Patent application title: PROCESS FOR THE PREPARATION OF AN OLEFIN
Jeroen Van Westrenen (Amsterdam, NL)
Leslie Andrew Chewter (Amsterdam, NL)
Ferry Winter (Amsterdam, NL)
IPC8 Class: AC07C100FI
Class name: Chemistry of hydrocarbon compounds plural serial diverse syntheses to produce unsaturate
Publication date: 2010-12-02
Patent application number: 20100305377
An olefin is prepared from an alkyl alcohol in a process, comprising the
steps: a) converting the alkyl alcohol into a dialkylether over a first
catalyst, to yield a dialkylether product stream containing alkyl
alcohol, dialkylether and water; b) separating the dialkylether product
stream into a vaporous dialkylether-rich stream and a liquid
water-containing stream which water-containing stream comprises at most
5% wt of alkyl alcohol, based on the total weight of water and alkyl
alcohol; and c) converting the vaporous dialkylether-rich stream to an
olefin over a second catalyst, wherein the dialkylether product stream is
enriched with a base.
1. A process for the preparation of an olefin from an alkyl alcohol which
process comprises the steps of:a) converting the alkyl alcohol into a
dialkylether over a first catalyst, to yield a dialkylether product
stream containing alkyl alcohol, dialkylether and water;b) separating the
dialkylether product stream into a vaporous dialkylether-rich stream and
a liquid water-containing stream which water-containing stream comprises
at most 5% wt of alkyl alcohol, based on the total weight of water and
alkyl alcohol; andc) converting the vaporous dialkylether-rich stream to
an olefin over a second catalyst,wherein the dialkylether product stream
is enriched with a base.
2. The process as claimed in claim 1, wherein the alkyl alcohol is methanol.
3. The process as claimed in claim 1, wherein the liquid water-containing stream contains up to 1% wt of alkyl alcohol, based on the total of water and alkyl alcohol.
4. The process as claimed in claim 1, wherein the conversion of dialkylether takes place in multiple reaction zones into each of which a portion of the vaporous dialkylether-rich stream is fed.
5. The process as claimed in claim 4, wherein the multiple reaction zones are arranged in series.
6. The process as claimed in claim 1, wherein the second catalyst includes molecular sieve catalyst compositions.
7. The process as claimed in claim 6, wherein the dialkylether-rich stream is converted over a catalyst comprising a zeolite selected from the group consisting of aluminosilicates having one-dimensional 10-ring channels.
8. The process as claimed in claim 1, wherein an olefinic co-feed is added to the vaporous dialkylether-rich stream in step c).
9. The process as claimed in claim 8, wherein the olefinic co-feed comprises at least 50% wt of butenes, based on the total weight of the olefinic co-feed.
10. The process according to claim 8, wherein the olefinic co-feed is a by-product of the olefins conversion of step c) which by-product is recycled.
11. The process according to claim 1, wherein a pH of at least 7 is maintained in the dialkylether product stream, in particular in a liquid water-containing fraction of the dialkylether product stream.
12. The process according to claim 1, wherein the base is selected from sodium hydroxide or potassium hydroxide or any other alkali metal or earth alkali metal bases, or mixtures thereof.
13. The process according to claim 1, wherein the dialkylether product stream is enriched with a base by adding the base to or contacting the base with at least a part of the dialkylether product stream.
The present invention relates to a process for the preparation of an
olefin from an alkyl alcohol. In particular it relates to a process
wherein an alkyl alcohol is converted to a dialkylether and,
subsequently, the reaction product is converted to an olefin, e.g.
propylene or ethylene.
Such a process is known from, e.g., EP-B 88494. In EP-B 88494 a process is described in which methanol is converted to dimethylether and water and, subsequently, the dimethylether is converted to olefins. The document describes that both the dimethylether preparation and the olefin production are exothermic. Therefore it is proposed to conduct the olefin production in several stages, wherein use is made of interstage cooling. Moreover, it is suggested that the product from the dimethylether preparation is subjected to indirect heat exchange with, e.g., water or the methanol reactant. In the process according to EP-B 88494 water that is formed at the dimethylether preparation is only partly separated and removed after the conversion of dimethylether to olefins, together with the water produced during the conversion of dimethylether. That means that water formed at the dimethylether preparation is present at the olefin production from dimethylether and methanol. Therefore the streams through the reaction stages for the olefin production are unnecessarily large. Moreover, the risk exists that these excessive amounts of water have a detrimental effect on the stability of the catalyst used.
In WO-A 2006/020083 a process is described wherein methanol is converted to dimethylether in the presence of a first catalyst. Dimethylether is subsequently converted to light olefins and water in the presence of a second catalyst. In one embodiment the methanol is contacted with the first catalyst to convert methanol into dimethylether and water. Then unreacted methanol, dimethylether and water are combined with a recycle stream to form a combined stream. The combined stream is then separated into a first overhead stream comprising dimethylether and methanol and a first bottoms stream comprising a weight majority of water. The first overhead stream with dimethylether and methanol is subsequently contacted with the second catalyst to effect the conversion to light olefins and water. Finally, a portion of the water from the conversion into olefins is removed and used as the recycle stream and combined with the stream comprising dimethylether, unreacted methanol and water. Although this process attempts to avoid an undue excess of water in the conversion to olefins, this process provides for an excess water in the combined stream which has a negative effect on the equilibrium of dimethylether such that it stimulates the formation of methanol.
The present invention has the objective to reduce the amounts of water in the process streams at the conversion of dialkylether to olefins. According to another objective the invention is to provide a process in which simple separation and efficient use of starting material is achieved. According to yet another objective, the amount of by-products in the feed-stream to the dialkylether conversion to olefins is lowered.
Accordingly, the present invention provides a process for the preparation of an olefin from an alkyl alcohol which process comprises the steps:
a) converting the alkyl alcohol into a dialkylether over a first catalyst, to yield a dialkylether product stream containing alkyl alcohol, dialkylether and water;b) separating the dialkylether product stream into a vaporous dialkylether-rich stream and a liquid water-containing stream which water-containing stream comprises at most 5% wt of alkyl alcohol, based on the total weight of water and alkyl alcohol; andc) converting the vaporous dialkylether-rich stream to an olefin over a second catalyst,wherein the dialkylether product stream is enriched with a base.
In the process according to the present invention excess water formed at the alkyl alcohol conversion and present in the dialkylether product stream is removed from this stream so that the process streams in the olefins manufacture have reduced water content. Further, the equilibrium obtained in the dialkylether product stream is not disturbed. Moreover, by allowing a relatively small amount of alkyl alcohol in the liquid water-containing stream, the separation in step b) can be simple, whereas the majority of unconverted alkyl alcohol is entrained with the vaporous dialkylether-rich stream and becomes so available for conversion to olefins in step c). Since no high purity of the vaporous dialkylether-rich stream is required a simple separation such as a cheap distillation or flash is sufficient.
In addition, the present process provides an elegant solution to get rid of by-products, that are formed in the production of dimethylether from methanol, by removal with the liquid water-containing stream. In particular the enrichment of the dialkylether product stream with a base forms products, in particular neutralization products, which can be removed with the water-containing stream.
It is observed that EP-A 340576 discloses a process for obtaining pure dimethylether by a sophisticated distillation process, wherein it is disclosed that remaining odor components can be removed from the pure dimethylether product by adding a base.
In the present process, the purity of the dialkylether product separation of the dialkylether product is not a major concern, neither is odor nuisance. However, it was found that by adding a base to all or part of the dialkylether-rich product stream, by-products from the methanol to dimethylether conversion can be effectively bound and removed with the water-rich phase, which are harmful in the downstream conversion to olefins, in particular corrosive components such as carboxylic acids.
In the process according to the present invention an alkyl alcohol is employed. Generally, the alkyl alcohol contains from 1 to 4 carbon atoms. Preferably, the alkyl alcohol is methanol. Optionally it may contain small amounts of C2-C4 alkyl alcohols, such as ethanol or isopropanol. The presence of such latter compounds will result in the formation of an amount of ethylmethyl ether and isopropylmethyl ether. More preferably, the alkyl alcohol is methanol with a purity of at least 99% w, preferably at least 99.5% w, based on the total weight of the reactants that are converted over the first catalyst, so that the dialkylether is substantially pure dimethylether.
The conversion of alkyl alcohol to dialkylether is known in the art. This conversion is an equilibrium reaction. In the conversion the alcohol is contacted at elevated temperature with a catalyst. In EP-A 340 576 a list of potential catalysts are described. These catalysts include the chlorides of iron, copper, tin, manganese and aluminium, and the sulphates of copper, chromium and aluminium. Also oxides of titanium, aluminium or barium can be used. Preferred catalysts include aluminium oxides and aluminium silicates. Alumina is particularly preferred as catalyst, especially gamma-alumina. Although the alkyl alcohol may be in the liquid phase the process is preferably carried out such that the alkyl alcohol is in the vapour phase. In this context the reaction is suitably carried out at a temperature of 140 to 500° C., preferably 200 to 400° C., and a pressure of 1 to 50 bar, preferably from 8-12 bar. In view of the exothermic nature of the conversion of alkyl alcohol to dialkylether the conversion of step a) is suitably carried out whilst the reaction mixture comprising the first catalyst is being cooled. It is possible to employ interstage cooling, similar to the cooling described in EP-B 88494 for the conversion of methanol to olefins. Preferably, the conversion of step a) is carried out in an isothermal fashion, such that the temperature in the reaction zone is kept within a range by means of cooling. The cooling is conducted preferably with indirect heat exchange. The indirect heat exchange may take place in the reactor itself, e.g. by cooling tubes at the wall of the reactor, or by using a multitubular reactor wherein the tubes are indirectly cooled. An external heat exchanger may also be used. In such a case the process streams are at least partly circulated through the external heat exchanger and the reaction zone.
The coolant can be selected from any convenient coolants. Suitable coolants include water and/or steam. However, it is particularly useful to use the alkyl alcohol that is to be converted to the dialkylether as the coolant. This has the advantage that the reaction temperature stays within the desired limits, and at the same time the feedstock for this reaction is heated to the desired starting temperature. The coolant may be brought into indirect contact with the process streams in a counter-current, cross-current or co-current manner. It has been found that the indirect contact is preferably accomplished in a co-current manner. In this way the starting temperature of the alkyl alcohol can be kept sufficiently high so that the reaction takes place smoothly, whereas the temperature increase will be kept sufficiently low to enable a satisfactory yield of dialkylether in the equilibrium reaction.
Advantageously a pH of at least 7 is maintained in the hot dialkylether product stream, in particular in a liquid water-containing fraction of the dialkylether product stream. This stream is enriched with a base to this end. In order to enrich the dialkylether product stream with a base, the base is suitably contacted with or added to the dialkylether product stream (or a fraction thereof), such that a pH of from 7 to 12 is achieved in a liquid water-containing fraction of the dialkylether product stream. Such a base can be sodium or potassium hydroxide, or any other alkali metal or alkaline earth metal bases or mixtures thereof. The base may be added to the hot dialkylether product stream or in any preceding stream.
In the process of the present invention the dialkylether product stream conveniently has a temperature of 200 to 400° C. In order to facilitate the separation of step b) the dialkyl product stream may be cooled. This may be achieved by flashing. However, suitably, the heat of this product stream is used to increase the temperature of the dialkylether that is to be used in the subsequent olefins manufacture, e.g., by heat exchange.
The ratio of dialkylether and alkyl alcohol in the dialkylether product stream may vary between wide ranges. Suitable ranges include a dialkylether to alkyl alcohol weight ratio of 0.5:1 to 100:1, preferably from 2:1 to 20:1. Suitably the reaction is led to equilibrium. This includes that the dialkylether to alkyl alcohol weight ratio may vary from 2:1 to 6:1. Evidently, the skilled person may decide to influence the equilibrium by applying different reaction conditions and/or by adding or withdrawing any of the reactants.
In step b) the dialkylether product stream may be separated in a simple separation unit, e.g., in a fractionation column. Since the alkyl alcohol is a valuable product and since it may react in the olefins manufacture step, the separation of the gas-liquid mixture yields a liquid water-containing stream and a vaporous dialkylether-rich stream, wherein the majority of the alkyl alcohol is contained in the vaporous dialkylether-rich stream. Therefore, the liquid water-containing stream contains at most 5% wt, preferably, at most 3% wt, more preferably at most 1% wt of alkyl alcohol, based on the total of water and alkyl alcohol. It is within the skill of the artisan to determine the correct conditions in a fractionation column to arrive at such a separation. He may choose the correct conditions based on, i.a., fractionation temperature, pressure, trays, reflux and reboiler ratios. The conditions are most preferably chosen such that the liquid-water stream contains insignificant amounts of alkyl alcohol. Since water is normally produced in the olefins manufacture step it is not required to remove all water from the dialkylether-rich stream. The dialkylether-rich stream suitably contains at most 5% wt, preferably at most 1% wt of water, based on the total weight of water, alkyl alcohol and dialkylether. The dialkylether product stream is preferably separated into the vaporous dialkylether-rich stream having a temperature of 75 to 140° C., and the liquid water-containing stream having a temperature of 80 to 175° C. The liquid-water stream can be discharged.
At least a portion of the vaporous dialkylether-rich stream is used in the conversion to an olefin in step c).
The olefins manufacture from dialkylether is known in the art. For instance, in the above-mentioned WO-A 2006/020083 the manufacture of olefins from dimethylether has been described. The catalysts described therein are also suitable for the process of the present invention. Such catalysts preferably include molecular sieve catalyst compositions. Excellent molecular sieves are silicoaluminophosphates (SAPO), such as SAPO-17, -18, -34, -35, -44, but also SAPO-5, -8, -11, -20, -31, -36, -37, -40, -41, -42, -47 and -56. Alternatively, the olefin manufacture may be accomplished by the use of an aluminosilicate catalyst. Suitable catalysts include those containing a zeolite of the MFI type, such as ZSM-5, the MTT type, such as ZSM-23, the TON group, such as ZSM-22, the STF-type, such as SSZ-35, the SFF type, such as SSZ-44 and the EU-2 type, such as ZSM-48. Preferably, the dialkylether-rich feed is converted over a catalyst comprising a zeolite that has one-dimensional 10-ring channels. Such a zeolite is more preferably selected from the group consisting of aluminosilicates of the MTT and TON type and mixtures thereof. The present invention is of particular advantage for processes wherein the olefin conversion is accomplished over a catalyst comprising a zeolite having one-dimensional 10-ring channels, in particular of the MTT and/or TON type, since it has been found that the hydrothermal deactivation of the catalyst is reduced when the dialkylether-rich feed stream contains no or only minor amounts, i.e.<5% wt, of water. Advantageously, the catalyst comprises one or more zeolites, of which at least 50% wt has one-dimensional 10-ring channels, such as zeolites of the MTT and/or TON type. In a particularly preferred embodiment the catalyst comprises in addition to one or more zeolites having one-dimensional 10-ring channels, such as of the MTT and/or TON type, a zeolite with more-dimensional channels in particular of the MFI type, more in particular ZSM-5, since this additional zeolite has an beneficial effect on the stability of the catalyst in the course of the process and under hydrothermal conditions.
Especially when the olefins manufacture is carried out over a catalyst containing one-dimensional 10-ring channels aluminosilicates, such as of the MTT or TON type, it may be advantageous to add an olefin-containing co-feed to the reaction zone together with the portion of the dialkylether-rich stream ("feed") when the latter feed is introduced into this reaction zone. It has been found that the catalytic conversion of dialkylether to olefins is enhanced when an olefin is present in the contact between dialkylether and catalyst. Therefore, suitably, an olefinic co-feed is added to the reaction zone together with the dialkylether-rich feed when one reaction zone is employed. When multiple reaction zones are employed, an olefinic co-feed is advantageously added to the part of the dialkylether-rich stream that is passed to the first reaction zone.
The olefinic co-feed may contain one olefin or a mixture of olefins. Apart from olefins, the olefinic co-feed may contain other hydrocarbon compounds, such as for example paraffinic, alkylaromatic, aromatic compounds or a mixture thereof. Preferably the olefinic co-feed comprises an olefinic fraction of more than 50 wt %, more preferably more than 60 wt %, still more preferably more than 70 wt %, which olefinic fraction consists of olefin(s). The olefinic co-feed can consist essentially of olefin(s).
Any non-olefinic compounds in the olefinic co-feed are preferably paraffinic compounds. If the olefinic co-feed contains any non-olefinic hydrocarbon, these are preferably paraffinic compounds. Such paraffinic compounds are preferably present in an amount in the range from 0 to 50 wt %, more preferably in the range from 0 to 40 wt %, still more preferably in the range from 0 to 30 wt %.
By an olefin is understood an organic compound containing at least two carbon atoms connected by a double bond. A wide range of olefins can be used. The olefin can be a mono-olefin, having one double bond, or a poly-olefin, having two or more double bonds. Preferably olefins present in the olefinic co-feed are mono-olefins.
The olefin(s) can be a linear, branched or cyclic olefin. Preferably olefins present in the olefinic co-feed are linear or branched olefins.
Preferred olefins have in the range from 2 to 12, preferably in the range from 3 to 10, and more preferably in the range from 4 to 8 carbon atoms.
Examples of suitable olefins that may be contained in the olefinic co-feed include ethene, propene, butene (one or more of 1-butene, 2-butene, and/or iso-butene (2-methyl-1-propene)), pentene (one or more of 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, and/or cyclopentene), hexene (one or more of 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-1-pentene, 3-methyl-2-pentene, 4-methyl-1-pentene, 4-methyl-2-pentene, 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 3,3-dimethyl-1-butene, methylcyclopentene and/or cyclohexene), heptenes, octenes, nonenes and decenes. The preference for specific olefins in the olefinic co-feed may depend on the purpose of the process.
In a preferred embodiment the olefinic co-feed preferably contains olefins having 4 or more carbon atoms (i.e. C4+ olefins), such as butenes, pentenes, hexenes and heptenes. More preferably the olefinic fraction of the olefinic co-feed comprises at least 50 wt % of butenes and/or pentenes, even more preferably at least 50% wt of butenes, most preferably at least 90 wt % of butenes. The butene may be 1-, 2-, or iso-butene. Most conveniently it is a mixture thereof. More preferably, the olefin that is added to the reaction zone is a by-product of the olefin conversion step c) of the present process which by-product contains 4 to 7, preferably just 4, carbon atoms and which is recycled to the reaction zone. These relatively higher olefins tend to facilitate the conversion of dialkylether to olefins such as propylene and ethylene. Hence, the olefinic co-feed is suitably a by-product of the olefins conversion of step c) which by-product is recycled.
The reaction conditions of the olefin manufacture include those that are mentioned in WO-A 2006/020083. Hence, a reaction temperature of 200 to 1000° C., preferably from 250 to 750° C., and a pressure from 0.1 kPa (1 mbar) to 5 MPa (50 bar), preferably from 100 kPa (1 bar) to 1.5 MPa (15 bar), are suitable reaction conditions.
The reaction of the dialkylether-rich feed may be carried out in a single reaction zone, as described in WO-A 2006/020083. However, it is preferred that the conversion takes place in several reaction zones into each of which vaporous dialkylether-rich feed is fed. Accordingly, part of the vaporous dialkylether-rich feed is passed to multiple reaction zones comprising a first reaction zone and one or more subsequent reaction zones, where the vaporous dialkylether-rich feed is converted to an olefin. Evidently, the multiple reaction zones may be operated in parallel. However, it is preferred that the multiple reaction zones are arranged in series. In that way at least part or substantially all of the product of the previous reaction zone is forwarded to the subsequent reaction zone. Also the catalyst of the previous reaction zone may be forwarded to the subsequent reaction zone together with its product, i.e. the entire effluent from a previous reaction zone can be forwarded. Hence, the number of reaction zones may suitably vary from 1 to 6, preferably from 2 to 4.
It is advantageous to ensure that the temperature of the vaporous dialkylether-rich feed that is passed to the only reaction zone or the temperature of the part of the vaporous dialkylether-rich feed that is passed to the first of multiple reaction zones has a temperature of 300 to 700° C. This allows that, after mixing with the catalyst and, optionally, with an olefinic co-feed, a reactor inlet temperature is provided at which the conversion quickly starts. To obtain this desired temperature it may be convenient to heat the dialkylether-rich feed that comes from step b) further. Since the conversion of dialkylether to olefins is exothermic the reaction temperature tends to increase. Further heating may be accomplished by use of an external heater or by mixing the feed with hot catalyst particles, e.g., when these particles are obtained from their regeneration. Since under these conditions also alkyl alcohol can be converted into olefins, it is beneficial to ensure that most, if not all, of unreacted alkyl alcohol from step a) of the current process is included in the dialkylether-rich feed.
As indicated above, it is preferred that the reaction is carried out in multiple reaction zones in series, into each of which zones dialkylether is fed as starting material. For the subsequent reaction zones, the dialkylether-rich feed does not need to have the same high temperature as the part that is fed to the first reaction zone. In these cases it suitably has a temperature of 50 to 350° C. The desired additional heat may be provided by the catalyst and/or product of the preceding reaction zone that has been heated by the exothermic reaction in this preceding reaction zone. The desired temperature may also be provided by any additional catalyst that is fed from a catalyst regeneration zone to such subsequent reaction zone. Moreover, there is no need to pass additional olefins into the subsequent reaction zones. Since a lower temperature may suffice for the vaporous dialkylether-rich feed the feed that comes straight from step b) may be used in any subsequent reaction zone without further heating steps and without addition of optional olefins. Alternatively, the dialkylether-rich feed may be cooled before being fed to a subsequent reaction zone.
The reaction zone or zones may be comprised in a variety of reactors. Suitable reactors include fixed bed reactors, fluidised bed reactor, circulating fluidised bed reactors, riser reactors, and the like. Suitable reactor types have been described in U.S. Pat. No. 4,076,796. Preferred reactors are riser reactors. Hence, the conversion of dialkylether to olefins is preferably carried out in multiple reaction zones wherein the multiple reaction zones have been executed as multiple riser reactors.
The process of the present invention will be elucidated by way of example, with reference to the accompanying Figures, wherein
FIG. 1 schematically shows a heat-integrated reactor-system in accordance with the invention;
FIGS. 2 and 3 show schematically further embodiments of a separation section for use in the invention.
In FIG. 1 a vaporous alkyl alcohol is passed via a line 1 through coolant tubes in a dialkylether reactor 2. As the formation of dialkylether from alkyl alcohol is exothermic, the vaporous alkyl alcohol is heated and the thus heated alkyl alcohol leaves the reactor as hot effluent via a line 3. The hot effluent is subsequently recycled to the reactor 2 but at the reaction side of the coolant tubes. The stream from line 1 and the one from line 3 are passed co-currently through reactor 2. In reactor 2 the alkyl alcohol is converted to dialkylether and water in contact with a suitable catalyst, e.g. gamma-alumina. A dialkylether product stream comprising dialkylether, water and alkyl alcohol leaves the reactor via a line 4. The hot dialkylether product stream may be cooled before being passed on to a separation section 5. The stream may be cooled in one or more stages, e.g., by indirect heat exchange and/or by flashing in a flash vessel wherein the pressure is reduced and the product stream is cooled (not shown). In the separation section 5, here depicted as a fractionation column, the dialkylether product stream is separated into a liquid stream 6 comprising water and preferably less than 1% wt alkyl alcohol, based on the total of water and alkyl alcohol, and a vaporous dialkylether-rich stream 7, comprising dialkylether, the majority of the alkyl alcohol and typically some water, such as more than 0.5 wt %, in particular more than 1 wt %, and less than 10 wt % or preferably less than 5 wt %, based on the total dialkylether-rich stream. A quantity of water in the feed stream for the conversion to olefins is typically not considered a problem, since water is also being formed in the conversion of dialkylether and alkyl alcohol to olefins. Also for this reason, a simple separation removing the bulk of the water is typically regarded sufficient. Other embodiments of a separation section will be discussed below. The stream in line 7 may be split into several portions. In the case of the present figure there are two portions, but it will be evident that when more portions are desired in view of the number of reactors the number can be adapted. The portion in line 8 is fed to a first riser reactor 10 of a serial riser reactor system, whereas the portion in line 9 is fed to a second riser reactor 20 of the serial riser reactor system. The stream in line 8 may be further heated (not shown), e.g. by additional heat exchange or other heating means. The stream is combined with a stream of an olefinic co-feed, comprising olefins with 4 and/or 5 carbon atoms which stream is provided via a line 27.
In the riser reactor 10 the streams from lines 8 and 27 are contacted with a suitable catalyst, provided via a line 16, and the formed combination of oxygenate (i.e. dialkylether and alkyl alcohol), olefin, water and catalyst is passed upwards and this combination leaves the riser reactor 10 via a line 11 as reaction product.
The lines 8 and 27 are shown as combined before entering the riser reactor 10, but it will be understood that each may debouch into riser reactor 10 separately. Alternatively, line 16 is shown as a separate line, but it will be understood that it may be combined with any of the two other lines 8 and 27 before entering the riser reactor 10.
Via line 11 the reaction product is passed to a separation means, e.g. a cyclone 12, from which catalyst particles are discharged via a line 13 and passed to a catalyst buffer vessel 15, and from which the vaporous reaction product, comprising dialkylether, olefins and water is withdrawn via line 14. This vaporous product in line 14 is combined with the portion of the dialkylether-rich feed in line 9 and passed to the second riser reactor 20, in which a similar reaction takes place as in riser reactor 10. Catalyst for riser reactor 20 is provided via line 17. The reaction product of the riser reactor 20 is discharged therefrom via line 21 and passed to a separation means 19, e.g. a cyclone. In the separation means catalyst particles are separated from the vaporous products and withdrawn from the separation means 19 via a line 18 and passed to the catalyst buffer vessel 15.
It will be realised that at the dialkylether conversion reaction some coke formation may take place, which coke may deposit on the catalyst particles. Therefore, it is advantageous to regenerate the catalyst particles periodically. Conveniently this may be achieved by continuously or periodically withdrawing part of the catalyst inventory of the catalyst buffer vessel 15 and passing it to a regeneration vessel (not shown), where typically coke is burned partially or substantially fully at temperatures of about 600° C. or more. The size of the portion sent to the regeneration vessel depends on the average degree of deactivation or coking, and on the regeneration conditions, e.g. partial or full burning of coke. The regenerated catalyst particles are recycled to the catalyst buffer vessel or to the riser reactor(s) directly. The regeneration is not shown in the figure.
As product from the separation means 19 an olefins-containing product stream is obtained in a line 22. This product is passed to a fractionation section, in the figure represented by a column 23 in which the olefins-containing product stream is separated into a light fraction 24, comprising light contaminants, such as carbon monoxide, carbon dioxide and methane, into an ethylene fraction 25, into a propylene fraction 26 and into a C4 olefin fraction 27. Optionally, one or more heavier fractions, e.g. fractions with hydrocarbons with 5, 6 or 7+ hydrocarbons may be withdrawn separately from the column 23 (not shown). The separation section also includes a line 28 for withdrawing water. The light fraction in line 24 is discharged, e.g., combusted as fuel. Ethylene and propylene are recovered as products. Water in fraction 28 is withdrawn, and the C4 fraction is recycled via line 27 to the dialkylether-rich stream in line 8.
FIG. 1 shows two riser reactors. It will be evident to the skilled person that only one reactor or more than two, e.g., 3 or 4, riser reactors may be used. Such use will also get the benefits of the present invention.
In another embodiment a serial riser reactor system is used that comprises e.g., three riser reactors that are serially arranged. Each riser reactor has at its lower portion one or more inlets, and at its upper portion one or more outlets. The outlet of the first riser reactor is connected with an inlet of the second riser. Likewise, the outlet of the second riser reactor is connected with an inlet of the third riser reactor.
During normal operation of the serial reactor system, the vaporous dialkylether-rich feed, olefinic co-feed and catalyst are fed to the first riser reactor. Conversion in the first riser over the catalyst forms an olefinic first reactor effluent comprising a gaseous product comprising olefins, and catalyst. Substantially the entire reactor effluent is fed to the inlet of the second riser reactor, together with a portion of the vaporous dialkylether-rich feed and additional catalyst. Although it is possible to also feed an olefinic co-feed to the second riser reactor, this is not needed and not necessarily advantageous, since the effluent from the first riser reactor already contains olefins.
Since additional catalyst is added to the second and third riser reactor, the mass flow rate (mass per unit of time) of oxygenate conversion catalyst in the second riser is higher than in the previous riser reactor. It is generally desired that the weight hourly space velocity remains substantially constant, i.e. not deviating more than 50% from that of the previous riser reactor. Therefore it is advantageous to arrange that the cross-section of the second riser reactor is larger than that of the first riser reactor. For cylindrical riser reactors, the increase in cross-section can also be expressed as an increase in diameter.
When the weight hourly space velocity is substantially constant, the time to flow through the riser reactor is the same for riser reactors of the same height.
The cross section of the third riser reactor is again larger than that of the second riser. It can be preferred to design each riser reactor and the respective catalyst throughput such that substantially full conversion of oxygenate is achieved in the riser reactor, this can be most desirable for the last riser reactor so that substantially no oxygenate forms part of the effluent from the last riser reactor.
The outlet from the last riser reactor is connected to a collector and separation means. The separation means can also be integrated with last riser reactor. It can be a large collector vessel combined with a plurality of cyclone separators, which can be internally housed in the collector vessel. The separation means has an outlet for vapour and an outlet for catalyst. The vapour contains olefins and may be treated in the same way as the vaporous product in line 22 of the Figure. The catalyst is returned to the riser reactors, whereas part may be regenerated as discussed in relation to the Figure.
FIGS. 2 and 3 show schematically further embodiments of a separation section 5, which can e.g. be included in any one of the embodiments discussed hereinabove. In the embodiment of FIG. 2 a dialkylether product stream 4 comprising dialkylether, alkyl alcohol and water, preferably still in the vaporous phase is passed to a flash vessel 48. In the flash vessel 48 the pressure is reduced and the product stream is cooled further to below the dew point of water. The vaporous effluent from the flash vessel 48 comprises most of the dialkylether and some alkyl alcohol and leaves the flash vessel via a line 49. The liquid effluent, comprising water and alkyl alcohol, leaves the flash vessel 48 via a line 50. The effluents from lines 49 and 50 are both fed into a fractionation column 51, whereby line 50 debouches into the fractionation column 51 at a point above the location where line 49 debouches into column 51. In fractionation column 51 the gas-liquid mixture, obtained from both streams, is separated into a liquid stream 6 comprising water and less than 5% wt alkyl alcohol, based on the total of water and alkyl alcohol, and a vaporous dialkylether-rich stream 7, comprising dialkylether, the majority of the alkyl alcohol and typically some water as discussed with reference to FIG. 1.
In FIG. 3, the fractionation column 51 is replaced by two fractionation columns 61 and 65. A stream 66 comprising predominantly dialkylether is recovered as top product from column 61. A stream 68 comprising predominantly alkyl alcohol and water is recovered as the bottom product and fed to the second column 65, where it is separated into a stream 67 predominantly comprising alkyl alcohol and into a liquid stream 6 comprising water and less than 5% wt alkyl alcohol, based on the total of water and alkyl alcohol. Part or all of the stream 67 can optionally be added to the stream 66 to form dialkylether-rich stream 7. This embodiment allows to remove a higher amount of water from the stream 7, but since the presence of some water is typically not a problem in conversion to olefins, this embodiment is not necessarily preferred.
In the embodiment of a separation section of FIG. 3, the stream 7 comprises 57.8 wt % of dimethylether, 15.7 wt % of methanol and 23.3 wt % of water. The stream 68 comprises 57.9 wt % water, 38.9 wt % methanol, and carboxylic acid impurities detected by gas chromatography were 10 ppm CH3COOH, 5 ppm C2H5COOH, 10 ppm C3H7COOH, and 5 ppm C4H9COOH. To the stream 68, NaOH (caustic) was added in a quantity of 0.01 g NaOH per ton of stream 4. No carboxylic acids could be detected in any one of the streams 66,67,6.
The base can be added at any effective location to the dialkylether-rich stream before or during its separation into the dialkylether-rich stream and the liquid water-containing stream. In the embodiments of the separation sections 5 discussed above, it can be added to one or more of the lines 4,49,50,68, or to any one of the columns/vessels 48,51,61,65.
Patent applications by Ferry Winter, Amsterdam NL
Patent applications by Jeroen Van Westrenen, Amsterdam NL
Patent applications by Leslie Andrew Chewter, Amsterdam NL
Patent applications in class To produce unsaturate
Patent applications in all subclasses To produce unsaturate