KR20160108320A - Process for the dimerization/oligomerization of mixed butenes over an ion-exchange resin catalyst - Google Patents

Abstract

An effective dimerization and oligomerization method of mixed butene feeds is provided using ion exchange resin-based catalysts. The dimerization and oligomerization methods include highly branched C8 and C8 + olefins (e.g., C12, C16 < RTI ID = 0.0 > And C20 olefins).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dimerization / oligomerization of mixed butenes through an ion-exchange resin catalyst,

The present invention relates to a process for the dimerization / oligomerization of olefins using ion-exchange resin catalysts under mild conditions to produce highly branched olefins with eight carbons and olefins with more than eight carbons, and more particularly to processes for the dimerization / (Mixed butenes) in a single step process.

Gasoline continues to be a major source of energy for internal combustion engines commonly used in powerplants, such as cars for the transport of people and goods. The standard measure for the performance of gasoline is the octane number. The most common octane number measurement methods are the Research Octane Number (RON), the Motor Octane Number (MON), and the Anti-Knock Index (AKI) - the average of the RON and MON values. Fuel with higher octane number can be used for higher-compression, higher performance engines. Therefore, there is an incentive for scientists to develop a new method to increase the octane number of gasoline.

In addition, increasingly restrictive fuel laws around the world merely reinforce these incentives. This attempt has been made to maintain fuel quality while reducing harmful emissions of the current fuel. One group of harmful substances present in gasoline, reduced by law, is aromatics (eg, benzene emissions). The aromatic content of gasoline should now be reduced to less than 35% by volume due to emissions-limit legislation (the United States has even lowered it to less than 25% by volume). The aromatics have the greatest contribution to RON, and thus the legally-mandated reduction in aromatic content of gasoline will cause a significant reduction in the amount of gasoline as well as a RON deficiency. In addition, fuel manufacturers should also be aware of the Reid Vapor Pressure (RVP) of the fuel, a measure of how quickly the fuel evaporates. The higher the RVP of the fuel, the faster its evaporation rate and, consequently, the greater contribution to the ozone layer. The RVP for fuel should typically be less than the normal atmospheric pressure of 14.7 psi. RVP is a particularly important measure of fuel during the summer when EPA strictly regulates RVP of gasoline sold at retail stores. During the summer, RVP in gasoline typically can not exceed 9.0 psi. Since aromatic compounds also have low RVP, a decrease in aromatic content in gasoline will also lead to increased RVP. Thus, there is currently an incentive to find new ways of retaining high gasoline octane prices while maintaining a low RVP within the framework of the new emissions regulations.

Several decades ago, lead was used as an additive to gasoline to increase the octane number of gasoline. However, lead has been removed from the gasoline blend in most countries due to its deleterious environmental impact. Over the past two decades, in part to respond to the need to increase octane prices in the absence of lead, gasoline sold in the US and elsewhere is still an oxygenate, methyl-3 Butyl-ether (MTBE) has been blended with up to 15% volume.

While MTBE has a low RVP, MTBE itself has been classified as a contaminant and potential human carcinogen. To make matters worse, many gasoline storage tanks have been leaked, and MTBE has been highly water-soluble and low in biodegradability, so MTBE has contaminated groundwater in many communities. Thus, the use of MTBE in gasoline sold in the United States has been substantially halted in recent years.

Currently, the proposed MTBE alternative is fermented grain ethanol from wheat or sugarcane. For example, US 4398920 (A) discloses a blended fuel comprising a mixture of warmed ethanol, acetone, and methanol from fermentation. The use of ethanol in gasoline blends is advantageous in many respects, including the fact that its higher blending RON and its toxicity are known in the art. However, the manufacture of ethanol can be economically sustainable only when it is expensive and given tax relief. In addition, the production of sufficient quantities of grain ethanol to meet the needs of the transportation industry has the side effect of hindering the use of grain crops as food. Furthermore, ethanol has a relatively low energy content compared to gasoline. Specifically, gasoline contains about 113,000 Btu's / gallon while ethanol contains about 76,000 Btu's / gallon. Ethanol also has high affinity for water and can not be mixed directly with gasoline in refineries, so this can only be added just before the last dispensing point of the network. Moreover, ethanol readily forms low-boiling azeotrope with the components of gasoline, resulting in higher RVPs varying from 17 to 22 psi at 10-15% blending levels. Higher RVPs associated with ethanol blends are particularly problematic during the summer. In addition, an excessively high ethanol concentration (about 10% by volume of ethanol) is believed to increase NO _x emissions.

Alkylates (e. G., Iso-octane and trimethylpentane) are also highly desirable substitutes for MTBE due to their positive effects on their higher RON, lower RVP, and emissions. Alkylation is a purification process consisting of the formation of highly branched paraffins by catalytic alkylation of light olefins such as propylene and butene with isobutane in the presence of sulfuric acid or hydrogen fluoride. From an environmental standpoint, both sulfuric acid and hydrogen fluoride are strong acids. Thus, the handling of enormous volumes of any acid during normal operation, the treatment of their by-products, and the transport of any acid for their recovery are highly hazardous due to their corrosiveness. As a result, the production of alkylates is not an environmentally friendly process.

Overall, there is a need for a method of making additional octane enhancers, taking into account cost and environmental issues, along with the need to maintain higher RON and lower RVP.

One such method of making octane enhancers is the dimerization and oligomerization of butenes to produce high-octane hydrocarbon constituents. The main compounds obtained from dimerization and oligomerization of mixed butenes are C8 and C12 olefins. Among these C8 olefins, diisobutene (DIB) is most preferred. DIB is a non-oxygenated fuel component with many advantages, such as higher RON, better anti-knock quality, and higher energy content as compared to MTBE and alkylate, as well as MTBE and lower RVP than ethanol. More specifically, highly branched octenes derived from butene dimerization and oligomerization (a) provide a very similar RON that increases with MTBE when added to the same low volume RON gasoline; (b) have a higher RON sensitivity compared to MTBE and alkylate, and thus have better anti-knock quality and higher combustion efficiency in modern and future spark ignition engines; (c) higher energy content and lower RVP compared to MTBE.

There are two main types of light aliphatic olefin dimerization mechanisms: metal-catalyzed coordination mechanisms and acid-catalyzed ion mechanisms. The coordination metal complex-catalyst method often uses nickel, cobalt, or Ziegler-type catalysts among others. These processes usually use n-butene as a starting material and generally produce head-to-tail and head-to-head dimerization and oligomerization of mostly linear olefins or predominantly olefinic double bonds. Although coordination metal complex-catalyst methods have been extensively studied, they are not the subject of the present invention.

In contrast, acid-catalyzed processes produce strongly branched olefins. The dimerization of isobutene is typically carried out using an acid catalyst comprising a sulfonic acid derivative, a zeolite, and an ion exchange resin. Sulfuric acid and hydrogen fluoride have often been used to catalyze dimerization of isobutene, but as mentioned above, these catalysts tend to be highly corrosive in nature.

Nickel oxide catalysts have also been used in the butene oligomerization process. However, these catalysts are rapidly inactivated due to coke formation, despite the fact that C8 olefins can be selectively obtained with a selectivity of 85%. These supported nickel-based catalysts also tend to produce less branched dimers or oligomers.

Zeolite-based catalysts have been reported to dimerize or oligomerize olefins in the 1970s. For example, DE 2347235 A1 teaches that dimerization of 1-butene through a zeolite catalyst with a 5% Ni content at 170 ° C / 40 atm provides 40.5% conversion and 81.8% selectivity of linear octene. However, even at 150 ° C, low n-butene dimerization activity and fast inactivation due to coking are detected. A small amount of hard coke is sufficient to prevent access of the reactants to the internal acid sites of the zeolite. Cracking is often observed when using zeolite-based catalysts.

The ionic (ionic) exchange resin catalyst reduces the negative environmental impact of the acid waste stream compared to inorganic acid catalysts. In addition, the ion exchange resin catalyst is at least corrosive and readily separates from the product. To date, ion exchange resin catalysts have been used only in selective isobutene dimerization processes to produce DIB and isoctene, since these products are useful octane enhancers. On the one hand, the feedstock is limited to isobutene (an isomer of butene) which results in the DIB being essentially exclusively formed. Other catalysts such as zeolites with or without nickel oxide and nickel appear to be inferior to the ion exchange resin catalysts of the present invention in activity, selectivity, and catalyst lifetime for the dimerization of mixed light olefins.

Thus, there is a need for efficient production of hydrocarbon components that have many advantages over MTBE, ethanol, or alkylate currently used as RON enhancers. Additionally, there is a need for such a process using ion exchange resin catalysts as they are at least corrosive and readily separable from the reaction product. Finally, there is a strong incentive to find an inexpensive way to make an octane enhancer due to the high manufacturing costs of other octane enhancers such as ethanol.

The present invention relates to a method of making an octane-enhancing fuel component that overcomes the disadvantages of other fuel components such as MTBE, ethanol, and alkylate. Specifically, in one embodiment, the present invention relates to a process for preparing C8 and C8 + olefins from dimerization and oligomerization reactions of mixed olefin (butene) feeds. The process comprises introducing a mixed butene liquid feed containing two or more butene isomers into a reactor with an acidic ion exchange resin catalyst under mild conditions.

In one embodiment, the mixed butene feed consists of all four butene isomers. In another embodiment, the mixed butene feed is comprised of two or more butene isomers and optionally other C2 to C5 olefins such as ethylene, propylene and pentene may be incorporated.

The mixed butene feed interacts with the ion exchange resin-based catalyst in the reactor and converts the mixed butene to higher olefins. The use of ion exchange resin-based catalysts under mild reaction conditions will prevent cracking and catalyst deactivation of the product, which is a significant advantage over other commercial oligomerization processes using nickel oxide or zeolite-based catalysts. Additionally, the use of ion-exchange resin catalysts in the butene dimerization / oligomerization reaction under mild conditions results in more highly branched C8 and C8 + olefin products compared to nickel oxide and zeolite-based catalysts, Which is a highly branched octene. In one embodiment, the ion exchange resin-based catalyst is a sulfonic acid cation exchanger in the form of hydrogen. However, in another embodiment, a polar compound such as butanol or water may be added to the catalyst to promote the chemical reaction.

In one embodiment, the temperature of the reactor is maintained at 30 to 160 占 폚, the pressure of the reactor is maintained at 20 to 100, and the liquid hourly space velocity (LHSV) of the reactor is maintained at about 0.33 hours.

A more complete understanding of the present invention and many of its features and advantages will be obtained with reference to the following detailed description and the accompanying drawings. It is important to note that this figure shows only one embodiment of the invention and is not therefore to be construed as limiting the scope of the invention.
Figure 1 illustrates an illustration of a fixed bed method in accordance with one embodiment of the present invention.

As mentioned earlier, the prior art includes many dimerization / oligomerization methods of iso-butene, but these methods are highly selective only for associated defects, such as one type of olefin (e.g., C8 olefin) The phosphorus olefins include those present in very small amounts. In particular, the prior art relates to the dimerization / oligomerization of one butene isomer (e.g., isobutene). In addition, some of these methods are technically complex and require several steps to process the feed stream.

The present invention relates to a process for the dimerization and oligomerization of mixed olefins (especially mixed butenes) via ion-exchange resin-based catalysts to overcome the deficiencies and limitations of the prior art and to produce highly branched C8 and C8 + olefins. More specifically, the present invention is a single step (single path) method performed under mild conditions resulting in high conversion rates as discussed below. For dimerization / oligomerization of selective isobutene in a mixed olefin mixture, an exemplary reaction temperature is about 30 to 100 < 0 > C. For dimerization / oligomerization of mixed butenes, exemplary reaction temperatures are from about 80 ° C to about 180 ° C.

Mixed olefins ( Butene )

Mixed butenes have four structural isomers, 1-butene, 2-cis-butene, 2-trans-butene, and isobutene. Optionally, other lower olefins such as propylene and ethylene may also be present in the feed as described below. In addition, the term "higher olefins" refers to olefins that are formed as products that are part of the process and have a higher number of carbon atoms than olefins in the initial feedstock introduced into the reactor.

Diisobutene ( DIB ) or Iso-octene

Diisobutene includes two isomers, 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene.

Oligomerization

Oligomerization of mixed butenes involves oligomerization of all butene isomers, including oligomerization (dimerization) of isobutene as well as other butene isomers.

Isobutene Dimerization

Ion-exchange resin

Typically, ionic (ion) exchange resins are very small plastic beads and therefore the structure of the resin is a polymer in which fixed ions are permanently attached. To preserve the electrical neutrality of the resin, each immobilized ion is neutralized with a counter ion. This counterion is dynamic and can move in and out of the resin bead. Each ion to bead (resin) must be replaced again by ions going out of the bead to preserve electrical neutrality. This is called ion exchange. Only ions with the same electrical signal are exchanged. Thus, the resin can come in both a cationic resin form and an anionic resin form. In order for ion exchange to be efficient, there must be a difference in affinity between ions in the resin and ions or ions that are to be removed from the solution. The resin should have a higher affinity for ions in the solution compared to the ions in the resin.

According to the present invention, an ion-exchange resin is widely defined as an insoluble substrate containing unstable ions capable of exchanging ions of the surrounding medium without major physical changes taking place in its structure. Resins suitable for use in the practice of the present invention include, but are not limited to, a sulfonic acid cation exchanger in the form of a hydrogen. However, it will be appreciated that other ion-exchange resins may be used if they are capable of performing the intended function and are suitable for use in the dimerization / oligomerization schemes described herein.

C8 olefins :

The mixture of C8 olefins mentioned in the present invention is mixed octene which is an equivalent of mixed butenes. There are a total of 72 octenomers, of which only a few have high RON values. There are two types of olefins: branched and linear (straight chain). Highly branched octene is a very important RON enhancer for gasoline and therefore it is desirable to produce these types of octenes. Some C 8 olefins are highly branched, such as dimethyl-hexene and trimethyl-pentene. C8 olefins may also be linear or have some branching that is not the subject of the present invention. It will also be appreciated that the cyclic product can also be produced by the present process.

C8 + olefin :

C8 + olefin means an oligomer of mixed butene having 12 or more carbon atoms. The cyclic product can also be formed by the present process.

The present invention Dimerization / Oligomerization  Way

As described herein, an effective method of producing highly branched C8 and C8 + olefins from olefins is provided as an embodiment of the present invention, and more particularly, highly branched olefins are formed. Additionally, a method of making a fuel composition comprising an oligomer made from butene and / or other olefins is also provided as an embodiment of the present invention.

For example, in one embodiment of the present invention, the mixed olefin feedstock is contacted with the catalyst as part of a single stage process (single pass) to produce a product stream comprising suitable reaction conditions and preferably oligomers. In another embodiment of the present invention, the non-reactive olefins may be recycled to produce a product stream of the oligomer. More specifically, the mixed butene feedstock is contacted with the catalyst under suitable reaction conditions to produce a product stream comprising highly branched C8 and C8 + olefins, including DIB. The product stream can be used with the fuel components to produce a fuel composition. The fuel composition of the fuel composition may be selected from gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker oil, or combinations thereof, or other suitable fuel components within the spirit of the present invention. In certain embodiments involving the preferred embodiment, the resulting fuel composition has increased RON and reduced RVP without the presence of other chemicals that may have deleterious effects on the environment.

The source of the mixed olefin stream can vary and can include any number of different sources of feedstock (stream) suitable for use in the present invention. For example, in some embodiments of the present invention, the mixed olefin stream may comprise an effluent stream from an FCC unit or a thermal cracking unit, a raffinate stream from an MTBE process, a raffinate stream from a TBA process, LPG) stream or a combination thereof. It will be further understood that other sources of mixed olefin streams are within the scope of the present invention. According to the disclosed embodiment, the mixed olefin stream may comprise a mixed butene stream. In another embodiment, the mixed olefin stream may be in the form of a mixed C3 to C5 olefin feed stream. However, in other embodiments, the mixed olefin stream may include one or more polypropylene, n-butylene, 2-butene, isobutylene, pentene, hexene, olefins having more than 6 carbons, and the like. Other suitable sources of mixed olefin streams and types of olefins will be apparent to those skilled in the art and are contemplated within the scope of the present invention.

According to one preferred embodiment of the invention, the mixed butene feed (stream / feedstock) used in the present invention is a mixture of two or more of 1-butene, isobutene, 2-trans- Is a liquid mixture of all four isomers. These relatively low mixed butene feeds may come directly from the refinery feed tail gas.

The different butene isomers have different activities for dimerization or oligomerization. For example, isobutene has a tendency to be dimerized or oligomerized. In contrast, it is generally very difficult to form the corresponding dimer or oligomer of 2-butene, especially 2-trans-butene. Thus, most conventional methods focus on selective dimerization of the butene isomers, the method of which is specifically tailored to dimerize an isomer of butene. Thus, this method limit results in the formation of a product stream predominantly of one olefin type. As mentioned herein, it is preferred to form a product stream containing DIB as well as other highly branched higher olefins.

According to the present invention, the present process is characterized in that all four isomers of butene are effectively dimerized (with the production of C12 olefins and smaller amounts of C12 + olefins) with high single pass conversions and high selectivity for C8 olefins under relatively mild conditions Or oligomerized.

In one embodiment, the mixed butene feed is composed of all four butene isomers in varying amounts as will be appreciated by review of the examples presented herein. However, according to another embodiment of the present invention as previously mentioned, the feed may comprise two or more butenes, as well as other C3 to C5 olefins such as propylene and ethylene.

Figure 1 illustrates one exemplary system 100 for performing dimerization / oligomerization of mixed butenes in accordance with the present invention. Figure 1 similarly shows an exemplary method flow. Figure 1 shows an implementation of the invention in a fixed bed method. The system 100 includes a reactor 110 that may be in the form of a fixed bed reactor vessel. The catalyst is loaded into a portion or area 112 of the reactor 110 as shown. In the illustrated embodiment, the catalyst is located in the center of the reactor 110. The reactor 110 itself is generally placed in a hotbox as shown at 120.

The reactants are conveyed to the reactor 110 in the following manner. A source of feedstock (e. G., A mixed butene feedstock) is identified at 130 and a source 130 is fluidly connected to the storage vessel 140 to store the feedstock in the reservoir 140 By means of a fluid conduit 131 (e.g. a pipe). As mentioned herein, the feedstock is typically a liquid stream.

A valve or flow control device 145 is disposed along the conduit to control the flow of feedstock to both the storage trough 140 and the reactor 10. In addition, means (150) for conveying the feedstock (mixed butene) to the reactor (110) at a desirable rate are provided. The means 150 is configured to communicate with the reservoir 140 via a conduit 141 and to cause the feedstock to be actively delivered to the reactor 110 at a desired flow rate. In one embodiment, the means 150 is in the form of a gas source (e.g., N ₂ ) used to pressurize the liquid feedstock into the reactor 110 at a desired rate (flow rate). The gas source 150 is connected to the reservoir 140 by means of a conduit (e.g., a pipe) that may include a valve 155 or the like to control gas flow to the reservoir 140.

The valve 145 may be in a position to close the flow from the source 130 to the reservoir 140; The feedstock stored in the reservoir 140 and the combined gas (from the source 150) are allowed to flow through the valve 145 to the reactor 110. The conduit 151 may lead from the valve 145 to the inlet 110 of the reactor. The conduit 151 may have a valve 153 that controls the flow of feedstock to the reactor inlet 110.

Before entering the inlet of the reactor 110, the feedstock passes through a heat exchanger 160 located between the valve 145 and the reactor 110. The heat exchanger 160 is configured to adjust the temperature of the feedstock to a preselected temperature (e.g., the selected reactor temperature) prior to the feedstock entering the reactor 110. After passing through the reactor 110 and contacting the catalyst in the region 112 the olefin product is formed as discussed herein and these products exit the outlet of the reactor 110 via the conduit 171 and into the separator 170 ). As described herein, the reactor 110 may be a single stage reactor in which feedstock flows therethrough and contacts the catalyst to form a product stream. Therefore, the conversion rate can be described as a single-path conversion rate.

The separator 170 may be in the form of a liquid / gas separator that flows through the conduit 173 before the olefin product having a high boiling point is cooled and is generally collected in a liquid sample indicated at 180. Unreacted feedstock is removed in separator 170 via a different outlet for further processing and / or collection. For example, unreacted feedstock (e. G., Unreacted butenes) can be analyzed by on-line gas chromatograph 190, flowing through conduit 175 or connected to conduit / line 178 leading to vent 179, Lt; RTI ID = 0.0 > 177 < / RTI > One or more valves may be included in line 177 as shown.

It will be appreciated that the product (liquid sample 180) may then be further processed and / or transported elsewhere.

According to one embodiment as referred to herein, fixed bed reactor 110 has at least one region 112 loaded with a solid ion exchange catalyst particularly suitable for use in the present invention. One exemplary solid ion exchange catalyst is a solid Bronsted acid catalyst. Thus, solid ion exchange catalysts may be of a type suitable for use in the present invention and are a type that brings about the dimerization / oligomerization of mixed olefins to form the preferred highly branched olefins (C8 and C8 + olefins).

Under the mild reaction conditions described herein, the type of the catalyst will prevent product cracking and will be less sensitive to the problems often encountered in other commercial oligomerization methods using catalyst deactivation-nickel oxide or zeolite-based catalysts. Furthermore, ion-exchange resin catalysts result in the production of more highly branched C8 and C8 + olefins with milder reaction conditions than nickel oxide and zeolite-based catalysts.

In some embodiments, the catalyst resin used is a sulfonic acid cation exchanger in the hydrogen form. Certain exemplary strong acid cation exchange resins are described below with reference to the disclosed embodiments. The stream of polar compounds may also be added to the catalyst of the reactor to promote the oligomerization / dimerization reaction. In one embodiment, the promoter feed may be an alcohol, such as butanol. In another embodiment, the promoter feed comprises water.

The reaction of the present invention occurs under mild reaction temperature. For selective dimerization / oligomerization of isobutene in the mixed olefin mixture, the reaction temperature is from 30 to 100 占 폚. For dimerization / oligomerization of mixed butenes, the reaction temperature is from 80 캜 to 180 캜. More specifically, the use of the mild conditions of the ion exchange resin catalyst and reactor 110 results in a non-corrosive, environmentally-friendly reaction, as opposed to what is typically observed in alkaline production. For example, in one embodiment, the temperature at which the reaction is carried out is about 30 ° C to achieve high selectivity for isobutene dimerization.

The systems and methods described herein are a continuous flow method in which a feed stream is continuously fed to a reactor.

The product of the present invention is in the form of a stream comprising predominantly C8 olefins and C12 olefins with minor amounts of C16 olefins, C16 + olefins, and cyclic compounds. Among the C8 olefins prepared, preferred are DIB as described herein, and DIB has favorable properties in terms of acting as an octane enhancer. The reaction of the present invention has a high selectivity for C12 olefins as well as C12 olefins-DIB. However, unlike the previous method of preparing DIB through selective dimerization of isobutene, the present invention uses a relatively low mixed butene feed to produce DIB and other valuable, highly branched C8 and C8 + olefins. On the one hand, the mixed butene feed used in the present invention is not specifically tailored to achieve high selective isobutene dimerization (i.e., the feedstock is not isobutene alone), but the mixed butene feed is not only DIB Other preferred olefins (e.g., highly branched higher olefins) are prepared as a result of the operating conditions and process steps described herein.

The products of the present invention, i.e. highly branched C8 and C8 + olefins having a high RON value, are very valuable to the fuel industry. As mentioned above, with increasingly restrictive regulations on gasoline, highly branched C8 and C8 + olefins provide alternative non-oxygenated octane enhancers satisfying these regulations. Specifically, highly branched C8 and C8 + olefins can increase RON and reduce RVP in the fuel without the negative environmental impact seen in MTBE or aromatics. The process of the present invention thus achieves this objective by producing a product which not only contains highly branched C8 olefins but also other highly branched olefins having a carbon number of more than 8.

The C8 and C8 + olefins prepared through the present invention can also be used as valuable feedstocks. In particular, the C8 and C8 + olefin products can be used in a wide variety of applications such as Fluid Catalytic Cracking (FCC) methods such as Deep Catalytic Cracking (DCC) and high severity flow catalyst cracking to produce highly demanding light olefins such as ethylene and propylene Can be used as an excellent feed for the High Severity Catalytic Cracking (HSFCC) process. Mixtures of dimers and trimers with a large number of allylic hydrogens are considerably more reactive and have proven to be the most desirable feedstock for FCC based cracking methods such as HSFCC and DCC. These C8 and C8 + products can also be used as intermediates in the synthesis of detergents, plasticizers, pesticides, lubricants, additives, flavors, pharmaceuticals and many other pure industrial chemicals.

Example

The following examples are provided to better illustrate embodiments of the present invention. It should be understood, however, that these embodiments are merely exemplary in nature and that method embodiments of the present invention are not necessarily so limited.

The following experiment was carried out in a test plant having the configuration and characteristics of the system 100 shown in FIG. In Examples 1 to 3, the feed stream comprises mixed butenes (mixed olefins), more particularly the composition of mixed butenes is: 1-butene 21%; 35% isobutene; 19% 2-cis-butene; And 25% of 2-trans-butene. Mixed butenes were obtained from a number of different commercial sources and in this experiment, and mixed butenes were obtained from Abdullah Hashim Gas Ltd. and used without any purification. The catalyst is an ion-exchange resin, and more particularly, the catalyst is manufactured by KaiRui Chemicals Co., Ltd. of China. Is an ion-exchange resin commercially available under the trade name 0008-3 from Kairui Chemicals Co. Ltd. This exemplary resin is a macroporous strong acid cation exchange resin which is composed of opaque beads and is a sulfonic acid cation exchange in the form of hydrogen.

It was loaded to a total of 30 mL of the catalyst in region 112 of reactor 110, a liquid hourly space velocity (liquid hourly space velocity, LHSV) from about 0.33 ^hours-1. The reaction conditions are listed in Table 1.

In the first embodiment, the reactor was maintained at a pressure of about 20 bar and a temperature of about 150 캜. The mixed butene feed contains all four butene isomers in the following percentages: 2-trans-butene (25%), 1-butene (21%), isobutene (35% 19%). Unless otherwise indicated, the percentages referred to herein are by weight. The test period was about 930 minutes. The results of the first embodiment are shown in Table 1 below.

Table 1 - Example 1

In the second embodiment, the reactor was maintained at a pressure of about 20 bar and a temperature of about 160 占 폚. The mixed butene feed contains all four butene isomers in the following percentages: 2-trans-butene (25%), 1-butene (21%), isobutene (35% 19%). The test period was about 1020 minutes. The results of the second embodiment are shown in Table 2 below.

Table 2 - Example 2

For the third embodiment, the reactor was maintained at a pressure of about 20 bar and a temperature of about 150 ° C. The mixed butene feed contains all four butene isomers in the following percentages: 2-trans-butene (25%), 1-butene (21%), isobutene (35% 19%). A water promoter feed was also added to the reactor at a rate of 0.01 g / min. The test period was about 480 minutes. The results of the third embodiment are shown in Table 3 below.

Table 3 - Example 3

While the selectivity to C8 to C12 olefins is 94% (Example 1), the average single pass conversion of the mixed butenes of the present invention is 84.5% (Example 3). The single pass conversion rates of the present invention are significantly higher than those reported in the literature for pure isobutene dimerization and 1-butene dimerization. The conversion rates reported here are very conservative. Based on the gas chromatographic (GC) analysis of the reaction inner butene and the reaction butene, the single pass conversion is greater than 90% in certain embodiments 3.

Thus, the present invention relates to a process for the preparation of a mixture of butenes in which a mixed butene undergoes dimerization / oligomerization (without an optional process configured to predominate one olefin product, but without a hydration step configured to produce an alcohol with the olefin as part of the product stream) Method (single path switching). As described herein, the methods and systems of the present invention comprise four butene isomers (including n-butene, trans-2-butene, iso-butene and cis-2-butene) (I. E., A mixed light olefin feed), and is implemented in a single stage reactor.

The methods and systems of the present invention provide several advantages over conventional dimerization / oligomerization methods. These advantages include: (1) providing alternative non-oxygenated octane enhancers, highly branched C8 and C8 + olefins to meet increasingly restrictive regulations and reductions in aromatics in gasoline; (2) elevating the relatively low-grade mixed butene; And (3) increasing the yield of precious light olefins of ethylene and propylene by recycling low butenes to premium cracking feeds (C8 to C16 olefins).

While the invention has been described above using specific embodiments thereof, there are many variations and modifications that will be apparent to those of ordinary skill in the art. Accordingly, the described embodiments are to be considered in all respects only as illustrative and not restrictive. Accordingly, the scope of the present invention is indicated by the appended claims rather than by the foregoing description. All changes within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (16)

Introducing a mixed olefin feed into the reactor vessel under oligomerization conditions;
Contacting the mixed olefin feed with an ion-exchange resin-based catalyst in a reactor to convert the mixed olefin to a mixed higher olefin; And
Preparing a product stream comprising a mixed olefin from the reactor vessel
Wherein the hydrocarbon feed comprises two or more different types of olefins having 2 to 5 carbons and wherein the blended higher olefins are selected from the group consisting of (1) olefins having 8 carbons and (2) ≪ / RTI > wherein the mixed olefin feed is dimerized and oligomerized to prepare a mixed olefin. The process of claim 1, wherein the mixed olefin feed comprises at least two butene isomers. 3. The process of claim 2, wherein the mixed olefin feed comprises all four isomers of butane. The method of claim 1, wherein the ion-exchange resin-based catalyst comprises a sulfonic acid cation exchanger in the form of hydrogen. The process of claim 1 wherein the blended higher olefins comprise an olefin having 8 carbons and an olefin having greater than 8 carbons. 6. The process of claim 5, wherein the blended higher olefin comprises diisobutene (DIB). 6. The process of claim 5, wherein the blended higher olefin comprises at least 50 weight percent of an olefin having eight carbons and at least 20 weight percent of an olefin having twelve carbons. The process of claim 5, wherein the olefin having 12 or more carbons is: (a) an olefin having 12 carbons; (b) an olefin having 16 carbons; And (c) an olefin having 20 carbons. 6. The process of claim 5, wherein the portion of the olefin having eight carbons formed as part of the product comprises a highly branched olefin comprising dimethyl-hexene and trimethyl-pentene. The method of claim 1, wherein the reactor vessel is maintained at a temperature of about 30 to 180 占 폚. The method of claim 1, further comprising introducing a catalyst promoter comprising a polar compound into the reactor. 12. The process of claim 11, wherein the accelerator is at least one of water and butanol. Introducing a mixed butene stream comprising mixed butene as part of a dimerization / oligomerization system under oligomerization conditions into a reactor vessel;
Contacting the mixed butene stream with the ion-exchange resin-based catalyst in a reactor to convert the mixed butene to a product stream comprising mixed olefins comprising a highly branched olefin having 8 carbons and an olefin having more than 8 carbons step; And
Combining the product stream with the fuel component to produce a fuel composition
Wherein the mixed butene comprises n-butene, trans-2-butene, iso-butene, and cis-2-butene;
Wherein the fuel component comprises gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker oil, or a combination thereof. 14. The process of claim 13, wherein the blended higher olefins comprise an olefin having eight carbons comprising diisobutene (DIB) and an olefin having more than eight carbons. 15. The process of claim 14, wherein the mixed olefin comprises at least 50 weight percent of an olefin having eight carbons and at least 20 weight percent of an olefin having more than eight carbons. 15. The process of claim 14, wherein the olefin having more than 8 carbons is: (a) an olefin having 12 carbons; (b) an olefin having 16 carbons; And (c) an olefin having 20 carbons.

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