KR820001444B1 - Process for preparation of aluminium modified sillida - Google Patents

Abstract

The title catalysts useful in the alkylation of benzene, C4 hydrocarbons, olefins, and paraffins and in the purifn. of exhaust gases, are manufd. by treating a Si or Ge deriv. with an Al compd. in aq. or alc. soln. in the presence of an alc., amino, or aminolac. clathrating compd., an alkali or alk. earth mineralizing agent, and an inorg. base. The same procedure can be used to prep. a ZSM-5 type zeolite(0.9±0.2) M2/nO.W2O3. (5-100)YO2ZH2O (M = Cation; n = cation valency; W = Al or Ga; Y = Si or Ge; Z = 0-40).

Description

Method for producing aluminum modified silica

1 and 2 are respectively the chard of the X-ray diffraction spectra of the product according to the present invention.

The present invention relates to silica modified with aluminum.

Numerous materials based on silica and alumina are known, some of which are natural and others which are artificial.

Among these materials, materials called zeolites are known and these materials have absorbency, properties as a molecure, and catalytic activity. Such materials contain different amounts of alumina in a wide range of ratios to silica. The maximum value of the non-silica alumina is 100/1, but the value of this ratio is generally very small and preferably about two.

These materials, which contain tetrahedral coordination aluminum in place of silicon, are electrically neutral and therefore contain cations that parallel charges due to the presence of aluminum atoms coordinated to tetrahedrons. Must contain. The protonic acidity of zeolite is due to the hydrogen atom introduced to exchange such cations. On the other hand, crystalline silica does not have a protonic charge because of its inherent properties and therefore does not exhibit acidic properties (not inherent to silicic acid).

Indeed, many crystalline silicas are known, from cristobarite to lingyurite, keatite and the like, and they are prepared according to methods well known in various scientific literatures.

Heideman, for example, obtains crystalline silica called silica X by reacting amorphous silica with 0,55% KOH at 180 ° C. for 2.5 days (see Beitr. Min. Petrog. 10,242. (1964)).

At the same time, these silicas have a specific surface area of about 10 m 2 / g and are also less stable and, within five days, change to cristobarite and then to quartz.

Recently, Flanigen et al. Have also obtained new crystalline silica (see Nature 271,512 (1978)). These silica lights have a high specific surface area and because of their hydrophobic nature, they propose to use them for the purification of contaminated water by organic matter.

An object of the present invention is to change the properties of crystalline silica to use it as a catalyst or to prepare a catalyst without changing the stability of such silica with aluminum. In fact, the inventors of the present invention have found that a substance different from zeolite is obtained in order to have a very high specific silica / alumina but not to have a minimum amount of aluminum having a crystalline silicon phosphate structure.

On the other hand, these new materials are clearly distinguished from crystalline silica in that the small amount of aluminum introduced varies the acidity in a wide range.

These materials actually have the same or higher protonic acidity of zeolites as their zeolites themselves, while retaining the very high structural stability of crystalline silica, whereas protonic zeolites X and Y are the only exceptions. Stone-based) is very unstable because it tends to be easily changed to stable silica alumina.

Silica alumina itself has almost low acidity. For example, commercially available silica alumina containing 25% by weight of alumina has a H ⁺ concentration of about 1 × 10 ⁻³ meq (milliequivalent) per 1 g of catalyst. It is also surprising that the present inventors have found that by appropriately controlling the amount of aluminum in the material, the acidity can be controlled and thus adapted to the range required by the reaction using it.

SUMMARY OF THE INVENTION An object of the present invention is to provide a silica modified with the best acidic properties and catalytic activity for a specific reaction by introducing aluminum atoms.

Another object of the present invention is to show a suitable method for the preparation of this kind of material.

Silica modified by introducing aluminum atoms has another general formula.

1 Si. (0.0012-0.0050) Al. Oy

In addition, the content of the crystallized water depends on the temperature of the simple element.

In order to obtain the aluminum-modified silica of the present invention, it is advantageous to employ the following operation method.

In aqueous, alcoholic or hydroalcoholic solutions, one or more mineralizers and cases for the inclusion or mooring of silicon derivatives and aluminum derivatives in some cases to promote crystallization. According to the present invention, the mixture obtained by adding an inorganic base and then reacted is crystallized with a main acid at 100 ° C. to 220 ° C. for several hours to several days, preferably 150 ° C. to 200 ° C. in a vessel, cooled, filtered, and dried. It is calcined at 550 ° C. to 700 ° C., preferably at 550 ° C. for 2 to 24 hours, washed with boiling distilled water dissolved in an ammonium salt, preferably ammonium nitrate or ammonium acetate to remove exchangeable cationic impurities and calcined under the conditions described above.

As the silicon derivative, silica gel (obtained by various methods) or tetraalkyloltosilicates such as tetraethyloltosilicate and tetramethyloltosilicate is used.

Aluminum derivatives, preferably among salts of aluminum, such as nitrates or nitrates.

Subsequent mooring or inclusions include tertiary amines, aminoalcohols, amino acids, polyalcohols and tetraalkylammonium (NR ₄ OH where R is an alkyl group having 1 to 5 carbon atoms) or tetraarylammonium (NA ₄ OH: where A is a phenyl group or an alkylphenyl group).

The mooring substance is a moderately large molecule with the function of generating a crystal structure having holes of a predetermined size. The optical agent is selected from hydroxides and halides of alkali or alkaline earth metals. For example, LiOH, NaOH, Ca (OH) ₂ , KBr, NaBr, NaI, CaI, CaBr ₂ .

The inorganic base to be added is selected from hydroxides of alkali or alkaline earth metals, preferably NaOH, KOH, Ca (OH) ₂ and ammonia.

The amount of the inorganic base and / or clathrate material to be used is generally below the stoichiometric amount with respect to silica, and preferably 0.05 to 0.50 mole per silica / mole.

The product thus obtained is specified by the protonic acidity which is influenced by changing the Si substituted ions to be introduced. For pure silica, the hydrogen ion concentration per gram of sample is 1 × 10 ⁻³ meq. This acidity is about 1 × 10 ⁻¹ meq. To be increased.

The material according to the present invention is characterized by a specific crystal structure as shown by the X-ray diffraction spectra shown in FIGS. 1 and 2. Moreover, 150 m <2> / g or more and generally 3000 m <2> / g have a high specific surface area.

Aluminum strongly alters the acidity of silica, but the presence of this aluminum produces crystalline materials. This specter is very similar to that reported by Nature 271.512 (1978) on silicate called crystalline silica and vice versa.

The silica modified with aluminum according to the invention is used alone or as a catalyst or as an absorbent by dispersing on an inert carrier with high and low specific surface area and porosity.

The carrier has a role to improve the physical and mechanical stability and catalytic properties of the materials involved. The method used to obtain the supported material is selected from those known in the art and those skilled in the art.

The amount of carrier is 1% to 90% but preferably 5% to 60%. Among the good carriers there may be mentioned cray, silica, alumina, diatomaceous earth silica alumina and the like.

The alumina-modified silica according to the present invention is used as a catalyst for various reactions, and these reactions include alkylation of benzene. More specifically, alkylation of benzene by ethylene and alkylation of benzene by ethanol.

The following are mentioned as another reaction to be reacted.

1. Reaction of alkylating toluene with methanol to produce xylene mainly paraxylene.

2. A clot that disproportionates toluene to produce primarily paraxylene.

3. Reaction of dimethylethyl and / or methanol or other lower alcohols to hydrocarbons (olefins and aromatics).

4. Crossing and Hydro Crossing

5. Isomerization of Nomal Paraffin and Naphthenes

6. Polymerization of Compounds Containing Olefin or Thitylene Bonds

7. Modification

8. Isomerization of polyalkyl-substituted aromatics, for example oltokisylene

9. Disproportionation of aromatics, especially toluene

10. Reaction of aliphatic carbonyl compounds at least partially with aromatic hydrocarbons

11. Separation of ethylbenzene from other C ₈ aromatic hydrocarbons.

12. Hydrogenation and Dehydrogenation of Hydrocarbons

13. Methanation

Some examples are given below to illustrate the invention without limiting it.

Example 1

This example relates to the production of porous crystalline silica TRS-22 in which aluminum is introduced as a silicon substituent in the crystal lattice.

A pyrex glass container kept in a nitrogen atmosphere at all times was filled with 80 g of detraethyl oltosilicate (TEOS) and heated to a temperature of 80 ° C. while stirring. Then, a solution containing 20 g of detrapropylammonium hydroxide (prepared with detrapropylammonium and moistened silver oxide, removed from inorganic alkali) is added to 80 ml of distilled water, until the mixture becomes homogeneous and transparent (about 1 Time) The stirring was continued at 80 ° C.

Next, 80 g of Al (NO ₃ ) ₃ 9H ₂ O dissolved in 50 ml of anhydrous ethanol was added. Immediately after, a dense gel was produced. Distilled water was added thereto to make the volume 200 ml, while stirring was actively performed as necessary. The mixture was then boiled to complete the hydrolysis and to remove all ethanol, ie the additions and those produced by the hydrolysis. The time used for these processes was 2 to 3 hours, and the gel slowly turned into a white object. This is a precursor to modified crystalline silica.

Distilled water was then added, and the container of the mixture was placed in an autograph and left to stand at a temperature of 155 ° C for 7 days. The solid produced after cooling was centrifuged for 15 minutes at a speed of 10,000 rpm, then re-sterilized in distilled water and centrifuged again. This washing process was repeated four times. The product was dried in a furnace at 120 ° C. This product showed crystallinity by X-ray diffraction.

Chemical analysis of the sample dried at 120 ° C. showed the following composition.

Alkali metals present are derived from reagents or glass because they are not deliberately added.

The impurity obtained in order to remove the alkali impurity present from a compound was prescribed | regulated for 16 hours at 550 degreeC under air flow, and then it wash | cleaned repeatedly with boiling distilled water which melt | dissolved ammonium acetate, and baked at 550 degreeC for 6 hours.

The specific surface area (measured by the BET method) was 444 m 2 / g. In addition, the proton concentration per 1 g of the sample was 1.5 × 10 ⁻¹ milliequivalents (meq).

Example 2

This example relates to the preparation of porous crystalline silica TRS-0 in which trace aluminum is introduced as a substituent of silicon in the crystal lattice.

The mixture was heated and boiled by adding 40 g of tetraethyloltosilicate (TEOS) and 120 ml of 20% (weight) solution of detrapropyl ammonium hydroxide to a Pyrex glass vessel equipped with a reflux condenser and maintained in a nitrogen atmosphere. What was obtained was a colorless transparent solution which remained transparent even after refluxing for a long time.

In this step, 30 mg of Al (NO ₃ ) ₃ 9H ₂ O was added, and the liquid became milky white, and white powder was separated from them by applying heat.

After boiling for 6 days, the mixture was cooled, the solid was driven on a filter, washed with distilled water, and dried at 100 ° C. The product dried at 100 ° C. showed crystallinity by X-ray diffraction spectroscopy. Subsequently, it baked for 16 hours at 550 degreeC under airflow, and it wash | cleaned repeatedly with boiling distilled water which melt | dissolved ammonium acetate again, and then solid substance was baked at 550 degreeC for 6 hours.

The chemical composition of the product thus obtained showed the following composition.

Traces of alkali metals present are thought to be derived from reagents and glass because they are not consciously added at all.

The specific surface area (BET method) of this product was 420 m 2 / g, and the proton concentration per 1 g of sample was 1.9 × 10 ⁻¹ meq.

Example 3

This example relates to the preparation of porous crystalline silica TRS-23 in which aluminum is introduced as a substituent of silicon in the crystal lattice. In the preparation of this silica, an organic base different from the bases used in Examples 1 and 2, namely Detraethylammonium hydrooxide was used.

In the same manner as in Example 1, it was dissolved in 80 g of detraethylol tosilicate, 68 ml of 25% (weight) aqueous solution of detraethylammonium hydroxide, and 50 ml of anhydrous ethanol. 80 mg of Al ₂ (NO ₃ ) ₃ 9H ₂ O and ₂ g of NaOH perlan dissolved in 10 ml of distilled water were reacted to maintain the mixture at 155 ° C. for 18 days.

The product dried at 120 ° C. showed crystallinity by X-ray diffraction. Sample (the firing to 550 ℃) concentration of furo tons per 1g is 1.1 × 10 ^- was 0meq.

Chemical analysis of the complete rinse and then calcining at 550 ° C. showed the following composition.

The specific surface area (BET method) was 470 m 2 / g and the concentration of protons per 1 g of sample was 4.3 × 10 ⁻³ meq.

Example 4

This example relates to the preparation of porous crystalline silica TRS-19 in which aluminum is introduced as a substituent of silicon in the crystal lattice, and in the preparation of this silica, an organic base different from the base used in the above-described embodiment, that is, tetrabutylammonium Hydrooxide was used.

In the same manner as in Example 1, a solution containing 100 mg of Al (NO ₃ ) ₃ 9H ₂ O in 50 g of tetraethyloltosilicate and 50 g of anhydrous ethanol; A solution containing 29 g obtained from one silver oxide) and ² g of NaOH dissolved in 20 ml of distilled water were reacted.

The product dried at 12 ° C. showed crystallinity by X-ray diffraction. The concentration of protons per gram of sample (fired at 550 ° C.) was 4.5 × 10 ⁻⁴ meq.

Chemical analysis of the complete rinse and then calcining at 550 ° C. showed the following composition.

The specific surface area (BET method) was 380 m 2 / g, and the proton concentration per 1 g of sample was 2.5 × 10 ⁻¹ meq.

1 is an X-ray diffraction spectrometer of the product obtained in the example.

Example 5

This embodiment relates to the production of porous crystalline silica TRS-20 in which aluminum is introduced as an element for modification in the substitution of silicon in the crystal lattice. In the production of this silica, no inorganic alkali base was present. Therefore, alkali cations are derived from trace impurities present in the reagents used.

In the same manner as in Example 1, 40 g of detraethylol tosilicate, a solution containing 100 mg of Al (NO ₃ ) ₃ .9H ₂ O in 50 ml of anhydrous ethanol and detrapropyl to obtain a product having no alkaline inorganic base 50 ml of 40% (weight) aqueous solution of ammonium hydroxide (obtained from detrafurophyllammonium bromide and wet silver oxide) was reacted, and the mixture was left at 150 ° C for 10 days.

The results of the X-ray diffraction showed that the sample dried at 120 ° C. was crystalline.

For use as a catalyst, the product was calcined at 550 ° C. for 16 hours in air, washed repeatedly with non-distilled water in which ammonium acetate was dissolved, and finally the solid was calcined again at 550 ° C. for 6 hours.

The chemical analysis of the product thus obtained showed that it had the following composition.

The specific surface area (BET method) was 500 m 2 / g, and the concentration of H ^{+ per} 1 g of the sample was 4.7 × 10 ⁻¹ meq.

Example 6

This example relates to the production of porous crystalline silica TRS-57 in which aluminum is introduced as a modifier in the crystal lattice. Triethanolamine was used in the manufacture of this silica.

In the same manner as in Example 1, 80 g of tetraethyloltosilicate and 27 g of triethanolamine dissolved in 50 ml of Al (NO ₃ ) ₃ .9H ₂ O 80 mg distilled water were dissolved in 50 ml of anhydrous ethanol.

Subsequently, 7 g of sodium hydroxide was added thereto, and the Virex glass container was placed in an autogravure and left at a temperature of 194 ° C for 7 days. It was found that the product dried at 120 ° C. showed crystallinity by X-ray diffraction. The X-ray diffraction spectrum of this product is shown in FIG.

The chemical composition of the sample baked at 550 degreeC showed the following composition.

Comparative Example 1

In this example, the modified crystalline silica TRS-22, prepared according to Example 1 but containing a cation concentration of 4.1 x 10 ^-4 meq. Per gram of sodium cation, showed no catalytic activity for dehydration. will be.

As a representative turbidity reaction, a reaction for producing dimethyl ether from methanol was employed.

A tubular reactor (electrically heated) with an internal diameter of 8 mm was filled with 4 ml (2 g) of a catalyst, which was a particle selection of 30 to 80 mesh (ASTM USA Siles). The reaction effluent was sampled downstream of the reactor and analyzed by gas chromatograph.

In order to remove the water adsorb | sucked, the catalyst was baked at 500 degreeC under nitrogen flow. Methanol was then supplied under respective conditions of 275 ° C. and then 400 ° C. at a space velocity (jungnang) (WHSV) of 1.5 g / G hour.

Analysis of the reaction effluent showed that only methanol was present at these two temperatures.

Apostasy Example 2

This example shows that the modified crystalline silica TRS-23 having a concentration of 1.1 × 10 ⁻⁰ meq. Per proton per catalyst prepared and prepared according to Example 3 does not have dehydration characteristics.

Using the same apparatus as in Comparative Example 1 and operating in the same manner, 4 mL (2.8 g) of a catalyst having a particle size of 30 to 80 mesh was charged, and the catalyst was heated to 500 ° C. under anhydrous nitrogen for 2 hours.

Methanol was supplied at a space velocity (WHSV) of 1.75 g / g at a temperature of 240 ° C, 300 ° C, and 400 ° C.

In any case, dimethyl ether was not detected at all in the reaction effluent and only methanol was supplied.

Example 7

This example shows that the modified crystalline silica TRS-22 prepared according to Example 1 and having a protonone concentration of 1.5 × 10 ⁻¹ meq./g exerts an excellent catalytic action in the dehydration reaction.

Using the same apparatus as in Comparative Example 1 and organization in the same manner, 5 ml (3.5 g) of a catalyst, which is a particle collection of 30 to 80 mesh, was charged to the reactor.

In order to remove the adsorbed water, the mixture was calcined under anhydrous nitrogen for 2 hours, and methanol was supplied at a space velocity (WHSV) of 1.5 g / g at the reactor temperature of 250 ° C and 265 ° C.

Analysis of the reactor effluent (which consists of dimethyl ether, unreacted methanol and water, and no side reactions were detected in the chromatography) shows the results listed in Table 1.

TABLE 1

Dehydration of Dimethyl Ether of Methanol by TRS-22

It can be seen that the crystalline silica according to the present invention exhibits a higher rate of change than that described in the specification of Japanese Patent Application Laid-Open No. 51-76207 for activated alumina treated with a silicon compound, and has excellent dehydration activity.

It is evident that TRS-22 is obtained with a rate of change of methanol equal to or greater than that obtained by reacting at 250 ° C and 265 ° C in WHSV 1.5, respectively.

Comparative Example 3

This example is prepared according to example 1, especially in hydrocarbons of dimethyl ether in modified crystalline silica TRS-22 containing sodium cations (the concentration of protons per 1 g of catalyst is 4.1 × 10 ⁻⁴ meq.). It shows activity in the conversion reaction to olefin.

An electrically heated tubular reactor with a diameter of 8 mm (inner diameter) was charged with 2 ml (1 g) of a catalyst having a particle size of 30 to 80 mesh.

In order to remove the water adsorbed initially, the catalyst was heated to 550 degreeC under nitrogen flow for 2 hours. In order to prevent condensation, gaseous dimethyl ether was supplied by a heated pipe. On the downstream side of the reactor, a properly heated sampling device was installed and the reaction effluent was introduced into gas chromatography to analyze the reaction product. Regarding the calculation of the rate of change, the methanol produced by the partial hydration of dimethyl ether is considered unreacted and thus the rate of bone change relates to the dimethyl ether changed to hydrocarbon, carbon monoxide and carbon dioxide.

The molar selectivity to the product is expressed as the number of moles of dimethyl ether changed to the specific substance relative to the total number of moles reacted.

The result obtained in this way is shown in a 2nd table | surface.

TABLE 2

Reaction of Dimethyl Ether to Hydrocarbon by Catalyst TRS-22

It can be seen from this table that too much carbon monoxide, carbon dioxide and methane are produced so that this catalyst is very active and therefore not a very selective one.

Example 8

This example was prepared in accordance with Example 1, and was subjected to the change reaction of dimethyl ether to hydrocarbons, especially lower olefins, by modified crystalline silica TRS-22 having a proton concentration per gram of sample of 1.5 × 10 ⁻¹ meq. It is about.

The same operation was carried out using the apparatus described in Example 7, and the reactor was charged with 3 ml (1.5 g) of catalyst having a particle size in the range of 30 to 80 mesh. In order to remove the water adsorbed, it heated at 550 degreeC under nitrogen flow for 2 hours. The obtained results are shown in Table 3.

Since the acidity has changed in comparison with the second table, it is evident that the behavior of the catalyst is improved in the Pras direction.

TABLE 3

Example 9

This example illustrates the activity in alkylation of benzene with ethylene of catalyst TRS-22 (1.5 × 10 ⁻¹ meq./g(H ⁺ )).

A tubular reactor (electrically heated) with an internal diameter of 8 mm was filled with 1.2 ml (0.8 g) of catalyst TRS-22 having a particle size of 30-50 mesh. Benzene was first fed to the preheater by means of a metering pump, combined with ethylene at the flow rate set here, and then fed to the reactor. The reaction product was analyzed by gas chromatography.

Table 4 shows the data for the tests conducted.

TABLE 4

Alkylation of Benzene with Ethylene

Catalyst: TRS-22

Pressure: 20kg / ㎠

Liquid space velocity (LHSV): 14

Molar ratio C ₆ H ₆ / C ₂ H ₄ : 7

Example 10

This example illustrates the regeneration of the catalyst according to the present invention.

More specifically, after using the catalyst (TRS-22) of the above-mentioned Example for reaction for 400 hours, it reproduced at 550 degreeC in the air stream adjusted moderately.

After the regeneration treatment was completed, the air was removed and calcined at 550 ° C. under nitrogen flow, and the reaction was then started again under the conditions as described above.

Table 5 shows the results of the tests we performed,

TABLE 5

Alkylation of Benzene with Ethylene

Catalyst: Regenerated TRS-22

Pressure: 20kg / ㎠

LHSV: 14

Molar ratio C ₆ H ₆ / C ₂ H ₄ : 7

Example 11

This example is intended to illustrate the activity of the catalyst TRS-0 in alkylation with ethanol of benzene.

A tubular reactor (electrically heated) having an internal diameter of 8 mm was filled with 1.2 ml (0.8 g) of a catalyst having a particle size of 30 to 50 mesh. The reaction mixture (molar ratio 5: 1) consisting of benzene and ethanol was fed to the preheater through a retrofit pump and then to the reactor.

The reaction was carried out at 440 ° C., and the reaction product was analyzed by gas chromatography.

Data on the tests conducted is shown in Table 6.

TABLE 6

Alkylation of Benzene with Ethanol

Catalyst: TRS-0

Temperature: 440 ℃

Pressure: 20kg / ㎠

Liquid Space Velocity (LHSV): 10

Molar ratio C ₆ H ₆ / C ₂ H ₅ OH: 4

Example 12

Aluminum-modified silica TRS-0.25 ml prepared according to Example 3 was impregnated with an aqueous solution of H ₂ PtCl ₆ , and the Pt content in the catalyst was 0.2% (weight). Platinum was reduced to elemental state under hydrogen at 600 ° C. and introduced into a tubular reactor (electrically heated) having an internal diameter of 20 mm.

The rate of reduction of automobile exhaust gas was checked using two representative reactions: oxidation of propylene to carbon dioxide and oxidation of carbon monoxide to carbon dioxide.

Test A

A gaseous feed consisting of 800 ppm of propylene, 8% oxygen and nitrogen residues was preheated to 120 ° C. and passed through the catalyst bed at a gas space velocity (GHSV) 50,000 (hour ⁻¹ ). 99% of propylene has changed. The same gas mixture was preheated to 90 ° C. and fed to the catalyst at GHSV 20,000 (hour ⁻¹ ), yielding a 99% change in propylene.

Test B

The gaseous feed with 2.5% CO, 8% oxygen and nitrogen residue was preheated to 80 ° C. and then passed through the catalyst bed at GHSV 20,000 (hour ⁻¹ ), resulting in a 59% change in CO.

The same gas mixture was preheated to the same temperature and fed to the catalyst at GHSV 50,000 (time ^- CO), resulting in a 99% change for CO. The above temperature, that is, 80 to 120 ° C., is 150 ° C. even if the same rate of change is obtained for propylene and carbon monoxide when the reaction is carried out at the same space velocity by the best commercially available catalyst used in a catalyst muffler. You should think of it as an exception because it doesn't work.

Example 13

This example illustrates the activity in alkylation with benzene with ethylene of catalyst TRS-57 prepared according to the method of Example 6.

The reaction was carried out in a fixed bed type tubular reactor (electrically heated) having an inner diameter of 8 mm. 1.2 mL (0.85 g) of catalyst of particle size 30-50 mesh were fed to the reactor. Benzene was first introduced into the preheater (where it was combined with a certain flow rate of ethylene) via a retrofit pump and then inserted into the reactor. The reaction effluent was analyzed by gas chromatography.

Table 7 shows the data on the tests performed.

TABLE 7

Alkylation of Benzene with Ethylene

Catalyst: 7TRS-57

Pressure: 20kg / ㎠

Temperature: 440 ℃

Liquid space velocity: 14

Molar ratio H ₆ H ₆ / C ₂ H ₄ : 7

The catalyst TRS-57 used for alkylation of benzene with ethylene described in Example 13 was regenerated there at 500 ° C. by an air stream diluted with nitrogen.

After completion of the regeneration treatment, the regenerated catalyst was used for alkylation of benzene with ethylene. The data shown in Table 8 clearly shows how such a catalyst is simply and advantageously regenerated.

TABLE 8

Alkylation of Benzene with Ethylene

Catalyst: TRS-57

Pressure: 20kg / ㎠

Temperature: 440 ℃

Liquid space velocity (LHSV): 14

Molar ratio C ₆ H ₆ / C ₂ H ₄ : 7

Example 15

This example is intended to illustrate the activity of the catalyst TRS-57 of Example 6 with respect to alkylation with ethanol of benzene.

An electrically heated fixed bed tubular reactor was charged with 1.2 ml (0.85 g) of catalyst of particle size 30-50 mesh. The reaction mixture consisting of benzene and ethanol was fed to the preheater via a retrofit pump and then to the reactor. The effluent was analyzed by gas chromatograph.

Table 9 shows the results of the tests conducted.

TABLE 9

Alkylation of Benzene with Ethanol

Catalyst: TRS-57

Pressure: 20kg / ㎠

Temperature: 440 ℃

Liquid Space Velocity (LHSV): 10

Molar ratio C ₆ H ₆ / C ₂ H ₅ OH: 5

A particular state of modified silica application in accordance with the present invention is the use of such aluminum modified silica as a catalyst in the alkylation of C ₄ hydrocarbons, olefins and / or paraffins to high octane hydrocarbons, wherein the modified silica is porous The specific surface area is 150 m <2> / g or more, and a composition corresponds to the said composition.

The following example 16 is in this particular application of the present invention.

Example 16

Since isobutene is alkylated with nomalbutene, the porous crystalline silica obtained in Example 5 (wherein aluminum is introduced as a substituent of silicon in the two crystal lattice) was used as a catalyst.

A small reactor as described in Reference Example 1 was charged with 3 ml (1.9 g) of catalyst of particle size 30-50 mesh. The operating conditions and the results obtained are shown in Table 10.

TABLE 10

Pressure: 20kg / ㎠

Molar ratio: Isobutene / Nolmalbutane: 15

Another embodiment of the invention is the preparation and use of zeolite type catalyst ZSM-5.

According to US Pat. No. 3,702,886, silica sol, ferrosil amorphous silica, silicon derivatives such as detraalkyloltosilicate, or aluminum derivatives such as sodium aluminate, aluminum sulfate, etc. It is known that zeolites of type ZSM-5 can be prepared by use in combination with an ammonium type base.

According to a modification of the present invention, the material to be crystallized according to the operation method of the present invention is amino alcohol, and the silicon compound, the germanium compound, the aluminum compound, and the gallium compound are used in a molar ratio SiO ₂ / Al ₂ O ₃ , GeO ₂ / Al ₂ It is confirmed that a ZSM-5 type zeolite can be obtained by using O ₃ , SiO ₂ / GaO ₃ , and GeO ₂ / Ga ₂ O ₃ in amounts of 5 to 100, preferably about 35, respectively.

It has an X-ray diffraction specter similar to the zeolite zeolite ZSM-5 prepared according to the present invention and corresponds to the following general formula.

(0.9 ± 0.2) M ₂ / nO. _{W 2 O 3 · (5-100)} YO 2 · ZH 2 0

Where M is a cation selected from H, NH ₄ metal cations and aminoalcohols, especially ethanolamine-derived cations, n is the valence of the aforementioned cation, W is aluminum or gallium and Y is silicon or gelium And Z is a number from 0 to 40.

A good form of such zeolite is W with aluminum and Y with silicon with a silica / alumina ratio of 10 to 60.

A very good zeolite preparation according to the present invention can be carried out by mixing the reagents in the following ratios (in moles of oxide).

Note) TETA is aminoalcohols, preferably triethanol amines.

The method according to this special state of the present invention includes each of the following steps.

Silicon or gelmanium derivatives and aluminum or masking derivatives are reacted with ethanolamine in aqueous, alcoholic or hydroalcohol solutions. In some cases, one or more mineralizers are added, such as hydroxides and / or halides of alkali metals or alkaline earth metals to promote crystallization.

The mixture was placed in a container and crystallized at a high temperature (150 ° C.-250 ° C.) for several hours to several days, preferably at 170 to 210 ° C. for 2 to 10 days, cooled, filtered on a filter, washed with purified water, and then obtained. And dried at 300 to 700 ° C., preferably at 550 ° C. for 2 to 24 hours in air, and then ammonium salt, preferably ammonium nitrate or ammonium acetate, cation exchanged, washed with distilled water and H ⁺ type product. When it obtained, it baked again on the conditions mentioned above.

The zeolite thus obtained is used as it is or by dilution at an appropriate dilution rate, or in accordance with the operation or other method known by zeolite ZSM-5 in the state of adding one or more elements for promoting the activity of the catalyst.

Several examples are illustrated to illustrate again the specific embodiments of the present invention for zeolite type catalysts.

Example 17

This example illustrates the preparation of zeolite ZSM-5 using triethanolamine.

60 g of Al (NO ₃ ) ₃ .9H ₂ O dissolved in 400 ml of 95% ethanol was added to a Virex glass container holding an atmosphere free of CO ₂ , and 600 g of detraethyloltosilicate was added while stirring. Immediately after the dissolution became clear, 200 g of triethanolamine dissolved in 400 ml of middle water was added and heated to 60 DEG C while stirring, and again 30 minutes later, a solution containing NaOH 13 was added to 200 g of distilled water, followed by 30 minutes in 400 ml of water. 22 g of dissolved NaOH (total amount of NaOH = 35 g) was added. Gel formation was seen. Stirring was continued several hours with vigorous. In the meantime, the temperature rose to 90 ° C., and thus ethanol (one supplied to the reaction and one produced by hydrolysis) was removed. In this step, the reaction mixture was transferred to Ouro Stainless Steel, contents 31, and hydrothermal reaction was initiated at 195 ° C. for 9 days.

The resulting product was then cooled to room temperature, filtered over a filter, washed several times with very hot distilled water and dried at 120 ° C.

The solid was calcined at 550 ° C. for 16 hours, and was repeatedly exchanged with ammonium acetate (or acetate) when hot (95 ° C.) and calcined at 550 ° C. for 6 hours to convert to H ⁺ . X-ray diffraction spectra were consistent with those reported in Table 1 of US Pat. No. 3,702,886.

Example 18

In the same manner as in Example 17, 880 g of detramethylol tosigate, 120 g of Al (NO ₃ ) ₃ .9H ₂ O, 400 g of triethanolamine dissolved in 800 ml of water, and 70 g of NaOH were reacted in 700 ml. The capacity was made about 9 L by adding distilled water with vigorous stirring to the mixture. The mixture was concentrated at a temperature of 80 ° C. for 30 hours to reduce the volume of the liquid to about 5 liters. The hydrothermal treatment was carried out at 190 ° C. for 8 days in a stainless steel zeurocreb equipped with a stirrer. The X-ray diffraction spectra of the obtained material corresponded to those of ZSM ^- 5 and the specific surface area was 380 m 2 / g. The ratio SiO ₂ / Al ₂ O ₃ was 38.

Example 19

9.6 g of sodium aluminate and 10 g of potassium hydride were dissolved in 200 ml of water. 208 g of triethanolamine dissolved in 100 ml of water was added to this transparent solution. The solution thus obtained was left to stir at 80 ° C. for 2 hours under an inert gas blanket. 40 g of potassium bromide dissolved in 150 ml of water was added to the crystallization accelerator.

Again, 345 g of Ludox colloidal silica (SiO ₂ 40%) dissolved in 1500 ml of water was slowly added. The obtained gel was aged at 90 ° C. for 24 hours under inert gas flow. The gel thus treated was crystallized at 198 ° C. for 10 days in a stainless steel autoclave.

In the same manner as in Example 20, zeolite ZSM-5 was obtained.

Claims (1)

As described above, in the aqueous solution, alcohol solution or hydroalcohol solution, the silicon derivative and the aluminum derivative are added with one or more mineralizers and inorganic bases, and the substance has an archivolt or clatihratng effect. After the reaction, the mixture was crystallized at a temperature of 100 ° C. to 220 ° C. for several hours to several days, followed by cooling, filtration and drying, firing at 300 ° C. to 700 ° C. in air for 2 to 24 hours, and boiling distilled water containing an ammonium salt. Method of producing an aluminum-modified silica having a porous crystal structure having the following general formula characterized in that after rinsing once again under the conditions as described above and having a surface area of 150 m 2 / g or more. 1 Si. (0.0012-0.0050) Al. Oy Wherein y is 2.0018 to 2.0075

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