CN102649667B - Method for catalytic dehydration of ethanol - Google Patents
Method for catalytic dehydration of ethanol Download PDFInfo
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- CN102649667B CN102649667B CN201110045565.8A CN201110045565A CN102649667B CN 102649667 B CN102649667 B CN 102649667B CN 201110045565 A CN201110045565 A CN 201110045565A CN 102649667 B CN102649667 B CN 102649667B
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Abstract
The invention relates to a method for catalytic dehydration of ethanol, and mainly solves the technical problem of low space velocity and low ethylene selectivity during the ethanol dehydration reaction process in the prior art. Through the adoption of the technical scheme that ethanol is taken as a raw material, at least one of water and C2 to C5 alcohols is taken as a termination agent, and under the conditions that the reaction temperature is 200 to 400 DEG C, the reaction pressure is 0.01 to 1.5 MPa, the contact time is 0.1 to 20 seconds, and the weight ratio of the raw material and the termination agent is (5 to 1,000) : 1, the raw material is in contact reaction with a catalyst in a fluidized bed to generate an ethylene-contained effluent, and the invention solves the problem of low reaction space velocity and low ethylene selectivity well, and can be used in the industrial production of increasing the yield of ethylene through catalytic dehydration of ethanol.
Description
Technical field
The present invention relates to a kind of method that alcohol catalysis reaction is dewatered, particularly, about adopting ethanol dehydration fluidized bed reactor coupling riser reactor, fast separating device and terminator technology, be practically applicable to the method that alcohol catalysis reaction is dewatered.
Background technology
Ethene is a kind of very important basic organic chemical industry raw material, and ethylene industry is the basis of petrochemical industry, occupies very consequence in national economy.In recent years, along with increasing rapidly of the derivative demands such as polyethylene, the demand of ethene was all increased year by year.At present, ethene is mainly raw material by Sweet natural gas or light petroleum fraction, adopt steam cracking process to make, but along with Sweet natural gas and light petroleum fraction price Continued, the method for some other approach increasing output of ethylene becomes the focus of concern.Especially along with the fast development of biotechnology, the technology of biological legal system ethanol is constantly perfect, and the source of raw material is increasingly extensive, and the cost of raw material is also more rational, makes producing ethylene from dehydration of ethanol technology enjoy attention.Producing ethylene from dehydration of ethanol technology has that flow process is short, equipment is few, it is little to invest, instant effect and the stronger feature such as supporting adaptability and market handiness.Producing ethylene from dehydration of ethanol technology involved in the present invention is a kind of competitive Technology.
The main reaction of producing ethylene from dehydration of ethanol is:
CH
3CH
2OH→CH
2＝CH
2+H
2O
Be that the reaction of a part alcohol catalysis obtains a part ethene and a part water.Certainly in catalytic dehydration of ethanol process, also unavoidably can there are some side reactions as generated ether, acetaldehyde, carbon monoxide, carbonic acid gas, higher olefins etc.
Document " Speciality Petrochemicals " the 1st phase in 1993, introduce a kind of employing for 35～37 pages
the research of molecular sieve catalyst to low-concentration ethanol ethene processed, result shows, when temperature of reaction is that 250～280 ℃, liquid air speed are 0.5～0.8 hour
-1, when feed ethanol mass concentration is 10% left and right, ethanol conversion is 99%, but liquid air speed is lower.
The 16th the 2nd phase of volume of document " chemical industry and engineering " nineteen ninety-five, introduce the development of NC1301 type catalyst for ethanol delydration to ethylene, this catalyzer main active component is γ-Al
2o
3, 350～440 ℃ of temperature of reaction, reaction pressure≤0.3MPa (absolute pressure), weight space velocity is 0.3～0.6 hour
-1, ethylene selectivity is only 97.5% left and right, air speed is lower.
USP423475 has reported producing ethylene from dehydration of ethanol technology, and it adopts oxide catalyst, and 320～450 ℃ of temperature of reaction, air speed is 0.4～0.6 hour
-1under condition, realize the conversion of ethanol, have equally the problem that air speed is low.
The subject matter that the related technology of above-mentioned document exists is that ethylene selectivity is low, the technical problem that air speed is low.
Summary of the invention
Technical problem to be solved by this invention is to exist in producing ethylene by ethanol dehydration process in previous literature technology, and ethylene selectivity is low, the problem that air speed is low, a kind of method that provides new alcohol catalysis reaction to dewater.The method, in producing ethylene by ethanol dehydration process, has ethylene selectivity high, the advantage that air speed is high.
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 of alcohol catalysis reaction dehydration, and take ethanol as raw material, to be selected from water, C
2～C
5at least one in alcohol is terminator, it is 200～400 ℃ in temperature of reaction, reaction pressure is 0.01～1.5MPa, be 0.1～20 second duration of contact, the weight ratio of raw material and terminator is under 5～1000: 1 condition, catalyzer contact reacts in raw material and fluidized-bed generates the effluent that contains ethene, wherein, fluidized-bed reactor is substantially by settling vessel (5), stripper (11) and interchanger (3) composition, comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), fast separating device (6), airway (7), cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13), wherein emulsion zone (A) is connected with riser tube (4) after the zone of transition (B) of undergauge structure, riser tube (4) upper end or end are provided with fast separating device (6), the spiral arm of fast separating device (6) is positioned at outside riser tube (4), in the airway (7) coaxially communicating with riser tube (4), airway (7) is positioned at settling vessel (5), and the freeboard of fluidized bed on top, negative area (C) is stretched in its upper end, and its lower end is positioned at the outer zone of transition of riser tube (4) (B) outer upper ends, cyclonic separator (8) is positioned at settling vessel (5), and outside airway (7), its top outlet communicates with collection chamber (9), collection chamber (9) is positioned at settling vessel (5) top and is connected with product gas outlet (10), stripper (11) one end is connected with the bottom of settling vessel (5), and the other end of stripper (11) is connected with inclined tube to be generated (13), between the bottom of settling vessel (5) and emulsion zone (A) hypomere, interchanger (3) is set, one end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A), sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, the bottom of sparger or grid distributor (2) is provided with material inlet (1), it is characterized in that, near riser tube (4) lower region, terminator inlet (15) is set.
In technique scheme, terminator inlet 15 is 0～4/5 of riser tube 4 length apart from the vertical range of riser tube 4 bottoms; Terminator inlet 15 distributes ringwise along riser tube 4 lower regions; The internal diameter of riser tube 4 is 1/15～1/2 of emulsion zone A external diameters, and the height of riser tube 4 is 1/5～5/1 of emulsion zone A height; Regenerator sloped tube 12 is 1/10～1/2 of emulsion zone A vertical height with emulsion zone A Link Port apart from emulsion zone A bottom vertical distance; The vertical height of zone of transition B is 1/20～1/2 of emulsion zone A vertical height; The gas inlet distance set air chamber 9 top vertical ranges of cyclonic separator 8 are 1/10～1/1 of settling vessel diameter.
In technique scheme, catalyzer is preferably selected from least one in ZSM-5 molecular sieve and SAPO-34 molecular sieve.Terminator is preferably selected from least one in water, methyl alcohol or ethanol; It is 210～350 ℃ that reaction conditions is preferably temperature of reaction, and reaction pressure is 0.01～0.8MPa, and be 0.2～20 second duration of contact, and the weight ratio of raw material and terminator is 10～500: 1.
Ethanol dehydration reaction is strong endothermic reaction, very crucial when the raising that is uniformly distributed selectivity to catalytic dehydration of ethanol product and catalytic efficiency of temperature.Adopt fluidized-bed reactor to realize being uniformly distributed of reaction bed temperature, this is very favourable and effective for improving reaction velocity.But realizing alcohol catalysis at the ethanol dehydration fluidized bed reactor of employing transforms in production ethylene process, object product ethene with catalyzer Long contact time situation under, still can continue to transform, especially at the settling zone of ethanol dehydration fluidized bed reactor, a large amount of unsegregated catalyzer can continue and reaction product generation secondary reaction under the condition of high temperature, make side reaction many, and amount of by-products is large, cause ethylene selectivity low, yield is low.The present invention injects terminator by the region, outlet position of leaving catalytic bed in catalyzer and reaction product, on the one hand, the terminator that temperature is lower contacts with pyroreaction mixture and catalyzer, can significantly reduce the temperature of reaction mixture and catalyzer, this can further accelerate the reduces heat process of pyroreaction mixture and catalyzer, the reaction mixture that temperature sharply reduces and catalyzer leave behind reaction zone, side reaction is few, avoid the generation of secondary reaction, further improved yield and the selectivity of object product.
Method of the present invention is produced ethene for alcohol catalysis reaction dehydration, use Fig. 1 shown device, employing ZSM-5 molecular sieve is catalyzer, and water is terminator, is 200～400 ℃ in temperature of reaction, reaction pressure is 0.01～1.5MPa, be 0.1～20 second duration of contact, and the weight ratio of raw material and terminator is that under 5～1000: 1 condition, the transformation efficiency of ethanol can reach 100%, the selectivity of ethene can be greater than 99%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the fluidized-bed reactor schematic diagram that the present invention adopts.
In Fig. 1, A is that emulsion zone, B are that zone of transition, C are negative areas, the 1st, material inlet, the 2nd, sparger or grid distributor, the 3rd, interchanger, the 4th, riser tube, the 5th, settling vessel, the 6th, fast separating device, the 7th, airway, the 8th, cyclonic separator, the 9th, collection chamber, 10 product gas outlets, the 11st, stripper, the 12nd, regenerator sloped tube, the 13rd, inclined tube to be generated, the 14th, stripped vapor entrance, the 15th, terminator inlet.
Fig. 1 Raw is introduced by material inlet 1, through gas distributor or grid distributor 2 distribute laggard enter emulsion zone A and the catalyzer contact reacts of fluidized-bed, catalyzer and reaction mixture enter riser tube 4 through zone of transition B; After vortex quick separation device 6 sharp separation of riser tube 4 upper ends (end), most of catalyzer enters the lower region of settling vessel C, the partially catalyzed agent that reaction mixture is carried secretly enters settling vessel 5 top dilute phase spaces and carries out secondary separation through cyclonic separator 8, gas product after separation enters collection chamber 9 through the outlet of cyclonic separator 8, is drawn by product gas outlet 10.Catalyzer after separating from cyclonic separator 8 returns to the lower region of settling vessel 5 through the dipleg of cyclonic separator 8.The reclaimable catalyst of the C bottom, negative area in settling vessel 5 enters stripper 11, after the stripped vapor stripping from stripped vapor entrance 14, enter revivifier (in figure, revivifier omits) through inclined tube 12 to be generated, regenerator enters ethanol dehydration fluidized bed reactor emulsion zone A through regenerator sloped tube 12.In addition, the partially catalyzed agent in settling vessel 5 enters ethanol dehydration fluidized bed reactor emulsion zone A bottom and continues to react with catalyst mix after interchanger 3 heat exchange, and whole process loops.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
With the fluidized-bed reactor of Fig. 1, wherein, terminator inlet is 1/5 of riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/10 of emulsion zone external diameter, and the height of riser tube is 1/4 of emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone Link Port are 1/5 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance, the vertical height of fluidized-bed reactor zone of transition is 1/10 of emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/5 of settling vessel diameter.Take SAPO-34 molecular sieve as catalyzer, ethanol is raw material, water is terminator, the weight ratio of raw material and terminator is 10: 1, and terminator feeding temperature is 40 ℃, 250 ℃ of temperature of reaction, 7 seconds duration of contact, under the condition that catalyzer and ethanol weight ratio are 0.4, ethanol conversion 100%, ethylene selectivity is 98.5%.
[embodiment 2]
With the fluidized-bed reactor of Fig. 1, wherein, terminator inlet is 1/8 of riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/12 of emulsion zone external diameter, and the height of riser tube is 1/2 of emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone Link Port are 1/3 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance, the vertical height of fluidized-bed reactor zone of transition is 1/5 of emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/3 of settling vessel diameter.Take ZSM-5 molecular sieve as catalyzer, water is terminator, the weight ratio of raw material and terminator is 5: 1, terminator feeding temperature is 30 ℃, and ethanol is raw material, 280 ℃ of temperature of reaction, 10 seconds duration of contact, under the condition that catalyzer and ethanol weight ratio are 0.4, ethanol conversion 100%, ethylene selectivity is 99.5%.
[embodiment 3]
With the fluidized-bed reactor of Fig. 1, wherein, terminator inlet is 1/15 of riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/6 of emulsion zone external diameter, and the height of riser tube is 1/3 of emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone Link Port are 1/8 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance, the vertical height of fluidized-bed reactor zone of transition is 1/6 of emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/4 of settling vessel diameter.Take ZSM-5 molecular sieve as catalyzer, propyl alcohol is terminator, the weight ratio of raw material and terminator is 50: 1, terminator feeding temperature is 30 ℃, and ethanol is raw material, 260 ℃ of temperature of reaction, 5 seconds duration of contact, under the condition that catalyzer and ethanol weight ratio are 0.3, ethanol conversion 100%, ethylene selectivity is 98.9%.
[embodiment 4]
With the fluidized-bed reactor of Fig. 1, wherein, terminator inlet is 1/15 of riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/18 of emulsion zone external diameter, and the height of riser tube is 1/6 of emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone Link Port are 1/5 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance, the vertical height of fluidized-bed reactor zone of transition is 1/10 of emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/8 of settling vessel diameter.Take SAPO-34 molecular sieve as catalyzer, ethanol is raw material, water is terminator, the weight ratio of raw material and terminator is 60: 1, and terminator feeding temperature is 40 ℃, 300 ℃ of temperature of reaction, 15 seconds duration of contact, under the condition that catalyzer and ethanol weight ratio are 0.3, ethanol conversion 100%, ethylene selectivity is 99.1%.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just reactor adopts fixed-bed reactor, and reaction result is: ethanol conversion 100%, ethylene selectivity is 96.5%.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just in ethanol dehydration reaction device, do not add terminator, reaction result is: ethanol conversion 100%, ethylene selectivity is 95.2%.
Claims (1)
1. the method for an alcohol catalysis reaction dehydration, raw material is introduced by the material inlet (1) of fluidized-bed reactor, through gas distributor or grid distributor (2) distribute laggard enter emulsion zone A and the catalyzer contact reacts of fluidized-bed, catalyzer and reaction mixture enter riser tube (4) through zone of transition B, after vortex quick separation device (6) sharp separation of riser tube (4) upper end, most of catalyzer enters the lower region of settling vessel C, the partially catalyzed agent that reaction mixture is carried secretly enters settling vessel (5) top dilute phase space and carries out secondary separation through cyclonic separator (8), gas product after separation enters collection chamber (9) through the outlet of cyclonic separator (8), drawn by product gas outlet (10), catalyzer after separating from cyclonic separator (8) returns to the lower region of settling vessel (5) through the dipleg of cyclonic separator (8), the reclaimable catalyst of the C bottom, negative area in settling vessel (5) enters stripper (11), after the stripped vapor stripping from stripped vapor entrance (14), enter revivifier through inclined tube to be generated (12), regenerator enters ethanol dehydration fluidized bed reactor emulsion zone A through regenerator sloped tube (12), in addition, partially catalyzed agent in settling vessel (5) enters ethanol dehydration fluidized bed reactor emulsion zone A bottom and continues to react with catalyst mix after interchanger (3) heat exchange, whole process loops,
In described fluidized-bed reactor, terminator inlet is 1/8 of riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/12 of emulsion zone external diameter, and the height of riser tube is 1/2 of emulsion zone height; Fluidized-bed reactor regenerator sloped tube and emulsion zone Link Port are 1/3 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance, the vertical height of fluidized-bed reactor zone of transition is 1/5 of emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/3 of settling vessel diameter; Take ZSM-5 molecular sieve as catalyzer, water is terminator, the weight ratio of raw material and terminator is 5: 1, terminator feeding temperature is 30 ℃, and ethanol is raw material, 280 ℃ of temperature of reaction, 10 seconds duration of contact, under the condition that catalyzer and ethanol weight ratio are 0.4, ethanol conversion 100%, ethylene selectivity is 99.5%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165027A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from oxygen-containing compounds |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101306969A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Reaction device for preparing low-carbon olefin from oxygen-containing compounds |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165027A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from oxygen-containing compounds |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101306969A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Reaction device for preparing low-carbon olefin from oxygen-containing compounds |
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