JPS5922990A - Preparation of liquid hydrocarbon rich in aromatic component - Google Patents

Abstract

PURPOSE:To prepare the titled liquid hydrocarbon, in high conversion and efficiency, with simple operation, by reacting a >=2C hydrocarbon raw material having low aromatic content using a crystalline silicate having a specific composition and specific X-ray diffraction pattern as a catalyst. CONSTITUTION:A liquid hydrocarbon rich in aromatic component is prepared from a >=2C hydrocarbon raw material having low aromatic content, by passing a gas containing the hydrocarbon raw material through a reactor filled with a catalyst comprising a crystalline silicate having a composition of formula pM2/nO.Al2O3.qSiO2(M is alkali metal or alkaline earth metal; n is atomic valence of M; 0.3<=p<=3.0; g>=10) in terms of the molar ratio after calcination in air at 550 deg.C and exhibiting the X-ray diffraction pattern shown in the table, and reacting the raw material gas at 200-550 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing liquid hydrocarbons with a high aromatic content. The present invention relates to a method for efficiently producing liquid hydrocarbons with a high aromatic content from hydrocarbons with a low content.

Various methods are known for converting hydrocarbons using crystalline aluminosilicate zeolite as a catalyst. For example, using ZSM-5 type zeolite,
A method for converting the above hydrocarbons into aromatic compounds (JP-A-49-41322), a method for converting olefins and/or paraffins having 2 to 4 carbon atoms into aromatic compounds using ZSM-based zeolite (JP-A No. 49-41322); 5o-/49255 publication, special mention publication 56-150253 publication), carbon number 2~
A method for converting a mixture containing olefins No. 5 into aromatics using crystalline silicate (Japanese Patent Application Laid-Open No. 56-05292
The first stage uses a ZSM-5 type zeolite catalyst, and the second stage uses a ZSM-5 type zeolite catalyst.
A method is known in which zeolite type 5 and a second molecular sieve of 4.5 to 67' are brought into contact with a mixed catalyst to convert them into aromatic compounds (@Kokai No. 5O-4029). In addition, a method for synthesizing this ZSM-5 type zeolite in the presence of a surfactant and a method for producing gasoline from methanol using this zeolite (Japanese Patent Application Laid-Open No. 5-11112)
7-77025) is also known.

However, all of these methods have various drawbacks, such as insufficient conversion to aromatic compounds and complicated operations.

Therefore, the present inventor conducted extensive research in order to overcome the drawbacks of the conventional technology and develop a method for efficiently obtaining a gasoline fraction rich in aromatics from hydrocarbons with low aromatic content and low utility value. . As a result, it was found that when a crystalline silicate with a completely new structure called "S-4" was used as a catalyst, gasoline with a high aromatic content could be efficiently obtained. The present invention was completed based on this knowledge.

That is, the present invention has a low aromatic content and a carbon number of 2.
In producing a liquid hydrocarbon rich in aromatic content from the above-mentioned raw material hydrocarbons, the sintering expressed in molar ratio after firing at 550°C in air is expressed by the general formula pMVr.
lo - pigeon 0.・qsi02 ... (I) (in the formula,
M represents an alkali metal and/or an alkaline earth metal, and n represents the valence of M.

Further, p and q are selected from the following range.

0.5≦p≦30, q≧+o) and whose x9J diffraction pattern is shown in Table 1. The present invention provides a method for producing liquid hydrocarbons having a low group content.

Table 1 Table 1 (continued) Irradiation -: (!u-Ka H wavelength: 1.5418A
As the raw material hydrocarbon in the method of the present invention, as mentioned above, a hydrocarbon having a low aromatic content and a carbon number of 2 or more is used. There are no particular restrictions on the type of hydrocarbon, and there is no restriction on the aromatic content either, but usually 15% or less is used. Specific examples of this raw material hydrocarbon include naphtha fractions such as light naphtha and heavy naphtha, especially fractions with carbon i4 or more and boiling point of 200'C or less, especially fractions with carbon number of 4 or more and boiling point of 14o'C or less. In addition, olefins and paraffins having 2 to 4 carbon atoms can be used alone or in combination, or in combination with the naphtha fraction.

Among these, it is preferable to use a positive mixture of the above-mentioned olefin fraction and an olefin having 2 to 4 carbon atoms, and in this case, the mixing ratio of both, that is, the olefin/naphtha fraction = αo5 to
9 (heavy JltJt), particularly preferably [118-5
When the paper weight ratio is set to 7 (heavy paper ratio), a liquid hydrocarbon with a significantly higher aromatic content is produced than when each is used alone, and a so-called synergistic effect can be produced.

Further, the catalyst used in the method of the present invention has a composition expressed by the molar ratio after being calcined at 550°C in air as described above, and whose X-ray diffraction pattern is expressed by the above general formula (I). It is a crystalline silicate (Eng.S.N. 4) shown in Table 1. In addition, alkali metals such as sodium and alkaline earth metals contained in the production of this crystalline silicate can be ion-exchanged by various methods and used as H-type or metal ion exchange type. In addition, in producing this crystalline silicate (Technical Sney 4),
(a) a silica source, (b) an alumina source, (C) an alkali metal and/or alkaline earth metal source, and (d) ethylene glycol or monoethanolamine;
and the molar ratio of each component is silica/alumina≧1゜ethylene glycol or monoethanolamine/yk
-a, a s~1a Ethylene gelicol or monoethanolamine ◇ Rica == 2~1o.

An aqueous mixture of hydroxyl groups/silica-101 to 0.5 may be reacted at 10o to 500"C until crystalline silicate is produced. More specific reaction conditions at this time include reaction temperature + uo to 5oo'
c. Preferably, the reaction may be carried out at 12°C to 20°C for 5 hours to 10 days, preferably for about 10 hours to 5 days,
Moreover, regarding pressure, it is usually carried out under self-pressure. Furthermore, the crystalline silicate production reaction system here is usually stirred 1.
The atmosphere is filled with inert gas if necessary. pH may be 7.5 or higher, particularly pH 7.5 to 12.
It is preferable to adjust it to a range of o.

After the above crystallization reaction, washing with water and further drying at about 120°C produces a crystalline silicate having the composition represented by the general formula (I) and the X-ray diffraction pattern shown in Table 1. 4) is obtained.

The method of the present invention is carried out by using a hydrocarbon with a low aromatic content as a raw material and contacting it with the crystalline silicate catalyst described above, and the reaction conditions at this time are usually normal pressure to 501<y /a+to pressure.

Preferably from normal pressure to 20, with a pressure of 9/iG and a temperature of 2
00~550°C1 Preferably 500~500''01 Weight space velocity (WH8V) O,1~50 hr-'
, preferably 05 to +Q br-'.

According to the method of the present invention as described above, liquid hydrocarbons such as gasoline fractions, which are rich in aromatic content and have extremely high utility value, can be efficiently converted from hydrocarbons with low aromatic content and low utility value. can be manufactured. Note that the U-quality gas produced as a by-product here can also be recycled and used as a raw material hydrocarbon.

Therefore, the method of the present invention can be widely used in petroleum refining, gasoline production, and various chemical industries.

Next, the present invention will be explained in more detail using examples.

Example 1 (1) Preparation of catalyst Aluminum sulfate (18 hydrate) 7.52y-, sulfuric acid (9
A solution consisting of 7%) + 7.65L and water + ooi
As a liquid, water glass (sio, 29.Owt%).

NatO9.4wt%, water 6t6wt%) 2M
A solution consisting of Y- and 46 ml of water was designated as Solution B. Solutions A and B were simultaneously gradually mixed dropwise into 100 ml of water, the pH was then adjusted to 9.5, and 576 ml of ethylene glyfur was further added and mixed. Subsequently, the resulting aqueous mixture was placed in a 1:1 volume autoclave, and reaction was carried out at 170° C. under autogenous pressure for 20 hours with stirring.

After cooling the reaction mixture, the product was washed five times with 1.54 g of water. The filtered solids were then dried at 120° C. for 6 hours to obtain 55.07 crystalline silicate (Technical Sney 4). The composition (molar ratio) of this product is 0.9 Na2
O-Ago, -74,OSin, -7,8H,0. The X-ray diffraction pattern of this product is also shown in Figure 1.

Furthermore, the obtained crystalline silicate (Engineering Sney 4) 11
The product was ion-exchanged twice with 1N ammonium nitrate of this grade, dried at 120°C, and then calcined in air at 550°C for 16 hours to form H-type. Furthermore, alumina sol equivalent to 20% alumina was added as a binder,
After extrusion molding and drying at 120°C for 3 hours, 550°C
A catalyst was obtained by calcining in air for 26 hours.

(2) A hydrocarbon reaction flow reactor is filled with the catalyst obtained in the above (11),
An olefin-containing gas having the composition shown in Table 2 was passed through this at normal pressure, 450°C, WH8V 1.0hr-'
The reaction was carried out under the following conditions. The results are shown in Table 4.

Example 2 Actual MIi Example 1 (In 21, the same operation as in Example 1 (2) was carried out except that a liquid hydrocarbon having the composition shown in Table 5 was used instead of the olefin-containing gas as the raw material hydrocarbon. The results are shown in Table 4.

Example 3 The same operation as in Example 1 (2) was performed except that a mixture (weight ratio) was used.

The results are shown in Table 4.

Example 4 Example 1 (2) Instead of the olefin-containing gas as the feedstock hydrocarbon, an olefin-containing gas having the composition shown in Table 2 and a liquid hydrocarbon having the composition shown in Table 3 were used.
Example 1 except that an o:5o (weight ratio) mixture was used.
The same operation as (2) was performed.

The results are shown in Table 4.

Table 2 Table 6 Table 1 The former is the olefin-containing gas WASV, and the latter is the liquid hydrocarbon WASV.

・2 The expected values are shown based on the results of Example 1.2.

[Brief explanation of drawings]

Figure 1 shows the crystalline silicate obtained in Example 1)
Three diffraction patterns are shown. Here, the incident angle by θ is shown. Patent Applicant: Idemitsu Kosan Co., Ltd. Procedural Amendment Process (Method) August 20, 1982 Director General of the Patent Office Kazuo Wakasugi 1, Indication of Case Patent Application 1982-+52142 λ Name of Invention Liquid carbonization rich in total aromatic content Hydrogen production method 5 Relationship with the case of the person making the amendment Patent applicant Idemitsu Kosan Co., Ltd. 4, Agent Address: 1-10 Kyobashi, Chuo-ku, Tokyo 104 Drawing & Contents of amendment Engraving of drawing (no change in content) )

Claims (1)

[Scope of Claims] (11) In producing a liquid hydrocarbon with a high aromatic content G from a raw material hydrocarbon with a low aromatic content and a carbon number of 2 or more, after calcination at 550°C in air, The composition expressed in molar ratio is the general formula pMy, O-k12
0.・qsio2 (where M is an alkali metal and/
Alternatively, it represents an alkaline earth metal, and n represents the valence of M. Further, p and q are selected from the following range. [15≦p≦5o, q≧I[J], and the X-ray diffraction pattern is +1.51±0
,2 Strong 11IL92 ± α2
Very strong 1α03±α2 Weak 7,85 ± α2 Moderate 6.08
10.15 Weak 5.61 015 Weak 5.24±α15 Weak 4.90±[115 Weak 4.51±1115 Very Strong 442±1
1 Weak 4.24±[11 Strong 414±01 Weak 589±α1 Strong 575±α1 Moderate 569±111 Very strong 561 Sat0
．． 1 Very strong 555±0.07
Moderate 543±a07 Strong 532 Sat α07 Weak! L16 107 Weak 2.97±αo7 Weak 2.85±α05 Weak 2.52±α05 Moderate A method for producing a liquid hydrocarbon rich in aromatic content, characterized by using a crystalline silicate as a catalyst. .