CN101134704A - Process for producing ethylene by ethanol dehydration - Google Patents
Process for producing ethylene by ethanol dehydration Download PDFInfo
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- CN101134704A CN101134704A CNA2007101336109A CN200710133610A CN101134704A CN 101134704 A CN101134704 A CN 101134704A CN A2007101336109 A CNA2007101336109 A CN A2007101336109A CN 200710133610 A CN200710133610 A CN 200710133610A CN 101134704 A CN101134704 A CN 101134704A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 239
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000005977 Ethylene Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008569 process Effects 0.000 title claims abstract description 42
- 238000006297 dehydration reaction Methods 0.000 title claims description 35
- 230000018044 dehydration Effects 0.000 title claims description 34
- 238000005406 washing Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000010168 coupling process Methods 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 230000008878 coupling Effects 0.000 claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 85
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 238000007791 dehumidification Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000463 material Substances 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 description 75
- 239000007789 gas Substances 0.000 description 59
- 238000005516 engineering process Methods 0.000 description 27
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- 238000006243 chemical reaction Methods 0.000 description 16
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
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- 238000005265 energy consumption Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000003139 buffering effect Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
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- 241000196324 Embryophyta Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 101100194816 Caenorhabditis elegans rig-3 gene Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
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- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention is the process of producing ethylene with ethanol obtained through fermenting biomass as the material, and provides one biomass path of preparing ethylene. The present invention features the coupling of ethanol distilling process and chemically catalytic ethylene preparing process. The ethylene producing process includes: distilling 5-45 % concentration ethanol solution to obtain mixed ethanol-water vapor, heating the mixed ethanol-water vapor to 150-350 deg.c, catalytic reaction in a gas-solid reactor to obtain coarse ethanol product, cooling, gas-liquid separating to eliminate components with boiling point higher than 70 deg.c and obtain ethylene gas, and washing, drying and refining to obtain ethylene product. The ethylene producing process has low comprehensive power consumption, low cost and high marketability.
Description
Technical field
The present invention relates to chemical technology field, being specifically related to a kind of is the technology that the material choice dehydration generates ethene with ethanol.
Background technology
Ethene is a kind of very important organic chemical industry's basic raw material, be called as " mother of petrochemical complex ", be mainly used to produce multiple important organic chemical industry's products such as polyethylene, polyvinyl chloride, oxyethane, ethylene glycol, dichloro dioxane, ethylbenzene, phenylethane, vinylbenzene, vinyl acetate between to for plastic.At present, ethylene production mainly adopts the production of petroleum catalystic pyrolysis both at home and abroad, the research that non-petroleum is produced ethene in recent years has new breakthrough, has reported to be that novel process, the patent CN86104433A of raw material hydrogenation preparing ethene reported that the method, the patent CN86102492A that produce ethene and propylene with ethane and propane selectivity have reported that the ethane low-temperature oxidative dehydrogenation produces method, patent CN1131190C and the patent CN1269341A of ethene and reported a kind of ethane oxidizing and cracking process to produce ethylene with acetylene as patent CN1569783A and patent CN1317468A; Patent CN1092171C, patent CN1280117A have reported method and the device with methane converting High-efficient Production ethene.But the inevitable demand side of these methods is to a fossil resource shortage and the serious difficult problem of environmental pollution, and the producing ethylene by ethanol dehydration technology is to be raw material with the ethanol that derives from agricultural byproducts, can avoid the dependence to petroleum resources like this.To oil-poor and based on agricultural the country and regional, production alcoholic acid raw material is easy to get and is guaranteed, established enough raw material bases for producing ethene, producing ethylene with ethyl alcohol seems and is even more important, and it is strong and have the technology of the market competitiveness that its key factor is to study a kind of new economy.Patent CN1884232A has reported a kind of microwave chemical method of preparing ethylene by catalytic dehydration of ethanol, this method is to be catalyzer with phosphoric acid salt, ethanol is that dehydration obtains ethene under the microwave of 300MHz～300GHz in frequency, but this method does not provide a kind of complete process program.Generally speaking, preparing ethylene by dehydrating ethanol has Sustainable development, the characteristic of clean and safe, and its feedstock pathway is as follows:
Alcohol production just begins in Ancient Times in China, is the renewable resources technology the most ripe, that experience is the abundantest of producing up to now, along with the generation of " oil crisis " in the world wide for the first time in 1976, makes bio-ethanol begin large-scale industrialization production.Be used to produce the alcoholic acid raw material and mainly contain starchiness class, molasses class, cellulosic class, sulphite papermaking wastewater and wild plant class etc.Industrial alcohol is produced more much lower than edible ethanol to the requirement of impurity, and its sophisticated purifying technique extensively adopts distillation technique, and Distallation systm has single tower, double tower, multitower differential distillation and heat pump distillation.The effect of distillation tower is that ethanol and volatile impunty and a part of water are separated from the maturing fermentation mash, and gets rid of the poor liquid of being made up of solid substance, non-volatility impurity and most of water, and the finished product alcohol gas obtains finished product alcohol through the water cooler condensation.In alcohol production, the distillation energy consumption accounts for 60%～70% of total energy consumption, and be cooled water, waste liquid etc. of wherein a large amount of heat energy are taken away and caused damage, and 1 ton of 95% alcohol gas is cooled to 25 ℃ from 85 ℃ and discharges 1.06 * 10
6KJ heat is equivalent to the 290kwh electric flux, if lower the temperature with 10 ℃ of cold water, water temperature rises to 45 ℃ of needs and consumes nearly 12 tons of water coolants.
Ethanol dehydration obtains the research of ethene and carries out comparison early, occurs being produced by the thermo-cracking of hydro carbons such as petroleum naphtha and Sweet natural gas the full scale plant of ethene afterwards, in the very fast ethanol dehydration method that replaced of developed country, has almost become whole sources of ethene at that time.But because the difference and the ethanol dehydration method of various countries' situation self have, some developing countries do not abandon the method for this production ethene.
The research of producing ethylene from dehydration of ethanol mainly contains catalyzer and technical study two portions, and wherein catalyst research is comparatively active.Since logical superheated silicon-dioxide and aluminum oxide obtained ethene with ethanol first, the scholar had carried out extensive studies to the catalyzer that uses, and from the data of report, the catalyzer that producing ethylene from dehydration of ethanol relates to has activated alumina, SiO
2-Al
2O
3, atlapulgite, phosphoric acid or barium white carried catalyst, Al
2O
3-MgO/SiO
2, molecular sieve etc., wherein activated alumina and HZSM-5 molecular sieve catalytic effect are better.Mass space velocity 0.3～the 0.7h of the use of activated alumina
-1, 350～500 ℃ of temperature; High speed development along with catalysis technique, molecular sieve research and development and the application in each field become the research focus, patent CN86101615A has reported that a kind of major ingredient is the producing ethylene with ethyl alcohol catalyzer of ZSM-5 molecular sieve and aluminium hydroxide, 250～390 ℃ of this catalyzer use range, ethanol air speed 1-4h
-1Patent CN101024194A has reported a kind of metal composite modified HZSM-5 molecular sieve catalyst and preparation method; Patent CN1923367 has reported the preparation and the application in the preparation biological ethane thereof of composite modified catalyst, but need be with rare gas element CO, N
2Be carrier, for product separation has brought inconvenience.No matter adopt which kind of catalyzer, be strong endothermic reaction because ethanol dehydration generates ethene, the about 46.8kJ/mol of reaction heat, the heat and mass condition also is the factor that influences technological process.Therefore except that the invention of carrying out the novel efficient catalyzer and study on the modification, adopting new reaction that is suitable for producing ethylene from dehydration of ethanol and separating technology is the direction of following biological ethane industrial development.
According to document and patent search result, both at home and abroad seldom to the technical study of preparing ethylene by dehydrating ethanol.At present there is the production equipment of two cover producing ethylene from dehydration of ethanol in China, a cover for external import, another set of be China's independent research.The weak point of two covering devices is except that reactor changes fixed bed into, other are the reprint of oil ethylene process substantially, and what adopt is the technology eighties in last century, no too many innovation and change, the competitive device that does not also design at the preparing ethylene by dehydrating ethanol characteristics fully so far.With concentration is 95% liquid ethanol, is 350～400 ℃ in temperature, and the activated alumina katalysis is produced ethene down and is still current main flow technology.Shortcoming is that system stability is poor, the production energy consumption height, and also ton ethene water loss is huge, and caustic scrubber easily stops up.
In the traditional technology, the raw material of producing ethene is 25 ℃ of liquid ethanol, must be through preheating, evaporation, overheated and react 4 processes, the heat energy of technological process consumption is calculated as follows: the thing thermal capacitance data that check in ethanol, ethene, water by chemical handbook, under isobaric condition, the thermal change of material is thermal capacitance C by formula
P=A+BT+CT
2+ DT
3, heat is with formula
Calculate, the evaporation of water enthalpy is 40.66kJ/mol, and alcoholic acid evaporation enthalpy is 38.72kJ/mol, and the reaction heat that calculates 240 ℃ of following ethanol dehydrations generation ethene is 47.53kJ/mol, and production process energy consumption distribution situation is seen Fig. 1.
As seen from Figure 1, the energy consumption of traditional biological ethylene production have an appointment 88% at water component, about 42% preheating or the evaporation that all is used for raw material in the ethanol.And steam superheating to temperature of reaction institute heat requirement less than twenty percent, the reaction heat that ethanol dehydration generates ethylene process consumption also only accounts for about 44% of whole energy consumption, so the cost of energy of conservation preheating and evaporation is one of emphasis of patent of the present invention.
In the traditional technology, the product that ethanol dehydration reaction obtains is removed sour gas such as carbonic acid gas after cooling off with quench tower (or claiming water wash column) again with soda-wash tower, process system fluctuation of service, the big and easily stifled tower of soda-wash tower of water consumption.Under catalyst action, the 1mol ethanol synthesis generates 1mol ethene and 1mol water, if alcohol concn is 95%, 53% (mol ratio) of then having an appointment in the product component is water; If is raw material with 50% ethanol, then about 71% (mol ratio) is water vapor in the product, and the temperature of product is generally about 350 ℃, and the condensation latent heat of water vapor is 40.66kJ/mol.The cooling of product often needs to consume a large amount of water coolants, and the waste water that is produced has increased the weight of the load of Sewage treatment systems; Because the service temperature height of quench tower, organic substances such as ethanol, ether, aldehydes are not thoroughly brought alkali cleaning workshop section into because of cleaning in the crude ethylene product, thereby cause the obstruction of soda-wash tower to happen occasionally.
The present invention is to be that catalytic material dehydration generates the novel process of producing ethene with ethanol, and this technology has been coupled, and ethanol distillation is purified and the technology of catalytic dehydration system ethene, by heat exchange network optimization the energy of system is fully utilized.Technology has reasonably solved the big and soda-wash tower blockage problem of water consumption, crude ethylene makes ethene reduce in the loss for the treatment of process through condensation separation, washing, drying and absorption and low temperature fractionation operation, improved ethylene yield, especially in conjunction with making alcohol production ethene have powerful competitive power behind the novel molecular sieve.
Summary of the invention
The object of the present invention is to provide the producing ethylene with ethyl alcohol technology that the cover production process is integrated and entire system is optimized, this technology is by energy consumption, the material consumption of ethanol purification with the optimization reduction producing ethylene from dehydration of ethanol of coupling, entire system heat exchange and the production technique of catalysis system ethene method, the deficiency of having avoided above-mentioned prior art to exist simultaneously.
The objective of the invention is to realize by following technical measures:
A kind of catalytic dehydration of ethanol is produced ethylene process, with ethanol distillation and chemical catalysis system ethylene process PROCESS COUPLING, concentration is that 5～45% ethanol obtain the alcohol-water mixed vapour through Distallation systm, entering after this alcohol-water mixed vapour continues to be heated to 150～350 ℃ and obtaining product through catalyst action in the gas-solid catalyticreactor is crude ethylene, after the crude ethylene cooling, use gas-liquid separation device to remove its mid-boiling point and obtain ethylene gas greater than 70 ℃ of components, ethylene gas is successively by washing, the dry and refining ethylene product that obtains.
Gas-solid catalyticreactor adopts isotherm formula fixed bed, multistage insulation bed or fluidized-bed, and reaction pressure is 0.05～1.5MPa, and temperature is 180～500 ℃.
The alcohol-water mixed vapour that obtains through Distallation systm is without cooling and liquefaction, directly by being that 200～400 ℃ crude ethylene is that the gas-to-gas heat exchanger and the gas superheater of thermal source is heated to 150～350 ℃ with temperature.
The concentration of ethanol scope is 45～98% in the alcohol-water mixed vapour, and preferred concentration range for is 55～95%.
The gaseous ethylene that the catalysis ethanol dehydration is generated and the mixture of water are called crude ethylene, and the crude ethylene temperature after the catalyzed reaction is 200～400 ℃, and the water molecules mol ratio that contains in the component surpasses 50%, and 1mol water vapor cooling condensation can discharge about 50kJ heat.Connect interchanger and condensing works behind the gas-solid catalyticreactor, feeding condensing works again after crude ethylene that catalyst action generates and alcohol-water mixed vapour are by the gas-to-gas heat exchanger heat exchange further cools off, the cooled temperature of crude ethylene is 30～100 ℃, components condense such as most of water, ethanol, ether, aldehydes and organic acid, waste heat comprises that sensible heat and condensation latent heat reclaim in interchanger, be used for preheating alcohol-water mixed vapour.
Connect gas-liquid separation device behind the condensing works, cooled crude ethylene enters gas-liquid separation device, gas-liquid separation device is used for separating components such as water that crude ethylene gas has been condensed and ethanol, and this liquid ingredient is assembled in the gas-liquid separation device bottom and separated from crude ethylene and be disposed to Sewage treatment systems.Because the boiling point of ethene is-103.9 ℃ and water insoluble, the discharging of liquid does not influence the output of ethene.Major ingredient in the gas phase is an ethene, and temperature is that 30～100 ℃ ethylene gas enters washing system.Washing system is made up of water wash column, compressor and soda-wash tower, and ethylene gas enters water wash column, compressor and soda-wash tower successively and washs; The soda-wash tower working pressure is 0.2～1.0Mpa, 30～85 ℃ of temperature, and washing section is established on the soda-wash tower top, and the aqueous solution after the washing is as the washing composition of water wash column.Ethylene gas after washing enters dehumidification system; Dehumidification system is made of two or more drying towers, when adopting two tower process then a tower be used for adsorption dewatering, another tower reproducing adsorbent.The inner siccative of loading of drying tower is a molecular sieve, is 3A, 4A or 5A type, and the adsorption dry of each drying tower and regenerating molecular sieve function are taken turns switch application; It is refining that ethene after dry enters the ethene refining system, and refining freezing low temperature fractionation or low temperature fractionation and the refining with adsorbents process combined of adopting of ethene reaches excellent level in the ethene purity requirement, i.e. the freezing distillation system of 99.95% employing ethene when above.The refining separating heavy of ethene is C such as butylene, butane
3Above alkane and part aromatic hydrocarbon, isolating light constituent comprises hydrogen, methane, ethane etc.
Ethylene gas removes boiling points such as ethanol in the ethylene gas, ether, aldehyde greater than 70 ℃ polarity organic molecule and carbonic acid gas through soda-wash tower in the technology washing process of the present invention; Through alkali cleaning, carbon dioxide content≤5mL/m in the ethylene gas
3Through super-dry, the content≤5mL/m of water in the ethylene gas
3C after making with extra care
3And C
3Above components contents≤20mL/m
3, the temperature of ethylene rectification tower is-50～-10 ℃ in the described low-temperature distillation process, the finished product ethene purity reaches more than 99.9%.
The present invention is a heat recovery and utilization in 200～400 ℃ of crude ethylenes to the temperature that catalytic dehydration of ethanol generates, and reclaims heat and comprises the sensible heat of ethene, water and the latent heat of water vapor.Fig. 2 has shown with the Different concentrations of alcohol to be 1 ton of ethene of raw material production, recycle heat energy data (because factor affecting such as heat-exchange equipment and utilization efficiency of heat energy in the crude ethylene gas of its generation, Fig. 2 data are the results that get after the theoretical total heat 90%, negative number representation heat release in the table).Therefore, alcohol concn is more little in coupling technique, and callable heat energy is big more in the generation product mixed gas.Analyze according to the heat conservation law, the heat energy of this part is the alcohol vapour condensation process part that water takes away that is cooled in the traditional alcohol distillation technology, and the present invention has saved the energy expenditure of raw material preheating and vaporization in the producing ethylene with ethyl alcohol technology in addition.
Beneficial effect of the present invention:
1. adopt product condensation in advance and separating technology that following advantage is arranged:
A, washing, drying, purified equipment and technology are not subjected to the influence of material concentration, and adaptive faculty is good.
B, low owing to entering the water wash column gas temperature, the operational condition of water wash column is easier to control, and ethanol, aldehydes and organic acid washing effect are strengthened.And in the producing ethylene by ethanol dehydration technology, aldehyde and organic acid are the essential substance that causes soda-wash tower to stop up, and remove these components in advance the method that solves the soda-wash tower blockage problem from the source is provided.
2. the present invention adopts near charging temperature of reaction for the thermal load that reduces reaction bed, unstripped gas can be carried by the pressure that pump or raw material superheater are produced, reaction is finished the afterreaction product and is entered the heat exchange condensing works and separate the liquid ingredient that is condensed, and uses gas-liquid separation technology to have following advantage:
The above component of 50% (mol ratio) is a water vapor in A, the reaction product, by the latent heat of the abundant recycle-water steam of heat exchange condensation;
B, high boiling point components such as water and ethanol in the separated product in advance make the feeding temperature and the flow that enter water, alkali mixing, washing device reduce, and are used to the water consumption cooling off and wash thereby saved, the processing power of raising washing tower.
3. the present invention adopts the method for ethanol distillation and chemical catalysis system ethylene process PROCESS COUPLING, makes the ethanol of rectifying tower output directly enter ethene workshop section with gaseous state.Reduced quantity, the alcohol gas condensation workshop section of rectifying tower than high density and high purity ethanol production technique, and the reflux ratio of rectifying tower is reduced.Coupling back feasible be cooled water, waste liquid etc. are taken away the power loss that causes and have been reduced more than 10%; And the raw material of ethene workshop section is because of need not through liquid preheating and vaporescence again, make water and ethanol component in theory energy consumption reduce by 88% and 42% respectively.
The present invention adopts ethanol distillation-heat exchange-ethene preparation-gas-liquid separation-washing-drying-ethene purified technical process, finishes the integrated of producing ethylene from dehydration of ethanol production process and entire system optimization.Facts have proved that this technology stability is strong, energy consumption, water consume low, have good economic competitiveness, the deficiency of having avoided prior art to exist simultaneously.
Description of drawings
Fig. 1 raw material is at production process power consumption situation synoptic diagram
(a) unit water yield preheating power consumption; (b) preheating of unit ethanol and reaction power consumption
Each material concentration of Fig. 2 is produced ethylene gas down and is reclaimed heat curve figure
Fig. 3 catalytic dehydration of ethanol is produced the ethylene process schema
Among the figure: 1. Distallation systm 2. gas-gas heat-exchanger rig 3. heating units 4. gas-solid catalyticreactor 5. condensing workss 6. gas-liquid separation devices 7. washing systems 8. dehumidification systems 9. ethene refining systems 10. water wash columns 11. compressors 12. soda-wash towers 13. ethylene gas cushion gas tanks
Embodiment
Process implementing example of the present invention illustrates in conjunction with Fig. 3:
(1) the fermentation alcohol mash is fed the Distallation systm of being made up of distillation tower 1, control is 55% ethanol raw material from the ethanol exit concentration of distillation tower, the ethanol raw material that obtains does not cool off, and directly is delivered to follow-up workshop section with material pipe, and the mass transport pipeline wraps up with lagging material;
(2) the alcohol-water mixed vapour of Distallation systm 1 makes it to be warmed up to 250 ℃ through gas-gas heat-exchanger rig 2 and heating unit 3 successively;
(3) the alcohol-water mixed vapour after heating up enters gas-solid catalyticreactor 4 and carries out catalyzed reaction; Adopt the isothermal shell and tube reactor, tubulation caliber 32mm, heating medium are fused salt, catalyzer adopts the HZSM-5 molecular sieve, and the bulk density of molecular sieve is 0.65kg/L, and loading in reaction tubes highly is 2600mm, the catalyzed reaction temperature is 200 ℃, the mass space velocity 2.5h of raw material
-1, reaction pressure 0.1MPa;
(4) reaction product is that ethene and water are formed crude ethylene gas (n
Ethene/ n
Water≈ 30/100), crude ethylene is cooled to 60 ℃ through gas-to-gas heat exchanger 2 and condensing works 5 again successively, and cooled crude ethylene separates its liquid ingredient through gas-liquid separation device 6, and liquid discharge is to Sewage treatment systems, and ethylene gas enters washing system 7;
(5) washing system 7 comprises water wash column 10, compressor 11 and soda-wash tower 12, and ethylene gas buffering gas tank 13 is set between water wash column 10 and the compressor 11; Ethylene gas washs by water wash column 10, ethylene gas buffering gas tank 13, compressor 11 and soda-wash tower 12 successively, and the foam removal of gas difference once after washing and the alkali cleaning;
(6) washing ethene is later removed wherein micro-moisture via the dehumidification system 8 of three drying towers compositions, and drying tower is loaded with the A5 molecular sieve.Dehumidification system is the uses in parallel of three towers, a tower is used for adsorption dewatering in two towers, and two other tower carries out adsorbent reactivation simultaneously, after first tower absorption is full, change that second tower is used for adsorption dewatering, first and third tower carries out adsorbent reactivation, use so in turn;
(7) dried ethylene gas enters ethene refining system 9, removes hydrogen, methane, ethane and C
3Above component obtains purity and is 99.9% ethylene product.
Embodiment 2
(1) the fermentation alcohol mash is fed the Distallation systm of being made up of distillation tower 1, Distallation systm 1 adopts two-tower rectification technology, obtaining concentration from second rectifying tower is 95% alcohol-water mixed vapour, the alcohol-water mixed vapour that obtains does not cool off, directly be delivered to catalysis system ethene workshop section with material pipe, the mass transport pipeline wraps up with lagging material;
(2) the alcohol-water mixed vapour of Distallation systm 1 makes it to be warmed up to 350 ℃ through gas-gas heat-exchanger rig 2 and heating unit 3 successively;
(3) the alcohol-water mixed vapour after heating up enters gas-solid catalyticreactor 4 and carries out catalyzed reaction, adopts the multiple-step adiabatic bed bioreactor, bed diameter 800mm; Catalyzer is an activated alumina, and the bulk density of catalyzer is 0.78kg/L, and loading in reaction tubes highly is 2600mm, and the catalyzed reaction temperature is 450 ℃, the mass space velocity 0.6h of raw material
-1, reaction pressure 0.2MPa;
(4) react the crude ethylene (n that obtains
Ethene/ n
Water≈ 9/10) pass through gas-gas heat-exchanger rig 2 and condensing works 5 postcooling to 60 ℃ successively, cooled crude ethylene separates its liquid ingredients through gas-liquid separation device 6, and liquid discharge is to Sewage treatment systems, and ethylene gas enters washing system 7;
(5) washing system 7 comprises water wash column 10, compressor 11 and soda-wash tower 12, and ethylene gas buffering gas tank 13 is set between water wash column 10 and the compressor 11; Ethylene gas washs by water wash column 10, ethylene gas buffering gas tank 13, compressor 11 and soda-wash tower 12 successively, and the foam removal of gas difference once after washing and the alkali cleaning;
(6) washing ethene is later removed wherein micro-moisture via the dehumidification system 8 of two towers compositions, and drying tower is loaded with the A3 molecular sieve.Dehumidification system is the uses in parallel of two towers, and a tower is used for adsorption dewatering in two towers, and another tower carries out adsorbent reactivation simultaneously, after first tower absorption is full, changes second tower and is used for adsorption dewatering;
(7) dried ethylene gas enters ethene refining system 9, removes hydrogen, methane, ethane and C
3Above component obtains purity and is 99.9% ethylene product.
(1) the fermentation alcohol mash is fed the Distallation systm of being made up of distillation tower 1, Distallation systm 1 adopts two-tower rectification technology.It is 95% alcohol-water mixed vapour that second rectifying tower obtains concentration, and the alcohol-water mixed vapour that obtains does not cool off, and directly is delivered to catalysis system ethene workshop section with material pipe, and the mass transport pipeline wraps up with lagging material;
(2) 95% alcohol-water mixed vapour of Distallation systm 1 is the ratio uniform mixing of 275: 41 (mass ratio be 7.38: 100) with 127 ℃, the water vapour of 0.25MPa with the molar weight ratio by the gas injection evenly mixing device, obtains concentration and be 75% alcohol-water mixed gas;
(3) concentration is that 75% alcohol-water mixed gas is warmed up to 280 ℃ by heating unit 3;
(4) the alcohol-water mixed vapour after heating up enters gas-solid catalyticreactor 4 and carries out catalyzed reaction, adopts fluidized-bed reactor, and catalyzer adopts the HZSM-5 molecular sieve, and the bulk density of molecular sieve is 0.6kg/L, and diameter is 4.5mm, and is spherical.The catalyzed reaction temperature is 280 ℃, the mass space velocity 2.0h of raw material
-1, reaction pressure 1.5MPa;
(5) react the crude ethylene (n that obtains
Ethene/ n
Water≈ 9/10) pass through gas-gas heat-exchanger rig 2 and condensing works 5 postcooling to 60 ℃ successively, cooled crude ethylene separates its liquid ingredients through gas-liquid separation device 6, and liquid discharge is to Sewage treatment systems, and ethylene gas enters washing system 7;
(6) washing system 7 comprises water wash column 10, compressor 11 and soda-wash tower 12, and ethylene gas buffering gas tank 13 is set between water wash column 10 and the compressor 11; Ethylene gas washs by water wash column 10, ethylene gas buffering gas tank 13, compressor 11 and soda-wash tower 12 successively, and the foam removal of gas difference once after washing and the alkali cleaning;
(7) washing ethene is later removed wherein micro-moisture via the dehumidification system 8 that two towers compose in parallel, drying tower is loaded with the A4 molecular sieve, dehumidification system is the uses in parallel of two towers, a tower is used for adsorption dewatering in two towers, another tower carries out adsorbent reactivation simultaneously, after first tower absorption is full, changes second tower and be used for adsorption dewatering;
(8) dried ethylene gas enters ethene refining system 9, removes hydrogen, methane, ethane and C
3Above component obtains purity and is 99.9% ethylene product.
Claims (9)
1. a catalytic dehydration of ethanol is produced ethylene process, it is characterized in that ethanol distillation and chemical catalysis system ethylene process PROCESS COUPLING, concentration is that 5～45% ethanol obtain the alcohol-water mixed vapour through Distallation systm, entering after this alcohol-water mixed vapour continues to be heated to 150～350 ℃ and obtaining product through catalyst action in the gas-solid catalyticreactor is crude ethylene, after the crude ethylene cooling, use gas-liquid separation device to remove its mid-boiling point and obtain ethylene gas greater than 70 ℃ of components, ethylene gas is successively by washing, the dry and refining ethylene product that obtains.
2. catalytic dehydration of ethanol as claimed in claim 1 is produced ethylene process, it is characterized in that alcohol-water mixed vapour that ethanol obtains through Distallation systm without cooling and liquefaction, directly by being that 200～400 ℃ crude ethylene is that the gas-gas heat-exchanger rig and the heating unit of thermal source is heated to 150～350 ℃ with temperature.
3. catalytic dehydration of ethanol as claimed in claim 1 is produced ethylene process, it is characterized in that the concentration of ethanol scope is 45～98% in the alcohol-water mixed vapour.
4. catalytic dehydration of ethanol as claimed in claim 3 is produced ethylene process, it is characterized in that the concentration of ethanol scope is 55～95% in the alcohol-water mixed vapour.
5. catalytic dehydration of ethanol as claimed in claim 1 is produced ethylene process, it is characterized in that described gas-solid catalyticreactor adopts isotherm formula fixed bed, multistage insulation bed or fluidized-bed.
6. catalytic dehydration of ethanol as claimed in claim 1 is produced ethylene process, it is characterized in that feeding condensing works again after crude ethylene that catalyst action generates and alcohol-water mixed vapour are by the gas-to-gas heat exchanger heat exchange further cools off, crude ethylene cooling afterwards temperature is 30～100 ℃.
7. catalytic dehydration of ethanol as claimed in claim 6 is produced ethylene process, it is characterized in that connecing gas-liquid separation device behind the described condensing works, and condensed water separates from crude ethylene with ethanol and is disposed to Sewage treatment systems.
8. catalytic dehydration of ethanol as claimed in claim 1 is produced ethylene process, and ethylene gas washs by water wash column, compressor and soda-wash tower successively; Gas after the washing enters the dehumidification system drying of being made up of two or more drying towers, and adopting 3A, 4A or 5A molecular sieve is siccative; Dried gas is made with extra care through the ethene refining system, refining freezing low temperature fractionation or low temperature fractionation and the refining with adsorbents process combined of adopting.
9. catalytic dehydration of ethanol as claimed in claim 8 is produced ethylene process, it is characterized in that after washing carbon dioxide content≤5mL/m in the ethylene gas
3Content≤the 5mL/m of water in the ethene of dry back
3The temperature of ethylene rectification tower is-50～-10 ℃ in the described low-temperature distillation process, C after making with extra care
3And C
3Above components contents≤20mL/m
3
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| JPS5940057B2 (en) * | 1979-05-31 | 1984-09-27 | 日揮化学株式会社 | Catalyst for ethylene production from ethanol |
| US4423270A (en) * | 1981-09-28 | 1983-12-27 | Pearson Donald E | Process for catalytic dehydration of ethanol vapor to ethylene |
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