KR101089886B1 - Process for removal of oxygenates from a paraffin stream - Google Patents

Abstract

The present invention provides a feed stream comprising at least one C ₁₀ to C ₁₅ feed paraffin, a C ₁₀ to C ₁₅ olefin rich paraffin stream and at least one oxygenate to at least one selected from silica gel, activated alumina and sodium X zeolite. And removing the oxygenate from the paraffin rich or olefin rich paraffin stream comprising passing through an adsorption bed comprising an adsorbent to remove substantially all of the oxygenate and recovering the paraffins. The second adsorption layer can be used to more completely remove this oxygenate.

Paraffin, Olefin, Oxygenate

Description

PROCESS FOR REMOVAL OF OXYGENATES FROM A PARAFFIN STREAM}

The present invention relates to a process for removing oxygenate from paraffin or paraffin and olefin mixtures. The present invention is particularly useful for removing oxygenates from C ₁₀ to C ₁₅ paraffins or mixtures of paraffins and olefins before using C ₁₀ to C ₁₅ paraffins or olefins or mixtures thereof in further processes or reactions.

There are many industrial applications for paraffins or olefins or mixtures thereof in the range of C ₁₀ to C ₁₅ . Among these, there is a use as a precursor for linear alkylbenzene benzene (LAB) used to prepare linear alkylbenzene sulfonate (LAS), which is a workhorse surfactant in the detergent industry. In addition, these paraffins or olefins or mixtures thereof can be used as precursors upgraded to higher value fuels. Interest in pollution caused by traditional fossil fuels has increased, and as the source of crude oil has decreased, interest in other energy sources has increased. One promising energy source is a synthetic product of lubricating oil and fuel, other products from natural gas or coal. Gases for fuel processes are often referred to as gas-to-liquids or GTLs, which are often produced by the Fischer-Tropsch process. See, for example, US 4,973,453, which is incorporated herein by reference. Linear paraffins and olefins in the range of C ₁₀ to C ₁₅ are of particular value with respect to these processes.

Synthetic preparation of hydrocarbons by the catalytic reaction of synthesis gas is well known and is generally referred to as a Fischer-Tropsch reaction. The Fischer-Tropsch process was developed in Germany in the early 20th century. It was commercially available in Germany during World War II and later in South Africa.

Syngas (mainly hydrogen and carbon monoxide) is produced from coal or natural gas (methane). The synthesis gas is then converted to liquid hydrocarbons. In many instances, the Fischer-Tropsch reaction for converting syngas was characterized by the following general scheme:

2H ₂ + CO catalyst → -CH _2- + H ₂ O

Hydrocarbon products resulting from the Fischer-Tropsch reaction range from high amounts of methane to high molecular weight paraffinic waxes containing more than 50 carbon atoms.

Many catalysts incorporating active metals such as iron, cobalt, ruthenium, rhenium and the like have been used to carry out this reaction, and both saturated and unsaturated hydrocarbons can be produced. Since the synthesis reaction is very exothermic and temperature sensitive, temperature control is necessary to maintain the desired hydrocarbon product selectivity.

Syngas used in the Fischer-Tropsch reaction can be prepared from natural gas, vaporized coal and other sources. A number of basic methods have been used to produce syngas ("syngas") used as feedstock in the Fischer-Tropsch reaction. Many methodologies and systems that have been used to prepare syngas include partial oxidation, steam reforming, self reforming or autothermal reforming. Both fixed and fluidized beds were used.

The reforming reaction is endothermic and often uses a catalyst containing nickel. Partial oxidation (non-contacting or contacting) involves synthesis stoichiometric combustion of light hydrocarbons such as methane. Partial oxidation reactions are typically carried out commercially using high purity oxygen.

In some cases, these syngas production methods can be combined to form other methods. Furthermore, a combination of steam reforming and partial oxidation has been used so far known as autothermal reforming which can use air as the oxygen containing gas for the partial oxidation reaction to produce synthesis gas. Autothermal reforming, a combination of partial oxidation and steam reforming, provides the heat generated during partial oxidation to the heat required for the endothermic steam reforming reaction. The autothermal reforming process typically can be carried out in a relatively inexpensive refractory lined carbon steel vessel and thus involves a relatively low cost.

In addition, the Fischer-Tropsch process for preparing paraffins and paraffin / olefin mixtures produces a wide range of oxygenates. These oxygenates, including aldehydes, acids, ketones and alcohols, are detrimental for a wide range of applications of such paraffins or olefins or mixtures thereof. In particular, the catalysts used to further treat the paraffins and paraffin / olefin mixtures with their desired end products are contaminated by oxygenates. Oxygenate content is 200 in the paraffin / and / or olefins stream untreated to treat the paraffins or olefins or mixtures thereof so as not to contaminate the adsorbent / catalyst or to be detrimental to the treatment of the paraffins or olefins or mixtures thereof. From about 400 parts per million (ppm) to less than 1 part per million.

Many different adsorption methods have been proposed for removing oxygenates from lower carbon paraffins, ie paraffins having an average of about C ₅ . For example, US Pat. No. 6,111,162 treats hydrocarbons having 3 to 8 carbon atoms by removing oxygenated contaminants with an adsorbent comprising silica gel. US Pat. No. 5,427,689 uses a sorption composition comprising aluminum borate and zirconium borate to prepare a number of compounds including water, alcohols, ethers, aldehydes, ketones, amines, mercaptans, organic sulfides and carboxylic acids from hydrocarbons containing 1 to 10 carbon atoms. The polar substance of was removed. US 4,404,118 teaches the removal of oxygenates from a stream comprising C ₄ hydrocarbons. However, until now, no method of sufficiently removing the oxygenate from the higher carbon (C ₁₀ to C ₁₅ ) paraffins and paraffin / olefin mixtures used in the method of the present invention has not been proposed. This mixture comprises 0 to 50% by weight olefin and 50 to 99.99% by weight paraffin. Many different oxygenates are often found in paraffin and paraffin / olefin mixture feeds prepared by the Fischer-Tropsch process and remove all oxygenate species for use in paraffin and paraffin / olefin mixtures in a wide range of processes. You need to find a general way to do this.

Thus, it is considered desirable to remove these compounds that coexist from paraffin and paraffin / olefin mixture feeds. In addition, in many applications of the present invention, it is desirable to be able to regenerate the adsorbent used to remove the oxygenate from the paraffin and paraffin / olefin mixture feed. Significant savings can be made in that the adsorbent can be reused after regeneration of the bed rather than frequent bed replacement.

Summary of the Invention

The present invention comprises the steps of passing a feed trend comprising at least one C ₁₀ -C ₁₅ feed paraffin, an olefin mixture and at least one oxygenate to remove substantially all of the oxygenate; And if present, a process for removing oxygenate from a stream comprising from 50 to 99.99% by weight of paraffin and from 0 to 50% by weight of olefin, comprising recovering the paraffin (s) and olefin. The level of oxygenate is below the level detectable using standard laboratory procedures such as gas chromatography. In some embodiments of the present invention, it is believed that it is necessary to direct the paraffin rich trend to the second adsorption layer comprising molecular sieves to ensure the completion of the oxygenate impurity removal. Typically, a 5A polishing layer is used to complete their removal from the paraffin rich stream. The present invention is particularly useful for purifying feed streams for certain reactions. Traces of oxygenate can have deleterious effects on the adsorbent / catalyst. The process improved by the removal of the oxygenate according to the invention is the process of dehydrogenation of normal paraffins to olefins and the separation of normal paraffins from branched and cyclic hydrocarbons. If the feed is a mixture of paraffins and olefins, this stream is suitable for the direct alkylation reaction with benzene after the oxygenate removal treatment before forming the alkylated benzene. Thus, one embodiment of the present invention provides a paraffin stream comprising C ₁₀ to C ₁₅ paraffins comprising at least one adsorbent selected from the group consisting of silica gel, activated alumina and alkali or alkaline earth metal cation exchange X-zeolites. Passing through the adsorbent bed above, the adsorbent removes substantially all of the oxygenate from the paraffin stream by adsorption, and then passes the paraffin stream through a reactor containing a dehydrogenation catalyst to pass at least a portion of the paraffin stream into an olefin. A method of dehydrogenation of normal paraffins to olefins, comprising the step of converting. Another embodiment of the invention provides a paraffin stream comprising C ₁₀ to C ₁₅ paraffins comprising at least one adsorbent layer comprising at least one adsorbent selected from the group consisting of silica gel, activated alumina and alkali or alkaline earth metal cation exchange X-zeolites. Passing through the adsorbent to remove substantially all of the oxygenate by adsorption from the paraffin stream, and then passing the paraffin stream through an adsorption bed comprising molecular sieve to separate n-paraffins from the paraffin stream. It includes a method to include.

Another embodiment of the invention provides a stream comprising 50 to 99.99% C ₁₀ to C ₁₅ paraffins and 0 to 50% olefins selected from the group consisting of silica gel, activated alumina and alkali or alkaline earth metal cation exchange X-zeolites. Passing through at least one adsorbent bed comprising at least one adsorbent, wherein the adsorbent removes substantially all of the oxygenate from the stream by adsorption, combining the benzene with the stream, and obtaining the alkylated stream with an alkylation catalyst. Passing through the reactor containing it to convert at least some of the olefins to alkylated benzene.

Detailed description of the invention

The present invention comprises the steps of passing a feed stream comprising at least one C ₁₀ to C ₁₅ feed paraffin or paraffin and olefin mixture and at least one oxygenate through an adsorption bed to remove substantially all of the oxygenate and paraffin or paraffin Recovering the oxygenate from the paraffin and olefin mixture or paraffin rich stream comprising recovering the olefin mixture. Typically, paraffin and olefin mixtures referred to herein as olefin rich streams will comprise up to 50% by weight of olefins with residues and impurities comprising paraffin. Up to 1% of the paraffin and olefin mixtures or paraffin rich streams will comprise oxygenate impurities which must be removed by the present invention. In paraffin rich streams, the stream typically contains 99% by weight of paraffin and sometimes up to 99.99% by weight of paraffin. It has been found that in these typical paraffin rich or olefin rich paraffin streams produced in the Fischer-Tropsch process, a technique for making gaseous liquid fuels, a number of hydrocarbon oxygenates are produced, including alcohols, aldehydes, ketones and acids. Substantially all oxyge for use of such paraffins or olefin rich paraffins without contaminating the adsorbents / catalysts used in these methods, such as the conversion of paraffins to olefins, alkylation of benzene and olefins and separation of n-paraffins from other paraffins. It is necessary to use a method of removing the nate. Table 1 illustrates an extensive list of oxygenates found in three samples of paraffin or olefin rich paraffins prior to treatment by the method of the present invention, all of which are removed by the method of the present invention. All numbers are in parts per million.

compound Feed 1 Feed 2 Feed 3 1-nonanol 1.6 12.1 3.6 2-nonanol <0.4 1.6 1.8 1-decanol 2.2 14.0 12.1 2-decanol 0.4 4.5 3.3 3-decanol <0.4 <0.4 9.2 4-decanol 0.3 4.2 3.1 Unk C10 Alcohol <0.4 <0.4 <0.4 1-Undecanol 1.6 9.0 4.3 2-undecanol 1.4 4.5 3.9 3-undecanol 0.9 3.3 4.8 4-Undecanol 0.6 2.1 5.2 Unk C11 Alcohol 0.8 3.2 5.7 1-dodecanol 0.5 1.0 1.4 2-dodecanol 4.6 8.0 <0.4 Unk C12 Alcohol 6.0 15.3 <1.0 1-tridecanol <0.4 <0.4 <0.4 Unk C13 Alcohol 3.1 6.7 <0.4 1-tetradecanol <0.4 <0.4 <0.4 Unk C14 Alcohol 1.0 0.5 <0.4 1-octane egg 4.5 4.9 4.3 1-nonanal 4.2 6.7 7.7 1-decanal 3.9 8.3 16.9 1-Undecanal 3.0 7.2 17.1 1-dodecanal <0.6 1.4 <1.0 1-tridecanal <0.5 <0.5 <1.0 2-heptanone 0.7 1.6 <0.4 2-octanone 1.5 3.8 <0.4 2-nonanion 2.4 6.6 0.6 2-decanon 3.1 10.1 2.9 2-Undecanon 3.3 11.3 3.5 2-dodecanol 1.6 5.7 1.0 Unk C11 Ketone 2.2 1.0 5.2 Unk C12 Ketone 1.3 5.4 6.1 Butanoic acid 3.3 1.2 1.6 Pentanic acid 6.7 2.4 1.6 Hexanoic acid 10.4 3.6 3.3 Heptanoic acid 12.8 4.5 4.3 Octanoic acid 14.3 4.7 6.7 Nonan 16.0 5.3 9.4 Decanoic acid 16.7 5.1 10.1 Undekansan 12.0 4.0 15.4 Lauric acid 6.6 2.4 12.6

Table 2 summarizes the types of oxygenates found in the feed.

compound Feed 1 Feed 2 Feed 3 Alcohol 25.0 90.0 58.4 Aldehyde 15.6 28.5 46.0 Ketone 12.6 39.1 8.0 mountain 98.8 33.2 65.0

In the practice of the present invention, a paraffin rich or olefin rich paraffin stream is first passed through an adsorption bed containing at least one adsorbent selected from the group consisting of silica gel, activated alumina and alkali or alkaline earth metal cation exchange X-zeolites. X-zeolites have a Si / Al ₂ ratio of 2.0 to 3.0. Preference is given to X-zeolites having a Si / Al ₂ ratio of 2, 2.3 or 2.5.

In addition to the removal of oxygenates, in some embodiments of the present invention, it is necessary to remove compounds containing other elements from group VIB of the Periodic Table of Elements. In particular, when using low quality gas well condensates containing up to 0.7% by weight mercaptans, sulfides and disulfides, this stream is detrimental to the platinum catalysts used to produce LAB. It is highly desirable to reduce the sulfur compound below wppm. Sulfur compounds can be removed using adsorbents known to those skilled in the art. It is advantageous to use an adsorption bed comprising a PEP adsorbent, ADS-102, available from UOP LLC of Des Plaines, Illinois.

The adsorption bed can only process paraffin rich or olefin rich paraffin streams, or can be integrated with chemical conversion processes using paraffin streams to effect other separations. The dedicated adsorption layer substantially removes oxygenate from the paraffin stream regardless of whether its only purpose is to pass through the paraffin stream alone or whether the paraffin stream is combined with a chemical conversion process stream to pass this bed through the bed. It is. In the integrated adsorption bed, the paraffin stream and the process stream are combined and the adsorption bed acts to remove one or more components in the process stream. For example, in an alkylation process that produces alkyl benzene from paraffins, the paraffins are dehydrogenated and the dehydrogenation stream is typically passed through an adsorption bed such as zeolite 13X to remove undesirable aromatics. In this process, the paraffin stream is preferably fed after dehydrogenation and prior to adsorption of aromatics and water in the adsorption layer.

If dedicated, the adsorption layer is typically operated at a temperature of 25 to 60 ° C., preferably at a temperature slightly above ambient temperature (40 ° C.). Although it has been found that this adsorption layer reduces the level of oxygenate below the level that can be measured by gas chromatography, all of the oxy Further measurements are needed to ensure that the ganate is removed. Thus, in a preferred embodiment of the present invention, it has been found that a second adsorption layer containing a 5A adsorbent operating at elevated temperatures of 150 to 200 ° C. removes any residual oxygenate not removed by the first layer. The adsorption bed integrated with the process using paraffin rich or olefin rich paraffin streams is generally operated under conditions suitable for the process.

The adsorption layer reaches its capacity for removing the oxygenate from the paraffin rich stream, followed by a regeneration procedure to remove the adsorbed oxygenate from the adsorption layer. The gas or liquid is sent through the layer, which is maintained at elevated temperature for a period of time sufficient for the layer to be regenerated through removal of the oxygenate. In one embodiment of the regeneration method, nitrogen was used as the regeneration gas at 3000 GHSV, and the layer was first heated to 130 ° C. for 2 hours and then the temperature was increased to 250 ° C. for more than 3 hours. Other regeneration gases or liquids can be used, such as available process streams. The layer can also be regenerated according to the procedure described in US 6,225,518 B1, which is incorporated herein by reference in its entirety. Usually, because of the low concentration of oxygenate, the process regenerates or replaces the integrated adsorption layer based on its performance.

FIG. 1 shows the feed breakthrough in 1000 ppm alumina adsorbent of 2-undecanone, 2-undecanol, decyl alcohol, lauric acid and 2-dodecanol, respectively.

FIG. 2 shows the feed breakthrough in 1000 ppm silica gel adsorbent of 2-undecanone, 2-undecanol, decyl alcohol, lauric acid and 2-dodecanol, respectively.

FIG. 3 depicts feed breakthrough in 1000 ppm of different silica gel adsorbents of 2-undecanone, 2-undecanol, decyl alcohol, lauric acid and 2-dodecanol, respectively.

FIG. 4 depicts feed breakthrough in 1000 ppm 13X adsorbent of 2-undecanone, 2-undecanol, decyl alcohol, lauric acid and 2-dodecanol, respectively.

Laboratory tests consisted of determining the removal content of oxygenate from hydrocarbons. The method was performed on a 20 ml stainless steel column. The column is installed in a sealed box and packed with 20 ml of adsorbent. Initially, the temperature of the sealed box is raised to the desired temperature (40 ° C. in this example). After stabilizing the temperature, the oxygenate containing hydrocarbon feed is introduced at a flow rate of 4 LHSV. Effluents are collected and analyzed for oxygenate impurities. The feed tested contained 1000 ppm of each of five typical kerosene containing oxygenate: 2-undecanone, 2-undecanol, decyl alcohol, lauric acid and 2-dodecanol. Very steep breakthroughs were recorded with alumina, silica gel and sodium X-type adsorbents. In FIG. 1, the alumina tested as adsorbent was spherical promoted alumina sold by Des Planes UOP LLC, Illinois as 9139A activated alumina. The capacity of the adsorbent was 21.95 wt%. In FIG. 2, the adsorbent was an Eagle 32-950 silica gel sold by Alabama Mobile Eagle Chemical Co, Inc. The capacity of the adsorbent was 19.76 wt%. In FIG. 3, the adsorbent used was silica gel Grace 408 sold by W. R. Grace of Grace Davison division, Columbia, Maryland. The capacity of the adsorbent was 32.33 wt%. In FIG. 4, Molsiv adsorbent MRG-E is used and sold by Death Planes UOP LLC, Illinois. The capacity of the adsorbent was 23.57 wt%. Each number represents the actual capacity of this adsorbent for the oxygenate with a steep breakthrough after the capacity of the adsorbent has been achieved. It is also noted that lauric acid is strongly adsorbed by the adsorbent in all four cases.

Claims (9)

A process for removing oxygenate from a stream comprising from 50 to 99.99% by weight of paraffin and from 0 to 50% by weight of olefins, a) a feed stream comprising at least 50 to 99.99% by weight of at least one C ₁₀ to C ₁₅ feed paraffin, 0 to 50% by weight olefins and at least one oxygenate is passed through an adsorbent bed to substantially all of the above Removing the oxygenate; And b) recovering the paraffin (s) and olefins to form a purified stream from the adsorption bed How to include. The process of claim 1 wherein the adsorption layer comprises at least one adsorbent selected from the group consisting of alumina, silica gel and alkali or alkaline earth metal cation exchanged X-zeolites. The method of claim 2, wherein the adsorption layer comprises NaX zeolite. The process of claim 1, wherein the adsorption layer is regenerated to remove the oxygenate, and the regeneration is performed by heating the adsorption layer to a sufficient temperature for a sufficient time and regenerating the regeneration gas. Passing through an adsorption bed to remove the desired portion of the oxygenate from the adsorbent. The process of claim 1, wherein the paraffin and olefin streams are passed through the adsorption bed and the purified stream is passed through a second adsorption bed comprising a 5 A adsorbent from the purified stream. Further removing the oxygenate. The process of claim 1, wherein the paraffin and olefin stream is a feed stream for a chemical conversion process using an adsorption bed and the adsorption bed for removing the oxygenate is adsorbed within the process. Method comprising a layer. The process of claim 6 wherein the chemical conversion process is for benzene alkylation comprising dehydrogenation of paraffins, removal of aromatics in the adsorption layer and reaction of dehydrogenated paraffins with benzene, wherein the adsorption layer for removal of oxygenate is A adsorption layer for removal of aromatics. 7. The process of claim 6 wherein said paraffin and olefin stream is fed to a chemical conversion process after dehydrogenation and prior to removal of aromatics from the adsorption bed.  8. The method of claim 7, further comprising separating the n-paraffins from the paraffin stream by passing the paraffin stream through an adsorption bed comprising molecular sieves.

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