JPS63197533A - Catalytic distillation catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to catalyst systems and in particular to reaction mixtures, i.e.
It relates to catalyst systems used in catalytic chemical reactions, in which separation of substances in products, by-products or starting materials is obtained by simultaneous distillation or fractional distillation of the catalytic chemical reaction.

In a particular application, the present invention provides 9
The invention is also particularly useful in separating isobutene from streams containing n-butene.

The present invention can also be used in the production of methyl tert-butyl ether from a stream containing a mixture of isobutyne and normal C4 olefins. The present invention provides n-
It is particularly effective in separating isobutyne from streams containing butenes.

Since the boiling points of isoolefins having 4 carbon atoms are close to each other, it is difficult to separate them from the corresponding normal olefins by simple fractional distillation. Conventional methods commonly practiced commercially involve selective absorption of inolefins by sulfuric acid and the resulting sulfuric acid extract containing isoolefins being diluted with steam, heated or treated with isoolefins. Separating olefins.

Isobutyne and diisobutene are valuable substances with a variety of uses. For example, isobutyne is one of the comonomers of butyl rubber, and diisobutene is an intermediate in the manufacture of detergents. N-butene is required in pure form as a raw material for homopolymerization and oxidative production of butadiene. One method to separate these components is the cold acid extraction process.
The method is to pass this mixture through something called edure. In this method, the stream is fed to a concentrated sulfuric acid bath. Separation is achieved by the solubility of isobutyne in sulfuric acid, and any n-butenes and other hydrocarbons present flow out the top.

Tidewell U.S. Patent 3,531
In an improved method reported in , 539, a C1 feed stream containing isobutyne is contacted with molecular sieves at elevated temperature and sufficient pressure to maintain a liquid phase.

Here, isobutyne is converted to diisobutene, which is easily separated from the stream by conventional separation methods.

Methyl tert-butyl ether (MTBB) is widely accepted as a non-hazardous octane improver for gasoline. One method for separating isobutyne or isoolefins from a mixture with the corresponding normal olefins and alkanes is to etherify the isoolefin with a C5 to C2 primary alcohol in the presence of an acidic cation exchange resin catalyst; Fractional distillation, often followed by cracking the ether into inolefins, separates low-boiling hydrocarbons from high-boiling ethers. Such a method is described in U.S. Pat.
．． 121.124F 3,270.081; and 3,
No. 170,000.

More recently, in view of the improved properties of ether octane, similar methods have been disclosed for the production and recovery of ethers1, e.g., U.S. Pat.
See 46.088.

A refrigeration variant of these processes, disclosed in US Pat. In this process, there are multiple zones of acidic ion exchange resin catalyst, which form isoolefin ethers that fall to the bottom of the column, while normal olefins H (and paraffins) are distilled off at the top. In particular, the catalyst is in the downcomer, where the reaction is to take place, and the distillation takes place on the trays of the column.

The present invention generally discloses catalyst systems used in chemical reactions in which substances in a reaction mixture are separated by distillation. In this reaction, it is planned to use reactants, products and inert substances that are liquid or gaseous under the conditions of the reaction.The reactants are single substances, such as isobutylene, which are themselves similar to each other. It may react to form diisobutylene in a C4 fluid containing normal butene. In this case normal butene is recovered from the top and diisobutylene from the bottom. The reactants may also be dissimilar materials, such as isobutyne and methanol, as described in detail herein, in any case such that reaction and distillation occur simultaneously over a fixed catalyst bed. The use of catalytic materials as catalysts and distillation packings has been discovered.

The invention also finds use in the process of separating isoolefins, preferably isoolefins having 4 to 6 carbon atoms, from streams containing mixtures with their corresponding normal olefins.

For example, the fluid includes isobutene-normal butene, isopentene and normal pentene, and isohexene and normal hexene.

The catalyst packing material is a central feature of the invention, without which the described method cannot be carried out. The catalyst system with the certain geometry used can be used in other processes. Such a process includes, for example,
To carry out the methods known in the art, there are methods in which the liquid phase is brought into contact with an aqueous or organic system. The process may also be carried out with conventionally used catalysts in other forms such as beads, pellets, etc. The distillation functional catalyst system of the present invention has a larger open backing as required for distillation. Therefore, if the catalyst packing of the present invention is used in a liquid phase process, it is necessary to obtain a liquid-catalyst contact comparable to that of, for example, a solid bed packed closely with small beads. , would require an even larger floor.

The catalytic material is not limited to a particular shape as long as the shape functions as a distillation filler, thus the catalytic material can be in the form of spheres, large lumps, sheets, tubes or spirals, similar to the conventional distillation shapes mentioned above. can be used.

Catalytic materials in the form of polymeric cells in the form of strings can also be used. However, these bubbles are used as a solid mass because the pressure drop due to such bubbles, even though they lack a large cell wall, is still very large and unsuitable for use as a distillation packing. I can't. The bubbles can be cut or crushed into usable shapes or spirally wound into sheets within the distillation column to provide a gas flow path through the column. This spiral reticulated sheet works in a similar manner to the resin bead cloth bags described herein.

The catalytic material is any material that is suitable for the reaction at hand, i.e. it may be an acidic catalyst or a basic catalyst or a catalyst such as their oxides or halides which are suitable for a number of catalytic reactions and routes. , the catalyst is a heterogeneous system with reactants or other fluids within the system.

For example, a heterogeneous reaction is the production of fumaric acid from methanol using iron oxide, or transesterification using a basic catalyst such as Na0Al.

The term "catalyst" or "catalytic material" is used to encompass any solid material that is recognized to act like a catalyst for the reaction under consideration.

This material is also a distillation packing, so it is a distillation part or component (note that there is no inert distillation in the column and, for example, below or above the catalyst packing, between beds of catalyst packing). There may also be a packing, and this inert distillation packing may also be mixed with the catalyst packing), so that the catalytic material can act as both a catalyst and a distillation packing. It is a component of a distillation system, i.e., a packing for a distillation column that has both distillation and catalytic functions.

It has been found that the resin beads in conventional fixed beds form a mass that is too tightly packed for upwardly flowing vapor and downwardly flowing liquid. However, by placing the resin beads in a number of pockets within a cloth belt, which is supported in the distillation column by an open wire mesh made of woven stainless steel wire and by twisting the two together, It has been found that this method allows the necessary flow, eliminates catalyst loss, allows normal swelling of the bead, and prevents bead breakage due to mechanical attrition. This new catalyst arrangement is also part of the invention.

This cloth can be any material that will not be damaged by the hydrocarbon feedstock or products under the reaction conditions; cotton or linen can be used, but glass or "Teflon" cloth is preferred; simply put, the desired catalyst The system includes a number of closed fabric pockets containing particulate catalyst material disposed within the column and supported by wire mesh in intimate association with the fabric.

Particulate catalyst materials are powders, small irregular pieces or shards, small beads, etc. It is not important that the catalytic material in the fabric pocket be of any particular shape as long as it has sufficient surface area to provide the appropriate reaction rate; the size of the catalytic particles is determined for each catalytic material. is best (because the porosity or effective internal area is different for different materials and will naturally affect the activity of the catalytic material.

What readily distinguishes the present invention from the prior art is that the prior art consistently uses a continuous liquid phase system to contact the olefin with the acidic catalyst, whereas the present invention uses a continuous liquid phase system to contact the olefin with the acidic catalyst, whereas the present invention The operation is carried out in a catalyst-filled thin column which is admitted to contain a vapor phase and some liquid phase.

The dimerization reaction of isobutyne and the fractional distillation of the resulting n-butene dimer mixture are carried out simultaneously. That is, as dimers form within the catalyst bed, lower boiling n-
Butenes are fractionated from the catalyst bed and removed from the top of the column, while high boiling dimers descend to the bottom of the column.

One problem with prior art bulk liquid phase reactions is temperature control. Distillation completely eliminates this problem.

Thus, the catalyst packing is of such a nature that vapor flow can pass through the catalyst bed, but still have sufficient area to contact the catalyst. The aforementioned Hau
In the nschild patent process, as the liquid in the column descends through the downcomer to the next lower tray, the catalyst packs into the downcomer and becomes flushed. The material from the downcomer is then fractionated on the lower tray as in a conventional column.

For example, in accordance with the present invention, high boiling reactants are in continuous contact with the catalyst and lower boiling reactants rising through the fixed catalyst bed, providing more opportunity for reaction. Similarly, the reaction can be brought to completion by removing the reaction products from the reaction mixture of a reversible reaction. Thus, even in a process characterized by catalytic reaction and distillation, the catalyst system of the present invention allows both functions to be performed in a single step. The device is very simple and can be used with any form of phlegm (
However, since a fixed bed of catalyst must be inserted into the column to fill the reaction zone), any packing will restrict the vapor flow in the column, and if alternative, unfilled passages are provided. It is accepted that steam will take the path of least resistance. Therefore, Hauns
In a reactor configuration such as that shown in the CHID patent, vapor contact or flow would not be able to proceed through the catalyst-filled downcomer.

The catalyst system of the present invention is also useful for reacting one component in a multicomponent feed while simultaneously separating unreacted components in the feed by fractional distillation.

Fractional distillation can also be used to recover the product overhead or as a bottom fraction. It can also be used to recover non-reactants such as n-butene from reaction mixtures of isobutene and methanol, n-butene being a feed stream component that is more difficult to separate than isobutene by other methods. be. Thus, the disclosed process can be used for special or selective reactions between relatively pure reactants and recovery of desired products from mixed feedstocks.

For any particular feed stream or selective reaction within it,
The particular conditions for the reaction will need to be determined by performing a few experiments using the invention described herein and using the information provided herein to carry out the process in accordance with the invention. .

Similarly, although this description is primarily directed to a mixed C1 stream that selectively reacts with isobutyne, other streams and processes may also be used, e.g.
In addition to dimerization, etherification, and isomerization, all other reactions are also considered: isomerization of butene-2 to butene-1 and simultaneous fractionation of the resulting isomerization mixture. It will be done. Examples include esterification, chlorination, hydration, dehydrohalogenation, alkylation, polymerization, and the like.

The reactants (and inerts) are generally organic compounds (
However, some inorganic compounds may be dissolved in it)
. Although C4 hydrocarbons are used as an example, any organic compound that is fluid, produces reaction products that are fluid under operating conditions, and can be fractionated to separate or recover materials from the reaction can be used. .

Therefore, at -1'IQ, this process is a method for simultaneously carrying out a chemical reaction to produce a reaction mixture and fractionation of the reaction mixture, comprising: (a) a distillation column reactor; The reactants are fed to the feed zone.

(b) At the same time: (1) contacting the reactants with a fixed bed catalyst charge in a low-temperature reaction zone;

(2) fractionating the reaction mixture obtained in the fixed bed catalyst, recovering a low boiling fraction of the reaction mixture from the top of the column and recovering a high boiling fraction of the reaction mixture as a bottom stream;

In this process, the reaction and fractionation are carried out simultaneously in a fixed catalyst bed, which acts as both a catalyst and a thin column packing in the distillation column reactor.

Additionally, the catalytic material can be in a shape that acts as a thin column packing, such as rings, saddles, poles, irregular shapes, sheets, tubes, packed in bags and placed on a grid or screen. Must be a helical or reticulated polymeric foam (the cellular structure of the foam is
The catalytic material must have a sufficiently large area so that the pressure drop through the column is not large, or otherwise be placed in thick sections or concentric tubes to permit vapor flow. is one component of the filtrate system that functions as a catalyst and filtrate column filler. In other words, it is a filling material for a shojo tower that has both a shojo function and a catalytic function.

One type of process using the catalyst system of the present invention is the production of methyl tert-butyl ether from a stream containing a mixture of isobutene and normal butene.

A method for producing methyl tert-butyl ether includes: (a) feeding a mixture comprising isobutyne and normal butene to a feed zone to a distillation column reactor;

(b) Feeding methanol to the feed zone. (e) simultaneously contacting (1) the mixture and methanol with a fixed bed acidic cation exchange resin charge in a low-temperature reaction zone;
Isobutyne is catalytically reacted with methanol to form methyl tert-butyl ether. (2) Fractionally distilling the resulting mixture of ether and positive olefin. (d) withdrawing ether from the distillation column reactor at a point below said feed zone; (e) withdrawing ether from the distillation column reactor at a point above said feed zone, preferably above said acidic cation exchange resin; Extract the olefin.

A particular example of a process using the catalyst system of the invention is the separation of isobutyne from a mixture containing normal butene and isobutyne. More generally, the present invention essentially eliminates C6 hydrocarbons, such as normal butane, isobutane, normal butene, isobutyne, butadiene (with small amounts of C1 and C3 hydrocarbons, i.e. if it is less than 10%, the C4 stream used to separate isobutyne from hydrocarbon streams, such as those that may be associated with

Generally, this method of separating isobutine involves the following.

(a) Feeding a mixture comprising isobutyne and normal butene and methanol to the feed zone of the distillation column reactor.

(b) At the same time, (1) bringing the above mixture and methanol into contact with a fixed-bed acidic cation exchange resin packing in a light reaction book;
Isobutyne is contacted with methanol to catalytically react the isobutyne with the methanol to form methyl tert-butyl ether.

(2) Fractionally distilling the resulting mixture containing methyl tert-butyl ether and normal butene.

(C) withdrawing the methyl tert-butyl ether from the distillation column reactor at a point above the feed zone;

(d) withdrawing normal butene from the distillation column reactor at a point above the feed zone;

Since the catalyst continues to exist as a distinct entity, the reaction system can be described as a heterogeneous system.

The catalyst can be used in the form of conventional thin packings such as Raschig rings, ball rings, saddles, etc.

Similarly, the resin can be used in particulate or beaded form as described herein.

Methanol can and is preferably present in stoichiometric amounts, although an excess of up to 10% is preferred, and slightly less than stoichiometric amounts can also be used. It must be recognized that the chemist, once he understands the basic invention, can optimize the exact conditions for catalyst variation and the ratio of methanol amounts for each particular device.

It has been found that the resin beads in a conventional fixed bed form a very dense mass for upward vapor flow and downward liquid flow. However, by placing the resin beads in a number of pockets in a cloth belt, which is woven by an open wire mesh made of stainless steel wire, and by twisting the two together, ) provides the necessary flow, prevents loss of catalyst, allows normal swelling of the beads, and prevents bead breakage due to mechanical friction. This new catalyst arrangement is described herein.

The etherification reaction of isobutyne and the fractional distillation of the resulting mixture of normal butene and ether are carried out simultaneously. That is, as ether is formed in the catalyst bed, lower boiling normal butenes are fractionated in the catalyst bed and removed from the top of the column, while higher boiling ethers fall to the bottom of the column.

One problem with prior art bulk liquid phase reactions is temperature control. Distillation completely eliminates this problem.

The above-mentioned Auschild patent is an improvement in that there is some etherification catalyst in the column, but etherification and distillation are not simultaneous. Etherification occurs only in the liquid phase in the downcomer. The subsequent distillation takes place on a tray, thus extremely limiting the reaction by inculcating only contact with the catalyst in the downflow of the reactants, encouraging practitioners to A conventional multistage fixed bed reaction for producing ether from isobutyne and alcohol was proposed before introducing various trays within the system.

Another type of reaction, which is closely related to MTBE production, is the production of high purity isobutyne from the dissociation of MTBH. This reaction feeds MTBE to a catalyst bed packing in a reaction-cooling column, recovers a methanol bottoms stream, and recovers a high purity (95%+) isobutyne overhead product, which contains the same acidic resin. Use a catalyst.

The feed zone is at the top of the catalyst bed.

Another closely related type of reaction is the reaction of methanol with isobutyne as described herein, but the amount of methanol is less than stoichiometric. Increasing the temperature (i.e. increasing the pressure inside the column)
favors the dimerization of isobutyne. A high purity diisobutane bottoms stream (less codimer than in the conventional form of the process for producing diisobutane from a Ca stream) is obtained.

The invention will be further explained by means of examples in connection with the accompanying drawings, in which: FIG.

In the accompanying drawings, FIG. 1 is a schematic diagram of a catalytic distillation column using a catalyst system according to the invention.

FIG. 2 is an elevational view of the catalyst belt packing.

FIG. 3 is a cross-sectional view of the catalyst belt packing, taken along arrow 3-3 in FIG. 2.

Mainly isobutane (1-C4), normal butane (n-Cn
), butene-1 (B-1), isobutyne (1-8)
A mixed C4 stream containing , trans-butene-2 (τB-2) and cis-butene-2 (GE-2) (with some minor impurities including butadiene) was treated with cold sulfuric acid to remove isobutene. Butylene concentrate can be obtained.

The removed isobutyne is converted from acid to polymer (mainly dimer).
Collected as Isoptene dimers (ie, also containing some other polymers) and butene i4 condensates are valuable products.

An alternative method for achieving this same separation has been discovered. It has been found that a thin light column packed with a suitably supported acid catalyst can produce a bottoms stream containing isobutyne polymer (predominantly dimer) and an overhead stream that is relatively free of isobutyne. Served. This is surprising because if the reaction were to be carried out on a conventional fixed catalyst bed, the catalysts used would normally produce primarily heavy isobutyne polymers and copolymers.

Mix C in a thin column packed with a suitably supported acid catalyst.
It has been found that feeding the 4 streams and methanol can produce a bottoms stream containing methyl tert-butyl ether and an overhead stream that is relatively free of isobutyne.

The success of the study of tōkyō was due to the understanding of the principles associated with distillation. First, because the reaction occurs simultaneously with distillation, the first reaction product, methyl tert-butyl ether (or diisobutylene), is removed from the reaction zone almost simultaneously as it is formed. This removal of the ether (or isobutyne polymer) minimized the decomposition of the ether and the linkages 1N (or, in the case of monomerization, chains extending to large polymer lengths) to form the isobutyne polymer. Second, since all C1 components are boiling, the reaction temperature is controlled by the boiling point of the C1 mixture in the system pressure.
The heat of reaction only boils more, no temperature rise occurs; third, the reaction accelerating power increases. This is because the reaction products are removed and do not trigger the reverse reaction (Le Chat-elier's principle).

As a result, much reaction rate and product distribution control can be achieved by adjusting the system pressure. In addition, by controlling the throughput (the reciprocal of the liquid hourly space velocity per hour of residence time), the product distribution and the extent of isobutane removal can be further controlled.

The boiling point of the C1 component at any given pressure determines the reactor temperature. That is, changes in the temperature of the system at constant pressure dictate changes in the components within the column. Therefore, in order to change the temperature, the pressure must be changed. Increasing the pressure will increase the temperature within the system. Generally, pressures in the range θ to 400 psig can be used, preferably in the range 30 to 150 psig. For CJ flow, this reaction is generally 10 to 300 ps! The pressure range is generally 10-100"
Equivalent to the temperature range of C.

The reaction of isobutine with itself is limited due to equilibrium. However, if the reaction is carried out in a shallow reaction tower, the product (
If diisobutane) is fractionated downward from the reaction zone, the equilibrium will always be disrupted and the reaction will never reach equilibrium. This is, of course, an advantage, as an effective conversion of 100x is achieved (provided that the catalyst bed is long enough that the isobutyne does not escape from it and go to the top with the n-butene). (limited), 1liffing the catalyst bed size is only a mechanical step that must be determined for each reactor and follow the reaction conditions.

This system can normally be considered anhydrous.

However, small amounts of red water often saturate the feedstock stream,
It exhibits a moisture content of approximately 400-600 pp-. The process continues to operate in the same way even in the presence of this amount of moisture. However, the following results were observed. (1) All reaction rates increase, but smaller reaction rates increase faster. (Although not mentioned previously, those skilled in the art will recognize that there are reactions in which isobutyne and butene react to form a "codimer." The rate of this reaction is typically much slower than the rate of the diisobutene reaction. ) (2) The amount of codimer increases. (3) A small amount of tertiary butanol is produced.

The feed to the distillation column reactor is at the lower end of the catalyst bed, preferably into the catalyst so that the isobutyne is immediately in contact with the catalyst.

The reaction between isobutyne and methanol is limited by equilibrium. However, when the reaction is carried out in a distillation column reactor and the product, ie methyl tertiary butyl ether (M?BE), is fractionated downward from the reaction zone, the equilibrium is always destroyed and the reaction never reaches equilibrium. .

This is, of course, an advantage; if the catalyst bed is of sufficient length that no isobutyne escapes from it and goes to the top with the n-butene, an effective conversion of 100x can be achieved. (This is a point that the Hauschid process cannot solve). Adjusting the size of the catalyst bed is only a mechanical step that must be determined for each reactor and according to the reaction conditions.

MTB [! The system may normally be considered anhydrous.

However, small amounts of moisture often saturate the feed stream and
It exhibits a moisture content of approximately 400-600 ppm. The process continues to operate in the same way even in the presence of this amount of moisture. Generally, this system is used with less than 1 mole of water in the raw material. However, water limitation is associated with the MTBE reaction. Quite clearly, when water is a reactant or a major component of the feed stream in accordance with the overarching invention, a significant amount of the desired water may be present.

The feed of the distillation column reactor takes place at the lower end of the catalyst bed for the MTBE reaction and is preferably fed into the catalyst to immediately contact the isobutyne and methanol with the catalyst characterized as the feed zone.

It is desirable to include reflux in the system, and the reflux ratio is used. In a commercial scale unit, a catalyst bed would be provided that provides a lower reflux ratio and therefore higher productivity per unit.

Cationic resins have been used in the prior art for this reaction. The catalyst for the new MTBB process is a cation exchange resin, monopolymer or copolymer, containing sulfonic acid groups and prepared by polymerization or copolymerization of aromatic vinyl compounds followed by sulfonation. Examples of aromatic vinyl compounds used to prepare the composite include styrene, vinyltoluene, vinylnaphthalene, vinylethylbenzene, methylstyrene, vinylchlorobenzene, vinylxylene, and the like. A large number of methods can be used to produce these polymers, 6 for example polymerization carried out alone or in admixture with other monovinyl compounds or in cross-linkage with polyvinyl compounds.

Examples include vinylbenzene, divinyltoluene, divinylphenyl ether, and others.

The polymers are prepared in the presence or absence of solvents or dispersants, and a variety of polymerization initiators can be used, such as inorganic or organic peroxides, persulfates, and the like.

Sulfonic acid groups can be introduced into these vinyl aromatic polymers by a variety of known methods, such as by sulfating the polymer with concentrated sulfuric acid or chlorosulfonic acid. In addition, sulfonic acid groups can be introduced into these polymers that already contain sulfonic acid groups, such as by copolymerizing sulfonic acid groups (see, e.g., U.S. Pat. No. 2,366,007). 0 For example,
By treatment with oleum, sulfuric acid containing sulfur trioxide. The treatment of fuming sulfuric acid t is preferably 0
carried out at ~150 °C, the sulfuric acid must contain sufficient sulfur dioxide after the reaction, and the resulting product should contain an average of 1.3 to 1.8 sulfonic acid groups per aromatic nucleus. Preferred, in particular, suitable polymers containing sulfonic acid groups are copolymers of aromatic monovinyl compounds and aromatic polyvinyl compounds, the latter in particular divinyl compounds, preferably with a polyvinylbenzene content in the copolymer. 1 to 20%, based on the weight of the combination (see, for example, West German Patent Specification No. 908,247).

Ion exchange resins are desirably used in particle sizes of about 0.25 to about 1 mm, although particle sizes of 0.15 m to about III m can also be used. Macronetworks are desirable for finer catalysts, which have a higher surface area, but also have a higher pressure drop through the reactor.

This is because a larger area is exposed and the swelling that all these resins undergo in non-aqueous hydrocarbon media is limited.

Other acid resins are likewise suitable. For example, perfluorosulfonic acid resins, which are copolymers of sulfonyl fluorovinyl ethyl and fluorine carbide, are described in great detail in the following references:

Dupont “Innovation”, Volume 4, No. 3, 1
Spring 973, or variations thereof, U.S. Pat.
No. 784,399, No. 3,770,567, No. 3.8
No. 49.243.

FIG. 1 provides an overview of a typical distillation column reactor in which the catalyst system of the present invention can be used. The column 10 is a 1 inch diameter 5 foot tall tube made of conventional glass 1/1
It includes a section 18 filled with 2 feet of 6 inch spirals and a section 18 filled with 3 feet of catalyst packing. The catalyst packing is shown in FIG. 2 and FIG.

FIG. 2 shows a cloth belt 30 wrapped in open wire mesh woven from stainless steel wire 31. The cloth belt 30 consists of a number of vertical pockets 32 sewn into bags. Each pocket 32 is filled with a resin catalyst 33.

The wire gauze supports the catalyst (belt) and provides some of the passage for the vapors past the catalyst beads, which otherwise would form a very dense bed with high pressure drop. As such, the flowing liquid comes into intimate contact with the vapor rising within the column.

As is contemplated in commercial-scale operations, the catalyst packing may consist of a layer of catalyst-filled cloth belts similar to those described above and any convenient suitable material such as corrugated wire screen or wire cloth or knitted wire mesh. The spaces between the belts will be made by stacking alternating layers of material, each layer oriented vertically, providing a vapor passage between the belts. The cylindrical resin-filled pockets will be oriented either vertically or horizontally. Vertical orientation is preferred for ease of fabrication and good vapor flow path distribution, and the height of this section of packing can range from a few inches to a few feet at any convenient time. Good dimensions may be selected.For ease of assembly and installation, the filling is divided into sections of desired shape and dimensions, each section being either a circumferential band or a tie wire depending on its dimensions and shape. Tie it up.

The complete assembly in the column consists of several cefsilanes arranged in layers, with the catalyst-filled belt oriented at right angles in successive layers to improve liquid and gas flow distribution. Ru. “An example of another arrangement that is useful but has some drawbacks would be a cage of wire cloth containing catalyst beads submerged in liquid on a regular sieve tray, due to the close weave of the wire mesh. The disadvantage would be that the steam flow would be restricted, but this disadvantage would be compensated by the beads moving freely within the basket, but this would cause friction, as well as Suspending the catalyst may create problems such as friction, maintaining suspension, and keeping the catalyst from leaving the tray.

In the experimental tower, the bag was made in the form of a cloth belt;
It is about 6 inches wide and has a narrow pocket about 3 inches wide sewn across the belt.

The spacing between each pocket is approximately 1/8 inch. These pockets are filled with catalyst beads to form approximately cylindrical containers, and the open ends are then sewn shut to confine the beads. The belt is then spirally twisted to fit inside the 1 inch tower. A strip of open wire mesh woven from stainless steel wire is twisted together with the belt, which separates the catalyst-filled fabric pockets and provides a vapor flow path.

In operation during dimerization, isobutyne containing C4 feed is introduced through line 11 into the lower end of catalyst zone 24, which includes catalyst bag and belt 25 as described above. The temperature and pressure within the column are such that the C4 raw material boils within the column. However, when the isobutyne contacts the catalyst, a dimer is formed which has a higher boiling point than the C4 stream and is carried to the bottom of the reactor and removed through line 20, although some of it is recovered through line 21. The other part is circulated through line 22 into Rebovilla 19 and through line 23 into column 10.
Return to the bottom of the page.

Meanwhile, n-butene rises through the catalyst zone 24,
The condenser 13 is sent out of the tower 10 through line 12.
from there through line 14 to accumulator 15 . A portion of it is recovered as a butene concentrate from line 16;
The other portion is returned through line 17 into column 10 as reflux.

In the lower cost examples (Examples 1, 2.3, 9.10), the C4 feed rate to the column is adjusted to maintain a bottoms temperature corresponding to a low C4 concentration. The catalyst used was Amberlite 15, manufactured by Philatelfia, Pennsylvania.
Manufactured by Rohm and Haas. The C4 raw material had the following composition.

One bottom one minute -Supreme X-isobutane 2.8n-butene
8.6 butene-1
24.6 Isobutine 50.
5 trans-butene-210,4 cis-butene-23,1 butadiene 0.5 ratio (butene-1/butene-2) 1.8 The experimental distillation/reaction column was a 1 inch diameter, 5 foot tall tube. The conventional glass 1/16 inch spiral packed bed is 2 feet long and the catalyst packed bed is 3 feet wide. The pilot lamp circumferential base is 3 inches in diameter with a 10 foot catalyst bed.
Typical 378 inches with a 5 foot ball ring fill layer.

In operation, isobutyne and methanol containing the C4 raw material are introduced into the lower end of the catalyst zone containing the catalyst bag and belt described above. The temperature and pressure inside the column are such that C4 and methanol boil in the column, but as isobutyne and alcohol come into contact with the catalyst, ether is produced, which is C4.
Since it has a higher boiling point than the stream, it is sent to the bottom of the reactor where it is removed.

-i, a part of it is recovered, and another part is recycled to the boiler and returned to the bottom of the tower.

In the meantime, the n-butene rises through the catalyst zone and is sent out of the column, from the condenser to the accumulator. In normal operation, some of it is recovered as butene concentrate and the other part is sent to the column as reflux. returned inside.

Next 1st episode U These examples are examples of the production of MTBH.

Example 1 I E-Kozaka! village tower
μ Kansai 7 Σushi Tower LH5V-"-1, Ohr LH5V-'=1.4h
r115g (190d) catalyst 2640g (4400d
)Catalyst system internal pressure 80 psig 100 ps
ig temperature tower bottom 228°F 260°F Catalyst bed middle 138'F 160'F Methanol co-supply 2.5 m/win
24m1/win reactor pan top 1gr/hr 120 3060
d/hr bottom, gr/hr 264
4980d/hr analysis 7mol% ■ Isobutane 6.1 6.6 6.1n
-Butene 18.0 15.5 15.8 Butene-140,640,547,0 Isobutyne 11.2 9.8 1.3 Trans-Butene-218,819,124,2 Cis-Butene-25,15,25 ,2 Butadiene 0.3 0.3 0.3 methanol and C45,57,81,3 tert-butylflucol 2.5 0,7
0.7 Methyl tertiary butyl ether (MTBB) 93.2 9
1.2 91.9C1 and heavy components 0.
8 0.3 6.1 The process operated using the present invention provides excellent MT under reasonable feed rate.
Supports BE yield.

*LH5V-1 is the volume of catalyst in the catalyst zone divided by the overhead withdrawal rate.

EXAMPLE 2 These examples are examples of producing highly pure isobutyne from methyl tert-butyl ether. A 1 inch laboratory column was used and 72 gr of contact thin packing was packed into the pockets of the fabric belt as described above. The catalyst was contained in the lower part of the reaction column, and the feedstock (MTBB) was fed to the top of the catalyst bed. Two experiments were conducted using two raw materials with different purity. The conditions and results are as follows.

Kotabi Group Soil i Raw material mole% MTBE 95.6χ 99.1χ Round 1 tower top m/hr 100 100 tower bottom Not recorded Not recorded Pressure car assembly
7080 1 degree-e Tower top 118 122 Tower bottom
212 220 Catalyst bed middle
214 217 minutes ■ Isobutane 0.02 0.05n-butene 0.4 0.01butene-10
,50,05 Isobutyne 96.5 99.6 Trans-butene-21.6 0.2 Cis-butene-2
0,91,2 Butadiene 0.03 0.011 yard
MTBfl and methanol? lTB[! In fact, Example 6 shows that a mixture of methanol and isobutyne or MT
An example of the flexibility of a process to produce high purity diisobutene from only BE using a 3 inch pilot plant surround.

In Example 7, the tower was improved by adding an additional 5 feet to the tower height. In Example 6, the column was packed with 5 feet of conventional Pall rings at the bottom, and an additional 2.5 feet of catalyst packing height at the top, topped with 5 feet of conventional Pall rings.
Two and a half feet of 4 inch saddles were filled. In both examples, methanol is fed to the top of the catalyst bed and C
Four feedstocks (as described above) were fed below the catalyst bed.

Feed rates were adjusted to obtain the desired product distribution.

On the day of the example, high purity methyl tert-butyl ether (99
χ) was fed to the column used in Example 7.

MTBE was fed to the column from the bottom of the catalyst bed.

Essentially no overhead stream was removed except that required for analysis. This example demonstrates a unique method for producing diisobutene with very little co-contamination. The conditions and results of each example are as follows.

Example ``Nie 1-dish dual-speed tower top, j! /hr 4.5 3.0
Essentially O bottom, 42/hr 4.5
4.2 4.5 pressure direction, Wangjiang 100
120 78 Melon 1 Nini 1 Tower top 155 158 82 Tower bottom
350 260 245 Middle part of catalyst bed 180 165 220 minute capture , 0 1.5 Butene-132,246,90,8 Isobutyne 6.2 Trace 69.6 Transbutene-2 28.5 24.2 0.4 Cis-Butene-29,45,0- Butadiene 0.2 0 .6 -Dimethyl ether 27.7 Gotaka MTBB 32.9 95.6 6
8.7 Unknown ether 2.2 0.1
Diisobutene 2.2.4-) Dimethylpentene-140,217,6 2,4,4-) Dimethylpentene-210,55,3 Codimer? , 1 0.1*
Gas phase chromatography area **Methanol was reduced to below stoichiometric amount.

! Iwao I1m System internal pressure kerf 0 psig Catalyst zone temperature -60°C Result: U needle two components (mol%
) 02 0? isobutane
5.8 4.6n-butane
20.0 28.7 Butene-1 31
．． 6 15.6 Isobutene 7.4
1.5 trans-butene-226,737,7 cis-butene-2 8.4 11.9 butadiene 0.18 0.03 ratio (
Butene-1/Butene-1) 1.2 0.3 Column top withdrawal at/hr) 480 160 Column bottom temperature 'C133171 Column bottom C< (mol%) 9.8 2.
7 Two components (mol%) Tertiary butyl alcohol 0.14 0.04 Diisobutene 61.6 51.5 Codimer 18.0 31.3 Triisobutyne 16.8 12.93.5
4.2 11 LH3V-1 is the volume of resin in the catalyst zone divided by the overhead withdrawal rate.

(The catalyst contained 115gr (190m) of catalyst)
Umbrella* Umbrella with Ca component removed by heating.

1 ship U System internal pressure car 40 psig Catalyst zone temperature = 40°C Component (mol%) 07-1''-isobutane 4.8 5.7n-butane
15.1 16.0 Butene-144,
343,8 Isobutyne 12.1 9.3 trans-butene-218,620゜0 cis-butene-24
,85,1 Butadiene 0.21 0.2 ratio (
Butene-1/Butene-1) 1.9. 1.7 ml of tower top extraction! /hr) 160 80
Bottom temperature "C142159 Bottom C4 (mol%) 3.0 0.4
Bottom component (mol%) Tertiary butyl alcohol 0.26 0.11 Diisobutene 75.0 74.5 Codimer 10.2 12.6 Triisobutene 11.6 10.22.9
2.6 This LH5V-1 is obtained by heating and removing the C4 component by increasing the volume of the catalyst in the catalyst zone.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a catalytic converter using a catalyst system according to the invention. 18--Conventional Packing Section 24--Catalyst Packing Section FIG. 2 is an elevational view of the catalyst system according to the invention. 30...-Cloth belt, 31--Wire Figure 3 is:
FIG. 3 is a sectional view taken along arrow 3-3 in FIG. 2; 32--Vertical pocket, 33--Resin catalyst.

Claims (1)

[Claims] 1. A catalyst system for use in a reaction-distillation column, comprising a plurality of closed fabric pockets containing particulate catalyst material therein, the plurality of fabric pockets being a single A catalyst system comprising: a cloth belt formed into a spiral ring; a wire mesh is disposed between the spiral rings, and these are arranged within the reaction-distillation column. 2. The catalyst system according to claim 1, wherein the pocket is substantially parallel to the axis of the helical ring. 3. The catalyst system according to claim 1, wherein the pocket extends along the axis of the helical ring. 4. Catalyst system according to claim 1, characterized in that the looped cloth belt is arranged vertically within the column. 5. The catalyst system according to claim (1), wherein the particulate catalyst material is an acidic cation exchange resin.