CN103030488A - Method for preparing ethylene by ethanol dehydration - Google Patents
Method for preparing ethylene by ethanol dehydration Download PDFInfo
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- CN103030488A CN103030488A CN2011102997548A CN201110299754A CN103030488A CN 103030488 A CN103030488 A CN 103030488A CN 2011102997548 A CN2011102997548 A CN 2011102997548A CN 201110299754 A CN201110299754 A CN 201110299754A CN 103030488 A CN103030488 A CN 103030488A
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Abstract
The invention relates to a method for preparing ethylene by ethanol dehydration, which mainly solves the problem of poor reaction stability in the prior art. Aiming at well solving the problem, the method adopts the technical scheme that ethanol is used as a raw material, the concentration of the ethanol in percentage by weight is 5% to 100%, and the reaction raw material comes into contact with a catalyst to generate the ethylene when the reaction temperature is 200 to 400 DEG C and the volume hourly space velocity is 0.1 to 15 h<-1> relative to the ethanol. The catalyst is a non-binder ZSM-5 molecular sieve. The method can be used for the industrial production of the ethylene prepared by the ethanol dehydration.
Description
Technical field
The present invention relates to a kind of method by preparing ethylene by dehydrating ethanol.
Background technology
Ethene 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 as basic Organic Chemicals and the flagship product of petrochemical industry.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 from now on Economic development.Ethanol can obtain through fermentation by plant amylum or wood fibre, and raw material sources are extensive, sufficient and renewable, can satisfy the needs of extensive biomass chemical industry development.Therefore, has ethene is obtained in part or all of replacement from oil great potential from producing ethylene from dehydration of ethanol.Producing ethylene by ethanol dehydration is traditional ethylene production route, continues to use this method in the country of some petroleum resources scarcities such as Brazil, India, Pakistan always and produces ethene.
Alumina catalyst is that present industrial producing ethylene from dehydration of ethanol is used relatively ripe catalyzer, the code name of the U.S. Halcon company development eighties in last century is that the catalyst performance of Syndol is best, but this catalyzer is compared [petrochemical complex with the zeolite catalyst of bibliographical information, 1987,16 (11): 764-768], reaction conditions is required harshness, temperature of reaction is high, the ethanol raw material concentration requirement is high, causes whole energy consumption high.Therefore, exploitation can be at a lower temperature, and the ethanol of low concentration is converted into the long life catalytic agent of ethene efficiently, become biomass by the key of system ethene in the middle of the ethanol.
The ZSM-5 zeolite molecular sieve is U.S. Mobil company at first synthetic [US 3702886], has (ten-ring straight hole road, two-dimentional ten-ring duct, the sinusoidal duct of aperture 0.54nm * 0.56nm and ten-ring, aperture are that 0.51nm * 0.54nm) is one of catalyzer that is most widely used.Belong to micro-pore zeolite, because it does not have cage, thus in catalytic process, be difficult for carbon distribution, and fabulous thermostability, acid resistance, shape selectivity, water vapor stability and hydrophobicity are arranged.
Hu Yaochi etc. [chemistry and biotechnology, 2007,24 (2): 19-21] have investigated respectively transition metal iron, manganese and the cobalt improved HZSM-5 impact on producing ethylene from dehydration of ethanol, and the best catalyzer of catalytic effect has been carried out the optimization of reaction conditions.The result shows: the catalytic performance of Co/HZSM-5 is best, uses this catalyzer 220 ℃, mass space velocity 2.5 hours
-1, volume fraction of ethanol is under 60% the reaction conditions, the transformation efficiency of ethanol and the selectivity of ethene be respectively up to 99.6% and 99.3%, but do not have stability data.
It is the NKC-03A zeolite catalyst that Pan Lvrang etc. [CN1009363B, 1990] in patent have introduced code name, and this catalyzer can use 250～390 ℃ of range of reaction temperature, air speed 1～5 hour
-1, the one way life cycle can be above 4 months.But this catalyzer low-temperature zone stability is not high, and temperature of reaction rises to more than 300 ℃ soon.
Sirinapa etc. [Int.J.Appl.Sci.Eng., 2006,4 (1): 21-32] have studied transition metal modified MOR zeolite becomes ethene to ethanol conversion catalytic performance.Found that the MOR catalyzer of Zn and Zn-Ag load has high ethylene selectivity, 10% ethanol, 350 ℃, air speed 1.0 hours
-1, react after 1 hour, the Zn/MOR catalyzer, ethanol conversion 100%, ethene contains 96.6% (mole) in the product, the Zn-Ag/MOR catalyzer, ethanol conversion 100%, ethene contains 98.0% (mole) in the product, but does not also have stability data.
Paula etc. [Catal.Lett., 2002,80 (3-4): 99-102] have studied the AM-11 zeolite that contains Nb to the catalytic performance of alcohols (ethanol, 1-propyl alcohol, n-butyl alcohol) Dehydration alkene.300 ℃ of temperature of reaction, WHSV=2 hour
-1Under the condition, ethanol conversion and ethylene selectivity all reach 100%, but stability only has 17 hours.
Raymond etc. [US4847223,1989] describe in detail by add CF in ZSM-5 molecular sieve
3SO
3The catalyzer of H (0.5～7%) has preferably catalytic performance 170-225 ℃ of temperature range; When Si/Al in 5～50 scopes, at 205 ℃, the transformation efficiency of ethanol reaches 99.2%, the selectivity of ethene is 95.6%.But the work-ing life of this catalyzer is very short.
In sum, the zeolite catalyst that adopts in the conventional art, the shortcoming that existence and stability is bad.
Summary of the invention
Technical problem to be solved by this invention is the problem that exists reaction stability bad in the conventional art, and a kind of new method by preparing ethylene by dehydrating ethanol is provided.The method has the advantages that catalytic activity height, selectivity are high, reaction stability is good.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method by preparing ethylene by dehydrating ethanol, take the ethanol of weight percent concentration as 5～100% as raw material, be 200～400 ℃ in temperature of reaction, be 0.1～15 hour with respect to the volume space velocity of ethanol
-1Under the condition, reaction raw materials contacts with catalyzer and generates ethene; Wherein used catalyzer is the adhesiveless ZSM-5 molecular sieve.
In the technique scheme, the SiO of adhesiveless ZSM-5 molecular sieve
2/ Al
2O
3=20～200.Temperature of reaction is preferably 220～350 ℃, is preferably 0.5～10 hour with respect to the volume space velocity of ethanol
-1
The adhesiveless ZSM-5 catalyzer prepares as follows among the present invention: a) to be selected from least a as the silicon source in diatomite, water glass, silicon sol or the White Carbon black, to be selected from least a as the aluminium source in sodium metaaluminate, Tai-Ace S 150 or the aluminum nitrate, adding aqueous sodium hydroxide solution mixes, pinch even, moulding, drying obtains presoma I.Precursor I Raw is (1～20) Na according to molar ratio computing
2O: Al
2O
3: (20～200) SiO
2B) with precursor I in the aqueous solution that contains tetraalkylammonium cation or organic amine aqueous solution steam, under 100～200 ℃ of conditions, processed 1～10 day, products therefrom obtains the adhesiveless ZSM-5 molecular sieve through washing, Template removal, ammonia exchange, roasting; The weight ratio of the aqueous solution of tetraalkylammonium cation and presoma I is for being 0.5～10, the aqueous solution mass concentration 5～80% of tetraalkylammonium cation.
In the technique scheme, can add or not add extrusion aid in the kneaded and formed process of precursor I, extrusion aid is selected from least a in field mountain valley with clumps of trees and bamboo powder or the starch, and the consumption of extrusion aid is 1～10% of presoma I weight.At least a in the preferred 4-propyl bromide of tetraalkylammonium cation or the TPAOH; At least a in the preferred ethamine of organic amine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, triethylamine or the hexanediamine.Precursor I preferably processed 2～8 days under 130～180 ℃ of conditions, formed the adhesiveless ZSM-5 molecular screen material.
The life-span basis for estimation of catalyzer is through after the same time reaction among the present invention, obtains the carbon distribution total amount of catalyzer by differential thermal analysis, thereby obtains the carbon distribution percentage of unit time catalyzer, be i.e. carbon distribution speed (unit: %/hour).This carbon distribution speed is larger, and the deactivation rate that catalyzer is corresponding is just faster, and the life-span of catalyzer is just shorter.
Zeolite molecular sieve has unique performance, is widely used in catalytic field.General synthetic zeolite molecular sieve is Powdered, is very restricted in catalytic applications, as catalyzer, must first with zeolite powder molecular sieve and binding agent moulding, make catalyzer have certain macro-size.So operation causes the zeolite molecular sieve effective surface area to reduce, and simultaneously, binding agent has stopped up the duct of zeolite molecular sieve to a certain extent, makes the diffusion of reactant be subject to impact.The present invention is by adopting the method that the moulding of sial material elder generation is changed into again the adhesiveless ZSM-5 molecular sieve, and not only available effective surface area is large, and catalytic active site is many; And having abundant pore structure, the duct is open, has eliminated to a certain extent the impact of diffusion, and catalyzer can be used more effectively; Avoided simultaneously the binding agent moulding to stop up the shortcoming of molecular sieve pore passage, the adhesiveless ZSM-5 molecular sieve pore passage is unimpeded, is beneficial to the diffusion of reactant and product, and therefore the formation of carbon distribution in the inhibited reaction process have better catalytic performance.Take the aqueous ethanolic solution of weight percent concentration as 75% as raw material, be 260 ℃ in temperature of reaction, be 8 hours with respect to the volume space velocity of aqueous ethanolic solution
-1Under the condition, ethanol conversion can reach 99.6%, and ethylene selectivity can reach 98.0%, the carbon distribution rate reduction 47.0%, obtained preferably technique effect.
Description of drawings
Fig. 1 is the XRD spectra of [embodiment 1] synthetic adhesiveless ZSM-5 molecular sieve.
Among Fig. 1, X-ray diffracting spectrum is 23.2,7.9, and there is strong diffraction peak at 24,8.8,23.6 and 24.4 degree places, illustrate that this zeolite has the MFI topological framework, are ZSM-5 molecular sieves.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Take by weighing 7.4 gram silicon sol (SiO
2Weight content 40%), adds again sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 6 Na
2O: Al
2O
3: 80 SiO
2, and add entry and mix, pinch even and extruded moulding.100 ℃ of dryings are 1 hour afterwards, pelletizing.Add in advance the mixture of 2 gram 4-propyl bromides and 10 gram distilled water in reactor, stainless (steel) wire is placed in the mixture top, the molecular sieve after the moulding is placed on the stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 150 ℃ to be processed 4 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours, and the XRD characterization result of sample is seen Fig. 1.Afterwards with resulting materials 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out at atmospheric fixed bed reaction unit, and the employing internal diameter is 10 millimeters stainless steel reactor, and loaded catalyst is 10 milliliters, and temperature of reaction is 250 ℃, reacts under the normal pressure, and raw material is 95% ethanol, air speed 1 hour
-1Reaction product is analyzed respectively after gas-liquid separation, and gas phase adopts HP6890 gas-chromatography, Al
2O
3Pillar, hydrogen flame detector; Liquid phase adopts HP4890, Plot Q kapillary pillar, hydrogen flame detector.React and the results are shown in Table 1 in 2 days.
[embodiment 2]
Take by weighing 7.4 gram silicon sol (SiO
2Weight content 40%), adds again sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 8 Na
2O: Al
2O
3: 100 SiO
2, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 1 hour afterwards, pelletizing.Add in advance the mixture of 2 gram TPAOH and 10 gram distilled water in reactor, stainless (steel) wire is placed in the mixture top, the molecular sieve after the moulding is placed on the stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 170 ℃ to be processed 3 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 3]
Take by weighing 7.4 gram silicon sol (SiO
2Weight content 40%), adds again sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 3.5 Na
2O: Al
2O
3: 60 SiO
2, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 2 hours afterwards, pelletizing.Add in advance the mixture of 6 gram quadrols and 10 gram distilled water in reactor, stainless (steel) wire is placed in the mixture top, the molecular sieve after the moulding is placed on the stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 180 ℃ to be processed 2 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 4]
Take by weighing 7.4 gram silicon sol (SiO
2Weight content 40%), adds again sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 9 Na
2O: Al
2O
3: 150 SiO
2, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 3 hours afterwards, pelletizing.Add in advance the mixture of 10 gram n-Butyl Amine 99s and 20 gram distilled water in reactor, stainless (steel) wire is placed in the mixture top, the molecular sieve after the moulding is placed on the stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 130 ℃ to be processed 7 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[Comparative Examples 1]
With NaZSM-5 molecular screen primary powder (SiO
2/ Al
2O
3Mol ratio is 70) removed template in 5 hours 550 ℃ of roastings.Resulting materials 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[Comparative Examples 2]
With NaZSM-5 molecular screen primary powder (SiO
2/ Al
2O
3Mol ratio is 70) mix with 1: 0.3 part by weight with boehmite.Add 0.5 mol/L salpeter solution and field mountain valley with clumps of trees and bamboo powder in the mixture, pinch even and extruded moulding, in 120 ℃ of dryings 10 hours, 550 ℃ of roastings 5 hours.Resulting materials 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[Comparative Examples 3]
With NaZSM-5 molecular screen primary powder (SiO
2/ Al
2O
3Mol ratio is 70) and silicon sol (SiO
2 Content 40%) mix with 1: 0.75 part by weight.Add field mountain valley with clumps of trees and bamboo powder in the mixture, pinch even and extruded moulding, in 120 ℃ of dryings 10 hours, 550 ℃ of roastings 5 hours.Resulting materials 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
[Comparative Examples 4]
By the performance of each step evaluate catalysts of [embodiment 1], just catalyzer adopts the industrial activated alumina catalyst of producing ethylene from dehydration of ethanol, reaction conditions and the results are shown in Table 1.
Table 1
Claims (3)
1. method by preparing ethylene by dehydrating ethanol take the ethanol of weight percent concentration as 5～100% as raw material, is 200～400 ℃ in temperature of reaction, is 0.1～15 hour with respect to the volume space velocity of ethanol
-1Under the condition, reaction raw materials contacts with catalyzer and generates ethene; Wherein used catalyzer is the adhesiveless ZSM-5 molecular sieve.
2. described method by preparing ethylene by dehydrating ethanol according to claim 1 is characterized in that the SiO of adhesiveless ZSM-5 molecular sieve
2/ Al
2O
3=20～200.
3. described method by preparing ethylene by dehydrating ethanol according to claim 1 is characterized in that temperature of reaction is 220～350 ℃, is 0.5～10 hour with respect to the volume space velocity of aqueous ethanolic solution
-1
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101615A (en) * | 1986-03-08 | 1986-07-30 | 南开大学 | A kind of catalyzer that can be used for producing ethylene from dehydration of ethanol |
| CN1974007A (en) * | 2006-12-21 | 2007-06-06 | 复旦大学 | Modified no-adhesive ZSM-5 zeolite catalyst and its prepn process |
| CN101121624A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing ethylene by ethanol dehydration |
-
2011
- 2011-09-29 CN CN2011102997548A patent/CN103030488A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101615A (en) * | 1986-03-08 | 1986-07-30 | 南开大学 | A kind of catalyzer that can be used for producing ethylene from dehydration of ethanol |
| CN101121624A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing ethylene by ethanol dehydration |
| CN1974007A (en) * | 2006-12-21 | 2007-06-06 | 复旦大学 | Modified no-adhesive ZSM-5 zeolite catalyst and its prepn process |
Non-Patent Citations (1)
| Title |
|---|
| WENYANG XU, ET AL.: "A novel method for the preparation of zeolite ZSM-5", 《J.CHEM.SOC., CHEM.COMMUN.》, 1 January 1990 (1990-01-01), pages 755 - 756 * |
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Application publication date: 20130410 |