CN101747136B - Technique for producing ethylene through catalyzing and dehydrating ethanol - Google Patents
Technique for producing ethylene through catalyzing and dehydrating ethanol Download PDFInfo
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- CN101747136B CN101747136B CN2008102312055A CN200810231205A CN101747136B CN 101747136 B CN101747136 B CN 101747136B CN 2008102312055 A CN2008102312055 A CN 2008102312055A CN 200810231205 A CN200810231205 A CN 200810231205A CN 101747136 B CN101747136 B CN 101747136B
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Abstract
The invention discloses a technique for producing ethylene through distilling, catalyzing and dehydrating ethanol. The step is as follows: a, fermented liquor is distilled by a distillation system to obtain ethanol with the concentration of more than 95 percent; b, the ethanol is purified by a filter system; c, the purified ethanol is put in a preheater to be heated to be 150 DEG C to 400 DEG C, the ethanol is mixed with superheated steam to obtain mixed steam, and the mixed steam enters a superheater; d, the mixed steam enters a gas-solid catalytic reactor, and undergoes the dehydration reaction under the action of catalyst to obtain crude ethylene; e, the crude ethylene is sent to a quench tower to be cooled, and then is treated by a gas-liquid separator to obtain ethylene gas; f, the ethylene gas is washed and dried in turn to obtain ethylene product. The invention has good whole stable performance, fully utilizes the material, effectively utilizes secondary steam and process watercirculation, reduces material consumption and energy consumption at maximum, improves the productivity and realizes the effective utilization of resource.
Description
Technical field
The present invention relates to technical field of biochemical industry, being specifically related to a kind of is the technology that the material choice dehydration generates bio-based ethene with ethanol.
Background technology
Ethene is described as " mother of petrochemical complex " as basic Organic Chemicals and the flagship product of petrochemical industry, and along with the fast development of ethene derivatives industries such as chemical industry, the energy, material, the product of ethene needs contradiction to become increasingly conspicuous.At present, ethylene production mainly adopts the production of petroleum catalystic pyrolysis both at home and abroad, research to non-petroleum production ethene in recent years has new breakthrough, reported with acetylene to be the novel process of raw material hydrogenation preparing ethene as patent CNi569783A and patent CN1317468A, patent CN86104433A has reported the method for producing ethene and propylene with ethane and propane selectivity, patent CN86102492A has reported the method that the ethane low-temperature oxidative dehydrogenation is produced ethene, patent CN1131190C and patent CN1269341A have reported a kind of ethane oxidizing and cracking process to produce ethylene: patent CN1092171C, and patent CN1280117A has reported method and the device with methane converting High-efficient Production ethene.But these methods unavoidably need in the face of fossil resource shortage and the serious difficult problem of environmental pollution, and bio-based ethene is the important topic of bio-based hardware and software platform compound, by bio-based ethene be the basis, can develop staple product up to a hundred thousands of kinds, with abundant farming, secondary product of forestry, waste is raw material, can be the fine chemical product of high added value with these resource conversion, when satisfying domestic and international economic construction demand, part has substituted valuable disposable resource-oil, makes contribution should be arranged setting up conservation-minded society.Technology how to optimize producing ethylene from dehydration of ethanol becomes the most important thing, reported the production method of utilizing ethanol to produce ethene as patent CN101172919 and CN101134704, perspective and novelty is arranged very much, key is to have a kind of system integration, resource, high efficiency of energy utilization and environmental protection, the technology that economic benefit and the market competitiveness are fabulous, its technology and catalyzer should be able to better be used for large-scale industrial production, in total system resource circulation, comprehensively, efficiently utilize situation that bigger breakthrough is arranged.
Summary of the invention
The object of the present invention is to provide the integrated technology of a kind of ethanol distillation and catalytic dehydration ethene coupling processed.
Ethanol of the present invention in order to achieve the above object is as follows through the processing step of catalytic dehydration production bio-based ethene:
A. to obtain concentration through Distallation systm be ethanol more than 95% to fermentation liquid;
B. with ethanol system's purifying after filtration;
C. the ethanol behind this purifying enters preheater, is heated to 150-400 ℃, ethanol is mixed obtaining mixed steam with superheated vapour, enters superheater then;
D. mixing steam enters in the gas-solid catalyticreactor, obtains crude ethylene through dehydration reaction under the effect of catalyzer;
E. after crude ethylene being sent into the quench tower cooling, use gas-liquid separation device to obtain ethylene gas;
F. ethylene gas obtains ethylene product by washing, drying successively.
Among the step b, filtering system comprises strainer, and the material of strainer is cotton, Mierocrystalline cellulose, glass fibre, polypropylene, nylon, polyphenylene sulfide fibre.
Among the step c, the alcohol-water mixing steam is directly by with secondary steam being the primary heater unit heating of thermal source.
In the steps d, ethanol is through dehydration reaction, the secondary steam that produces during by quench tower is used for the preheating of ethanol distillation and alcohol-water mixing steam, and the water that the dehydration back produces is as process water, and described process water comprises the dilution feedwater of boiler and produces the low-pressure steam water.
In the steps d, described catalyzer is HZSM-5 molecular sieve or α-Al
2O
3
Connect gas-liquid separation device behind the described condensing works, condensed water and ethanol raw material as a supplement return raw material mixing preheating.
Among the step f, ethylene gas washs by water wash column, compressor and soda-wash tower successively; Gas after the washing enters the dehumidification system of being made up of two or more drying towers and carries out drying; Dried gas by surge tank, after inspection after construction, is sent into storage tank after compressing through ethylene compression system.
Adopt above technical scheme, ethanol is the system height purification process after filtration, from solved the blockage problem of soda-wash tower at all, reduces the cleaning interval; Reduce impurity to activeconstituents or the erosion of carrier; Avoided the poisonous substance effect in the raw material to make poisoning of catalyst; Eliminated the active surface conductively-closed that hydrocarbon molecule causes at surperficial coking and carbon deposit; Prevented the obstruction that takes place under impact and the pressure load, guaranteed that reaction carries out smoothly.Adopt single tower multipass circulating reaction, R=6～8, non-intermittent production improved the thoroughness of reaction and the stability of systematicness and reactive system, is fit to large-scale industrial production.Catalyzer passes through modified optimization, lower coke deposit rate, avoid poisoning of catalyst, improve activity stability, improve acid simultaneously and distribute, the research in the duct that narrows, thus make the three-dimensional restriction in duct strengthen whole selectivity, the stability of improving, and then homogeneity and the stability of raising reactor assembly, improve life of catalyst.At every turn without the alcohol-water mixing steam of complete reaction raw material as a supplement, by the low-pressure steam revivifier, multistage circulation produces low-pressure steam, and heat energy repeatedly utilizes, and has strengthened the thoroughness of reaction, has reduced waste and the environmental pollution of raw material to greatest extent.The integration of cycle gas system and circulating water system, the consumption of having saved water, the energy has to greatest extent reduced the generation of waste water.The entire system stability is good, and prepared using is abundant, and secondary steam and the efficient utilization of process water circulation have reduced material consumption, energy consumption to greatest extent, have improved productive rate, have realized the efficient utilization of resource.
Description of drawings
Accompanying drawing is the schema of the technology of ethanol dehydration suitability for industrialized production bio-based ethene.
Embodiment
Embodiment 1
The alcohol mash that ferments is sent into the Distallation systm of being made up of distillation tower, control obtains the bio-ethanol of concentration 95%, do not cool off, directly the ethanol with 85 ℃ of the content 95% above temperature of producing passes through strainer 1, the material of strainer is cotton, it also can be polyphenylene sulfide fibre, Mierocrystalline cellulose, glass fibre, polypropylene, macromolecular materials such as nylon, be sent to preheating in the preheater 2 again, at 460 ℃, 1.5Mpa under the pressure, ratio with 1:1.5 (m/m), ethanol mixed obtaining 350 ℃ mixing steam with superheated vapour, the mass transport pipeline wraps up with lagging material.
Enter superheater 3, superheater amount to absorb heat=10.7 millimeter kilocalorie/times, steam be designed to 65 tons/time, be designed to 0.65Mp pressure, adopt 321 stainless steel tubes.Device is saved idle part can be by from the preheating of 120 ℃～135 ℃ of oiler feed thinners, produce 74 tons of steam/time.Gas mixture imports in the dehydration tower 4, by α-Al
2O
3Catalyst layer, 101m
3Catalyzer, at the inner high bed of 4.4m of filling separately of dehydration tower, the Ceramic Balls that adds 1/2 inch of 150mm at mesh screen is made bottom, supports with fence above, and gas velocity remains on 4000h
-1, maintaining the temperature at about 300 ℃, the reaction times is 16min, ethanol generation intramolecular dehydration is converted into crude ethylene under this environment.
The crude ethylene that to derive in dehydration tower and the mixed gas of water are introduced the quench tower 5, the bed of design 3.5m 38mm stainless steel annular thing (Pall ring gets final product) in the tower, the attached 5m bed filler in bottom (top 2.5m 50mm stainless steel or Pall ring, bottom 2.5m the 75mm corrugated filler of Mai Tepaike plate or stainless steel lattice Ritchie grid filler), design pressure=0.6Mp, 155 ℃ of design temperatures.Reduce crude ethylene and steam temperature rapidly, obtain simultaneously about 200 ℃～400 ℃, the secondary steam of 2.0Mpa imports in the production system and utilizes again.Through condensed crude ethylene-water mixed gas again, temperature is at 30-100 ℃, and crude ethylene content reaches more than 90% in the system of resultant.
The crude ethylene gas of content more than 90% is passed through soda-wash tower 6, adopt 30% NaOH, 50mm stainless steel (or polypropylene) the Pall ring filling batch of design 3.1m in the tower, the top arranges 5 bubble-cap wash traies, design pressure=0.6Mp, 80 ℃ of temperature, after washing, the unreacted ethanol of denier and aldehyde material contained in the gas mixture of resultant are removed.
Crude ethylene gas after the washing is sent to dehydration tower 7, design 4.5m stainless steel structured packing in the tower, vacuum, temperature=130 ℃, the water smoking has two towers to finish jointly, obtains process water.Described process water comprises the dilution feedwater of boiler and produces the low-pressure steam water.
Crude ethylene gas after the dehydration is sent to drying tower 8, has 30 in the tower by the valve tray of stainless steel 410 parcels, stainless valve, vacuum, 210 ℃ of temperature remove the ethene that residue moisture content can get 99.9% (V/V), and product enters in the storage tank 9 by compression set 10.
Embodiment 2
The alcohol mash that ferments sent into by distillation tower form Distallation systm, Distallation systm process using two-tower rectification, notice that second tower of control obtains the bio-ethanol of concentration more than 95%, do not cool off, directly the ethanol with 90 ℃ of the content 95% above temperature of producing passes through strainer, is sent in the preheater again, under 400 ℃, 1.8Mpa pressure, with the ratio of 1:1.5 (m/m), ethanol mixed obtaining 250 ℃ mixing steam with superheated vapour, the mass transport pipeline wraps up with lagging material.
Enter superheater, superheater amount to absorb heat=10.7 millimeter kilocalorie/times, steam be designed to 65 tons/time, be designed to 0.65Mp pressure, adopt 321 stainless steel tubes, gas mixture imports in the dehydration tower, under uniform temp and pressure by α-Al
2O
3Catalyst layer, 101m
3Catalyzer is filled the high bed of 4.4m separately in inside, and the Ceramic Balls that adds 1/2 inch of 200mm at mesh screen is made bottom, supports with fence above, and gas velocity remains on 4200h
-1, maintaining the temperature at about 400 ℃, the reaction times is 22min, ethanol generation intramolecular dehydration is converted into crude ethylene under this environment.
The mixed gas of the crude ethylene-water that will derive in dehydration tower is introduced the quench tower, the bed of design 3.6m 38mm stainless steel annular thing (Pall ring gets final product) in the tower, the attached 5m bed filler in bottom (top 3m 50mm stainless steel or Pall ring, bottom 2m the 75mm corrugated filler of Mai Tepaike plate or stainless steel lattice Ritchie grid filler), design pressure=0.7Mp, 155 ℃ of design temperatures.Reduce crude ethylene and steam temperature rapidly, obtain simultaneously about 300 ℃, the steam about 1.5Mpa imports in the production system and utilizes again.Through condensed crude ethylene, water mixed gas again, temperature is about 90 ℃, and crude ethylene content reaches more than 90% in the resultant system.
Crude ethylene, the gas of content more than 90% is passed through soda-wash tower (30% NaOH), 50mm stainless steel (or polypropylene) the Pall ring filling batch that 3.6m is arranged in the tower, the top arranges 5 bubble-cap wash traies, design pressure=0.7Mp, after 80 ℃ of washings of temperature, the unreacted ethanol of denier and aldehyde material contained in the gas mixture of resultant are removed.
Crude ethylene gas after the washing is sent to dehydration tower, design 4.5m stainless steel structured packing in the tower, vacuum, design temperature=130 ℃, the water smoking has two towers to finish jointly, obtains process water.Add the vacuum dehydration column reboiler, 1040m
2Vertical tube side setting, tube side design vacuum, 130 ℃ of temperature, shell side gauge pressure=3Kg, 150 ℃ of temperature are passed through vacuum dehydration column reboiler, reparation technology steam with process water.
Crude ethylene gas after the dehydration is sent to drying tower, has 30 in the tower by the valve tray of stainless steel 410 parcels, stainless valve, vacuum, 210 ℃ of temperature remove the ethene that residue moisture content can get 99.9% (V/V), and product enters in the storage tank by compression set.
Embodiment 3
The alcohol mash that ferments sent into by distillation tower form Distallation systm, Distallation systm process using two-tower rectification, control second tower and obtain the ethanol of concentration more than 95%, do not cool off, directly with the content of producing 95%, the ethanol that temperature is 95 ℃-pass through strainer, be sent to then in the preheater, under 340 ℃, 2Mpa pressure, with the ratio of 1:1.5 (m/m), ethanol mixed obtaining 150 ℃ mixing steam with superheated vapour, the mass transport pipeline wraps up with lagging material.
Enter superheater, superheater amount to absorb heat=10.7 millimeter kilocalorie/times, steam be designed to 65 tons/time, be designed to 0.65Mp pressure, adopt 321 stainless steel tubes, gas mixture imports in the dehydration tower, under uniform temp and pressure, (pass through the composite modified processing of water vapor by composite modified nanometer HZSM-5 molecular sieve catalyst layer, steam treatment can remove framework aluminum, reduces coke deposit rate and improves activity stability, also can improve acid simultaneously and distribute, the duct narrows, thereby the three-dimensional restriction in duct is strengthened improves selectivity), adopt the isothermal shell and tube reactor, heating medium is fused salt, the bulk density of molecular sieve is 0.5kg/L, loading in reaction tubes is 2000mm highly, and the temperature of reaction during catalysis is 175-200 ℃, and the mass space velocity of raw material is 3900h
-1, ethanol generation intramolecular dehydration is converted into crude ethylene under this environment.
The crude ethylene that to derive in dehydration tower and the mixed gas of water are introduced the quench tower, the bed of design 3.6m 38mm stainless steel annular thing (Pall ring gets final product) in the tower, the attached 5m bed filler in bottom (top 3m 50mm stainless steel or Pall ring, bottom 2m the 75mm corrugated filler of Mai Tepaike plate or stainless steel lattice Ritchie grid filler), design pressure=0.7Mp, 155 ℃ of design temperatures.Reduce crude ethylene and steam temperature rapidly, obtain simultaneously about 300 ℃, the steam about 1.5Mpa imports in the production system and utilizes again.Through condensed crude ethylene, water gas mixture again, temperature is about 90 ℃, and crude ethylene content reaches more than 90% in the resultant system.
Crude ethylene, the gas of content more than 90% is passed through soda-wash tower (30% NaOH), 50mm stainless steel (or polypropylene) the Pall ring filling batch of design 3.0m in the tower, the top arranges 5 bubble-cap wash traies, design pressure=0.7Mp, after 80 ℃ of washings of temperature, the unreacted ethanol of denier and aldehyde material contained in the gas mixture of resultant are removed.
Crude ethylene gas after the washing is sent to dehydration tower, design 4.5m stainless steel structured packing in the tower, vacuum, design temperature=130 ℃, the water smoking has three towers to finish jointly, a tower is used for adsorption dewatering in two towers, two other tower carries out absorption regeneration simultaneously, after first tower absorption is saturated, changes second tower and carries out the regeneration of sorbent material for adsorption dewatering, first and third tower, replace successively and use, and obtain process water.Add the vacuum dehydration column reboiler, 1040m
2Vertical tube side setting, tube side design vacuum, 130 ℃ of temperature, shell side gauge pressure=3Kg, 150 ℃ of temperature are passed through vacuum dehydration column reboiler, reparation technology steam with process water.
Crude ethylene gas after the dehydration is sent to drying tower (filling the sorbent material that special especially artificial zeolite does water in the dry tower body), there are 30 in the tower by the valve tray of stainless steel 410 parcels, stainless valve, vacuum, 210 ℃ of temperature, remove the ethene that residue moisture content can get 99.9% (V/V), product enters in the storage tank by compression set.
Claims (1)
1. an ethanol is characterized in that through the technology of catalytic dehydration production bio-based ethene:
A. the alcohol mash that ferments is sent into the Distallation systm of being made up of distillation tower, control obtains the ethanol of concentration 95%, do not cool off, directly the ethanol with 85 ℃ of content 95%, the temperature of producing passes through strainer, the material of strainer is cotton, polyphenylene sulfide fibre, Mierocrystalline cellulose, glass fibre, polypropylene or nylon, be sent to preheating in the preheater again, under 460 ℃, 1.5Mpa pressure, ratio with 1: 1.5 (m/m), ethanol mixed obtaining 350 ℃ mixing steam with superheated vapour, the mass transport pipeline wraps up with lagging material;
B. mixing steam enters superheater, and superheater amount to absorb heat=10.7 millimeter kilocalorie/times, steam be designed to 65 tons/time, be designed to 0.65Mp pressure, adopt 321 stainless steel tubes; Mixing steam imports in the dehydration tower, by α-Al
2O
3Catalyst layer, 101m
3Catalyzer, at the inner high bed of 4.4m of filling separately of dehydration tower, the Ceramic Balls that adds the 150mm1/2 inch at mesh screen is made bottom, supports with fence above, and gas velocity remains on 4000h
-1, maintaining the temperature at about 300 ℃, the reaction times is 16min, ethanol generation intramolecular dehydration is converted into crude ethylene under this environment;
C. the mixed gas of the crude ethylene that will derive in dehydration tower and water is introduced the quench tower, the bed 38mm Pall ring of design 3.5m in the tower, the attached 5m bed filler in bottom, design pressure=0.6Mp, 155 ℃ of design temperatures, the top 2.5m usefulness 50mm stainless steel of described 5m bed filler or Pall ring, bottom 2.5m the 75mm corrugated filler of Mai Tepaike plate or stainless steel lattice Ritchie grid filler; Reduce crude ethylene and steam temperature rapidly, obtain simultaneously about 200 ℃～400 ℃, the secondary steam of 2.0Mpa imports in the production system and utilizes again; Through condensed crude ethylene-water mixed gas again, temperature is at 30-100 ℃, and crude ethylene content reaches more than 90% in the system of resultant;
D. the crude ethylene gas of content more than 90% is passed through soda-wash tower, adopt 30% NaOH, 50mm stainless steel or the polyacrylic Pall ring filling batch of design 3.1m in the tower, the top arranges 5 bubble-cap wash traies, design pressure=0.6Mp, 80 ℃ of temperature, after washing, the unreacted ethanol of denier and aldehyde material contained in the gas mixture of resultant are removed;
E. the crude ethylene gas after will washing is sent to dehydration tower, design 4.5m stainless steel structured packing in the tower, and vacuum, temperature=130 ℃, the water smoking has two towers to finish jointly, obtains process water;
F. the crude ethylene gas after will dewatering is sent to drying tower, has 30 in the tower by the valve tray of stainless steel 410 parcels, stainless valve, vacuum, 210 ℃ of temperature remove the ethene that residue moisture content can get 99.9% (V/V), and product enters in the storage tank by compression set.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102312055A CN101747136B (en) | 2008-12-04 | 2008-12-04 | Technique for producing ethylene through catalyzing and dehydrating ethanol |
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| CN2008102312055A CN101747136B (en) | 2008-12-04 | 2008-12-04 | Technique for producing ethylene through catalyzing and dehydrating ethanol |
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| CN101747136A CN101747136A (en) | 2010-06-23 |
| CN101747136B true CN101747136B (en) | 2013-09-25 |
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| CN103121898B (en) * | 2011-11-18 | 2015-04-08 | 中国石油化工股份有限公司 | Separating and recycling method of products containing ethylene |
| CN104230622B (en) * | 2013-06-17 | 2016-08-17 | 中国石油化工股份有限公司 | The production method of producing ethylene from dehydration of ethanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727214A (en) * | 1986-01-30 | 1988-02-23 | De Belgische Statt-L'etat Belge | Process for obtaining ethylene from ethanol |
| CN101134704A (en) * | 2007-10-16 | 2008-03-05 | 南京工业大学 | Process for producing ethylene by ethanol dehydration |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727214A (en) * | 1986-01-30 | 1988-02-23 | De Belgische Statt-L'etat Belge | Process for obtaining ethylene from ethanol |
| CN101134704A (en) * | 2007-10-16 | 2008-03-05 | 南京工业大学 | Process for producing ethylene by ethanol dehydration |
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