JPS59166588A - Production of aromatic hydrocarbon mixture - Google Patents

Abstract

PURPOSE:To obtain an aromatic hydrocarbon mixture useful as a gasoline component in high yield for a long term, by bringing an aliphatic hydrocarbon obtained by thermal cracking reaction, etc. into contact with a special and novel crystalline silicate catalyst. CONSTITUTION:(A) A hydrocarbon containing 1-10C paraffin and olefin is brought into contact with (B) a catalyst consisting of a crystalline silicate having the chemical composition of the formula (R is mono- or bivalent cation; n is the valence of R; M is trivalent transition metal and/or Al<3+>; a, b and y are numbers satisfying a+b=1; a >=0; b>=0; y>=5) expressed in molar ratios of oxides to give the aimed mixture. The catalyst (B) is preferably obtained by reacting an organic compound, e.g. propylamine, with a mixture obtained by adding hydrochloric acid to water glass, bismuth chloride and water, and calcining the resultant solid component.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for converting aliphatic hydrocarbons into aromatic compounds to produce aromatic hydrocarbon mixtures.

More specifically, it relates to a method for producing an aromatic hydrocarbon mixture by bringing all hydrocarbons containing paraffins and olefins having 1 to 1 carbon atoms into contact with a special crystalline silicate.

Mixtures of aromatic hydrocarbons are widely used as gasoline.

In general, they can be obtained by distillation of petroleum or by conversion of heavier petroleum fractions, such as catalytic cracking.

Octane number of the hydrocarbon mixture obtained in this way?
In order to improve this, a method has been adopted in which total catalytic modification is performed to increase the aromatic content.

It has been well known that solid silicon acidic catalysts called crystalline aluminosilicate zeolites are used in such reforming and conversion reactions of petroleum fractions. For example, many methods have been proposed for cracking high molecular weight products into lower molecular weight products, such as catalytic cracking of heavy petroleum fractions, and for improving the octane number of hydrocarbon mixtures (U.S. Pat. No. 3+40249, 51402
No. 51, No. 3,140,255, No. 3,400,072 and U.S. Patent Application No. 8,65,470).

The present invention does not relate to the above-mentioned general hydrocarbon conversion method, but is useful as a gasoline component from aliphatic hydrocarbons, that is, hydrocarbons containing paraffins and olefins having 1 to 10 carbon atoms, obtained by distillation, thermal decomposition, etc. The present invention relates to a method for producing aromatic compounds.

Conventionally, the above-mentioned crystalline aluminosilicate zeolite has been widely used as a catalyst for converting such aliphatic hydrocarbons into aromatic compounds having a boiling point range of gasoline. 56-14
0954, Japanese Unexamined Patent Publication No. 55-124722, etc.

By the way, a certain type of crystalline silicate recently synthesized for the first time by the present inventors is extremely effective as a catalyst for the conversion reaction to the aromatic compound, and is not only more active than conventional crystalline aluminosilicates, but also has higher activity than conventional crystalline aluminosilicates. The present invention was achieved by discovering the groundbreaking fact that the selectivity and durability are much improved.

That is, the present invention provides a method for directly converting aliphatic hydrocarbons into aromatic compounds that can be obtained in high yield over a long period of time using a novel crystalline silicate catalyst.
When producing an aromatic hydrocarbon mixture from a hydrocarbon containing 10 paraffins and olefins, the molar ratio of oxides (dehydrated form) is (0,1-2) R540・(aB1203・bM2)
o3]・yS102 [In the above formula, R: one or more monovalent or divalent cations, n: valence of R, M: one or more trivalent transition metal cations and/or aluminum ions, ay by7 is an arbitrary number that satisfies the following range. a+b=+, a≧o, b≧0, y≧5].

The aliphatic hydrocarbon in the present invention refers to a paraffin- and olefin-containing hydrocarbon having 1 to 10 carbon atoms, and each may be a single hydrocarbon or a mixture thereof.

In addition to the above paraffins and olefins, naphthenes,
It may also be a mixture containing all aromatic hydrocarbons and alcohols.

In an embodiment of the present invention, the reaction temperature is 100 to 800°C,
Preferably, when the olefin content is large, the range is 200 to 200.
The temperature range is 500°C, or 300-700°C when the paraffin content is high.

Further, the aromatic hydrocarbon mixture in the present invention refers to a hydrocarbon mixture containing 1% by weight or more of aromatic hydrocarbons, and also includes aliphatic hydrocarbons (paraffins, olefins), etc.

The crystalline silicate used in the present invention includes the following silica sources, bismuth sources, transition metal and/or alumina sources, alkali sources, water, and special organic compounds. The reaction mixture containing grapes (including those to which acid is added for pH adjustment) is synthesized by a hydrothermal synthesis reaction as a starting material.

The source of silica can be any source of silica compounds commonly used in zeolite synthesis, such as solid silica powder, colloidal silica, or silicates such as water glass. used.

As the bismuth source or the transition metal source, compounds such as bismuth or transition metal sulfates, nitrates, and chlorides are used.

Moreover, the trivalent transition metal ion (M) in the present invention,!
: refers to trivalent cations of Group VIII elements such as iron-cobalt, rhodium, ruthenium, and palladium, rare earth elements such as lanthanum and cerium, and elements such as titanium, vanadium, chromium, niobium, mental, and antimony.

The source of alumina is most preferably sodium aluminate, but compounds such as chlorides, nitrates, sulfates, oxides or hydroxides may also be used.

As the alkali source, a hydroxide of an alkali metal such as sodium or an alkaline earth metal such as calcium, or a compound with aluminic acid or silicic acid is used. As a special organic compound that is one of the raw materials for hydrothermal synthesis of crystalline silicate, the following can be used.

+11 Organic amines: primary organic amines such as n-propylamine and monoethanolamine
secondary amines such as dipropylamine, jetanolamine, tertiary amines such as tolylamine and toluethanolamine, or ethylenediamine, diglycolamine, etc., or halogenated with the above compounds. Mixtures with hydrocarbons (propyl bromide, etc.), quaternary ammonium salts such as tetrapropylammonium salts, etc. (2) Organic ♀ compounds other than organic amines: pyridine, pyrazine, pyrazole, etc. (3) Alcohols alone or Mixtures with ammonia: Monoalcohols such as ethanol, diols such as ethylene glycol, or mixtures of the above alcohols and ammonia. These various organic compounds are examples, and the present invention is not limited to these in any way. isn't it.

i! , ri, monovalent or divalent cation (scale) in the present invention
means alkali metal ion, alkaline earth metal ion,
The ions of the organic compounds mentioned above, or the hydrogen ions and other ions formed through processes such as calcination and ion exchange? As expected.

The crystalline silicate used in the present invention is one in which part or all of At in the structure of conventional zeolite is replaced with bismuth or other transition metals, and further has a structure of 5in2/(
Bi203+M2O3) ratio is 5 or more and is produced starting from a reaction mixture with the following molar composition.

SiO+/ (BtzO,,+M2o3) 5~30
00 (Favorability L< is 10-200) OH-/5i020-10 (Favorability L< is 0.2-0.
8) H20/810. 2~I OOO (good performance 10~200) Organic compound/(Bh○3+M2O1) I ~10
0 (preferably 5 to 50) The crystalline silicate used in the present invention is synthesized by heating the raw material mixture at a temperature and time sufficient to generate crystalline silicate, but the hydrothermal synthesis temperature is 80
-300°C, preferably 130-200°C, and the hydrothermal synthesis time is 0.5-14 days, preferably 1-200°C.
It is the 10th. Although the pressure is not particularly limited, it is preferable to carry out the test under its own pressure.

The hydrothermal synthesis reaction is continued by heating the raw material mixture to the desired temperature and stirring if necessary until the crystalline silicate is formed. After crystals have thus formed, the reaction mixture is cooled to room temperature, filtered, washed thoroughly with water, and the crystals are separated. Furthermore, drying (9) is usually performed at 100°C or higher for about 5 to 24 hours.

The crystalline silicate produced by the above-mentioned method can be used as a catalyst as it is or by mixing it with a binder, etc. that has been conventionally used for catalyst molding, and molding it into an appropriate size using well-known techniques. be done.

The crystalline silicate of the present invention is a regularly porous crystalline material having a certain crystal structure and generally exhibits the X-ray diffraction pattern shown in Table 1.

Table 1 Standard techniques were used to obtain the data in Table 1 above. The irradiation is alpha rays for copper. 0 is the intensity of the strongest peak, and 0/0 is the relative intensity.

Preferably, the crystalline silicate is heated in air at a temperature ranging from 400 to 700°C for 2 to 4 hours before use as a catalyst.
Activated by heating for 8 hours.

The alkali metal present in this crystalline silicate can be exchanged with one or more other cations by conventional methods to form Hl.
It may also be a crystalline silicate of p or other metal cation type such as iron, rhodium, ruthenium, gallium, etc. For example, methods for ion exchange into H-type include a method in which the crystalline silicate produced by the method described above is calcined to remove all organic compounds, and then immersed in strong hydrochloric acid to directly convert it into H-type. There is a method in which the material is immersed in an aqueous solution of an ammonium compound to form the NH4 type, and then fired to form the IH type.

Furthermore, this crystalline silicate can be impregnated with a compound of 71 or more metals for use as a catalyst. Suitable metals include copper, zinc, chromium, lead, antimony, bismuth, titanium, vanadium, manganese, iron, cobalt, nickel,
Examples include ruthenium, rhodium, palladium, platinum, lanthanum, and cerium.

The impregnated silicate preferably contains from 01 to 5.0 weight percent metal oxide. The compounds of the metals used are suitably those which decompose on application of heat to give the corresponding oxides and which are soluble in water, such as nitrates or chlorides.

Mixtures of crystalline silicates and metal oxides are thus prepared by impregnation with an aqueous solution of the compound of the desired metal and dry calcination.

As shown in the examples, the catalyst obtained in the above manner is a conventional catalyst for the reaction of producing an aromatic hydrocarbon mixture useful as a gasoline component from a CI''-010 paraffin- and olefin-containing hydrocarbon. It exhibits high catalytic activity and durability not found in other countries.

Hereinafter, the present invention will be specifically explained with reference to Examples.

[Example 1] Crystalline silicate was synthesized as follows and nine glasses,
Bismuth chloride, Mizuon 56 N, 2o・J, O, ・80
Mix to have a molar ratio of Sin, 1600H20, and add hydrochloric acid to this. After adding an appropriate amount and adjusting the pH of the above mixture to around 9, add propylamine as an organic compound, 20 times the number of moles of propyl bromide Q Bi2O3, mix well, and place in a 500 CO stainless steel autoclave. I staked out.

While stirring the above mixture at about 500 rpm,
Let it react at 0℃ for 6 days. After cooling, remove the solid content, wash thoroughly with water until the pH of the washing water becomes approximately 8, and heat at 110°C for 1 hour.
It was dried for 2 hours and fired at 550°C for 3 hours.

The crystal grain size of the product was around 1 μm, and the composition excluding organic compounds was Q, 4 Na20-Bi2O3.805i02 in dehydrated form. This is called crystalline silicate 1.

When synthesizing this crystalline silicate 1, it is possible to use nitric acid instead of hydrochloric acid among the raw materials, bismuth nitrate instead of bismuth chloride, or silica sol instead of water glass. A similar silicate was also obtained.

Furthermore, a similar silicate was obtained by reacting at 170° C. for 2 days at 180° C. instead of 160° C. for 3 days as the hydrothermal synthesis conditions.

Bi of bismuth chloride when preparing raw materials for crystalline silicate 1
The procedure for preparing crystalline silicate 1 was repeated as shown in Table 2, except that the entire mixture of bismuth chloride and aluminum chloride was added so that the number of moles in terms of 2O3 and the number of moles of B1-203 and Al2O3 were the same. Crystalline silicates 2-5 were prepared as follows.

Table 2 When preparing crystalline silicate 2, ferric chloride, ruthenium chloride, lanthanum chloride, neodymium chloride, chromium chloride, titanium chloride, vanadium chloride, and antimony chloride were used in place of aluminum chloride, each with At20 in terms of oxide.
Crystalline silicates 6 to 1 were prepared by repeating the same operation as for crystalline silicate 2 except that the same number of moles as in Example 3 were added. The composition of these crystalline silicates excluding organic compounds is expressed as the molar ratio of oxides (dehydrated form):
0,5~0.6) Na20-(0,9Bi203-
0, + MzO3).

Here, M is Fe, Ru, IJ, Nd,
T1 % ■, Cr, Sb (crystalline silicate No.6~
13).

The preparation procedure for crystalline silicate 1 was repeated except that instead of propylamine and propyl bromide in crystalline silicate 1, the following organic compound was added 20 times the number of moles of bismuth oxide to produce the crystalline silicate shown in Table 3. 14-22 were prepared.

Table 3 The compositions of these crystalline silicates 14 to 20 excluding organic compounds are expressed as molar ratios of oxides (dehydrated form) (0, I to 0.6) Na2O・Bi2O3・805
i02 detsu7j.

In addition, in crystalline silicate 1, 81021B at the time of preparation
Crystalline silicate 21.22.2!1 was prepared by repeating the same operation as crystalline silicate 2 except that the hOs ratio was changed to 20.200 or 400.

The powder X-ray diffraction patterns of the above crystalline silicates 1 to 26 satisfied the patterns shown in Table 15, and it was confirmed that the crystalline silicates 1 to 26 were crystalline substances with an SiO2 content of 90% by weight or more.

[Comparative example]

In Example 1, aluminum sulfate was used instead of bismuth chloride? using and keeping other inorganic compounds the same, Is 6 Na2o # At2o3” 80 SiO
The molar ratio of tetrapropylammonium bromide 'i At203 was adjusted to 2.1600H20, and an appropriate amount of chloride was added thereto to adjust the pH of the mixture to around 9. The same operation as in Example 1 was repeated except that twice the amount was added. The composition of this product excluding organic compounds, expressed in dehydrated form, was 0,5 Na2O.A103.80 SiO2. The X-ray diffraction pattern of this powder is
It was the same as ZSM-5 (crystalline aluminosilicate) described in Publication No. 64.

[Example 2] Crystalline silicate synthesized in Example 1 and ZSll-5 type zeolite synthesized in Comparative Example)? r, IN hydrochloric acid and treated at 80° C. for 7 days. This was washed and filtered, then dried at t+o'c for 12 hours, and then catalytically reacted with propylene using a catalyst (molded to the size of 1 to 3 cubes) calcined at 550°C. The reaction conditions were atmospheric pressure, 350
°C, WH8V: 5 h-'. The results shown in Table 4 were obtained, and during the synthesis of crystalline silicate 1,
For crystalline silicate 1-2 synthesized using silica sol fragments instead of water glass, the same results as in the case of crystalline silicate 1 shown in Table 4, which were brought into contact under the same conditions as above, were obtained.

[Example 3] Among the catalysts tested in Example 2, crystalline silicate 1,
2 and comparative zeolite (ZSM-s) were subsequently subjected to WH at 350°C and atmospheric pressure to check their durability.
A catalytic reaction of propylene was carried out at 8V: 5h-''. As a result, ZSM-5 began to deteriorate when treated with 1f of catalyst and 5of dipropylene; however, in the case of crystalline silicate 1゜2, 1 propylene per 1f
No deterioration occurred until 5GOf treatment. In the case of ZSM-5, the reason for the rapid deterioration is that, as can be seen from the results in Table 4, the ratio of (4+016) in the aromatic group is 2 to 3 times higher than that of the crystalline silicate according to the present invention. It is estimated to be.

[Example 4] Crystalline silicates 1 and 2 synthesized in Example 1 were treated in the same manner as in Example 2, and gold pieces were then subjected to a catalytic reaction with a mixture of propylene and methanol. The reaction conditions are
Atmospheric pressure, 560° C., W'H9V: 4.6 h". The results shown in Table 5 were obtained.

Table 5 Feed material 0H30H+ D (g/h)csa613
．． 25 (g/h) [Example 5] Catalytic reaction of a mixed gas containing 01 to C5 olefins and paraffins using a catalyst prepared by treating crystalline silicate 1 synthesized in Example 1 in the same manner as in Example 2. under atmospheric pressure,
When the test was carried out at 320°C and WH8V: 3h-1, the following results were obtained.

CHa 0.8
0.602H60,20,4C! , H411,23,0 03Hs5.5 10.5 c3u, 22.6 3.304H
1, + 1.6 16.804H,29,4
5, + 08H125,94,4 0sH+o I 2.8 1.70
5/HC! 60.3 Aromatic ratio -28.5 Since the feed gas in this example has the same composition as the light gas used in gasoline total synthesis using methanol as a raw material, the first stage reactor first converts methanol to gasoline total. C that is synthesized and produced as a by-product! ~C5 light gas? It can also be applied to a process in which gasoline is obtained by passing it through a second stage reactor filled with the catalyst according to the present invention to maximize the gasoline yield.

[Example 6] Crystalline silicates 1 and 2 synthesized in Example 1 were synthesized in Example 2.
Catalytic reaction of n-hexane using catalysts treated in the same manner as ? Atmospheric pressure, 600℃, Wl-1sV:
When the test was carried out at 1.5 h-'', the results shown in Table 6 were obtained.

Table 6 [Example 7] Crystalline silicate 2 synthesized in Example 1 was treated with a catalyst in the same manner as in Example 2, and light naphtha or cracked naphtha having the composition shown in Table 7 was used as a raw material at atmospheric pressure. Below,
For light naphtha, LH8V: jh", 55
At 0'C(7) condition and for cracked naphtha, LH8V
: t 5 h-” and 400° C., the results shown in Table 7 were obtained.

Table 7 As is clear from the above examples, according to the method of the present invention, an aromatic hydrocarbon mixture that can be used directly as gasoline from aliphatic hydrocarbons containing paraffins and olefins having 1 to 10 carbon atoms can be produced with high selectivity. Furthermore, the crystalline silicate obtained in accordance with the present invention has excellent durability and can be operated for a long period of time.

It should be noted that the examples shown are merely illustrative and do not limit the present invention.

In addition, although the results in a fixed bed are shown in the examples, this does not specifically limit the reaction type, and it goes without saying that a fluidized bed, pneumatic conveyance type, or other type of reactor may be used. do not have.

Sub-agent: 1) Akira Sub-agent Ryo Hagi Hara -

Claims (1)

[Claims] Expressed in molar ratio (dehydrated form) of paraffins, olefin-containing hydrocarbons, and oxides having 1 to 10 carbon atoms, (0,1 to 2) Rg O・(aB iz○3+bM
203]・yS102 [In the above formula, R: one or more monovalent or divalent cations, n: valence of H, M: one or more trivalent transition metal ions and/or aluminum Ion, a+b=+ a≧o, b≧0% 7
A method for producing an aromatic hydrocarbon mixture, characterized in that the mixture is brought into contact with a crystalline silicate having a chemical composition of ≧5].