JPS60135485A - Method for dewaxing hydrocarbon fraction - Google Patents

Abstract

PURPOSE:To dewax efficiently a hydrocarbon fraction and to lower pour point, by bringing the hydrocarbon fraction in the presence of hydrogen into contact with a catalyst mainly composed of a mordenite type zeolite contg. a platinum metallic component and having a specified composition. CONSTITUTION:An aq. reaction mixture contg. a silica source such as silicic acid, an alumina source such as aluminum sulfate, an alkali soure such as caustic soda and a platinum metal source such as chloroplatinic acid is preped. so as to give a composition within the range of SiO2/Al2O3=9-50, OH<->/SiO2=0.1- 0.5 (OH<-> being alkali source), H2O/SiO2=10-50 and M/SiO2=1X10<-8>-1X10<-2> (M is platinum metal source) in a molar ratio. The mixture is then reacted at 140-200 deg.C to crystallize it, thus obtaining a catalyst mainly composed of a mordenite type zeolite contg. a platinum metallic component. A hydrocarbon fraction such as gas oil is brought into contact with the catalyst in the presence of hydrogen to dewax it.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a method for improving the fluidity of hydrocarbon fractions, and more specifically to a method for dewaxing hydrocarbon fractions represented by petroleum fractions. [Prior art and its problems] Recently, kerosene, light oil, and A heavy oil, which are called middle distillates, have been increasing their share in petroleum demand.

Demand for B and C heavy oils is decreasing rapidly, and one effective way to increase the yield of middle distillates mentioned above is to lower the pour point, etc. of light oil and A heavy oil base materials. It will be done. Generally, when using hydrocarbon fractions for various purposes, it is important to improve their fluidity during storage, transportation, and combustion.

Increasing fluidity increases the flexibility of crude oil selection in oil refining, greatly improves the handling of petroleum products in the winter, and increases the yield of middle distillates, among other benefits. You can say it's big.

From this point of view, a method has been proposed in which the wax content in the hydrocarbon fraction is selectively separated and removed by using it as a zeolite catalyst to completely lower the pour point of the hydrocarbon fraction. Three types of zeolites are known, examples of which are shown below.

(1) Zeolites capable of adsorbing n-halafine but not hydrocarbons having a molecular diameter larger than isoparaffin: A-type zeolite (Japanese Patent Publication No. 45-30963), erionite (Japanese Patent Publication No. 47-32723).

(2) Zeolite that can adsorb n-halafine and monomethyl-substituted paraffin, but cannot adsorb hydrocarbons containing quaternary carbon atoms such as 2,2-dimethylbutane: ZSM
-5 Zeolite (Special Publication No. 49-34444).

(3) Zeolite that can adsorb hydrocarbons containing quaternary carbon atoms such as neopentane but has a smaller pore diameter than Y-type zeolite: mordenite (Japanese Patent Publication No. 31856/1983).

In these conventional techniques, the main component of wax is wax n-
Using a pebbly zeolite with a paraffin molecular diameter of about 5A and a relatively small pore size, decomposition of n-paraffin was carried out.
The main focus is on increasing the selectivity of Among the three types of zeolites mentioned above, it is thought that pores large enough to adsorb monomethyl-substituted paraffins are suitable, and various attempts have been made to improve catalysts based on ZSM 5 zeolite (2). ZSM-23 and -35 zeolites with pore sizes intermediate between 1) and (2) have been proposed (Japanese Patent Application Laid-open No. 131091/1983).
Due to the recent crude oil situation, the use of high pour point heavy oil has been increasing in particular. The dewaxing activity of this high pour point heavy oil cannot be said to be sufficient in the prior art. As a result of careful investigation into the causes of this, it was found that the higher the pour point of the hydrocarbon fraction, the less the n-paraffin component contained in the wax component. In hydrocarbons close to the eaves fraction, most of the wax components were n-paraffins.

High pour point hydrocarbon fractions are wax components.

n-paraffin is a slightly branched paraffin;
The main components were naphthenic hydrocarbons or hydrocarbons. Judging from this wax component, mordenite type zeolite with a relatively large pore size is considered to be suitable as a catalyst component. However, when mordenite-type zeolite was evaluated as a catalyst, its dewaxing activity was low and it could not be used. In order to increase the activity, there is a method of treating 1 mordenite type zeolite with a strong acid solution to dealumate it and make it into high silica mordenite.This method increases the dewaxing activity, but it causes severe deterioration over time and is problematic. It comes out. Furthermore, in order to improve this aging deterioration, it has been disclosed in the Hydrogenation Components publication that a platinum group component is preferably introduced into high silica mordenite by ion exchange treatment (for example, Japanese Patent Publication No. 4-7-48482). However, platinum group components are ionized.

Even when it exists as an iron, it also exists as a signature ion, so ion exchange with mordenite is very difficult.

Ion exchange is easy near the outer surface of mordenite crystals, but it is difficult to exchange ions inside the crystals. Therefore, the ion exchange rate of platinum group ions within the crystals is non-uniform. When platinum group ions that have been ion-exchanged near the outer surface are used in a reaction, they are easily reduced to metal in a reducing atmosphere and agglomerated.Therefore, although the aging deterioration of dewaxing activity is somewhat improved, Kai＜B
Not done. In order to further solve this problem, the inventors of the present invention have conducted a number of experiments. As a result, the process of synthesizing 2-mordenite type zeolite, that is, adding a platinum group metal component to an aqueous aluminosilicate gel as a reaction mixture. Presence of Hydrogen 1 A hydrocarbon fraction is brought into contact with a catalyst mainly composed of mordenite type zeolite l-i, in which platinum group metal components are uniformly dispersed and included in crystals produced by crystallization in the presence of hydrogen. [Objective of the Invention] The object of the present invention is to apply a dewaxing reaction of a high pour point hydrocarbon fraction to a hydrocarbon fraction 4). The purpose of the present invention is to provide a novel catalyst suitable for
) source, an alkali (Of(-)) and a platinum group (M) source, and a platinum group metal component-containing mordenite type zeolite obtained by preparing an aqueous reaction mixture and crystallizing it at 140 to 200°C. This invention relates to a dewaxing method characterized by contacting a hydrocarbon fraction with a catalyst in the presence of hydrogen.

The silica source used for crystallizing the mordenite-type zeolite containing platinum group metal components according to the present invention includes:
Examples include silica sol, silica gel, silica airgel, silica hydrogel, silicic acid, sodium silicate, and silicate ester.

Examples of the alumina source include sodium aluminate, aluminum sulfate, aluminum nitrate, alumina sol, alumina gel, activated alumina, gamma alumina, and alpha alumina. Examples of the alkali source include caustic soda and caustic potash, but caustic soda is preferred. Note that, for example, when sodium silicate is used as a silica source and sodium aluminate is used as an alumina source, it goes without saying that these simultaneously serve as an alkali source. Examples of platinum group metal components include platinum dipalladium, ruthenium, and rhodium. Examples of the platinum source include chloroplatinic acid and ammonium chloroplatinate. Examples of the palladium source include palladium chloride, tetraammine palladium chloride, ammonium tetrachloropalladate, etc., and examples of the ruthenium source include rudenium chloride, ammonium ruthenate chloride, potassium ruthenate, and the like. Examples of the rhodium source include rhodium chloride, thorium rhodium chloride, and ammonium rhodium chloride. Particularly preferred as these platinum group metal components are platinum and palladium.

In addition, carboxylic acids and their salts, alcohols, amines, quaternary alkylammoniums, etc. may be added to the aqueous reaction mixture according to the present invention as additives. These additives speed up the crystallization rate, change the shape of the crystallites, and influence the fine 11+i structure of the crystals. In particular, carboxylic acids and their salts are preferably used as additives. When carboxylic acids and their salts (A) are used, their electrodynamic properties appear when they are added in a molar ratio of CAAt203 in the range of 0.1 to 100 relative to the lumina (Al2Og) source of the mixture. Examples of carboxylic acids and their salts include succinic acid, tartaric acid, citric acid,
Examples include toluic acid, salicylic acid, salts thereof, etc., and an aqueous reaction mixture using these raw materials has the following reaction mixture composition ratio expressed in molar ratio: More preferred range: S 102/kl 20 B 9-50 15~40O
H-/S i O20,15-Jo, 50 0.15 material, 40H20/5i02 10~50 10~50M/
5iO21 mowing o5 ~ l mowing 0-” lXl0 ~ lXl0
It can be prepared to fit in. It goes without saying that when a carboxylic acid is used as an additive in the reaction mixture, the alkali l) k of the reaction mixture 011- is calculated assuming that the carboxylic acid -COO11 reacts with the alkali, and this aqueous reaction mixture is stirred. It is preferable that the slurry be made into a uniform slurry. In order to form a uniform slurry-like mixture, careful attention must be paid to the mixing order, time, and stirring noise. Prior to crystallization, the aqueous reaction mixture slurry may be subjected to a so-called aging operation in which it is left at a temperature lower than 1 degree, for example at room temperature, for several days to several days. The operation may be omitted. The reaction conditions for crystallization are a reaction temperature of 140 to 200°C, and a reaction time of preferably 5 hours to 30 days, preferably 10 hours to 10 days. Optimal reaction conditions depend on the raw materials used or the composition of the aqueous reaction mixture. The lower the reaction temperature, the longer the crystallization time is required, and the higher the reaction temperature, the longer the crystallization time is required.
Generally, the crystallization time is shortened. However, if the temperature is too low or the iH degree is too high, the material becomes amorphous or forms undesirable crystals. Similarly, the reaction time is
If the time is too short or too long, it can become amorphous or transform into other undesirable crystals.

After the warping, the mixture is crystallized by placing it in a sealed autoclave made of steel, stainless steel, or lined with Teflon. Therefore, the anti-tail, (usually,
It is carried out under naturally occurring pressure depending on the humidity. The reaction mixture is preferably kept in a homogeneous state by stirring continuously or periodically during crystallization. Particularly when the reaction temperature is high, it is preferable to stir and mix thoroughly. After cooling, the crystallized reaction product is poured out from the closed container and washed with water once. The zeolite that has been washed with water is dried if necessary.

In this way, a mordenite type zeolite containing a platinum group metal component having an X-ray diffraction pattern shown in Table 1 is produced. Measurement of the X-ray diffraction pattern is carried out according to conventional methods. In other words, X-ray irradiation can cause damage to copper.
One diffraction pattern is obtained using a Geiger counter spectrometer equipped with a recording device. From this diffraction pattern, the relative intensity t00I/MAX (IMAX is the strongest line) and the lattice spacing d (unit: angstrom A) are determined. however.

The relative strength (100I MAX) is VS = very strong.

S is strong, M is intermediate strength, and W is weak.

Table 1 X-Ray Diffraction Pattern The silica/alumina ratio of the mordenite-type zeolites produced varies from about 9 to about 35. The silica/alumina ratio of the zeolite depends on the zeolite synthesis conditions, but especially the silica/alumina ratio of the aqueous reaction mixture (SiO2/A
t2O8), 7/l/h') degrees (OH-'/
5iO2).

The preferred silica/alumina ratio for mordenite-type zeolites used in the present invention is from about 12 to about 25.

The mordenite type zeolite containing platinum group metal components synthesized in this manner is alkaline as it is and does not have sufficient solid acidity. It is preferable that the mordenite-type zeolite K used in the reaction of the present invention be imparted with solid acidity to form an acid form. As is well known, acid-type mordenite-type zeolite has polyvalent cations such as hydrogen ions, ammonium ions, or rare earth ions as cations in the zeolite. This ion exchange is obtained by ion-exchanging at least a part of the plucarium ions of a zeolite having alkali metal ions with hydrogen ions, ammonium ions, or polyvalent cations. This is preferably carried out by treating with a solution containing hydrogen ions and/or hydrogen ion precursors and completely introducing hydrogen ions and/or hydrogen ion precursors. The ion exchange treatment is generally carried out in an aqueous solution, and the acids that can be used include inorganic acids and organic acids, with inorganic acids being the most common. , as an s-organic acid,
Examples include hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, etc.
Of course, other materials may be used as long as they contain hydrogen ions. When an inorganic acid is used, it is not preferable to treat the zeolite with a highly concentrated solution because it may cause a so-called dealumination treatment in which aluminum is removed from the mordenite type zeolite, or cause deterioration or destruction of the zeolite. The concentration of the acid preferably used varies greatly depending on the type of acid, so it is difficult to determine it unambiguously.
So you need to be very careful.

As ammonium salt compounds, inorganic ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, aqueous ammonia, etc., or ammonium salts of organic acids such as ammonium formate, ammonium acetate, ammonium citrate, etc. can be used as well. Preferred is an inorganic ammonium salt. The ammonium salt used is preferably used as a solution of α05 to 4 normal, more preferably as a solution of about 01 to 2 normal. As a method for ion exchange of mordenite-type zeolite) with an acid and/or ammonium salt solution, when processing in the bunch method, the solid-liquid ratio is at least an amount that allows the zeolite to come into sufficient contact with the liquid, specifically about l 17Kg or more is preferable. The processing time is
About 0.1 to 72 hours is sufficient, preferably about 0.1 to 72 hours.
5 to 24 hours. The treatment temperature may be below the boiling point, but it is preferable to heat it to promote the ion exchange rate. In the case of flow treatment, a fixed bed method, a fluidized bed method, etc. can be used, but it is necessary to take measures to prevent uneven flow of the fluid or non-uniform ion exchange treatment. Mordenite type zeolite is ion exchange treated.

It is then washed with water. Preferably, distilled water is used as the washing liquid, and the water washing may be carried out by a batch type β sieve (or a flow type 1,7). An ammonium ion is introduced.

Solid acid gives vomiting. Mordenite-type zeolite may contain hydrogen ions and/or cations other than their precursors.

In this way, the mordenite-type zeolite containing platinum group metal components is subjected to ion exchange treatment to improve solid acidity, but surprisingly, the platinum group metal components contained in the zeolite are not affected by this ion exchange treatment. The apparatus that can be used for the reaction of the present invention may be either a fixed bed or a fluidized bed. In the case of a fixed bed system, the smaller the catalyst particle size is, the more preferable it is from the point of view of the effective number of catalysts.However, if the particle size is too small and too potassium, the pressure loss will increase, which is not preferable. There is a preferable range for the particle size.The preferably used particle size is 00
5 to 10 mm, more preferably 03 to 3 mm. The synthesized mordenite-type zeolite is usually
It is in powder form. Therefore, in order to obtain a catalyst having such a preferable range, compression molding is a method that requires molding.

Examples include extrusion molding. Particularly in the case of extrusion molding, in order to improve the moldability, it is preferable to use a binder that imparts strength k to the molded product. Of course, it goes without saying that there is no need to use a binder if it can be sufficiently molded without a binder. Examples of the binder include naturally occurring clays such as kaolin, bentonite, and montmorillonite, and synthetic products such as silica sol, alumina sol, and alumina gel. The amount of calories added to the binder is 70% by weight or less, preferably 30% by weight or less. Such molding may be performed before the mordenite-type zeolite is subjected to ion exchange treatment.
However, ion exchange may be performed after molding.

The catalyst prepared as described above is dried before use and then calcined. Drying is carried out at 50 to 250°C for 0.1 hour or more, preferably 0.5 to 48 hours.

Firing is carried out at 300-700°C for 0.1 hour or more, preferably at 400-600°C for 05-24 hours. Firing is performed in the air, an inert gas, or an atmosphere consisting of these and water vapor. By such firing, ammonium ions introduced in the ion exchange process are converted into hydrogen ions, and hydrogen ions are further removed during the firing process. As the temperature is raised, the catalyst is converted to a decationized type, and of course catalysts in this form can also be used satisfactorily.

As described above, the prepared catalyst can be used completely under the following reaction conditions. That is, the reaction operating temperature is 200
-500°C, preferably 250-450°C. The reaction operating pressure is 100Kq/aaG from an atmospheric field, preferably 10 to 9/cJG to 50Kr/cn! -G. Liquid time space velocity (LH), which refers to the total contact time of the reaction
8V) 1. 'J' is 0.1-10 hr-1, preferably 0.5-4.0 hr-'. The ratio of hydrogen to hydrocarbon is 100 to 1000 N i+? /n? , preferably 200 to 800 N-JAn'.

As a feedstock, is it wax obtained from crude oil, tar sands2 oil sands, coal, etc.? Various hydrocarbon fractions can be used, including:

〔Effect of the invention〕

Mortenite-type zeolite containing platinum group metal components?
High pour point hydrocarbon fractions can be efficiently dewaxed using the catalyst as the main component.

Hereinafter, the present invention will be explained with reference to examples. In this example, the catalyst performance was evaluated under the following conditions.

(1) Raw wood” Name: Desulfurized vacuum gas oil? Jii point (10-90%) (℃) 32F) -490
Pour point C℃) +32.5 Total sulfur (wt%) o, os (2) Reaction conditions LH3V (hr) 2.0 Reaction power (Kri7nI G) 35 H2/FeecL (N-m, 4/m7 ) 500 Reaction humidity (°C) 3OO (3) Evaluation Distill the reaction product and measure the pour point of the fraction with a boiling point of 165°C or higher.

Example 1 12.5 grams of solid caustic soda and 125 grams of tartaric acid were dissolved in 340 grams of water. 175 grams of aluminate sorter solution was added to this solution to make a homogeneous solution. Gradually add 6 eL0 duram of silicic acid powder to this mixed solution while stirring to form a slurry.

Add 0.9% of the tetraamine palladium chloride solution to this slurry.
A reaction mixture was prepared by adding 4 grams and stirring vigorously. The composition ratio (molar ratio) of this reaction mixture is as follows: b
One.

5i02/At20g 30 Of(-/5102 α25 IhO/SiO220 Pd, /5iO28,4 0-4 to//At208 2.5 The reaction mixture was placed in a 500 mt autoclave and sealed, and the P 4rL was poured while stirring. The reaction was carried out at 160°C for 72 hours. After the reaction was completed, the product was removed from the autoclave and
Wash with distilled water until the pH is almost neutral.

It was passed through the mouth and dried at 120°C overnight. The obtained product was a mordenite type zeolite having the X-ray diffraction pattern shown in Table 1. Its composition was Si0□ 871 weight ratio AL208 a09 Na20 4.77 Pa 0.04 in anhydrous state, and the silica/alumina ratio was 1&3.

The zeolite powder thus obtained was solidified with an aqueous ammonium chloride solution of α187 normality (t/l (g)), heated to 80 to 90°C, and subjected to ion exchange treatment for 30 minutes. After that, it was passed through the mouth and subjected to ion exchange treatment in the same manner again. This operation was repeated 5 times. After the ion exchange treatment, it was thoroughly washed with distilled water and dried overnight at 110°C. This ion exchange treated zeolite powder Alumina sol was added as a binder to Anovena (At20a, 15% by weight) and thoroughly kneaded. After kneading, it was formed into particles with a size of 10 to 24 meshes (JIS sieve) and dried overnight at 110°C.

Thereafter, it was fired at 500° C. for 2 hours in the presence of air.

The catalyst thus obtained was evaluated using desulfurized vacuum gas oil.

The pour point after distillation of the reaction product was -15.0°C. After the reaction had continued for 200 hours, the pour point of the product was measured in the same manner and was found to be -75°C.

Example 2 A mordenite-type zeolite was synthesized in the same manner as in Example 1, using an ammonium chloroplatinate solution instead of the tetraammineno-4-radium chloride solution.

The obtained mordenite-type zeolite was evaluated as a catalyst in the same manner as in Example 1. After distilling the reaction product and measuring the pour point, the result was -10.0°C. After continuing the reaction for 20 hours, the pour point of the product was measured in the same way: -5,
At 0℃, there are two.

Example 3 4.37 grams of solid caustic soda was dissolved in 338 grams of water. 2g of sodium aluminate solution was added to this solution to form a homogeneous solution. Add 6 silicate powder to this mixture.
6.0 grams were added to form a slurry, and 2.82 grams of tetraammine palladium chloride solution was added to this slurry, followed by further stirring to prepare a reaction mixture. The composition ratio (molar ratio) of this reaction mixture was 9 as follows: 5i02/At20320 01-i7si020.275 1hO/5i0220 Pd/5i0z 1.0X10'' The reaction mixture was placed in a 500me autoclave and sealed. Thereafter, the mixture was reacted at 165° C. for 92 hours while stirring at 4ft.

After the reaction was completed, the product was taken out from the autoclave (9), washed with distilled water until the H concentration was almost neutral, passed through the mouth, and dried at 120° C. overnight. The obtained product was a mordenite type zeolite having the X-ray diffraction pattern shown in Table 1. Its composition in anhydrous state was 5 iOz 84.6 A7208 9.7 Na 20 5.6 Pa 0.12 ll and the silica/alumina ratio was 14.8.

The zeolite powder thus obtained was used as a catalyst and evaluated in the same manner as in Example 1. The reaction product was completely distilled and the pour point was measured to be -12.5°C. After continuing the reaction for 200 hours, the pour point of the product was similarly determined to be -75°C.

Example 4 14.7 grams of solid caustic soda and 3s grams of tartarite were dissolved in 338 grams of water. 18.1 grams of aldimic acid noda bath solution was added to this solution to obtain a homogeneous solution.

To this mixed solution, 6a0 g of silicic acid powder was gradually added while stirring to form a slurry, and 049 g of tetraamminepalladium chloride solution was added to this slurry and further stirred to prepare a reaction mixture.

The composition ratio (molar ratio) of this reaction mixture is as follows:

S3-02/Al2O,40 OH/5iO20,31 1-I20/5i0220 Pd/5i0z 2.3X10-3 A/A1208 2.5 The reaction mixture was placed in a 500 liter autoclave, sealed, and then stirred. Crystallization was performed at 160°C for 72 hours.

After the reaction is complete, the product is removed from the autoclave and
Rinse with distilled water until pH is almost neutral, sip through mouth, 12
It was dried overnight at 0°C. The product obtained was a mordenite type zeolite having the X-ray diffraction pattern shown in Table 1. Its composition in anhydrous state was 5iCh 89.4 weight ratio At20a a5 Na20 &9 Pa 0.19, and the silica/alumina ratio was 23.4.

The zeolite powder thus obtained was used as a catalyst and evaluated in the same manner as in Example 1. The reaction product was distilled and the pour point was measured and found to be -75°C.

After the reaction continued for 200 hours, the pour point of the product was similarly measured and found to be -25°C.

Comparative Example 1 A mordenite-type zeolite was synthesized in the same manner as in Example 1 without using the tetraammine palladium chloride solution.

The composition of the obtained zeolite is 5iOz 8←5 Chonggang% AL20a 34 Na20 5.1 pa　’　o, o.

So, I obtained a mordenite type zeolite containing S, B, and palladium and having an alumina/alumina ratio of 175.

Using this zeolite, a catalyst was prepared and evaluated in the same manner as in Example 1. The reaction product was distilled and the pour point was determined to be +2.5°C. After continuing the reaction for 20 hours, the pour point of the product was similarly determined to be +25.0°C. It can be seen that the dewaxing activity was low and the activity deteriorated significantly over time. Comparative Example 2 The mordenite type zeolite powder obtained in Comparative Example 1 was subjected to ion exchange treatment with an aqueous ammonium chloride solution in the same manner as in Example 1.

Subsequently, solid-liquid 5 was added to a tetraamine palladium chloride solution containing 0.04 weight percent of palladium metal.
(L/h) and left at 80 to 90°C for 1 hour to perform ion exchange treatment. After that, we talked.

It was thoroughly washed with distilled water and dried at 110°C overnight.

The zeolite powder thus obtained was evaluated as a catalyst in the same manner as in Example 1. The reaction product was distilled and the pour point was measured, and the result was -2-5°C.

After continuing the reaction for 20 hours, the pour point of the product was similarly determined to be +12.5°C. This result shows that the activity deteriorates significantly over time.

Patent applicant: Toshi Co., Ltd. Same as above: Fudo Oil Co., Ltd. Agent: Patent Attorney Katsu Ono Same as above Reiko Ohno Same as above: Ryunosuke Ohno

Claims (1)

Claims: An aqueous reaction mixture comprising a silica source, an alumina source, an alkali source and a platinum group metal source, expressed in molar ratios. SiO2/A4zOa' 9~50 OH7S i 02 0.10~0.50HzO/5i
02 10~50 M/5i021XlO~1x1o-2 (However, 0■ (= indicates alkali source t, MU platinum group metal source)
1. A method for dewaxing a hydrocarbon fraction, which comprises bringing the hydrocarbon fraction into contact with a catalyst mainly composed of mordenite-type zeolite '4 containing a platinum group metal component crystallized at .degree. C. in the presence of hydrogen.