KR100197923B1 - Bound pillared clay for use in the production of alkyl aromatic compounds - Google Patents

Abstract

The present invention is to disperse the clay in the metal columnar joints, to separate the resulting columnar clay, to wash and dry the columnar clay, to form a dough of columnar joint clay and the binder compound, and to extrude the drum And an alkyl aromatic compound comprising reacting an alkylating agent and an aromatic compound selected from the group consisting of olefins, alkyl halides and alkyl alcohols under alkylation conditions in an alkylation zone in the presence of a catalyst prepared by firing the extrudate. It relates to a method for producing.

Description

Bonded columnar clay for the production of alkyl aromatic compounds

The present invention relates to columnar joint clay for the production of alkyl aromatic compounds.

Alkyl aromatic compounds form important compounds that can be used as intermediates in many industries, such as, for example, polymeric materials, plasticizers and detergents. Conventionally, alkyl aromatic compounds have been prepared by alkylating an aromatic compound with an alkylating agent in the presence of an acid catalyst. Examples of these acid catalysts include sulfuric acid and hydrogen fluoride because they have relatively good activity for their intended purpose.

However, there are some inherent disadvantages in using these acid liquids, such as sulfuric acid or hydrofluoric acid. Conventional acids are inherently corrosive and dangerous and require special handling and equipment.

The use of these acids also raises the environmental risks presented here. Thus, it may be desirable to use safer and simpler catalysts, preferably solid catalysts, in fixed bed reactors to produce the desired compounds.

Using a simple manufacturing process can save money on capital investments, so producers can offer cheaper products.

In this regard, solid alkylation catalysts can now be used to perform the desired alkylation to provide products equivalent in quality to those obtained using liquid acid catalysts, while at the same time improving the activity of the catalyst and the selectivity of the product as well. I found it possible.

Natural clays such as smectites, vermiculite and bentonites are semicrystalline aluminosilicate layers (leaf-like structures) that are bound together by Van der Waals and electrostatic forces. Consists of.

Anionic charges on the siliceous layer are neutralized by cations present in the interlamellar spaces. These cations, typically Na ⁺ and Ca ^2+, are separated by large amounts of inorganic cations such as Fe ³⁺ or Cr ³⁺ , or metal hydroxy polymer cations such as [Al ₁₃ O ₄ (OH) ₂₄ ( H ₂ O) ₁₂ ] ⁷⁺ or [Zr (OH) ₂ .4H ₂ O] ₄ ⁸⁺ .

The polymer cations serve as pillars that hold the clay layers apart.

Columnar joint clays are known to catalyze many reactions, such as alkylation, cracking, ester formation, dimerization, oligomerization reactions, and the like. The reaction catalyzed by columnar joint clay is M. Outlined by J. M. Adams, Applied Clay Science, Vol. 2, pp. 309-342, 1987.

Among these reactions, alkylation reactions are of particular interest.

For example, United States, in particular US Pat. No. 4,499,319, describes filling clays such as montmorillonite ion-exchanged with metal cations, for example chromium and aluminum, used to alkylate aromatic compounds. Other examples include US Pat. No. 4,605,806, which discloses hydrogen ion-exchanged columnar clay; Metal cation exchanged synthetic hectorite type clays useful for alkylation of aromatic hydrocarbons and US Pat. No. 3,965,043, which discloses metal cation exchanged triocta headal 2: 1 fill-layer-lattice smectite type clays. U.S. Patent No. 3,979,331 is disclosed.

With respect to the prior art, it has now been found that alkylation of aromatic compounds can be achieved by using columnar cutting clays which are mixed with binder compounds to form the desired catalyst composition by extruding, drying and calcining the resulting dough.

The resulting catalyst has excellent properties in terms of activity of the catalyst and selectivity of the product obtained by the alkylation reaction.

The present invention relates to the preparation of alkyl aromatic compounds and to catalysts that can be used to carry out the desired reactions. More specifically, the present invention provides a highly biodegradable detergent that minimizes the production of foam or soap bubbles on the water surface by causing bacteria to act on this alkyl chain and degrade the detergent due to the presence of linear alkyl substituents on the aromatic ring. It relates to a process for preparing alkyl aromatic compounds that can be used to prepare.

By using the catalyst of the present invention, it is possible to obtain straight chain alkyl aryl cleaners, in particular due to the good selectivity of the catalyst for alpha olefins to obtain the desired alkyl aromatic product.

When using the catalyst of the present invention, the activity of the catalyst is maintained for a relatively long time, and an alkylation method can be carried out to selectively obtain the product from the reaction.

It is therefore an object of the present invention to provide a catalyst composition that can be used to effect alkylation of aromatic compounds.

Another object of the present invention is to provide a necessary method for producing an alkyl aromatic compound in addition to providing a method for preparing the catalyst composition as described above.

In one aspect of the invention, embodiments of the invention disperse clay in metallic pilaring agent sol, isolate the resulting columnar clay, wash and dry the columnar clay, and the columnar clay and binder In the presence of a solid catalyst prepared by forming a kneading of the compound, extruding the kneading, and calcining the resulting extrudate, the aromatic compound is converted into an olefin, an alkyl halide and an alkyl alcohol under alkylation conditions in an alkylation zone. A method for producing an alkyl aromatic compound comprising reacting with an alkylating agent selected from the group consisting of.

A particular embodiment of the invention is to disperse bentonite clay in a metallic columnar sol sol consisting of aluminum chlorohydrol solution, to separate columnar clay, to wash the columnar clay, and to dry the clay and then to dry the clay. And alumina solution are mixed to form a dough, the dough is extruded, the dough is dried, and a temperature of 80 ° C to 450 ° C and 1482 to 7000 in the presence of a preferred solid catalyst prepared by firing the dried extrudate. At a pressure of KPa (200 sowl 1000 Psig), an aromatic consisting of reacting benzene with an alkylating agent consisting of a mixture of olefins containing 2 to 20, preferably 9 to 15 carbon atoms, in the chain and recovering the alkylated benzene It is a manufacturing method of a compound.

The composite catalyst of the present invention comprises columnar cutting clay which is treated with a binder compound to extrude, and the extrudate is dried and calcined to form a desired catalyst.

One component of the catalyst of the invention consists of clay.

Both natural and synthetic clays can be used, examples being bentonite, sepiolite, laponite, vermiculite, montmorillonite, kaolin, palygorskite (attapulgus), hectorite, claw Light, beadellite, saponite and nontronite, although not limited thereto.

Among the clays, laponite ^™ is synthetic clay (manufactured by LaPorte Co.), and montmorillonite, hectorite, baydelite and saponite have synthetic analogues.

These clays (both natural and synthetic analogues) can be used as such (or synthesized), or these clays can be prepared by columnar clays by ion exchange with metals or by introducing pillars between layers to modify them. have.

Clays including all of the clays listed above may be ion exchanged with one or more metals selected from the group consisting of Fe ³⁺ , Cr ³⁺ , Al ³⁺ , Ti ⁴⁺ and Zr ⁴⁺ .

The clays into which the pillars are introduced are smectite clays (natural and synthetic) which are hectorite, baydelite, laponite ^™ , nontronite, saponite and montmorillonite.

The clays can be columnarized by any known method using metallic columnar jellys, in particular oxychlorides of aluminum, zirconium, lanthanum, cerium and titanium. It should be noted that the clay and metallic columnar jellys listed above, including both natural and synthetic, are merely representative forms of clay and columnar joints that may be used in the present invention, and the present invention is not limited to the clay and columnar joints. .

After the clay is columnarized by dispersing the clay in a columnar solution, the resulting columnar clay is separated from the mother liquor, washed with water to remove excess metal salts, and dried.

The dried columnar clay is then mixed with a binder consisting of silica, alumina, titania, zirconia, aluminum phosphate and the like in a preferred embodiment of the present invention.

In other words, it is to be understood that these compounds are merely exemplary binder compound forms that may be used in the present invention, and the present invention is not limited to these compounds.

Mixing of the columnar clay and the binder compound is accomplished by adding the columnar clay to a paste of the binder compound to form a dough. The dough is then extruded through a die to obtain a catalyst of the desired particle shape and size, and then at a temperature of ambient temperature (20-25 ° C. to 150 ° C.), about 1 hour to 16 hours depending on the temperature used. Dry for time.

After the extrudate is dried, it is aged in an air atmosphere or an air atmosphere containing about 1 to 20% of steam at a temperature range of 300 to 800 ° C. for about 1 to 20 hours.

Alkylation of aromatic compounds using the complex catalyst of the present invention can be carried out by any suitable method using batch or continuous operation. The aromatic compound treated with the alkylating agent may be a monocyclic or polycyclic compound.

In addition, aromatic compounds may contain substituents on the ring, and examples of these aromatic compounds include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, naphthalene, isomeric methyl naphthalene and isomeric ethyl Naphthalene, anthracene, chrysene, pyrene, and the like.

Alkylating agents used as the second component in the production method include olefins having 2 to 20 carbon atoms, alkyl halides, alcohols and the like.

Some specific examples of these alkylating agents include ethylene, propylene, isomeric butenes, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, Nonadecene, eicosene, and the like; Methyl chloride, ethyl chloride, propyl chloride, butyl chloride, hexyl chloride, octyl chloride, decyl chloride, dodecyl chloride, tetradecyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, heptyl bromide, nonyl bromide, unbrominated bromide Etc; Methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, etc. are mentioned.

It can also be seen that the olefin mixture is also used as an alkylating agent.

The alkylation reaction can be carried out in a batch operation by placing the aromatic compound and the alkylating agent together with the complex catalyst in a suitable apparatus such as a rotary or mixed autoclave.

In a preferred embodiment of the invention, the alkyl aromatic compound amount is present in excess of the alkylating agent in the reaction mixture, preferably in the range of 2: 1 to 20: 1 moles of aromatic compound per mole of alkylating agent.

The reactor is sealed and heated to a predetermined operating temperature. At this time, the operating temperature may be 80 ℃ to 450 ℃. In addition, in order to effectively perform the reaction in the liquid phase, it is pressurized to maintain an operating pressure of 1482 to 7000 kpa (200 to 1000 psig).

The operating pressure used can be obtained by introducing an inert gas such as nitrogen, helium, argon, etc. when the alkylating agent is in liquid phase. In contrast, when the alkylating agent used is gaseous, part of the operating pressure is covered by the original pressure of the gaseous alkylating agent and the rest is provided due to the presence of an inert gas.

When the reaction is complete (which may take from about 0.5 to about 4 hours or longer) the heating is stopped, the overpressure is evacuated after the reactor and its contents have cooled to room temperature and the autoclave is opened to recover the reaction mixture. .

The desired alkyl aromatic compound can then be separated and recovered from the unreacted starting material using conventional methods such as fractional distillation.

When the alkylation reaction of the present invention is carried out continuously, some complex catalyst is added to the reactor. At this time, the reactor may be tubular. After heating the reactor to the desired operating temperature and reaching the desired operating pressure, the reactants consisting of the aromatic compound and the alkylating agent are continuously passed through the catalyst bed at an hourly liquid space velocity of 0.25 to 2 hr ⁻¹ or more.

After passing through the catalyst bed for a predetermined period of time, the reactor effluent is continuously discharged and introduced into conventional separation means to separate and recover the desired alkyl aromatics so that unreacted starting materials form part of the feedstock. May be recycled into the reactor.

In the case of the complex catalyst of the present invention which is inherently solid, various types of continuous operation methods may be used. For example, aromatic compounds and alkylating agents can be passed through the bed in an upflow or downflow while maintaining the catalyst in the reactor as a fixed bed.

In addition, this fluidized bed operation may be used in which the catalyst bed and reactants are passed through the reactor in the forward or reverse direction. Likewise, the slurry type operation may use a slurry type operation in which the catalyst is carried to the reactor as one or both of the reactants as a slurry.

The catalysts and methods of the present invention are described in the following examples.

Example 1

Columnar joints were obtained by diluting a 50% aluminum chlorohydrol solution with a sufficient amount of water to obtain a 0.484 molar solution, followed by digesting the solution at 95 ° C. for 3 hours.

Bentonite clay was then dispersed in columnar joints at about 65 ° C. for 2 hours. The amount of bentonite clay used was used such that the ratio of aluminum / clay was sufficient to meet 7.0 millimoles of aluminum per gram of dry clay.

The clay was allowed to columnar with the aluminum compound and then separated from the mother liquor, then washed thoroughly with water to remove excess aluminum sol and reducing the chlorine concentration in the columnar clay.

The columnar joint clay cake was then dried in a thin plate to a temperature of about 100 ° C. to prevent the formation of fine coagulum.

The catalyst of the present invention was prepared by wetting 200 g of alumina with 800 g of deionized water and then mixing it sufficiently. Then, 29.1 cc of nitric acid was slowly added with sufficient mixing. 800 g of columnar joint clay prepared as described above was added to the alumina mixture while sufficiently stirring the compounds.

The dough thus formed was extruded through a die to form an extrudate of 0.8 mm (1/32 inch) diameter. The extrudate was then dried at a temperature of 110-150 ° C. for about 16 hours, then placed in an oven, warmed to 400 ° C. for 2 hours, and held at 400 ° C. for 2 hours further under a flowing air atmosphere. Fired.

This extrudate was then recovered and termed catalyst A. For comparison purposes, this extrudate was washed and cut into 10-40 mesh (0.4-2 mm) sizes for testing.

Example 2

A comparative second catalyst (not the catalyst of the invention) was prepared in a similar manner to Example 1 as described above, i.e., by diluting the aluminum chlorohydrol solution with water and digesting at 95 ° C for 3 hours.

Bentonite clay was then dispersed in columnar paste and the dispersion was held at about 65 ° C. for 2 hours. The clay was columnar jointed with an aluminum solution, separated from the mother liquor and dried to prepare a filter cake and calcined at 400 ° C. for 2 hours. Columnar joint clay was then cut into 0.4-2 mm mesh sizes for testing. This catalyst was named Catalyst B.

Example 3

For the purpose of comparison, a third catalyst (not the catalyst of the invention) consisting of montmorillonite clay trade name Filtrol 24 clay was prepared. This catalyst was named Catalyst C.

Example 4

25 cc of each of the three catalysts of Examples 1 to 3 were placed in a tubular stainless steel reactor having an internal diameter of 12.7 mm (1/2 inch) and used for the alkylation reaction. An alkylating agent, consisting of a mixture of benzene and olefins containing 10 to 14 carbon atoms, was introduced into the reactor at a liquid space velocity of 2 ^{hr −1} per hour mixed with a benzene / olefin feed molar ratio of 8: 1.

The reactor was maintained at 150 ° C. and 3550 kPa (500 psig) pressure. The product recovered from the reactor was analyzed to determine olefin conversion (%), detergent alkylate selectivity (%) and linearity percentage (%).

The results of these analyzes are shown in the following table.

From the table above, the detergent alkylate selectivity (%), which can be defined as the total weight of monoalkyl benzene divided by the total weight of all products including dialkyl benzene, olefinic oligomer and monoalkyl benzene, is determined by the catalyst of the present invention. It can be seen that in all cases consisting of columnar clay mixed with a binder it is always larger than the catalyst without the binder.

Therefore, this makes it clear that the binder is present in admixture with columnar clay to obtain a larger amount of the desired product comprising monoalkyl benzene which can be used as an intermediate in the preparation of biodegradable detergents.

Claims (8)

Dispersing clay in a metal pillaring agent stroke, separating the resultant columnar clay, washing and drying the columnar clay, and selecting from the group consisting of the columnar clay and alumina, silica, titania, zirconia and aluminum phosphate Alkylation conditions in the alkylation zone in the presence of a solid catalyst consisting of columnar cutting clay and a binder compound, which are formed by forming a semi-anhydride of the resulting binder compound, extruding the dough and then firing the extrudate. And reacting with an alkylating agent selected from the group consisting of olefins, alkyl halides and alkyl alcohols. The method of claim 1 wherein said alkylation conditions comprise a temperature of 80 ° C. to 450 ° C. and a pressure of 1482 to 7000 kPa. The method of claim 1 wherein the alkylating agent contains 1 to 20 carbon atoms. 4. A process according to any one of claims 1 to 3, wherein said alkylating agent contains 9 to 15 carbon atoms. The process according to claim 1, wherein the aromatic compound is benzene or toluene or naphthalene. The clay according to any one of claims 1 to 3, wherein the clay is burnonite, vermiculite, montmorillonite, kaolin, sepiolite, polygorskite, hectorite, chlorite, baydelite, saponite, nontronite and Wherein the metallic columnar jelly is selected from the group consisting of oxychlorides of aluminum, zirconium, lanthanum, cerium and titanium. The method according to any one of claims 1 to 3, wherein the amount of the binder compound is 5 to 50% by weight of the columnar clay. A binder compound selected from the group consisting of clay and alumina, silica, titania, zirconia and aluminum phosphate, the clay being dispersed in a metal columnar sol, the resulting columnar clay being separated, the columnar joint clay washed and dried An alkylation catalyst consisting of columnar joint clay and a binder prepared by forming a semi-anhydride of the product, extruding the dough, and calcining the extrudate.