WO2007134415A2 - Process for production of ethylene from ethyl alcohol - Google Patents
Process for production of ethylene from ethyl alcohol Download PDFInfo
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- WO2007134415A2 WO2007134415A2 PCT/BR2007/000119 BR2007000119W WO2007134415A2 WO 2007134415 A2 WO2007134415 A2 WO 2007134415A2 BR 2007000119 W BR2007000119 W BR 2007000119W WO 2007134415 A2 WO2007134415 A2 WO 2007134415A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
Definitions
- the present invention concerns a process for obtainment of ethylene through dehydration of ethyl alcohol (ethanol) , more specifically, from ethanol contained in hydrafeed alcohol (AEHC) or in anhydrous alcohol (AEAC) , in the presence of a catalyst, in an adiabatic reactor.
- ethanol ethyl alcohol
- AEHC hydrafeed alcohol
- AEAC hydrous alcohol
- One objective of the present invention is to use a given amount of a reactor effluent, as heating fluid, which consists in the mixture of ethylene - water vapor and others, generated in ethanol dehydration and a given amount of overheated vapor, yielded from the water generated in ethanol dehydration, and condensed in the reactor effluent.
- ethanol a renewable raw material for production of ethylene
- present process which shows low investment and low power consumption, allows the production of ethylene at much lower cost and with CO 2 emission much lower than those observed in the production of ethylene from fossil fuel traditionally used.
- the present invention will facilitate the integration of the ethylene alcohol process to other projects, namely:
- the capacity of the units was small (up to 10.000 tons of ethylene/year) , and the campaign time for these reactors was of three to four weeks, being from two to three weeks operating and one week for burning the coke deposited in the catalyst and realignment of the reactor.
- the unit was constituted by three sets of furnace/serial reactor, each set being fed with a certain amount of alcohol.
- reaction system of the prior art has the following disadvantages:
- the present invention aims at improving technically the previous process, aiming at simplification of the process that, consequently leads to the reduction in cost production of ethylene from ethanol, in the aspects relating to costs for capital, utilities, operation, supervision and maintenance, which would create conditions for maintaining the cost for ethylene on low level, in event of a considerable increase on alcohol price.
- the present invention consists in the optimization and simplification of ethylene production process from hydrated ethyl alcohol or anhydrous ethyl alcohol, by catalytic dehydration of ethanol, that is obtained with the operation in a more compact unit in relation to the prior art, which will facilitate the operation, since only one set of furnace/reactor will be controlled, instead of sets of 3 furnaces and 3 reactors, in serial, that will lead to reduction of investment cost and operational cost.
- the process of the present invention shows the following advantages in relation to BR PI 7705256:
- Catalytic Cracking and Delayed Coking contain a large amount of basic petrochemical products (propene, n-butene,- raw material for butadiene) superior to that produced in the three (3) Units, which use naphtha as raw material.
- the use of such flows to produce basic petrochemical products and the employment of the production process of ethylene from ethanol, will allow the Units to attend the market of olefin basic petrochemical products, with naphtha possible of being produced from national oil being used in the production of aromatics .
- the adoption of this alternative schedule of feeding the Units will enable the Country to effectively achieve self-sufficiency in the production of fuels and petrochemical raw materials.
- the present invention concerns a dehydration process of ethyl alcohol in an adiabatic reactor of fixed bed, consisting of the reaction section of one set of furnace/reactor, replacing the three sets of furnace/serial reactor of the process previously used in the prior art, which had the first unit designed for 60,000 ton of ethylene/year, but had previously produced 110,000 ton of ethylene/year.
- the effluent flow of the reaction area is sent to the separation section, which will have a capacity compatible to produce ethylene.
- the flow sent to the separation section, where ethylene is the main product, is constituted by the mixture of ethylene, water vapor, non-converted ethanol, which will be recycled to extinction, and other products generated from contaminants eventually present in AEHC/AEAC that will be recovered for other uses.
- the water vapor sent to the separation section originates from two sources: - from water contained in AEHC/AEAC used as raw material;
- the capacity of the equipment involved in this water processing in the separation section is quite smaller than that necessary in previous technique, disclosed in BR PI7705256, that uses water vapor from external source as a heating fluid in the first reactor.
- the rate of water/ethylene production is of 0.7292 kg/kg, whereas in previous process (BR PI 7705256) is of 1.8427 kg/kg.
- the difference is due the fact that in previous process a significant portion of water originates from condensation of external water vapor used in the first reactor.
- the present invention aims at industrially using all water produced in the process of ethanol dehydration, corresponding to 64,29% of ethylene production that will receive the treatment necessary to achieve the required quality (process water, cooling water and boiler water) .
- the invention also aims at the optimization of heat exchange in furnaces and between the process flows, aiming at reducing consumption of fuel, of cooling water and minimization of residual flows.
- reaction system of the present invention may be better observed in Figure 1, described herein, and in the following example.
- Figure 1 represents a flowchart of the process of reaction section, with a view of the system and the recycle flows, necessary for the operation.
- hydrated ethyl alcohol stored is transferred through line (1) and pumped in (Bl) to the operational system through line (2) at a suitable pressure, passing through heat exchangers (Tl), where it is heated by thermal exchange with the heat flow (13) of the final effluent of the reactor (ethylene + water vapor), following through line (3), where it is mixed in (M2) with the flow of recycle water (16), said recycle water originating from the vessel (Vl), where it was separated from crude ethylene and pumped in (B2) , following said mixture of ethyl alcohol/recycle water through line (4), being heated in the convection section of a furnace (Fl) , going through line (5) up to a mixer (Ml), where a given amount of compressed gaseous recycle (12) is added, said mixture going through line (6) to the heat exchangers (12) , where it is heated by the flow (9) of the total effluent of the reactor (Rl)/ then, said mixture is fed through line (7)
- the referred to flow (9) originating from the reactor (Rl) , firstly goes through the heat exchangers (12) , allowing a suitable heat exchange with the mixture flow (ethanol, recycle water, ethylene vapor/water vapor) of line (6), before the same is fed into said furnace (Fl) through line (7), and said flow (9) is then directed through line (10) to the flow divisor (Dl) .
- said line flow (10) is separated in two flows: a first flow (11), which constitutes the gaseous recycle and will be compressed in a compressor (Cl), going through line (12) and mixed to the flow (5) (ethanol + recycle water) in (Ml) at a molar rate ranging from 3.3 to 4.5 and which will constitute in flow (6) to be directed to the reactor (Rl); a second flow, that goes through line (13) to the heat exchangers (Tl), that preheats hydrated alcohol, and then is sent through line (14) to the separating vessel (Vl) . From this separating vessel, a flow of crude ethylene goes through line (17) to the water washing area.
- an ethylene flow is produced with high purity, that is sent through line (18) to the section of final purification, that comprises the steps of compression, drying and cryogenic fractionation, where ethylene is obtained in the required specification.
- Another aqueous flow (19) is sent to the area for water treatment and purification.
- water vapor is fed into the system through line (20)
- process treated water is fed into the system through line (21) in the separating vessel (Vl) .
- the mass relation between heating fluids and the charge may range in a ratio of 2.5 to 4.5, preferably in a rate of 2.8 to 4.0.
- Catalysts used in the present invention may be selected between gama-alumina, zeolites and others.
- spatial speed may range from 0.25 to 0.35 kg of ethanol/h per kg of catalyst, preferably using the ratio of 0.29 to 0.31.
- a charge flow in a flow rate of 1318.1 kgmol/h of hydrated alcohol originating from storage is pumped at a pressure around 13.73 bar to the operational system, where it is heated in a heat exchanger by thermal exchange with
- the reactor effluent that is placed at a temperature of 397.3 0 C, after being cooled by heat exchange with the mixture to be heated in the furnace is divided in the proportion of 2:3 of recycle flow to the flow of the end product, that will go to the separation area.
- the consumption for ethylene final purification is not included (ethylene super-fractionating) that, at most, is of the same magnitude of a similar and traditional tower of a Petrochemical Unit.
- Table I of conversion relating to analysis of effluent flows of the end product
- Table II relating to weight composition of ethylene and byproducts thereof .
Abstract
The present invention concerns the process for obtainment of ethylene through ethyl alcohol dehydration (ethanol), more specifically, from ethanol contained in hydrated alcohol (AEHC) or in anhydrous alcohol (AEAC), in the presence of a catalyst, in an adiabatic reactor. One objective of the present invention is to use a given amount of reactor effluent as heating fluid, which consists in the mixture of ethylene - water vapor and others, generated in ethanol dehydration and a given amount of water, produced by condensation of the water contained in the reactor effluent. Water generated in the reaction system and water originating from the charge of AEHC/AEAC form the aqueous effluent of the unit. Other objectives achieved in the present invention with modifications of the reaction system and use of heat fluids, which are obtained in the reaction system itself, are: 1) maximization of utilization of the heat generated in the process flow, with consequent reduction in the consumption of utilities; 2) reduction in the number of equipment, that allows the reduction of operation personnel and investment, and consequently, the reduction of capital costs and the unit servicing. The flow sent to the separation section, where ethylene is the main product, is constituted by the mixture of ethylene, water vapor, non-converted ethanol, which will be recycled to extinction, and other products generated from contaminants eventually present in AEHC/AEAC that will be recovered for other uses.
Description
"PROCESS FOR PRODUCTION OF ETHYLENE FROM ETHYL ALCOHOL".
The present invention concerns a process for obtainment of ethylene through dehydration of ethyl alcohol (ethanol) , more specifically, from ethanol contained in hydrafeed alcohol (AEHC) or in anhydrous alcohol (AEAC) , in the presence of a catalyst, in an adiabatic reactor.
Production of ethylene by ethanol dehydration, with the presence of a catalyst is an endothermic reaction, which reaction heat in the adiabatic process is provided by hydrated alcohol (AEHC) or anhydrous alcohol (AEAC) , overheated and, mainly, by one or more heating fluids that circulate in the process, maintaining the temperature in the reactor at suitable levels, to give a high conversion of ethanol to ethylene.
One objective of the present invention is to use a given amount of a reactor effluent, as heating fluid, which consists in the mixture of ethylene - water vapor and others, generated in ethanol dehydration and a given amount of overheated vapor, yielded from the water generated in ethanol dehydration, and condensed in the reactor effluent.
Other objectives achieved in the present invention with modifications of the reaction system and with the use of heating fluids, which are obtained in the reaction system itself, are:
1) Maximization of heat utilization in the process flow, with the consequent reduction in the consumption of utilities;
2) Reduction in the number of equipment, that allows the reduction of operation personnel and investment, and consequently, the reduction of capital costs and unit servicing. The use of such heating fluids, substituting the water vapor from external source, used in Brazilian Patent PI 7705256, allows that the reaction of total conversion of ethanol to ethylene, water vapor and others may be carried out using a smaller number of equipment in the reaction area, such as only one furnace, one reactor, one compressor and two benches of heat exchangers that transfer heat between the process flow.
Also, the wash-out of the overheated water vapor from external source, as a heating source for the system in usual operation of the unit and the consequent reduction in the consumption of cooling water, should lead to significant reductions in investment and production cost.
The use of ethanol, a renewable raw material for production of ethylene, using the present process, which shows low investment and low power consumption, allows the production of ethylene at much lower cost and with CO2 emission much lower than those observed in the production of ethylene from fossil fuel traditionally used.
The present invention, with the simplification presented, will facilitate the integration of the ethylene alcohol process to other projects, namely:
In Petrochemical Units, that use naphtha as raw material, through the association of ethylene production process from alcohol, with the
production of ethylene co-products from refinery flows. The result of this association is the reduction in consumption of naphtha, making the country effectively self-sufficient in the production of fuels and raw material for the petrochemical industry, using exclusively national petroleum, making real the Brazilian dream for becoming independent from imported petroleum and byproducts . - In ethylene derivatives manufacturing companies, to produce such raw material and increase its competitiveness ;
In alcohol producing regions, through the association of distilleries with the companies holding the technology for production of the selected ethylene derivative, allowing the creation of new centers of sustainable development in the hinterland of the Country.
Comments on the price for alcohol presented in a study developed by Petrobras - "Business opportunities for
Petrobras in alcohol external market" - showed that the average cost for production of alcohol in the country in
2003 was of US$ 0,16/L, and that the average sales price in the distilleries, free of freight and taxes was of US$ 0,22/L. This production cost was confirmed by alcohol manufacturers at the Seminar "Alcohol: Potential Generator of Foreign Exchange Credits and Jobs", held at BNDES, Rio de Janeiro, in August 2003.
Marketing prices for alcohol are influenced by the production seazonability, international sugar and alcohol market, the exchange rate and, mainly, by speculation with this commodity. Anyhow, what cannot be ignored is that a great difference actually exists between the prices for alcohol, at non-speculative situations, and naphtha price in the international market, where petroleum exceeds US$ 60,0/B. The simplicity of the process and the great difference of prices between these raw material ensure the economic feasibility of alcohol for producing ethylene, and justify the negotiations that should be carried out between the industry and alcohol manufacturers in order to keep the prices for this product at reasonable levels, since this will benefit all of us.
PRIOR ART
It is known that by mid 70' s, ethylene alcohol was produced in tubular reactors, installed in parallel, in which overheated alcohol would pass through pipes filled with a catalyst (alumina) , while a heating fluid (dowtherm) would circulate in the casing, providing heat for ethanol dehydration.
The capacity of the units was small (up to 10.000 tons of ethylene/year) , and the campaign time for these reactors was of three to four weeks, being from two to three weeks operating and one week for burning the coke deposited in the catalyst and realignment of the reactor.
The previous Patent Brazilian Application PI 7705256 made by the same author, modified this technology and showed that the formation of ethylene is highly favored at
reaction temperatures above 360°C, in an adiabatic reactor, and also that other factors are limitative of the reaction and should be taken into consideration, such as thermal decomposition of ethyl alcohol, "which leads to undesirable byproducts, such as, acetaldehyde, methane, etc, the occurrence of formation of excessive byproducts at the catalyst surface, such as coke formation, which causes its deactivation, needing regeneration.
In order to solve such problems, it is proposed in Brazilian Patent Application PI 7705256, the supply of heat necessary for the reaction from external source, through the introduction in the reactor, simultaneously to the feeding of ethyl alcohol charge, a heating fluid, sensible heat carrier, in this case, water vapor, at high temperature, in such a way to allow the reaction to occur at the desired temperature and would also carry out coke removal, increasing the campaign time of the reactor.
If in PI 7705256 only a set of furnace/reactor would be used, the vapor amount necessary for ethanol dehydration to ethylene would be very high, burdening the process, then it is proposed to use the overheated vapor only in the I" set furnace/reactor and the employment of serial reactors, in order to make the unit economically feasible. Thus, upon being implemented, the unit was constituted by three sets of furnace/serial reactor, each set being fed with a certain amount of alcohol.
The previous process showed the use of water vapor as an advantage, which, in addition to act as a heating fluid, promoted the removal of coke deposited in the
catalyst, increasing the campaign time of the reactor. In rebuttal, there was the additional cost for this water vapor and for the investment in the heat exchange system for condensation of this water vapor, and the consequent increase in the consumption of cooling water.
Thus, the reaction system of the prior art has the following disadvantages:
Requires 3 sets of furnace/serial reactor Has higher operation cost, due to the use of external vapor and cooling water for condensing it, Has higher investment in the heat exchange equipment and separation/water purification. The Brazilian Patent Application PI 8101487, which was not commercially used, describes the same technology, but with the concern that the reaction is not damaged with the temperature drop in the catalyst bed, caused by the exclusive dependency of heat externally supplied by the heat carrying fluid. Thus, it is proposed that when starting the operation, there is a control of recycling, so that an established reaction regime is achieved. Therefore, a high pressure is applied on the charge to be processed, composed of ethanol and a flow of hot gaseous recycles. This high pressure is maintained at the dehydration and purification steps of the product, so that the end product to be purified by cryogenic distilling is not submitted to another compression step, since the pressure suitable for this partition was already achieved. However, this process was not made available since it requires high investments and high demand for power.
BRIEF DESCRIPTION OF THE INVENTION
With the high increase of petroleum price in 2004, the technology in Brazilian Patent Application PI 7705256 showed to be promising, what led us to develop a comparative study of this technology before the use of naphtha, used in the three (3) Units for production of ethylene and its byproducts.
The study revealed that the production cost for ethylene from ethanol was quite lower than the price for ethylene produced in the Units. It can be noted that in 2004, the average price for Brent petroleum was of US$38/B, much lower than the value around US$60/B, exercised in 2006.
The present invention aims at improving technically the previous process, aiming at simplification of the process that, consequently leads to the reduction in cost production of ethylene from ethanol, in the aspects relating to costs for capital, utilities, operation, supervision and maintenance, which would create conditions for maintaining the cost for ethylene on low level, in event of a considerable increase on alcohol price.
Other economic factors have justified the improvement of BR PI7705256, such as the investment rate per ton of ethylene, given hereunder, which will be even lower in the present invention.
The consumption of fuel and utilities in the unit of ethane pyrolisis is also much higher than that of a plant with the same capacity that would adopt the process configuration used in previous technology (PI 7705256) .
More specifically, the present invention consists in the optimization and simplification of ethylene production process from hydrated ethyl alcohol or anhydrous ethyl alcohol, by catalytic dehydration of ethanol, that is obtained with the operation in a more compact unit in relation to the prior art, which will facilitate the operation, since only one set of furnace/reactor will be controlled, instead of sets of 3 furnaces and 3 reactors, in serial, that will lead to reduction of investment cost and operational cost.
The process of the present invention shows the following advantages in relation to BR PI 7705256:
- Reduction of the number of equipment, since it is constituted by one set of furnace/reactor, which causes the reduction on costs of capital and system maintenance/
- Possibility to use parallel reactors and not serial;
- Obtainment of ethylene with the required grade of purity;
- Non-utilization of water vapor from external source in usual operation; - Reduction of water production in usual operation and in the consumption of cooling water, with the consequent reduction in cost for utilities. Considering the political/economic factors, the present process showed to be advantageous, in the case of Brazil, in view of the following aspects:
Stresses observed in oil international market, responsible for great increases in the price for this commodity and its byproducts, mainly from naphtha, used in large amount as raw material in Brazilian Units: 14,064,321 m3 or 9,985,668 ton, in 2004;
Brazilian difficulties for producing naphtha to comply with the demand from the Units, considering that the national oil is predominantly of heavy type, what makes the country import naphtha (5,382,662 m3 or 3,821,689 ton), import light oils (24,5% of the total oil processed in 2004) and export our exceeding heavy oil at a price about 35% lower than the imported light oil;
- Possibility to produce ethylene from ethanol, a renewable raw material, using a process of low investment and operation cost, if compared with the traditional projects, that use fossil fuels as raw material;
- Increase of jobs with the expansion of the alcohol production to produce ethylene, a high value added product,
- Low consumption of power in the production of ethylene from ethanol and, consequently, the reduced CO2 emission that favors the environment;
- The majority of refineries in the Country is of large size, where the GLP flows from the Units of
Catalytic Cracking and Delayed Coking contain a large amount of basic petrochemical products (propene, n-butene,- raw material for butadiene) superior to that produced in the three (3) Units, which use naphtha as raw material. The use of such flows to produce basic petrochemical products and the employment of the production process of ethylene from ethanol, will allow the Units to attend the market of olefin basic petrochemical products, with naphtha possible of being produced from national oil being used in the production of aromatics . The adoption of this alternative schedule of feeding the Units will enable the Country to effectively achieve self-sufficiency in the production of fuels and petrochemical raw materials.
DETAILED DESCRIPTION QF THE INVENTION The present invention concerns a dehydration process of ethyl alcohol in an adiabatic reactor of fixed bed, consisting of the reaction section of one set of furnace/reactor, replacing the three sets of furnace/serial reactor of the process previously used in the prior art, which had the first unit designed for 60,000 ton of ethylene/year, but had previously produced 110,000 ton of ethylene/year.
In the present invention, the effluent flow of the reaction area is sent to the separation section, which
will have a capacity compatible to produce ethylene.
The flow sent to the separation section, where ethylene is the main product, is constituted by the mixture of ethylene, water vapor, non-converted ethanol, which will be recycled to extinction, and other products generated from contaminants eventually present in AEHC/AEAC that will be recovered for other uses.
In the present invention, the water vapor sent to the separation section originates from two sources: - from water contained in AEHC/AEAC used as raw material;
- from water generated in ethanol dehydration. This vapor will be condensed, receiving the water produced for the necessary treatment for its use in the industrial process, including boiler water.
Thus, the capacity of the equipment involved in this water processing in the separation section is quite smaller than that necessary in previous technique, disclosed in BR PI7705256, that uses water vapor from external source as a heating fluid in the first reactor.
Comparatively, in the present invention, using AEHC, the rate of water/ethylene production is of 0.7292 kg/kg, whereas in previous process (BR PI 7705256) is of 1.8427 kg/kg. The difference is due the fact that in previous process a significant portion of water originates from condensation of external water vapor used in the first reactor.
More specifically, the present invention aims at industrially using all water produced in the process of
ethanol dehydration, corresponding to 64,29% of ethylene production that will receive the treatment necessary to achieve the required quality (process water, cooling water and boiler water) . The invention also aims at the optimization of heat exchange in furnaces and between the process flows, aiming at reducing consumption of fuel, of cooling water and minimization of residual flows.
The reaction system of the present invention may be better observed in Figure 1, described herein, and in the following example.
Additional characteristics and advantages of the process, according to the present invention, will become more apparent as from the following description, presenting a typical embodiment, supplied with the only purpose of indication and not limitation, having the following attached drawing as reference.
Figure 1 represents a flowchart of the process of reaction section, with a view of the system and the recycle flows, necessary for the operation.
Thus, according to the simplified flowchart in Figure 1, hydrated ethyl alcohol stored is transferred through line (1) and pumped in (Bl) to the operational system through line (2) at a suitable pressure, passing through heat exchangers (Tl), where it is heated by thermal exchange with the heat flow (13) of the final effluent of the reactor (ethylene + water vapor), following through line (3), where it is mixed in (M2) with the flow of recycle water (16), said recycle water originating from
the vessel (Vl), where it was separated from crude ethylene and pumped in (B2) , following said mixture of ethyl alcohol/recycle water through line (4), being heated in the convection section of a furnace (Fl) , going through line (5) up to a mixer (Ml), where a given amount of compressed gaseous recycle (12) is added, said mixture going through line (6) to the heat exchangers (12) , where it is heated by the flow (9) of the total effluent of the reactor (Rl)/ then, said mixture is fed through line (7) in the radiation section of the furnace (Fl), for heating up to a temperature between 460 and 500°C, and then it is sent through line (8) to the reactor (Rl), which contains in its inner , part a catalyst fixed bed, being that said reactor (Rl) operates at a pressure rate of 10,0 to 16,0 kg/cm2 and at temperatures ranging from 47O0C to 485°C.
The referred to flow (9) , originating from the reactor (Rl) , firstly goes through the heat exchangers (12) , allowing a suitable heat exchange with the mixture flow (ethanol, recycle water, ethylene vapor/water vapor) of line (6), before the same is fed into said furnace (Fl) through line (7), and said flow (9) is then directed through line (10) to the flow divisor (Dl) . In this divisor, said line flow (10) is separated in two flows: a first flow (11), which constitutes the gaseous recycle and will be compressed in a compressor (Cl), going through line (12) and mixed to the flow (5) (ethanol + recycle water) in (Ml) at a molar rate ranging from 3.3 to 4.5 and which will constitute in flow (6) to be directed to the reactor (Rl); a second flow, that goes through line (13)
to the heat exchangers (Tl), that preheats hydrated alcohol, and then is sent through line (14) to the separating vessel (Vl) . From this separating vessel, a flow of crude ethylene goes through line (17) to the water washing area. After washing the flow (17), an ethylene flow is produced with high purity, that is sent through line (18) to the section of final purification, that comprises the steps of compression, drying and cryogenic fractionation, where ethylene is obtained in the required specification. Another aqueous flow (19) is sent to the area for water treatment and purification.
In the initial start-up of the unit, water vapor is fed into the system through line (20) , and/or process treated water is fed into the system through line (21) in the separating vessel (Vl) .
In the present process, the mass relation between heating fluids and the charge may range in a ratio of 2.5 to 4.5, preferably in a rate of 2.8 to 4.0.
Catalysts used in the present invention may be selected between gama-alumina, zeolites and others.
Depending on the type of catalyst, spatial speed may range from 0.25 to 0.35 kg of ethanol/h per kg of catalyst, preferably using the ratio of 0.29 to 0.31.
We give hereunder an example, with the exclusive purpose of showing the functioning and efficiency of feeding charge convention in the invention process, without limiting character. Ethylene production considered in this example is of 250,000 ton of ethylene/year .
EXAMPLE 1
A charge flow in a flow rate of 1318.1 kgmol/h of hydrated alcohol originating from storage is pumped at a pressure around 13.73 bar to the operational system, where it is heated in a heat exchanger by thermal exchange with
11048.0 kgmol/h of part of the reactor effluent flow
(ethylene and water vapor) at a temperature of 1780C, then being mixed to 8029.0 kgmol/h of a recycle flow of the reactor product, consisting of ethylene and water vapor, and then going to a second exchanger, where it will be heated by thermal exchange of the reactor total effluent, which is placed at a temperature of approximately 397.30C, reaching a temperature of 296.7 0C, then being heated in the radiation section of the furnace at a temperature around 481.0 0C, necessary for the reaction, in the reactor, in alumina catalyst. The reactor effluent that is placed at a temperature of 397.30C, after being cooled by heat exchange with the mixture to be heated in the furnace is divided in the proportion of 2:3 of recycle flow to the flow of the end product, that will go to the separation area.
The specific consumption of the reaction-separation area for this case is: 1080 kW/ton of ethylene and 50 nrVton of ethylene of cooling water (ΔT = H0C) . The consumption for ethylene final purification is not included (ethylene super-fractionating) that, at most, is of the same magnitude of a similar and traditional tower of a Petrochemical Unit.
Hereunder, is presented Table I of conversion, relating to analysis of effluent flows of the end product and Table II, relating to weight composition of ethylene and byproducts thereof .
TABLE II. ETHYLENE FOR FINAL PURIFICATION (18) (D
Ethylene for Purification
Vapor Fraction 1.0000
Temperature: (C) 16.00
Pressure: (bar) 19.61
Molar Flow (kgmol/h) 1104
Mass Flow (kg/h) 3.096e-f-0.04
Molecular Weight 28.04
Component Molar Fraction
H20 0.00063
Ethanol 0.00007
Acetic Acid 0.00000
Acetaldehyde 0.00002
Ethyl acetate 0.00013
Alcohol C4+ 0.00001
Methane 0.00058
Ethane 0.00149
Propene 0.00059
1-Butene 0.00270
Ethylene 0.99378
Total 1.00000
[I) After washing with water, compression and cooling, sent for drying and cryogenic fractioning.
TABLE I - PROPERTY OF FLOWS
Flow 1 2 8 10 14 17
Vapor Fraction 0.0000 0.0000 1.0000 1.0000 1.0000 1.0000
Temperature (C) 25.00 25.24 481.0 178.0 156.6 156.6
10 Pressure (bar) 1.961 13.73 11.93 10.93 10.53 10.63
Molar Flow (kgmole/h) 1318.1 1318.1 8545.7 9642.8 3085.7 2415.7
Mass Flow (kg/h) 5.44S5e+004 5.4455e+004 2.0815+005 2.0815e+005 6.6663e+004 5.4592e+004
15
Composition (Molar fraction)
Flow 1 2 8 10 14 17
20 Acetic acid 0.000025 0.000025 0.000012 0.000011 0.000011 0.000014
Ethanol 0.830169 0.830169 0.128483 0.000569 0.000569 0.000722
Acetaldehyde 0.000069 0.000069 0.000034 0.000030 0.000030 0.000038
Ethyl acetate 0.000046 0.000046 0.000022 0.000020 0.000020 0.000025
Alcohol C4+ 0.000035 0.000035 0.000017 0.000015 0.000015 0.000020
25 H2O 0.169655 0.169655 0.599083 0.644218 0.644218 0.545647
Ethane 0.000000 0.000000 0.000000 0.000159 0.000159 0.000204
Propene 0.000000 0.000000 0.000000 0.000045 0.000045 0.000058
1-Butene 0.000000 0.000000 O.OOOOD0 0.000256 0.000255 0.000199
Ethylene 0.000000 0.000000 0.272358 0.354659 0.354659 0.453024
30 Methane 0.000000 0.000000 0.000000 0.000117 0.000117 0.000150
35
Claims
1. PROCESS FOR PRODUCTION OF ETHYLENE FROM ETHYL ALCOHOL, characterized in that stored hydrated ethyl alcohol (AEHC) or anhydrous ethyl alcohol (ABAC) is transferred through line (1) and pumped in (Bl) to the operational system through line (2) at a suitable pressure, passing through heat exchangers (Tl) , where it is heated by thermal exchange with the heat flow (10) from the final effluent (ethylene + water vapor) , going through line (3) , where it is mixed in (M2) with flow (16) of recycle water, said recycle water being originated from the separator (Vl), where it was condensed and separated and pumped in (B2) , said mixture of ethyl alcohol/recycle going through line (4) , being heated in the convection section of an oven (Fl) , following through line (5) up to a mixer (Ml) , where it is mixed to the compressed gaseous portion of the effluent recycle flow (12) , said mixture going through line (6) to the heat exchangers (T2), where it is heated by the total flow (9) , effluent of the reactor (Rl) , and then, said mixture (6) fed through line (7) to a furnace (Fl) for heating up to a temperature ranging between 460 and 5000C, and then sent through line (8) to the reactor (Rl) F which contains in its inner part a catalyst fixed bed, where the mixture of ethylene/water vapor is obtained and then directed to the sections of separation, washing and purification.
2. PROCESS, according to Claim 1, characterized in that said reactor (Rl) operates at a pressure range of 10 to 16 kg/cm2 and at temperatures ranging from 47O0C to 4850C.
3. PROCESS, according to Claim 1, characterized in that in the beginning of the process, water vapor is fed into the system through line (20) , and/or process water is fed through line (21) .
4. PROCESS, according to Claim 1, characterized in that said heat flow (9) effluent from the reactor (Rl), firstly goes through heat exchangers (T2) prior to the final separation and washing steps, allowing a suitable heat exchange with the flow mixture (ethanol, ethylene and water vapor) of line (6) , before the same is fed into said furnace (Fl) through line (7) and said flow (9) being then directed through line (10) to the flow divisor (Dl) .
5. PROCESS, according to Claims 1 or 4, characterized in that said flow (10) that passes through a flow divisor (Dl), is then divided into 2 flows: the first flow (11), that constitutes the gaseous recycle, which will be compressed in a compressor (Cl) , following through line (12) and mixed to the flow (ethanol + water recycle) in the mixer (Ml), will constitute the flow (6), to be directed to the reactor (Rl) ; the second flow, that is now going through line (13) to the heat exchangers (Tl) and is fed through line (14) to the separation vessel of the product in the separator (Vl) .
6. PROCESS, according to Claims 1 or 5, characterized in that said flow (14) that feeds the vessel (Vl), is then divided into 2 flows: the first flow (15), that constitutes the aqueous recycle, which will be compressed in a pump (B2), going through line (16) and mixed to ethanol flow in the mixer (M2), will constitute the flow (4), to be directed to the reactor (Rl) ; the second part of the flow now goes through line (17) , to the -washing and. purification sections, where finally ethylene in the required specification is obtained.
7. PROCESS,- according to Claim 5r characterized in that the flow (12) , which constitutes the recycle, after compression is mixed to the flow (ethanol + water recycle) , in the mixer (Ml) at a molar proportion that ranges from 3.0 to 5.5.
8. PROCESS, according to any of Claims 1 a 6, characterized in that the mass relation of the recycle flow
(sensible heat/charge), may range at a ratio of 2.5 to 4.5, preferably, at a ratio of 2.8 to 4.0.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0601803 BRPI0601803A (en) | 2006-05-18 | 2006-05-18 | process for producing ethylene from ethyl alcohol |
| BR0601803-3 | 2006-05-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2007134415A2 true WO2007134415A2 (en) | 2007-11-29 |
| WO2007134415A3 WO2007134415A3 (en) | 2009-06-04 |
Family
ID=38723639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2007/000119 WO2007134415A2 (en) | 2006-05-18 | 2007-05-17 | Process for production of ethylene from ethyl alcohol |
Country Status (2)
| Country | Link |
|---|---|
| BR (1) | BRPI0601803A (en) |
| WO (1) | WO2007134415A2 (en) |
Cited By (14)
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| WO2009098268A1 (en) * | 2008-02-07 | 2009-08-13 | Total Petrochemicals Research Feluy | Dehydration of alcohols in the presence of an inert component |
| EP2108636A1 (en) * | 2008-04-11 | 2009-10-14 | Total Petrochemicals Research Feluy | Dehydration of alcohols in the presence of an inert component. |
| EP2123736A1 (en) | 2008-05-19 | 2009-11-25 | C.E.-Technology Limited | Method for producing diesel fuels and aviation fuels from C1-C5 alcohols |
| US20130012749A1 (en) * | 2010-03-16 | 2013-01-10 | Yu Liu | Catalytic composition for production of olefins with decreased oxygenate byproducts |
| WO2013011208A1 (en) | 2011-07-21 | 2013-01-24 | IFP Energies Nouvelles | Low-energy consumption method for dehydrating ethanol into ethylene |
| WO2013050669A1 (en) | 2011-10-07 | 2013-04-11 | IFP Energies Nouvelles | Method for dehydrating ethanol diluted in ethylene with low energy consumption without water recycling |
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| US20110098518A1 (en) * | 2008-02-07 | 2011-04-28 | Delphine Minoux | Dehydration of Alcohols in the Presence of an Inert Component |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2007134415A3 (en) | 2009-06-04 |
| BRPI0601803A (en) | 2008-02-19 |
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