from dehydration of ethanol according to claim 1, it is characterized in that with weight parts, the consumption of HMS molecular sieve is 1 ~ 50 part.
3. the method for producing ethylene from dehydration of ethanol according to claim 2, it is characterized in that with weight parts, the consumption of HMS molecular sieve is 2 ~ 20 parts.
4. the method for producing ethylene from dehydration of ethanol according to claim 1, is characterized in that temperature of reaction is 200 ~ 450 DEG C.
5. the method for producing ethylene from dehydration of ethanol according to claim 4, is characterized in that temperature of reaction is 250 ~ 450 DEG C.
6. the method for producing ethylene from dehydration of ethanol according to claim 1, is characterized in that the liquid volume air speed of ethanol is 0.5 ~ 20 hour
-1.
7. the method for producing ethylene from dehydration of ethanol according to claim 6, is characterized in that the liquid volume air speed of ethanol is 0.5 ~ 15 hour
-1.
8. the method for producing ethylene from dehydration of ethanol according to claim 1, it is characterized in that catalyzer can be prepared by the following method: to be dissolved in by cetylamine in deionized water and ethanol after stirring and dissolving, add tetraethoxy, methyl silicate wherein at least one silicon source again, stirred at ambient temperature is even, then adds boehmite, stir 1 ~ 20 hour, room temperature ~ 120 DEG C crystallization 0.5 ~ 5 day, filters, and dries, roasting, obtains described catalyzer; Silicon source is with SiO
2meter, SiO
2: ethanol: HAD:H
2the mol ratio of O is 1:(1 ~ 15): (0.1 ~ 1): (10 ~ 100).
9. the method for producing ethylene from dehydration of ethanol according to claim 8, is characterized in that SiO
2: ethanol: HAD:H
2the mol ratio of O is 1:(2 ~ 11): (0.3 ~ 0.8): (15 ~ 80).
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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 |
| CN103664452A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing ethylene by dehydration of alcohol |
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2014
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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 |
| CN103664452A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing ethylene by dehydration of alcohol |
Non-Patent Citations (1)
| Title |
|---|
| A. TUEL等: "Synthesis and Characterization of Trivalent Metal Containing Mesoporous Silicas Obtained by a Neutral Templating Route", 《CHEMISTRY OF MATERIAL》 * |
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