JPH0557193A - Formed phosphoric acid catalyst for use in organic compound conversion and method for converting organic compound using said catalyst - Google Patents

Abstract

PURPOSE: To maintain a desirable void content between particles and to make possible a raw material to be converted flow in a catalyst bed without interruption by constituting a catalyst from a solid binder mixed with phosphoric acid which has a higher ratio of an outer surface area to the catalyst than a value obtained from a specified equation and an extrusion molded mixture. CONSTITUTION: A solid catalyst mixture is obtained by using an extrusion molded product of a mixture of phosphoric acid with a solid binder having a higher ratio of an outer surface area to the catalyst than a value obtained from an equation (in which, D denotes a maximal typical diameter and L denotes a length of an extrusion molded product). Thereby, a form of the catalyst is not destructed, decomposed or swelled during operations. Therefore, a converting operation of org. compounds can be carried out quite efficiently and continuously by using the catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst used to solve the problem of coke-induced swelling of phosphoric acid catalyst particles used to accelerate the conversion of organic compounds.

[0002]

(Formula II)

3SiO ₂ + 4H ₃ PO ₄ → Si ₃ (PO ₄ ) ₄ + 6H ₂ O SiO ₂ + 2H ₃ PO ₄ → SiP ₂ O ₇ + 3H ₂ O In the above reaction, phosphoric acid reacts with silicon, the stoichiometry and reaction conditions It is shown to produce both types of phosphates according to. Silicon orthophosphate can also be dehydrated during drying to create pyrous silicon phosphate, which is believed to be an alternative mechanism to pyrosilicone formation. The conversion of orthosilicon phosphate to pyrousic silicon phosphate also depends on factors such as temperature and hydration, as shown in <Formula III> below. [Formula III] Si ₃ (PO ₄ ) ₄ + 2H ₃ PO ₄ → 3SiP ₂ O ₇ + 3H ₂ O Si ₃ (PO ₄ ) ₄ + Heating → 2SiP ₂ O ₇ + SiO ₂

The formulation of these catalysts is known, for example, in US Pat. No. 2,586,852 which describes solid phosphoric acid composed of a mixture of kaolin, crystalline silicon and phosphoric acid. Other patents that describe various methods of forming this catalyst mixture include US Pat.
2,650,201, 2,833,727, 2,871,199 and 3,112,3
There are 50 etc. A disadvantage of using these catalyst mixtures during polymerization or alkylation reactions is that the catalyst particles tend to disintegrate to form a solid bed, making it difficult for the feed to pass through the catalyst bed. Similarly, even if the catalyst particles do not disintegrate, there is a tendency for coke to precipitate on them and increase in volume or swell, which further reduces the space between the particles and makes it difficult to pass through the bed. It is therefore clear that the space between the catalyst particles is important and indeed considered essential in avoiding excessive pressure drops. Since the space between particles or the porosity is basically important, it has no tendency to lower the porosity, and no matter how the catalyst expands, the porosity is not excessively lost, which is stable. It is necessary to provide catalyst particles that provide sufficient porosity such that pressure is maintained.

With respect to the prior art, there are numerous patents showing various forms of catalyst particles. However, as detailed below, these particles are composed of a substrate having a catalytically active metal deposited thereon or a catalytically free metal-free zeolite catalyst. An example of these prior art patents is a porous structure where the major portion is alumina and the minor portion is silica with a catalytic metal having molybdenum, cobalt nickel, or a mixture thereof deposited on the catalytic substrate. U.S. Pat. No. 3,966,644 showing oxidative hydrotreating catalyst particles
There is. U.S. Pat.Nos. 4,328,130 and 4,342,643 consist of refractory oxides such as alumina, silica, silica-alumina, magnesium, in the form of metals, metal oxides, metal sulfides, and, if necessary, aluminosilicate zeolites. Shows a catalyst with a shaped pore containing a transition metal active in. U.S. Pat.No. 4,370,
492 discloses a carrier such as silicic acid having a noble metal as its constituent. Similarly, U.S. Pat.No. 4,495,307 also has deposited on it alumina, silica, having a metal hydride selected from Group VIB and Group VII of the Periodic Table,
Alternatively, a molded catalyst composed of a catalyst base material such as silica-alumina is disclosed. U.S. Pat.No. 4,391,740
Is a stretched extruded product of a base catalyst such as alumina or silica having as its composition a catalytic metal such as molybdenum, tungsten, nickel or cobalt. The preferred form of this catalyst is bumped or bumped. It describes a catalyst for hydrotreating heavy carbonaceous feedstocks, such as oval or elliptical shapes, in the none configuration. U.S. Pat.Nos. 4,394,303, 4,489,173 and 4,606,815 are all for hydrotreating hydrocarbon feedstocks in the form of crumbs, and wherein the substrate comprises a catalyst metal such as molybdenum, tungsten, or cobalt as its composition. Disclosed is a molded catalyst composed of a refractory inorganic oxide or clay contained therein. Similarly, other forms of catalyst particles having a flake-like shape are disclosed in U.S. Pat. Nos. 4,028,227, 4,495,307 and 4,534,855. The first of these references uses a catalyst substrate such as alumina saturated with cobalt and / or molybdenum, the remaining two examples use only alumina. Other conventional U.S. patents are U.S. Pat.
Disclosed are molded particles such as 4,441,990. This patent discloses a hollow, molded catalyst extrudate having an essentially rectangular or triangular cross section. The catalyst particles are
It consists of a support on which metal can be attached. The specific catalyst particles listed include alumina, or alumina mixed with zeolite as a support material and containing cobalt, molybdenum oxide, copper or zinc oxide as an additional metal. Yet another U.S. patent discloses a molded catalyst having a packed catalytic reactor comprised of a plurality of flanges around a central post element and a retainer comprised of a cylindrical metal having a catalytic surface. is doing. In addition, U.S. Pat.
Solid catalyst particles are mixed with a fiber-forming polyolefin, and then the mixture is mechanically sheared to form a mat of catalyst particles entrapped in the polyolefin.
A shaped solid catalyst is then disclosed in which the mat is mechanically shaped to provide the desired catalyst particles. Similarly, US patents disclosing shaped catalyst particles include US Pat. Nos. 4,652,687 and 4,717,781. These patents describe shaped particles that are multi-lobed or cylindrical in shape. However, these particles are used as oxidation catalysts and are composed of Group VIII noble metals, Group IVA metals, and Group IA or IIA metals as compositions of metal oxide supports such as alumina.

[0005]

The present invention relates to shaped catalyst particles for use in a catalyst conversion process for converting various organic compounds into useful products. Once formed in the catalyst bed, the catalyst particles tend to disintegrate or decompose during the process in which they are used. Alternatively, the catalyst tends to swell even if it does not disintegrate or decompose. The disintegration and swelling of the catalyst in the catalyst bed reduces the spaces between the particles, causing a pressure drop between the bed inlet and the bed outlet. The clogging of the space between the catalyst particles requires a continuous increase in pressure or replacement of the catalyst bed to remove it and make the process effective. In order to reduce the need for catalyst replacement and the use of increased pressure, both of which increase the cost of the process and make it uneconomical to carry out the process, catalyst particles having certain morphologies of these problems It has been discovered that this can be overcome by adopting. By using cylindrical or polymerized debris shaped particles of the type described in more detail below, it is possible to maintain the porosity between the catalyst particles and prevent pressure loss due to excessive pressure drop through the catalyst bed. Is. Polymerized small fragment-shaped, tubular, ridge-shaped, grooved, or solid phosphoric acid catalyst particles having a molding shape according to the present invention such as a cylindrical shape with fine grooves are used in either polymerization or alkylation reaction. From 10% of their initial size
A phosphoric acid catalyst with a sufficient porosity so that it may swell in the quantitative range of 150% or increase in volume, even if there is a pressure drop through the catalyst bed, will drop only slightly. provide.

[0006]

The present invention relates to shaped catalyst particles which can be used for the conversion of organic compounds, and more particularly to the polymerization or alkylation of organic hydrocarbons. Furthermore, the present invention also relates to methods of using these shaped catalyst particles to obtain the desired product as a result of the method in which the catalysts are used.
By using a catalyst having a molded shape such as a multi-lobed shape, the process can be influenced in such a way that the occurrence of unwanted pressure drops can be significantly reduced. Therefore, it is an object of the present invention that it can be used for hydrocarbon conversion such as polymerization or alkylation, and has the ability to maintain a desired degree of porosity between particles, and thereby be converted. The raw material to be flowed can flow through the catalyst bed without interruption of the raw material.

Another invention is to provide a process for the conversion of organic compounds using the shaped catalyst particles according to the invention in order to obtain the desired product in an economical manner. One embodiment of the present invention is made of a molded extruded mixture composed of a solid binder mixed with phosphoric acid having an outer surface area to catalyst ratio greater than the value determined by <Formula I> below. , A solid catalyst composition for the conversion of organic compounds. [Formula I] Here, D is the maximum representative diameter, and L is the length of the extruded product.

Another embodiment of the present invention is a solid binder mixed with phosphoric acid, wherein the ratio of the external surface area to the catalyst is larger than the value determined by the following <Formula I> under the conversion condition of the organic compound. It is a method for conversion of an organic compound, which comprises contacting a solid catalyst made of a molded extrusion processed product and recovering the resulting conversion product. [Formula I] Here, D is the maximum representative diameter, and L is the length of the extruded product. One particular embodiment of the invention is
3-8 composed of diatomaceous earth mixed with polyphosphoric acid
Is a solid catalyst composition for the conversion of organic compounds made of polymerized flake shaped particles, wherein the polyphosphoric acid is present in a quantity of 10% by weight of the composition. A particular embodiment of the present invention is to use an olefinic feed stream containing 2 to 6 carbon atoms at a temperature of 100 ° C to 400 ° C and 1 to 50 ° C.
In a pressure range of 0 atm (101.3-50650 KPa), a method of contacting with a solid catalyst composed of polymerized flake shaped particles composed of diatomaceous earth mixed with phosphoric acid to recover the resulting polymerization product is there.

The solid phosphoric acid shaped catalyst according to the present invention comprises a solid binder mixed with phosphoric acid, preferably having a valence of 5
It is composed of phosphoric acid of phosphorus. This acid constitutes 10% to 80% of the final catalyst mixture produced. Among various phosphorus acids, orthophosphoric acid (H ₃ PO ₄ ) and pyrophosphoric acid (H ₄ P _4
2 O ₇ ) and the like are commonly used in primary mixtures primarily because of their low price and availability. However, the present invention does not require the use thereof, and other types of phosphoric acid may be used as long as they can be used. However, each catalyst made from a different acid and a slightly different procedure has its own effect, so that different types of phosphoric acid used have the same effect in any organic reaction. It does not mean to create.

When orthophosphoric acid is used as one of the primary components, aqueous solutions of various concentrations can be used,
For example, an acid containing H ₃ PO ₄ at a concentration of about 75% to 100% or orthophosphoric acid containing a certain amount of free phosphorus pentoxide can be used. This means that the normal acid can contain a certain proportion of pyrotic acid corresponding to the primary phase of dehydration of orthophosphoric acid. In these concentration ranges, these acids are liquids of varying viscosities and can be easily mixed with solid silica absorbents. Triphosphoric acid of the formula H ₅ P ₃ O ₁₀ can also be used as one of the starting materials for the preparation of the catalyst according to the invention. These catalyst compounds can also be prepared from orthophosphoric acid, pyrophosphoric acid, triphosphoric acid and other polyphosphoric acids. A phosphoric acid mixture, commonly referred to as polyphosphoric acid, can also be used in this method. Polyphosphoric acid and orthophosphoric acid mixtures can also be used in this way. Polyphosphates or heating at orthophosphoric acid or Asesei phosphoric acid or a mixture in a suitable apparatus such as a carbon lining trays heated by flue gas, or other, the P ₂ O ₅ in the normal weight basis It is formed by any suitable method that produces a phosphoric acid mixture containing 79% to 85%. Yes, phosphoric acid and 79.4
The liquid mixture with% P ₂ O ₅ was analyzed to give 24.5% orthophosphoric acid (H ₂ PO ₄ ), 45.2% pyrophosphoric acid (H ₄ P ₂ O ₇ ), 26.0% triphosphoric acid (H ₂ PO ₄ ). ₅ P ₃ PO _{1 0),} and it was found to contain 4.3% of unidentified phosphate on a weight basis. Another phosphoric acid, which is somewhat more concentrated than the ones mentioned above and has 84% P ₂ O ₅ on a weight basis, is, by analysis, 57% on a weight basis.
Of triphosphoric acid (H ₅ P ₃ O ₁₀ ), 5% by weight of orthophosphoric acid (H ₃ PO ₄ ), and 10% by weight of unidentified phosphoric acid.

Another phosphoric acid which can be used in the preparation of the synthetic catalyst according to the invention is tetraphosphoric acid. This is a general formula and is represented by H ₆ P ₄ O ₁₃ which corresponds to the double oxide formula: 3H ₂ P ₂ O _5, which means that 3 molecules of water are formed by 4 molecules of orthophosphoric acid H ₃ PO _4. It can be thought of as the acid that results from being lost. The tetraphosphoric acid can be prepared by slow or controlled dehydration of orthophosphoric acid and pyrophosphoric acid, or heating, or by adding an appropriate amount of phosphorus pentoxide to these acids.
When using the latter procedure, phosphoric anhydride is added slowly to 520% of the weight of water present. After standing at room temperature for a considerable time, tetraphosphoric acid crystals were separated from the viscous liquid, these crystals melt at about 93 ° F (34 ° C) and have a specific gravity of 1.1886 at a temperature of 60 ° F (16 ° C). It can be seen that it is. However, as long as the crude tetraphosphoric acid mixture is incorporated into the polycyclic aromatic hydrocarbon and solid silica absorbent, it is unnecessary to crystallize the tetraphosphoric acid prior to its use in preparing the solid catalyst.

Materials that can be used as an absorber or carrier of phosphorus oxyacid can be roughly classified into two types. The first class is composed of materials based primarily on silicic acid properties, including diatomaceous earth, and artificially prepared porous silica. The second type of material that can be used with the first type, or in combination with it, is usually composed of a fixed amount of aluminum silicate, various acid clay or bentonite, montmorillonite, Contains normal materials such as acid-treated clay. Each absorber, or support, used has a special effect on the effectiveness of the catalyst composition, which is not necessarily the same as other materials of that type.

The catalyst compound which can be used in the present invention is phosphorus oxyacid, and in a preferred embodiment of the present invention,
Solid binders consisting of silicic acid materials are mixed at a temperature in the range of 10 ° to 230 ° C., preferably in the range of 95 ° to 200 ° C. to form a mixture in which 10 by weight is contained.
It is prepared by presenting an oxygen acid of phosphorus in an amount greater than or equal to%. One example of this is polyphosphoric acid (82
% P ₂ O ₅ content) to about 170 ° C. and then the heated acid is mixed with diatomaceous earth that was previously kept at room temperature to form a mixture. Polyphosphoric acid and diatomaceous earth form a mixture of phosphorus pentoxide to diatomaceous earth in a weight ratio in the range of 2.5 to 7.5. Although this mixture appears to be a bit sloppy or almost dry, it is pressed in the form of a hydraulic press or auger type extrudate, which
It has the plasticity to form the mixture into particles of desired shape.

The catalyst particles are in the form of polymer flake and contain 3 to 8 flake so that when the catalyst is placed in the bed, it maintains sufficient porosity, which Even if the catalyst particles swell or the volume increases, the smooth flow of the raw material can pass through the bed without the pressure drop so much. The catalyst particles have a length of 0.075 to 0.75 inches (1.9-
19 mm), the ratio of the external surface to the catalyst volume is [4 / D +
2 / L] or more, where D is the maximum representative diameter and L is the length of the extruded product. Usually, D is chosen to be less than or equal to L, and more typically 1 / 4-3 / 4 of L. Furthermore, the mold through which the dough is extruded is made so as to form small lobes, each of which has a length of 0.
In the range of 01D to 0.3D, meanwhile, the average width of the small pieces is
It is in the range of 0.01D to 0.5D. By producing a catalyst having such a particle shape, it becomes possible to obtain a catalyst having greater effectiveness and stability corresponding to that obtained when a catalyst having a more usual shape is used. The final particles may be solid or, if desired, may have a split in the center of the particles. The catalyst composition extruded through this mold is
In that state, the mold is in a heated state, and the mold through which the catalyst is extruded is preheated to a preset temperature of, for example, about 170 ° C. Extruded catalyst particles in the form of polymer flakes can be heated at 300 ° C to 400 ° C in air, nitrogen, flue gas, or some other inert gas.
It is calcined at a temperature in the range of 0 ° C, preferably in the range of 550 ° to 675 ° C for a period of 0.25 to 8 hours, preferably 0.5 to 2 hours.

Another catalyst mixture of the invention, which is composed of a mixture of solid binder and phosphorus acid, is simply tubular in shape,
Alternatively, it can consist of a tube having a plurality of intersecting veins inside which give the particles a wheel-like shape. The length of the catalyst particles is in the range of 0.050 to 0.75 inch (1.3 to 19 mm), and the ratio of the shape surface to the total volume of the catalyst is such that D is the average outer diameter of the whole particles and L is the length of the extruded product. That is, it is larger than the numerical value indicated by [4 / D + 2 / L]. In this case, the shaped surface means the macroscopic surface area of the entire surface of the catalyst, including the inner wall area of the channel but not the surface area associated with all micropores. Further, the total volume means a solid catalyst volume including the channel volume. The inner and outer diameters of a channel are d ₀ / d, where d ₁ is the maximum internal transverse dimension of any channel and d ₀ is the outer dimension of the wall surrounding the channel measured along the line of dimension d _1. Limited to ₁ being a ratio between 1.1 and 8.0. This ratio of channel diameters is large enough for flow purposes and is chosen to provide a channel in which the wall thickness around the channel is structurally well suited for support. Yet another shape or form of catalyst comprising a mixture of solid binder and phosphoric acid has ridges, grooves or channels with two ridges, grooves or channels on its surface. Composed of cylinders that range from 10 to 10. As in the case of polymerized flake-like catalyst particles, they may be solid or may have cracks, and the ratio to the catalyst volume of the outer surface is represented by the following <Formula I>.
It is larger than the value obtained in. [Formula I]

The catalyst calcined as described above polymerizes olefinic hydrocarbons, in particular conventional gaseous olefinic hydrocarbons to form conventional liquid hydrocarbons used as components of gasoline. However, it shows activity. When used to convert olefinic hydrocarbons to polymers,
Calcination catalysts formed as described herein are preferably made of conventional steel, through which
Used as a bed in a heated reactor to which preheated hydrocarbon pieces are sent. Thus, while the solid catalyst of this process can be used to treat a mixture of olefin-containing hydrocarbon vapors to promote olefin polymerization, the same catalyst can be used during the polymerization of olefinic hydrocarbons such as butylene during gasoline In order to be a component, it can be used under operating conditions suitable for maintaining liquid phase operation. When used in the polymerization of conventional gaseous olefins, the formed, calcined catalyst particles are usually placed in a vertical, cylindrical processing tower, and the olefin-containing gas mixture is heated to a temperature of 150 ° to 400 ° C. Ranges and pressures of 1 to 100 atmospheres (101.3 to 130 kPa) are passed downwardly therethrough. These conditions are particularly suitable when dealing with olefin-containing materials, such as stabilizer reflux containing about 10 to 50% or more polyolefin and butylene.
When used in a mixture consisting essentially of butane and butylene, the catalyst has a temperature range of 100 ° to 400 ° C.,
And it is effective under preferable conditions for maximum utilization of both ordinary butylene and isobutylene, including mixed polymerization in a pressure range of about 5 to 500 atm (506 to 50650 kPa).

The catalysts of this invention are also useful in the alkylation of aromatic hydrocarbons with alkylating agents. The alkylating agent filled in the alkylation reaction zone is selected from a group of various materials including monoolefins, diolefins, polyolefins, acetylene hydrocarbons, etc., and alkyl halogen compounds, alcohols, ethers, and esters, The latter includes alkyl sulphates and various esters of carboxylic acids. Preferred olefin-acting compounds are olefinic hydrocarbons consisting of mono-olefins containing one double bond per molecule. The mono-olefins that can be used as the olefin-acting compound in the process of the present invention can be either conventional gaseous or conventional liquids, ethylene, propylene, 1-butene, 2-butene, isobutylene, and various higher molecular weight compounds. Includes normally liquid olefins such as pentene, hexene, octene and mixtures thereof, and higher molecular weights such as propylene trimer, propylene tetramer, and propylene pentamer.
It includes liquid olefins, including various olefin polymers having 9 to 18 carbon atoms per molecule. Cycloolefins such as cyclopentane, methylcyclopentane, cyclohexene, methylcyclohexene are also available, but the results are not necessarily the same.
Other hydrocarbons containing from 2 to 18 carbon atoms such as paraffins and naphthenes are also present in the alkylating agent. When the catalyst of the present invention is used in an aromatic alkylation reaction, the monoolefin preferably contains at least 2 and no more than 14 carbon atoms. More specifically, it is desirable that the monoolefin be propylene. The aromatic raw materials to be mixed and filled in the alkylation reaction zone with the alkylating agent may be benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene (1,3,5-trimethyl). Benzene), pseudocumene (1,2,4-trimethylbenzene), hemimelitene (1,2,3-trimethylbenzene), ethylbenzene, o-dimethylbenzene, m-dimethylbenzene,
monocyclic alkyl-substituted benzene such as p-diethylbenzene,
And naphthalene, alkyl-substituted naphthalene, anthracene, and other aromatic compounds, including polycyclic aromatic compounds.

In a continuous process for alkylating aromatic hydrocarbons with olefins, the above-described reactants are continuously fed to a pressure vessel containing a solid phosphoric acid catalyst according to the present invention. This mixture is added to the alkylation reaction zone containing an alkylation catalyst in a constant amount or in a variable amount. Usually, the aromatic raw material and the olefinic alkylating agent are used in the ratio of 1: 1 to 20: 1, preferably 2: 1 to 1
Contact at a molar ratio of 0: 1. The preferred feed mole ratio helps maximize catalyst life by minimizing catalyst deactivation due to significant deposition of coke and material on the catalyst. The catalyst is placed in one bed in the reaction vessel or divided into a plurality of beds in one reactor. The alkylation reaction system can include one or a plurality of reaction vessels in series. The feed to the reaction zone is either vertically from bottom to top or top to bottom through the catalyst bed in a standard plug flow reactor, or across the catalyst bed in a radial flow type reactor. Alternatively, the flow may be in the horizontal direction. In some instances, it may be desirable to cool the reactants in order to dissipate the heat of reaction in order to keep the reaction temperature in the preferred range, thereby suppressing the formation of undesired polyalkylaromatics. .. Aromatic feed olefins, cooling streams of alkylating agents, alkyls, to dissipate heat and supply higher amounts of olefin alkylating agent and unreacted aromatic feed to various locations within the reaction zone. Agent, or reactor effluent,
Alternatively, a mixture thereof can be injected into the alkylation reaction system. This is achieved, for example, by feeding the cooling stream components in a single stage reactor multiple times through efficiently arranged inlet paths leading to the reaction zone. The amount and composition of the cooling material charged into the single-stage reaction system or the multi-stage reaction system can be changed as necessary. The advantage of multiple injections of coolant is that the process eliminates the need for costly cooling equipment and improves the selectivity for the formation of the required alkylaromatic compounds. , Providing a larger heat sink, and optimizing the olefin to aromatics ratio across the reaction zone, which results in increased yields of the desired monoalkylated aromatics. Suitable temperatures for use in this process are those that initiate a reaction between the aromatic feedstock and the particular olefin used to selectively produce the desired monoalkylaromatic compound. Generally, the suitable temperature for use is
The temperature is 100 ° to 390 ° C, particularly 150 ° to 275 ° C. Suitable pressures for use in this process are preferably 1 atmosphere (101.3 kPa) or higher, but should not exceed 130 atmospheres (13269 kPa). Particularly preferred pressure range is 10 to 40 atmospheres
(1013 to 4052 kPa), and liquid hourly space velocity (LHSV) based on benzene and supply rate is 0.5 to 50 hr ▲ Superscript −
▼ ¹ The combination of temperature and pressure used here should basically be a combination that causes a liquid phase or an alkylation reaction. In liquid phase operations that produce alkylaromatics, the catalyst is constantly washed by the reactants, thus preventing the deposition of precursors of coke on the catalyst. This reduces the amount of carbon formation on the catalyst, where catalyst life is compared to gas phase alkylation processes where coke formation and catalyst deactivation are major issues. become longer. In addition, a preferably adjusted amount of water is added to the alkylation reaction zone. To prevent water loss from the catalyst and subsequent reduction in catalysis, a constant amount of water or steam, such as steam, is added to substantially balance the steam pressure of the alkylation catalyst described above. Be done. This amount of water varies from 0.01 to 6% of the volume of organic material charged to the alkylation reaction zone. Usually after this, this water is removed with the light by-product stream collected in the first separation zone. With the tubular or polymerized flake shaped shaped particles of the present invention, when using a continuous type operation in which the solid phosphoric acid catalyst is placed as a fixed bed in the reaction zone, appropriate operating conditions including pressure are used. It is possible to maintain. This appropriate operating pressure will remain fairly constant during use, even if the catalyst particles swell due to various conditions, including the volume of coke on the surface of the catalyst particles. The size or volume of the particles is
Even with a 10% to 150% increase, it is possible to maintain a sufficient amount of voids in the reactor, which allows the process to be kept at fairly constant operating conditions.

While the above description has been centered primarily on the use of continuous type operations, it is contemplated that the conversion of organic compounds may be carried out in batch type operations. When this type of operation is used, a certain amount of the desired catalyst is placed in a suitable device, which comprises, for example, a rotary or stirred type autoclave, and the device is charged with one or more organic compounds to be converted. The device at 1 to 100 atmospheres or more (1
100 ° to 400 at pressures ranging from 01.3 to 10130 kPa)
Heated to the desired operating temperature of ° C. As long as this method is carried out in the liquid or vapor phase, pressure does not seem to be the most important variable. Therefore, the pressure used to promote this reaction can be selected purely from the most favorable pressures based on economic considerations, and the specific reaction which is subjected to the process under the required processing conditions. Product stability is obtained. Then, at the end of the predetermined residence time, the device and its contents can be cooled to room temperature, excess pressure is released and, for example, polymerized olefinic hydrocarbons or alkylaromatic compounds are filtered or centrifuged. The catalyst is recovered and separated from the catalyst by a usual method, and further separated and recovered from other unreacted substances by a usual method such as fractional distillation and crystallization. Examples of the present invention relating to molded catalyst particles will be described below.

[0020]

【Example】

REFERENCE EXAMPLE 1-PRIOR ART A cylindrical extruded product of a solid catalyst composition composed of polyphosphoric acid and a diatomaceous earth binder and containing 73.1 weight percent phosphoric acid as polyphosphoric acid was placed in a reactor, and C
₃ and C ₄ paraffins and olefins, and 250ppm
A feed stream consisting of some H ₂ O was contacted to maintain hydration of the catalyst for a time sufficient to produce 40 gallons of olefin polymer per pound of catalyst.
During this operation, the pressure drop through the reactor is 2psi to 36p
increased to si (13.8 to 248 kPa). At the end of this operation,
The catalyst used was removed from the reactor tube and inspected. Reactor tube depth 5 to 10 feet (1524-3048m
A representative sample taken from m) showed significant swelling compared to a sample of virgin catalyst, with the catalyst particles compacted into a single solid material with significantly reduced voids.

Example 1 Experimental plant tests have been carried out in order to quantify the swelling that occurs on catalyst particles of the composition of the invention during use for olefin polymerization. Twenty individual test pellets of extruded solid catalyst composition composed of polyphosphoric acid and diatomaceous earth binder were each molded into a 0.3 x 0.4 cm cube. Measure the volume and weight of each cube and then use 5 stainless steel baskets in a 7/8 inch (19.6 mm) ID reactor to isolate each catalyst cube from everything else. I put it in. Three tests were carried out, in each of these tests a hydrocarbon composed of an equal amount of propylene and a commercially produced propylene polymer with 1 weight percent H ₂ O added at 375 ° C. 300psi (2175kPa), and 17hr ▲
-The reactor was placed under ¹ WHSV condition for 4, 20 and 30 hours respectively. After the end of the designated time, the used catalyst cubes were collected and weighed and volume measured. The increase in weight and volume compared with the weight and volume of the unused catalyst is as shown in Table 1.

[Table 1] Test times Flow time Weight% increase amount Volume% increase amount 1 4 9 ± 7 26 ± 11 2 20 34 ± 12 91 ± 25 3 30 55 55 ± 15 122 ± 32

Example 2 According to engineering calculation and engineering design information developed over many years, the physical attributes of a solid phosphoric acid catalyst composed of a mixture of phosphoric acid and a solid binder are shown in Table 4 below. Becomes

[Table 4] Calculation attributes

Further, when used as a catalyst in a reactor, the catalyst particles have the porosity shown in the table below.

TABLE 3 Shape ABD piece density porosity solid cylindrical 0.990 1.65 0.400 cubic lobular shape 0.908 1.65 0.450 tubular cylindrical 0.795 1.65 0.518

According to engineering calculations, the properties of solid phosphoric acid catalysts of various shapes exhibit the performances shown in Table 3 when used as polymerization catalysts in the reactor. In this case, a raw material composed of a mixture of propylene and propane of about 50/50%, a raw material of butylene and butane of about 50/50%, or a raw material of a mixture of propylene, butylene, propane and butane in almost the same ratio. But about 200
Input temperature of ℃, 1000psi (6998kPa), 2.5hr ▲
▼ It is passed over the catalyst in the tubular reactor which is kept in the condition of LHSV of ¹ .

[Table 2] It should be noted in the above calculation that the catalyst particles having the shape of cubic clefts or tubular cylinders can be used to feed the raw materials without causing a large pressure drop that makes the method impossible to carry out. To maintain a sufficient amount of porosity to pass over the catalyst. For example, relative time 100
The pressure drop with solid cylindrical particles at 50 psi (345 k
Pa), whereas in the case of cubic lobed particles,
17.8 psi (123 kPa) and the pressure drop for tubular cylindrical particles is only 5.9 psi (41 kPa). The pressure drop or P at relative time 150 is 1.000 psi (6895 kP
a) or more, whereas 102ps for cubic clefts
i (703 kPa), and 15.1 psi (104 kPa) for tubular cylinders. This pressure drop would stop the flow of feed through the reactor when using a solid cylinder. Similar calculations also show that the same results would be obtained with catalyst particles having shapes such as ridges, grooves, or channeled cylinders. Thus, from the above calculations, the use of a catalyst having the desired shape allows retention of a sufficient amount of porosity during operation as compared to catalyst particles previously used in this type of reaction. It is obvious.

[0025]

INDUSTRIAL APPLICABILITY The present invention is a phosphoric acid catalyst for converting an organic compound whose shape does not change, decompose or swell during operation. Therefore, the use of this catalyst is a useful invention in which the conversion operation of the organic compound can be carried out extremely efficiently and continuously.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07C 15/00 8619-4H // C07B 61/00 300 (72) Inventor Paul Tay. Virginia United States, 6005 Arlington Heights, Wall Natsuto Street 1302, Illinois (72) Inventor Harold You. Hammershire Yves United States, 60553 Illinois, Western Springs, Central Ave Any 4377

Claims (9)

[Claims] 1. An organic compound-converted solid made from a molded extruded product of a mixture of phosphoric acid and a solid binder, the ratio of which is larger than the value determined by the following <formula (I)>, in which the ratio of the external surface area to the catalyst volume is larger than Catalyst mixture. [Formula I] Here, D is the maximum representative diameter, and L is the length of the extruded product. 2. The solid catalyst mixture of claim 1, wherein the extrudate is made of polymerized flake shaped, tubular, ridged, grooved, or channeled cylindrical particles. 3. The solid catalyst mixture according to claim 1, wherein the binder is composed of diatomaceous earth or artificially prepared silica. 4. The solid catalyst mixture of claim 1, 2 or 3 wherein the shaped extrudate has an aperture in its central portion. 5. The solid catalyst of any of claims 1 to 4, wherein the shaped extrudate increases in diameter, thereby increasing the volume of the extrudate by 10% -150% from the initial volume. 6. An organic compound is contacted with a solid catalyst mixture made of the extruded product according to any one of claims 1 to 5 under conversion conditions, and the conversion product produced is recovered. Method for converting organic compounds. 7. The method of claim 6 wherein the conversion conditions include a temperature of 100 ° -400 ° C. and a pressure of about 1 atmosphere to 500 atmospheres (101.3-50650 kPa). 8. The method according to claim 6, wherein the conversion method is alkylation of an aromatic compound with an alkylating agent. 9. The method of claim 6 or 7 wherein the conversion process is the polymerization of an olefinic hydrocarbon containing about 2-4 carbon atoms.
the method of.