Method for regenerating catalyst for the alkylation of olefins isoparaffins

 

(57) Abstract:

The invention relates to a new method of regenerating catalyst alkylation, which contains a sulfone component and method of removal mechanisms of alkylation catalyst, and the specified sulfon is sulfolane, and KRM-absorbent material selected from the group consisting of aluminum oxide, carbon and mixtures thereof. 11 C.p. f-crystals, 3 tab., 2 Il.

The invention relates to the regeneration of the catalytic composition used in the process of conversion of hydrocarbons. In particular, the invention relates to regeneration of a catalytic mixture comprising the compound of the sulfone and the connection of the hydrogen halide used in the alkylation of olefinic hydrocarbons, isoparaffin hydrocarbons.

Recently it was found that a mixture containing the compound of the sulfone and the connection of the hydrogen halide, is an effective catalyst for use in the alkylation of olefinic hydrocarbons, isoparaffin hydrocarbons to obtain alkylate petrol reaction product, or alkylate. This discovery is disclosed or claimed, or both, in several patent applications, such as application Serial N 07/877,336 Abbott and Randoiph, from 01.05.92 hme or more atoms of the hydrocarbon, and highly desirable gasoline is a component of the mixture due to its high octane as fuel for engines.

Despite the fact that the way in which use of the catalytic composition, comprising sulfonovy component and a component of the hydrogen halide, get alkylate very high quality, a side effect from the use of this method in the production of alkylate is the formation of some polymer side reaction products, such as products, specified as oil, soluble in acid, or LOC (ASO). These polymeric by-products of the reaction are indicated as oil, soluble in acid, because they are soluble in the catalyst used in the alkylation process: and, therefore, remain in the phase of the catalyst, when alkylate petrol product obtained by contact of the mixture of hydrocarbons from the alkylation catalyst is separated from the alkylation catalyst. In the method of alkylation, which continuously separates the phase of the catalyst from the reaction product of alkylation for reuse in the reaction zone of the process, the catalyst has the education KRM. After some time the concentration of the KRM will reach n is alkilirovanija, including sulfonovy component and the component of the hydrogen halide, has a beneficial effect on the process of hydrogen halide, has a beneficial effect on the alkylation process or product. However, higher concentrations of LOC in the alkylation catalyst have an adverse impact on the catalytic activity and final product alkylate petrol. The concentration of the LOC in the alkylation catalyst, which exceeds certain limits, will lead to lower final octane alkylate petrol product, with the growing increase in the concentration of KRM generate increasing reduction in octane alkylate.

In conventional methods of alkylation, in which the catalyst using hydrogen fluoride (HF), as opposed to using the above-mentioned new catalyst comprising sulfonovy component, and a halide component, there are some known methods used for the removal mechanisms of the HF catalyst used in a continuous alkylation process. In particular, process, or regenerate, a sufficient portion of the HF catalyst used in the alkylation process, in order to remove the number of LOC pcredemo transmission part of the HF catalyst in deformirujuschij vessel, whereby HF released from KRM using vaporous hydrocarbon, such as isobutane, with the HF exits the Stripping vessel as part of the vapor top stream, and KRM comes out of the Stripping vessel as the bottom stream for further processing.

Despite the fact that conventional methods of regeneration of the catalyst alkylation work well for the regeneration of normal HF catalyst, conventional tools cannot be used for the regeneration of catalytic alkylation mixture, which includes sulfonovy component. This is because the temperature limits boiling mechanisms overlap with boiling points of some sulfones, such as sulfolane. Therefore, simple methods of distillation used to separate HF from the LOC cannot be used for effective regeneration sulfon-containing alkylation catalyst. Additionally, it is necessary to separate from KRM sulfone, in order to restore sulfon for reuse as a catalyst in the alkylation process.

Therefore, the purpose of this invention is to develop a new method for the regeneration of catalysts for alkylation.

Another purpose of this and the component.

The next objective of this invention to provide a new composition of oil, soluble in acid, obtained as a by-product of the reaction in the method of alkylation, which use a catalyst containing sulfonovy component.

Thus, the method of the present invention relates to the alkylation of olefinic hydrocarbons of the paraffin hydrocarbons by using a catalytic mixture comprising sulfonovy component. Sulfon-containing mixture comprising sulfon and KRM, is subjected to contact with an adsorbent to remove at least part of the component KRM sulfon-containing mixture.

The composition of the present invention is an oil-soluble acid, obtained as a by-product of the reaction in the method of alkylation, including the stage of contacting a mixture of hydrocarbons including olefins and ISO, with a catalytic mixture comprising sulfonovy component and the component of the hydrogen halide.

In Fig. 1 presents a schematic representation of the method, which is one embodiment of the invention; Fig. 2 presents a graph showing the ability of activated plastics technology: turning & the.

Other objectives and advantages of the invention are evident from the subsequent detailed description of the invention and the accompanying claims.

The new composition of the oil, soluble in acid, the present invention is obtained as a side product of the reaction in the method of alkylation, including the stage of contacting a mixture of hydrocarbons which includes olefins and ISO, with the alkylation catalyst, which comprises, consists of, or consists essentially of a component of the hydrogen halide and sulfonic component. In this description and in the claims, the term oil-soluble acid, or LOC, means such United polymers, which are vysokooktanovyj oils obtained in the reactions of hydrocarbons catalyzed by acid. Detailed description and characteristics of some types of the United polymers oils are presented in Journal of Chemical and Engineering Data in the article, Miron and Lee. The molecular structure of the United polymers. so 8, No. 1, S. 150-160. This article here is the link. Physical properties-mechanisms depend on the particular processed hydrocarbons, the catalyst used in the method, contaminants of raw materials such as hydrogen sulfide, butadiene, omogo here of the term, KRM will be the United polymer, which is obtained as a byproduct in the catalyzed reaction of monoolefins with the ISO using a catalytic mixture comprising, consisting of, or consisting essentially of sulfonic component and the component of the hydrogen halide. The preferred monoolefins for use in catalyzed reactions are those which have from three to five carbon atoms, and the preferred ISO are those that are from four to six carbon atoms. Preferred sulfonic component is sulfolan, but preferred component of the hydrogen halide is hydrogen fluoride.

A byproduct KRM obtained from the reaction of hydrocarbons catalyzed sulfon-containing alkylation catalyst, can be further characterized by the fact that it has a specific gravity relative to water at 60oF as a reference point, in the range of about 0.8 to 1.0, the average molecular weight in the range of about 250-350, and bromine number in the range of about 40-350.

Component hydrogen halide catalyst composition or catalyst mixture can be selected from the group connection status is rd. The preferred component of the hydrogen halide, however, is hydrogen fluoride, which can be used in the catalytic composition in the anhydrous form; but, in General, a component of hydrogen fluoride, which is used, can have a small amount of water. In catalytic composition comprising hydrogen fluoride and sulfolane, the amount of water present in any case can not be more than about 30 wt.% the total weight of the component hydrogen fluoride, which includes water.

Preferably, the amount of water present in the hydrogen fluoride is less than about 10 wt.%. Most preferably, the amount of water present in the hydrogen fluoride is less than about 7 wt.%. When the links here on the component of the hydrogen halide, or, in particular, to a component of the fluoride of hydrogen, the catalytic compositions of the invention should be understood that these terms signify that the hydrogen halide is either anhydrous mixture, or nerazvodnoy mixture. References to the weight percentage of water contained in the component of the hydrogen halide, means the ratio of water mass to the total mass of water and hydrogen halide, multiplied by the cylinder is I in this invention, are the sulfones of General formula

R-SO2-R',

in which R and R' are monovalent carbon alkyl or aryl substituents, and each contains from 1 to 8 carbon atoms. Examples of such substitutes include dimethyl sulfone, di-n-propylsulfonyl, diphenylsulfone, etilmetansul and acyclic sulfones in which SO2the group is linked to a hydrocarbon ring. In this case, R and R' together form a branched or unbranched divalent carbon component, preferably containing 3-12 carbon atoms. Among the latter, in particular, are more appropriate tetramethylarsonium or sulfolane, 3-methylsulfone and 2,4-dimethylsulfone, because they have the advantage of being liquid under the operating conditions of the process used here. These sulfones may also have substituents, in particular one or more halogen atoms, such as, for example, chlorotrimethylsilane. These sulfones can usefully be used in the form of mixtures.

The alkylation catalyst used in the method of alkylation, which receive KRM side reaction product may contain, consist of or consist essentially of a halide component of vtoroligovoy, in which the hydrocarbon mixture is brought into contact with the alkylation catalyst having sulfolan as it sulfonic component, and hydrogen fluoride as a component of the hydrogen halide. When the alkylation catalyst includes sulfolane and hydrogen fluoride, it is possible to achieve good results alkylation at a weight ratio of hydrogen fluoride to sulfolane in the alkylation catalyst in the range of about 1:1 to 40:1. The preferred weight ratio of hydrogen fluoride to sulfolane may lie in the range of approximately 2.3:1 to 19:1, and more preferably, it may lie in the range 3:1 to 9:1.

To obtain the LOC by-product from flowing out of the stream or the product of the alkylation reaction can be any suitable means to highlight LOC byproduct of the product alkylate petrol. One example of suitable means of selection is the assumption of phase separation between the alkylation catalyst and alkylate petrol product, which is usually a mixture silkroadonline paraffin hydrocarbons, other paraffin hydrocarbons, other paraffin hydrocarbons and alkylate with the subsequent removal mechanisms of phase catalyst CLASS="ptx2">

To obtain selectivity of the alkylation reaction of the present invention to the production of desirable silkroadonline aliphatic hydrocarbons having seven or more carbon atoms, the reaction zone is desirable substantial stoichiometric excess of isoparaffin hydrocarbons. It is assumed that the molar ratio of isoparaffin hydrocarbons to olefinic hydrocarbons in the present invention comprise about 2:1 to 25:1. Preferably, the molar ratio of isoparaffin-to-olefin will be within the range of about 5-20; and, most preferably, will be in the range of 8-15. We emphasize, however, that the above ranges for the molar ratio of isoparaffin-to-olefin are those ranges that were found, are practical operating ranges from a commercial point of view; but, in General, the larger the ratio isoparaffin-to-olefin in the alkylation reaction, the better the quality of the resulting alkylate.

The present invention assumes that the temperature of the alkylation reaction are in the range of about 0-150oF. lower temperatures are more conducive alkylation reaction of isoparaffin with olefin compared to konkuriruyuschej temperatures. The temperature in this range, and preferably in the range of about 30-150oF, provide good selectivity for alkylation of isoparaffin with olefin at attractive from a commercial point of view the speed of reactions. Most preferably, however, the temperature of the alkylation should be within the range of 50-120oF.

The present invention assumes that the pressure of the reaction can vary from a pressure sufficient to maintain reactants in the liquid phase, to about fifteen (15) ATM pressure. Reactive hydrocarbons usually can be in a gaseous state at temperatures alkylation reaction, so are preferred pressure of the reaction in the range from about 40 pounds per square inch (psig) to about 60 psig. When all the reactants are in the liquid phase, high blood pressure has no significant effect on the reaction of alkylation.

The time of contact of the hydrocarbon reactants in the reaction zone, the alkylation, in the presence of the alkylation catalyst of the present invention, should be sufficient to ensure essentially complete conversion of the reacting olefin in the alkylation zone. Preferably, the contact time of leitneria of isoparaffin-to-olefin in the range of about 2:1 25: 1, where the mixture alkylation reaction contains approximately 40-90% vol. phase catalyst and about 60-10% vol. the hydrocarbon phase, and where support good contact of the olefin with isoparaffins in the reaction zone, it is possible to achieve essentially complete conversion of olefin and bulk velocity of the olefin in the range of about 0.1-200 volumes of olefin per hour per volume of catalyst (about/about/h). The optimum flow rate will depend on the type of reactive isoparaffins and olefins, the specific compositions of the alkylation catalyst and the reaction conditions for the alkylation. Therefore, the preferred contact times are sufficient to ensure the flow rate of the olefin in the range of about 0.1-200 (V/V/h) and allow essentially complete conversion of the reacting olefin in the alkylation zone.

The alkylation process can be performed in the operating mode or type of portions or a continuous way, although for economic reasons it is preferable to carry out the process continuously. In General it is established that in the process of alkylation, the closer the contact between the feedstock and the catalyst, the better the quality of the product alkylate petrol. With this in mind, the present method when the operation portions of otlicials the tx2">

In continuous mode, in one embodiment, the reagents may be located at sufficient pressures and temperatures to retain their essentially in the liquid phase and then continuously introduced through a distribution device in the reaction zone. Distribution devices may be nozzles, nozzles, porous tips, etc. Then the reagents can be displaced from the catalyst by conventional means of mixing, such as with a mechanical stirrer drive or turbulence of the flowing system. After sufficient time the product can then continuously separated from the catalyst and to remove from the reaction system, while the partially spent catalyst returns to the reactor. As described here, part of the catalyst can be continuously regenerate or reactivate any suitable processing and return to the alkylation reactor.

One of the variants of the present invention includes a method of removing mechanisms of sulfon-containing mixture comprising sulfonovy component and LOC, with absorbent material suitable for removal of at least part of the LOC component specified sulfon-containing mixture, to obtain processed sulfon-containing mixture. Adsorbers is aluminum oxide, carbon and mixtures thereof. Preferably sulfonovy component sulfon-containing mixture is sulfolan. KRM component sulfon-containing mixture may be present in an amount of not more than about 20 wt. % of sulfonic component. Preferably the concentration of the LOC is less than 15 wt. % of sulfonic component, and most preferably, the LOC will be present at a concentration of less than 10 wt.%. Processed sulfon-containing mixture will have a lower concentration of KRM, in General, constituting less than 2 wt.% sulfon-containing mixture. Preferably, the LOC will be present in amount less than 1 wt.%, most preferably, the LOC will be present in amount less than 0.1 wt.%.

Another variant of the method of this invention involves the resolution of problems associated with the regeneration of sulfon-containing mixtures of alkylation catalyst, by removing at least part of the mechanisms contained in such mixtures. Accumulation mechanisms in sulfon-containing catalysts for the alkylation takes place when the process of alkylation continuously reuses its catalyst. In a continuous alkylation process KRM side product of the reaction will be obraceni, which can have negative effects on the performance of the catalyst and, ultimately, on the quality of the product of alkylation. In General, it is desirable to maintain the concentration of LOC in sulfon-containing alkylation catalyst at not more than about 20 wt.% from the catalyst, and the weight percentage of the LOC specified in the total weight of the catalytic mixture, excluding LOC component. Preferably the concentration of the LOC in sulfon-containing alkylation catalyst is less than about 15 wt.%, most preferably, the concentration of the LOC is less than 10 wt.%. While maintaining a low concentration mechanisms in sulfon-containing catalytic mixture may be some advantages in the way, but I believe that the concentration LOC greater than about 10 wt.% from catalyst will have an adverse effect on the performance of the catalyst.

Thus, in order to maintain catalytic activity sulfon-containing mixture of alkylation catalyst, the catalyst must be processed to remove at least part of the mechanisms contained in this catalyst. To achieve this, sulfon-containing mixture of catalyst alkylation bring the mixture containing a series of alkylation catalyst. It should be noted that in General it is desirable to have at least part of the hydrogen halide sulfolan-containing alkylation mixture, remote until contact is obtained sulfon-containing mixture, which includes sulfonovy component, a component of hydrogen halide and LOC, with the absorbent material, thereby removing at least part of the LOC component. Therefore, sulfon-containing mixture will be sulfon-containing catalytic alkylation mixture having at least part of the hydrogen halide remote. You can use any suitable method for separating a component of the hydrogen halide from sulfon-containing mixture of alkylation catalyst, such as for example, thin-layer separation, distillation, extraction, deformirovanie and other suitable separation methods. One of the preferred methods is to use tools deformirovaniya to separate sulfon-containing mixture of alkylation catalyst in the upper stream, comprising the main portion of the component of the hydrogen halide sulfon-containing alkylation catalyst, and a bottom stream comprising sulfon-containing mixture, with the use of maroobra the concentration of the component of the hydrogen halide in sulfon-containing mixture will be less than about 10 wt.% mixture, where the weight percent is determined by the mass fraction of hydrogen halide to the total mass of hydrogen halide and sulfone, multiplied by 100 to obtain percentage. Because it is very difficult to remove all of the hydrogen halide from the mixture, the lower limit of the concentration of hydrogen halide from a practical point of view may be closer to about 0.1 wt.%, but, preferably, the concentration may be less than 0.1 wt.%. Thus, the range of concentration of hydrogen halide in the mixture may be within the range of about 0.1-10 wt. %. Preferably, however, the concentration may be within the range of about 0.1 to 7.5 wt.%, and most preferably, it may have values in the range of 0.1-5.0 wt.%.

In General, absorbent material offered by this invention can be contained within a vessel that defines an area of contact, which sulfon-containing mixture can be subjected to contact with the absorbent material. However, the invention is not limited to the use of standard vessels for determining the area of contact, can be any suitable means known in the art, for contacting sulfon-containing with the n-containing mixture, can be any adsorbent, which can either appropriately or effectively, to remove at least part of the LOC component contained in such a mixture. Preferably, the absorbent material selected from the group consisting of alumina, carbon and mixtures thereof.

Carbon adsorption material can be any activated carbon material, which is suitable for use in accordance with the fact, as suggested by this invention, and for the selective removal of at least part of the LOC component contained in sulfon-containing mixture. Activated hydrocarbon adsorbent may vary its large specific surface area, which can vary from approximately 300 m2/g to about 2500 m2/g, as determined by the standard test method D 3663-84 American society for testing and materials (ASTM), entitled "Standard test method for surface area of catalysts", ASTM standard test D 3663-84 provided herewith and forms part of this link. Also the activated carbon adsorbent can be further characterized by the diameter of its pores, which can have values in the range of approximately 10-50 microns is artny test method using mercury porometry". Standard ASTM test D 4284-88 provided herewith and forms part of his reference. In General it is desirable to use commercially available activated carbon. One such commercially available activated carbon is, for example, the product known under the trade name Calgon Filtrasorb 400, which is produced and sold in the market Calgon Carbon Corporation.

Absorbent material based on aluminum oxide can be any alumina suitable for use in accordance with the fact, as suggested by this invention, and for the selective removal of at least part of the LOC component contained in sulfon-containing mixture, or for use as a neutralizing agent to remove at least part of the component of the hydrogen halide sulfon-containing stream. Such suitable oxides include aluminum, for example, many commercially available activated alumina and calcined alumina. In General, the material of the aluminum oxide will have a surface area in the range of about 150-500 m2/g, as determined by ASTM D 3663-84. Also, the diameter of pores of the material of the aluminum oxide will have values in the range of about 25-125 microns, as determined the x commercially available alumina is a product known under the trade designation HF-200, manufactured and sold on the market company Alcoa. The preferred aluminum oxide for use in this invention is calcined alumina, with gamma crystalline structure, also known as gamma-alumina, and other oxides of aluminum, such as Chi-alumina having a surface area greater than about 50 m2/,

The process conditions under which sulfon-containing mixture is subjected to contact with the absorbent composition may be any conditions that are suitable or effective for removal of at least part of the concentration LOC of a mixture of alkylation catalyst. I believe that the effectiveness of an adsorbent material to remove the not-too-depends on the pressure at the contact, since it is considered that the phenomenon of adsorption is the result of interaction of the solid-liquid; however, the process pressure should be less than about 0.5 atmospheres of absolute pressure and can have values in the range up to about 30 atmospheres, or more absolute pressure. Most normal operating pressure will in General lie the range from about atmospheric pressure to primernaya, you can use any suitable temperature that provides effective removal of at least part of the mechanisms of sulfon-containing mixture. Typically, the upper and lower temperature limits are determined by the physical characteristics of the treated mixture and the physical characteristics of the mechanisms contained in such a mixture. When considering the lower limit of the temperature it should be noted that the melting point of pure sulfolane is about 81,3-82,0oF, but when sulfolane is in the form of a mixture of water and hydrogen fluoride, the melting temperature is much lower. Therefore, the lower limit of the temperature probe approaches the 0oF. with regard to the upper limit temperature, it is determined by such factors as the initial boiling point LOC, and the temperature at which sulfonovy component mixture begins to thermally decompose. Thus, the upper temperature probe is approaching 400oF. Therefore, the temperature of contact in General will be within the range of about 0-400oF. Preferably, the temperature probe will be within the range of about 50-350oF, and most preferably will be within the range of 60-3252and NaOH; basic oxides such as zinc oxide and tin oxide; and amphoteric oxides, such as alumina. Preferred neutralizing agents can include various types of aluminum oxide and hydroxide compounds. The most preferred neutralizing agent is gamma-alumina.

As described previously, it is desirable that the component of the hydrogen halide sulfon-containing mixture of alkylation catalyst, contaminated LOC, would be minimized to contacting the resulting sulfon-containing mixture with a neutralizing agent. In particular, when a significant part of sulfon-containing mixture of alkylation catalyst comprises a hydrogen halide, for example, when the mass ratio of hydrogen halide to sulfolane is in the range of about 1:1 to 40:1, preferably, the main part of the hydrogen halide has been removed from the catalytic mixture to obtain sulfon-containing mixture or restored catalytic mixture. This sulfon-containing mixture or regenerative catalytic mixture may include, consist of, or consist essentially of sulfonic component, a component of hydrogen halide and KRM. In General is the Eney, than about 10 wt.% the catalytic mixture, where the mass percentage is determined by the mass fraction of hydrogen halide to the total mass of hydrogen halide and sulfone, multiplied by 100 to obtain percentage. Because it is very difficult to remove all of the hydrogen halide from the catalytic mixture, the lower limit of the concentration of hydrogen halide may be closer to about 0.1 wt.%, but, preferably, the lower limit of the concentration of hydrogen halide may be less than 0.1 wt.%. Thus, the range of concentration of hydrogen halide in the regenerative catalytic mixture may vary approximately 0.1 to 10 wt.%. Preferably, however, the concentration may vary in the range of about 0.1 to 7.5 wt.% and most preferably, it can vary in the range of 0.1-5.0 wt.%.

With regard to the use of a neutralizing agent or neutralizing material, regenerative catalytic mixture having a content of hydrogen halide, is brought into contact with a neutralizing material, thereby removing a significant part of the hydrogen halide from the regenerative catalytic mixture to obtain a neutralized sulfon-containing mixture. Neutral is, who will have a concentration of less than about 2.0 wt.%. Preferably neutralized sulfon-containing catalytic mixture will have a concentration less than about 1.0 wt.%, and most preferably, it will have a concentration of less than 0.1 wt.% the hydrogen halide.

Neutralization regenerative catalytic mixture or sulfon-containing mixture will allow further processing or purification neutralized sulfon-containing mixture to remove at least part of the LOC component, not the remote during stage neutralization. A significant part of the LOC component neutralized catalyst is removed by contacting it with an adsorbent material suitable for removal of a significant part of KRM component contained therein, to obtain a regenerated catalyst mixture or processed sulfon-containing mixture. KRM component of the regenerated catalytic mixture or processed sulfon-containing mixture will, in most cases, be present at a concentration of less than about 2 wt.% from the total mass sulfonic component. Preferably the weight percentage of the mechanisms present in the treated sulfon-containing mixture, mosinee than 0.1 wt.%. The regenerated catalyst mixture or processed sulfon-containing mixture can be reused as part of sulfon-containing mixture of alkylation catalyst, comprising, consisting of, or consisting essentially of sulfone and hydrogen halide.

With regard to Fig. 1, there is depicted a schematic representation of the process of alkylation of 10. A mixture of hydrocarbons, including olefins and ISO, is introduced into the reactor riser 12 through the channel 14. The reactor riser 12 defines a reaction zone in which the hydrocarbon mixture is brought into contact or mixed with a catalytic mixture comprising sulfolane and hydrogen fluoride, to obtain a reaction product and by-product of the reaction. The olefin mixture of hydrocarbons usually include one or more olefins having three to five carbon atoms, and ISO mixtures of hydrocarbons will usually have from four to six carbon atoms. The catalytic mixture is introduced into the reactor riser 12 through the channel 16. The mixture of the mixture of hydrocarbons and catalyst mixture passes through the reaction zone defined by the reactor riser 12, where the reaction occurs, in which the olefin mixture of hydrocarbons interact with isometsa side product of the reaction mechanisms. The output stream of the response of the reactor riser 12 is held in the vessel, a settling tank 18, which defines a separation zone for separating alkylate petrol reaction product from the catalytic mixture to obtain a specific reaction product 20 and a separate catalyst mixture 22. Separate catalytic mixture 22 will contain a significant amount of side-product of the alkylation reaction mechanisms. Separate the reaction product 20 is a processing flow downward through the channel 21. The separated catalyst mixture 22 can be recycled through the channels 24 and 16 in the reactor riser 12 for reuse as a mixture of alkylation catalyst. In the channel 24 is inserted refrigerator catalyst 26, which defines the area of heat transfer for heat exchange between the individual catalyst mixture 22 and such liquid coolant, such as water.

At least part, sometimes specified as the slip stream or flow of braking, the separated catalyst mixture 22 passes through the channel 28 in desorbers column 30, which defines a separation zone for separation of the slip stream of the separated catalyst mixture 22 on the upper stream comprising the major part of the hydrogen fluoride contained in the pot is the first thread will also contain the main part of the side reaction product KRM, contained in the slip stream. Through channel 32 introducing vaporous isobutane to deformirovaniya of hydrogen fluoride from the slip stream. The upper stream passes through the channel 34 in the vessel-tank 18, where hydrogen fluoride reunite with the separated catalyst mixture 22 for reuse, and deformirujuschij isobutane connect with a separated reaction product 20.

The bottom stream from desorbitada columns 30 passes through the channel 36 in the first vessel for contact 38, which contains an adsorbent material and defines a separation zone for removal by adsorption or neutralization of a substantial portion of the hydrogen fluoride contained in the lower stream, to obtain a neutralized the bottom of the stream.

Then neutralized bottom stream passes through the channel 40 to the second vessel for contact 42, which contains an adsorbent material and defines a separation zone for the removal of a substantial portion mechanisms contained in the neutralized lower stream, to obtain a regenerated catalyst, or Sultanova stream that is essentially free from LOC and hydrogen fluoride. This sulfolane stream passes through the channel 44 in the vessel sump 18, Volnovaha component mixture of alkylation catalyst.

The following examples demonstrate the advantages of the present invention. These examples are presented only to illustrate, and there is no intention to limit the invention set forth in the accompanying claims.

Example 1. Received KRM by-product obtained from the reaction of hydrocarbons catalyzed by the catalytic mixture of sulfolane and HF, to determine some of its physical properties. The catalytic mixture used in the reaction of hydrocarbons, had a mass ratio of HF to sulfolane about 1.5; and the hydrocarbon loading consisted of isobutane and 2-butenes (60% TRANS, 40% CIS isomers) at a molar ratio of isobutane to 2-butenes about 11. The reaction temperature was approximately 90oF, and the pressure of the reaction was about 90 psig. Table. 1 represents some physical properties, including distillation, obtained mechanisms of reactions of hydrocarbons.

Example 2. This example, in General, describes the experimental method used to obtain data related to the adsorption properties of carbon, aluminum oxide and mixtures thereof, and properties in the neutralization of aluminum oxide.

The usual experimental procedure for testing the use of Matera is Lana and mechanisms included the use of a glass cylinder with a diameter of approximately one inch and a length of 12-24 inches. At the bottom of the cylinder was placed either glass wool or glass beads, to provide the substrate for the active material, and on top of the active material were placed either glass beads or glass wool, to assist in providing uniform distribution of sulfolane-containing mixture of the active material. Optional glass cylinder was heated to induce flow sulfolane-containing mixture through a layer of active material. Sulfolane-containing mixture had a mass ratio sulfolan:KRM approximately 9:1. The color of the obtained filtrate served as an indication of when the adsorption capacity of the active material was consumed, and thereby detect when the experiment was completed.

Example 3. This example illustrates the unexpected correlation between the ability of activated carbon to adsorb LOC from sulfolane-containing mixture of sulfolane and LOC as a function of the concentration of hydrogen fluoride in sulfolane-containing mixture.

The experimental method used to obtain the data presented in table. 2 is essentially similar to that described in example 2. Installed various concentrations of hydrogen fluoride in sulfolane-containing cm is unexpectedly shows the level of acid concentration in sulfolane-containing mixture has an important effect on the ability of activated carbon adsorption mechanisms. These data are also depicted on the graph in Fig. 2.

Example 4. This example demonstrates that various commercial available aluminum oxide can suitably be used to remove HF from sulfolane-containing mixture of sulfolane and mechanisms, either by adsorption or neutralization. Also, this example demonstrates that the alumina can adsorb part of the mechanisms contained in sulfolane-containing compound, and also perform the function of neutralization.

The experimental method used to obtain the data presented in table. 3 is essentially similar to that described in example 2, except that the pH of the output stream of the cylinder was determined when the neutralization ability of aluminum oxide was used, and sulfolane-containing mixture was 5 wt.% the HF concentration. The data presented in the table.3, demonstrate that various commercially available aluminum oxide can suitably be used to neutralize sulfolane-containing mixture with some adsorption mechanisms to kontaktirajte the invention is described from the point of view of the present preferred variant, reasonable variation and modification are possible for specialists. Such changes and modifications fall within the scope of the described invention and the appended claims.

1. Method for regenerating catalyst for the alkylation isoparaffins the olefin-based hydrogen fluoride by removing from the reaction mixture of oil, soluble in acid, which is a side reaction product, wherein the oil-soluble acid is removed from the reaction mixture containing the catalyst is hydrogen fluoride, sulfon General formula

R SO2R1,

where R and R1independently monovalent hydrocarbon radical, represents an alkyl or aryl with 1 to 8 carbon atoms, or R and R1together, branched or unbranched divalent hydrocarbon fragment with 3 to 12 carbon atoms, forming a SO2ring, and R and R1may be substituted by one or more atoms of halogen,

and oil, soluble in acid, by contacting this mixture with an adsorbent oil material selected from the group comprising aluminum oxide, carbon and a mixture thereof.

2. The method according to p. 1, characterized in that as the sulfone catalyst SIM material of the main part of the hydrogen fluoride is removed by deformirovaniya vaporous liquid absorber with getting the top of the thread containing hydrogen fluoride and desorbers liquid, and a bottom stream containing sulfon and oil, soluble in acid.

4. The method according to p. 3, characterized in that as a liquid absorber using isobutane.

5. The method according to p. 3, characterized in that the main part of the hydrogen fluoride is removed from a mixture containing sulfon and hydrogen fluoride with a concentration of 1% or less, preferably 0.1% or less.

6. The method according to PP. 3 and 4, wherein before contacting the reaction mixture with an adsorbent material, or simultaneously with contacting the reaction mixture is treated with a neutralizing agent to reduce the concentration of hydrogen fluoride to a concentration of 1 wt. or less, preferably 0.1 wt. or less of the total content of the sulfone and hydrogen fluoride.

7. The method according to p. 6, characterized in that the neutralizing agent is aluminum oxide.

8. The method according to PP.6 and 7, in which the neutralized reaction mixture is in contact with the carbon as an absorbent material.

9. The method according to PP.1 to 8, characterized in that the contacting with the adsorbent material is carried out with the aim of reducing the oil content of soluble is contacting absorbent material is performed under a pressure from atmospheric up to 0.4 MPa and a temperature of 10 177oC.

11. The method according to PP.3 to 10, characterized in that sulfon after the removal of oil recycle to the alkylation process.

12. The method according to PP.3 and 4, characterized in that the hydrogen fluoride contained in the upper stream, separated from desorbitada fluid and recycle to the alkylation process.

 

Same patents:

FIELD: chemistry.

SUBSTANCE: description is given of a method of obtaining an active phase of a heterogeneous catalyst based on oxides or mixed oxides of transition metals, chosen from a group containing Mo, V, Te, Nb, through successive mixture of aqueous solutions of molybdenum tellurate, vanadium sulphate and niobium oxalate. An aqueous solution of vanadium sulphate is added to the molybdenum tellurate solution first, obtaining a suspension after mixing, which is then added to niobium oxalate. The obtained mixture is further intensively stirred for 10 minutes, kept in an autoclave at 175C for 50 hours and after filtration and washing, roasted at 600C in a stream of inert gas. The heterogeneous catalyst for oxidative dehydrogenation of gaseous mixtures of hydrocarbons is a composite material in form of a mechanical mixture of solid dispersion powders obtained from an active phase and an inactive phase with specific surface area of 1-10 m/g, relative the active dispersion matrix. The method of obtaining the catalyst involves mechanical mixture of powders of active and inactive phases with subsequent pressing, crushing and grading the particles through sieving. Described also is a method of oxidative dehydrogenation of ethane, in which a gas mixture, containing oxygen and ethane in ratio ranging between 1:2.5 and 1:3.5, is fed at pressure of 1 atm and bulk speed of 500-30000 h-1 into a flow reactor with a stationary layer of the heterogeneous catalyst described above, heated to 380-420C.

EFFECT: increased output of the dehydrogenation process, while maintaining high conversion and selectivity.

11 cl, 1 tbl, 4 ex

FIELD: process engineering.

SUBSTANCE: invention relates to chemical industry. System for alkylating olefines by paraffin comprises alkylation reactor and settling tank that comprises top part 122, intermediate part 108 and bottom part 124. Intermediate part 108 comprises at least one system of plates 112 including at least one perforated plate 114 with multiple orifices 116 and a layer of nozzle 118 arranged below said perforated plate 114. Hydrocarbon raw material is fed into reactor 100 via pipeline 104. Settling tank communicates with alkylation reactor 100 via pipeline 106.

EFFECT: lower concentration of organic fluorides in alkylation product.

21 cl, 2 tbl, 8 dwg, 1 ex

FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.

SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.

EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.

20 cl, 2 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to regeneration of basic anionite catalysts for process of production of alkylene glycols via hydration of corresponding alkylene oxides. Method according to invention consists in treatment of spent catalyst with aqueous solution of inorganic salts of iodine and inorganic acids or with hydroiodic acid aqueous solution.

EFFECT: achieved complete restoration of initial volume and selectivity of catalyst and thereby prolonged lifetime of expensive anionite catalyst.

1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method involves, for example: (a) evaporation of said oxidised discharge stream, containing terephthalic acid, metallic catalyst, impurities, water and solvent, in the first zone of an evaporator to obtain a vapour stream and a concentrated suspension of the discharge stream; and (b) evaporation of the said concentrated suspension of the discharge stream in the second zone of the evaporator to obtain a stream rich in solvent and a high-concentration suspension of the discharge stream, where the said second zone of the evaporator has an evaporator operating at temperature ranging from 20C to 70C, where from 75 to 99 wt % of the said solvent and water is removed by evaporation from the said oxidised discharge stream at step (a) and (b); (c) the said high-concentration suspension of the discharge stream is filtered in a zone for separating solid products and liquid to form a filtered product and a mother liquid; (d) washing the said filtered product using washing substances fed into the said zone for separating solid products and liquid to form a washed filtered product and washing filtrate; and dehydration of the said filtered product in the said zone for separating solid products and liquid to form a dehydrated filtered product; where the said zone for separating solid products and liquid has at least one pressure filtration device, where the said pressure filtration device works at pressure ranging from 1 atmosphere to 50 atmospheres; (e) mixing water and optionally extractive solvent with the said mother liquid and with all of the said washing filtrate or its portion in the mixing zone to form an aqueous mixture; (f) bringing the extractive solvent into contact with the said aqueous mixture in the extraction zone to form a stream of extract and a purified stream, where the said metallic catalyst is extracted from the said purified stream.

EFFECT: improved method of extracting metallic catalyst from an oxidised discharge stream obtained during production of terephthalic acid.

36 cl, 3 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention describes method for extraction of homogeneous ruthenium catalyst from glycolic acid hydrogenation reaction product, glycolic acid esters and/or glycolic acid oligomers under action of extractant containing hydrophobic solvent and optional hydrophilic solvent. Ruthenium catalyst, which may include 1,1,1-tris(diaryl- or dialkylfosfinomethyl)alkane ligands, can be extracted from hydrophobic extract phase as result of extraction under action of hydrophilic solvent and sent for recycling in process of producing ethylene glycol as result of glycolic acid and glycolic acid derivatives hydrogenation.

EFFECT: technical result is effective method of ruthenium-1,1,1-tris(diaryl- or dialkylfosfinomethyl)alkane catalyst compositions extracting from glycolic acid hydrogenation waste product till maximum extraction of catalyst system at minimal costs in combined method, taking into account stages of both reaction and separation for producing ethylene glycol.

29 cl, 7 dwg, 26 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to methods of producing a hydroformylation catalyst solution for storage, wherein catalyst solution contains: A. a transition metal in combination with one or more organophosphorus ligands, (B). a certain concentration of acid particles and C. water. First version of method includes a step for reducing concentration of acid particles in catalyst solution to not more than 200 ppm. Second version of method includes a step of mixing catalyst solution with aqueous buffer solution, containing one or more materials, which will neutralise and/or absorb, at least 50 % of acid particles.

EFFECT: proposed versions of method enable to reduce degradation of organophosphorus ligands during temporary suspension of hydroformylation process.

21 cl

FIELD: chemistry.

SUBSTANCE: method of hydrotreating diesel fuel at a temperature of 340-390C, pressure 3-9 MPa, volumetric consumption of raw materials 1.0-2.5 h-1, volume ratio hydrogen/raw materials 300-600 m3/m3 in the presence of a regenerated catalyst having a pore volume of 0.3-0.8 ml/g, a specific surface area of 150-280 m2/g, an average pore diameter of 6-15 nm, including molybdenum, cobalt, sulfur and a carrier in its composition is described. Molybdenum and cobalt are contained in the catalyst in the form of a mixture of complex compounds Co(C6H6O7), H4[Mo4(C6H5O7)2O11], H3[Co(OH)6Mo6O18], sulfur is contained in the form of sulfate anion SO42-, in the following concentrations, wt %: Co(C6H6O7) - 5,1-18,0; H4[Mo4(C6H5O7)2O11] - 7,5-15,0; H3[Co(OH)6Mo6O18] - 4,3-19,0; SO42- - 0,5-2,30; carrier - the rest. Cobalt citrates can be coordinated to molybdenum citrate H4[Mo4(C6H5O7)2O11] and to 6-molybdocobaltate H3[Co(OH)6Mo6O18].

EFFECT: invention makes it possible to produce hydrotreated diesel fuels containing not more than 10 ppm of sulfur in the presence of regenerated catalysts.

3 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: treatment method involves flowable hydroformylation reaction product contacting with an aqueous buffer solution to neutralise at least some of the acid phosphorus compound to form a neutralised acid phosphorus compound. The hydroformylation reaction product comprises an acidic phosphorus compound, a metal complex catalyst with an organophosphorus ligand that contains a group 8, 9 or 10 metal complex forming an organophosphorus ligand complex and optionally a free organophosphorus ligand. The buffer solution contains at least one unsaturated aliphatic carboxylic acid salt. Salt concentration in the buffer solution is 0.001-0.8 M and the pH value of the buffer solution is in the range of 6-8.

EFFECT: effective buffer removal of acid by-products from phosphite ligand degradation and promotion of selective hydrolysis of diorganophosphite by-products without adverse effect on the hydroformylation process.

7 cl, 1 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing poly-alpha-olefin compound. Method involves combined oligomerization of a mixture containing about from 60 to 90 weight% of 1-dodecene and about from 10 to 40 weight% of 1-decene in the presence of BF3 as a catalyst and alcoholic promoter at temperature in the range about from 20°C to 60°C followed by distilling the mixture and hydrogenation to yield poly-alpha-olefin. Product has kinematic viscosity in the range about from 4 to 6 centistokes at 100°C, loss by Noak mass in the range about from 4% to 9%, viscosity index in the range about from 130 to 145 and fluidity loss temperature in the range about from -60°C to -50°C.

EFFECT: improved method of synthesis.

11 cl, 9 tbl, 14 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to preparation of linear dimmers of α-methylstyrene, in particular 2,4-diphenyl-4-methylpenth-1-ene used preparation of polymers used as growth regulators, plasticizers, lacquer solvents, and dielectric liquids. Process is accomplished via dimmerization of α-methylstyrene using, as catalyst, tin(III) chloride at SnCl2/α-methylstyrene molar ratio 1.6:23 at 55°C and atmospheric pressure. Reaction time is 10 min. Selectivity of formation of desired product is 96.1% and α-methylstyrene conversion is 70%.

EFFECT: improved process characteristics and simplified procedure.

FIELD: technological processes.

SUBSTANCE: disclosed is a catalyst composition for oligomerisation of ethylene containing (i) an at least partially hydrolysed transition metal compound which can be obtained by controlled addition of water to a transition metal compound of the general formula MXm(OR')4-m or MXm(OOCR')4-m, where R' is an alkyl, alkenyl, aryl, aralkyl or cycloalkyl group, X is a halogen, preferably Cl or Br, and m denotes a number from 0 to 4, preferably 0-3; and (ii) an organoaluminium compound as a cocatalyst. The molar ratio of water to the transition metal compound is the range of (0.01-3):1. The invention also discloses a method for oligomerisation of ethylene and a method of producing the catalyst composition.

EFFECT: catalyst composition increases the degree of purity of obtained alpha-olefins and minimises formation of wax/polymer in the reactor.

12 cl, 2 tbl, 7 ex

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