JPS6123689A - Production of lcgo having low pour point - Google Patents

Abstract

PURPOSE:To produce LCGO having a low pour point in a good yield, by using a catalyst composed of three specified elements in a method for obtaining LCGO (having a boiling range nearly equal to that of kerosine or gas oil) by catalitically cracking gas oil. CONSTITUTION:A three-component catalyst composed of 35-94.5wt% inorg. oxide matrix component (A) (e.g. silica/alumina gel), 5-50wt% faujasite X (B) having a pore size of 9-10Angstrom which has been subjected to an ion exchange treatment with rare earth metal ion, and 0.5-15wt% crystalline aluminosilicate (C) [pore size:7Angstrom or below; SiO2/Al2O3 (molar ratio): 10-150] which has been subjected to an ion exchange treatment with rare earth metal ion, is used. Pref. reaction conditions are such that the temp. is 450-650 deg.C, the pressure is atmospheric pressure to 7kg/cm<2>, the wt. ratio of catalyst/oil is 1-25, the oil contact time is 0.5sec-10min.

Description

DETAILED DESCRIPTION OF THE INVENTION A. OBJECTS OF THE INVENTION (INDUSTRIAL APPLICATION FIELD) The present invention relates to a method for manufacturing LCGO. For more details,
The present invention catalytically cracks gas oil to produce LCG with a low pour point.
The present invention relates to a method for producing O.

(Prior art) LCGO is an oil that has approximately the same boiling point range as kerosene and diesel oil produced by the catalytic cracking method of gas oil, and the catalyst system used in the production of LCGO has conventionally been composed of zeolite and a matrix. It is common to use a so-called zeolite catalyst. In this case, the zeolite component consists of X or Y type faujasite with a pore size of approximately 9 to 19 pores, and the matrix component consists of silica-alumina gel or clay. Most of the hydrocarbons in gas oil undergo a cracking reaction in the above-mentioned catalyst system, but their decomposability varies depending on the type of hydrocarbon, and the susceptibility to catalytic cracking is approximately as follows.

Olefins - long chain aromatics〉naphthenic isoparaffins〉
Normal paraffins, that is, normal paraffins, have low decomposition properties, so they remain in large quantities in the product, and therefore LCGO fractions also contain carbon atoms in the range of 12 to 20 carbon atoms (the pour point of normal paraffins is relatively high, especially Those with carbon number 16 or more are LCG
Because of the large amount of O (which is thought to control the pour point of O) contained, there was a certain limit to lowering the pour point of conventional LCGO.

Although such limitations can be improved to some extent by process operations, there is a disadvantage that the yield of LCGO decreases when the effect is small.

On the other hand, as a catalyst technology for catalytic cracking, catalyst systems different from those mentioned above, such as faujasite improved USY, ZSM-5, or mordenite, have been developed (for example, In
d, Eng, Chem, , Prod, Res, De
v, +Vo1.17. Na3, 1978, U.S. Patent No. 3,950,242, U.S. Patent No. 4.137.152,
British Patent No. 1,486,927), these are aimed at improving the quality of cracked naphtha or reducing the coke (carbonaceous material deposited on the catalyst) yield;
It cannot be used as is because of its lower pour point.

(Problems to be Solved by the Invention) As a result of intensive research to improve the conventional drawbacks, the present inventors have improved the selective decomposition activity of the catalyst used for normal paraffins, thereby increasing the yield of LCGO. It has been discovered that the pour point of LCGO can be significantly lowered without extremely deteriorating the coke yield or significantly increasing the coke yield, and the present invention has been achieved based on this discovery.

Therefore, a first object of the present invention is to provide a method for producing low pour point LCGO in good yield by catalytically cracking gas oil.

A second object of the invention is to provide a catalyst suitable for producing low pour point LCGO by catalytic cracking of gas oil.

Furthermore, a third object of the present invention is to provide reaction conditions suitable for producing low pour point LCGO by catalytic cracking of gas oil.

9. Structure of the Invention (Means for Solving Problems) The above aspects of the present invention are as follows: In the method for producing LdGO by catalytic cracking of gas oil, as a catalyst: ■At least one selected from rare earth metals, hydrogen, and alkaline earth metals
A zeolite consisting of faujasite and a zeolite component of at least one of TSZ, mordenite, or ferrierite ion-exchanged with ions of one element selected from platinum group elements and having a pore size of about 7 Å or less. This was achieved by using a three-component catalyst.

The matrix component (2) of the catalyst used in the present invention can be arbitrarily selected from known ones, but
In particular, it is preferable to use an inorganic oxide containing silica and alumina, such as silica-alumina gel and/or clay, from the viewpoint of maintaining the activity of the zeolite and the mechanical strength of the catalyst.

Component (2) of the catalyst used in the present invention can be arbitrarily selected from known faujasites, among which faujasite type X and faujasite Y type.
In particular, X-type or Y-type faujasite ion-exchanged with ions of at least one element selected from rare earth metals, hydrogen, and alkaline earth metals is preferred. This component (2) is a zeolite with a pore size of about 9 to about 10 people and can decompose the coke precursor generated during the catalytic cracking reaction. can suppress the increase in

However, with only the above ingredients (■) and (■), as mentioned above,
A large amount of normal paraffin remains in the produced LCGO, but in the present invention, since a molecular shape selective catalyst is used as the third component, this third zeolite component can be used to improve the /(Craffin can be selectively decomposed. For this purpose, the third zeolite component needs to have the following properties.

The pore size should be in the range of about 4.3 to about 7 to function as a molecular sieve in the molecular size range of +a+al paraffins.

(b) It has sufficient solid acidity to decompose normal paraffins.

fcl has excellent heat resistance and functions well as a catalyst at about 600 to 800°C.

That is, the above requirements for fa) and fbl are such that by selectively decomposing normal paraffins, L CG O yield 1
It acts non-selectively on coke precursors and coke components with large molecular sizes in order to significantly lower its pour point and prevent an increase in coke yield. It is necessary to do so. or(
The requirement of C1 is necessary to stably maintain the requirements of (al and (bl) described above. If the zeolite has these three requirements of (al to fcl), Among them, at least one component selected from TSZ, mordenite, and ferrierite with a pore size of 76 or less, especially rare earth metals, hydrogen, nickel, cobalt, and platinum group elements. It is preferable to use zeolite which has been ion-exchanged with ions of at least one element selected from among these.

Here, TSZ has the same meaning as TSZ crystalline aluminosilicate, and the details of its content and manufacturing method are as disclosed in JP-A-58-45111.

In the present invention, ion exchange of zeolite can be easily performed by a known method.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

<Example> Various molecular shape selective zeolites were added to the FCC equilibrium catalyst sampled from the regeneration tower of the actual device and the commercially available new FCC catalyst, and MicroActivity Te5
t (abbreviated as MAT), experiments were conducted on the effect on the pour point of the LCGO fraction.

(Preparation of Samples) Equilibrium and new catalysts were used as base catalysts, and 0 to 10% by weight of two types of zeolites having molecular shape selectivity were added thereto.

One of the molecular shape selective zeolites is ZSM-5,
The other is a crystalline aluminosilicate (hereinafter referred to as TSZ) prepared without the use of organic cations.

TSZ has a similar crystal structure to ZSM-5. The history of the parent catalyst and the preparation of the molecular shape selective zeolite are as shown below.

(1) Base catalyst The following three types of base catalysts were used.

■Mother catalyst A: FCC equilibrium catalyst sampled from the regeneration tower of the actual device ■Mother catalyst B: SZC manufactured by Catalysts & Chemicals Co., Ltd. 78
Catalyst treated with steam at 8°C for 16 hours ■ Base catalyst C: Preparation of catalyst (2) ZSM-5, which differs only in lot from the catalyst in (2) 5i02/A according to U.S. Pat. No. 3,702,886
It was prepared so that the β203 molar ratio was 50. The main composition after ammonium ion exchange and calcination is as follows.

A7!203; 3.51% by weight 5i02; 93.1% by weight Na2O; 0.07% by weight (Si02/Al2203 molar ratio -45) H-TSZ
(100), H-TSZ (25), only the alumina source among the raw materials was converted into a predetermined Si 02 / A 1
1203 and prepared in the same manner as described above.

However, the numbers in ) represent the 5L02/A42203 molar ratio (the same applies hereinafter).

N i -TSZ (50) Nitsui”'C is H-T
SZ was heated to 18°C at 40°C using one normal N1(NO3)2.
Obtained by ion exchange for hours.

Regarding Pt-TSZ (50), platinum was supported using H-TSZ by a dipping method from an N2PtC#5 melt at a predetermined concentration.

H-TSZ (I Q O) obtained in this way,
The chemical compositions of N1-TSZ (50) and Pt-TSZ (25) are as follows.

H-TSZ (100 Sin2 96.8 Weight% AI!203
1.98 wt% Na2O0.01 wt% Ni-pt
--Ni-TSZ (50) Si02 93.3 wt% A6203
3.30 wt% Na2O 0.02 wt% NiO, 74 wt% Pt
--Pt-TSZ (25 Si02 90.8 wt% A#203
6.17 wt% Na2O0.01 wt% Ni-PL
O, 48% by weight (4) Preparation of mordenite-type crystalline aluminosilicate In the raw material composition, 5i02/Ajl! A hydrogen-type crystalline aluminosilicate was prepared in the same manner as H-TSZ, with a molar ratio of 203 to 20.

X-ray analysis (FIG. 3) shows that this crystalline aluminosilicate has a mordenite crystal structure.

The chemical composition is as follows.

AA203; 7.57% by weight 5i02; 89.2% by weight Na2O; 0.02% by weight (5) Preparation of ferrierite type crystalline aluminosilicate Using tetramethylammonium hydroxide as the organic cation, 5i02 in the raw material composition /Aff
A hydrogen type crystalline aluminosilicate was prepared generally in accordance with US Pat. No. 3,702,886, with a molar ratio of 203 to 30. X-ray analysis (FIG. 4) shows that the obtained crystalline aluminosilicate has a ferrierite crystal structure. The chemical composition is as follows.

An203; 6.77% by weight 5i02; 90.1% by weight Na20; 1-34% by weight The following 14 types of catalyst samples were prepared from the above-mentioned base catalyst and various shape-selective zeolites.

1, Δ Base catalyst A 2.1χH-ZSM-5/8 H- to base catalyst A
1% by weight of ZSM-5 added to 3.5χH-ZSM-5/A base catalyst)
1-Addition of 5% by weight of ZSM-5 4.B Base catalyst B5.1χH-
TSZ(50)/B H-TSZ(
50) added 1% by weight 6.5χ old TSZ (50) /B Base catalyst B
Added 5% by weight of H-TSZ (50) to 7.5χ H-TSZ (100)/B Base catalyst B
Addition of 5% by weight of H-TSZ(100) to 8.5χn-zsn-5(50)/B Addition of 5% by weight of H-ZSM-5(50) to base catalyst B9.5χH
-ZSM-5(too)/B H-Z in base catalyst B
Addition of 5% by weight of SM-5 (100) 10, C base catalyst C 11, N to 5XNi-TSZ(50)/C base catalyst C
Added 5% by weight of i-TSZ (50) However, the numbers in ) are 5i02/Aj! 203 molar ratio.

12.5χpt-rSZ(25)/C host catalyst c with P
Addition of 5% by weight of t-TSZ (25) 13.5χ mordenite/c Addition of 5% by weight of mordenite to base catalyst C 14.10χ Ferrierite/C Addition of 10% by weight of ferrierite to base catalyst C (MAT evaluation) Various types LCGO by addition of molecular shape selective zeolite
In order to examine the influence of the above-mentioned 14 samples on the pour point, MAT was conducted under the following conditions.

MAT reaction conditions Raw material oil 260/454℃ Heavy gas oil Reaction temperature 482℃ Catalyst amount 5g Reaction time 80 seconds Weight hourly space velocity 7.4 g/hr/g Note that sample 4
For ~12, before reaction test
1 was subjected to steam treatment at 788°C for 16 hours. Sample 13
The same treatment was applied to the base catalyst of Sample 14 as well.

The pour point comparison of LCGO was performed using the normal paraffin peak intensity in the gas chromatography distillation data of the liquid product for Samples 1 to 3, and the estimated value from the gas chromatography data for Samples 4 to 14. MAT data in Table 1 and Table 2
Shown below.

(1) Samples 1 to 3 As is clear from the gas chromatography distillation charts in Figures 5, 6, and 7, when ZSM-5 is not added, LCGO
Normal paraffin peak of fraction (12 to 20 carbon atoms)
Although these peaks were very large, these peaks were significantly reduced by adding 1% or 5% by weight of ZSM-5.

Considering that the normal paraffin content is a factor that greatly influences the pour point of LCGO, it can be expected that the pour point of the LCGO fraction is significantly lowered.

In addition, there was almost no difference due to the difference in the amount added, and ZSM-5
This suggests that in a fresh state, even a small amount of addition of about 1% by weight can have a sufficient effect.

(2) Samples 4 to 12 Even after steaming under the harsh conditions of 788 °C and 16 hours, as shown in Tables 1 and 2, LC at 5 to 15 °C
A decrease in QO pour point can be expected. This suggests that TSZ has excellent high-temperature hydrothermal stability, and the FCC
This shows that it has practical utility as an active component of a catalyst.

Among the various TSZs, those with a 5toz/Aβ203 molar ratio of 50 and in which the cation was hydrogen or di-nokel showed high performance.

In terms of yield, the decrease in LCGO yield selectivity is relatively small, and carbon yield does not increase significantly for some catalyst systems.

(3) Samples 13 to 14 By adding 5% by weight and 10% by weight of Fresonoille mordenite or ferrierite, respectively, the LCGO pour points were lowered by 15°C and 5°C, respectively.

(Effects of the Invention) According to the present invention, due to the catalytic effect of the molecular shape selective catalyst partially contained in the catalyst for catalytic cracking, normal paraffin, which would remain in the product in the conventional technology, is removed. Since it can be decomposed, gas oil can be efficiently catalytically cracked to produce LCGO with a low pour point, so the present invention has great significance.

[Brief explanation of drawings]

FIG. 1 is an X-ray diffraction pattern of hydrogen ion exchange type TSZ crystalline aluminosilicate. FIG. 2 is an X-ray diffraction pattern of ZSM-5. FIG. 3 is an X-ray diffraction pattern of a mordenite-type crystalline aluminosilicate. FIG. 4 is an X-ray diffraction pattern of a ferrierite type crystalline aluminosilicate. FIG. 5 is a gas chromatograph of the liquid product obtained from Sample 1. The numbers in the figure represent the number of carbon atoms in normal paraffin. FIG. 6 is a gas chromatograph of the liquid product obtained from Sample 2. The numbers in the figure represent the number of carbon atoms in normal paraffin. FIG. 7 is a gas chromatograph of the liquid product obtained from Sample 3. The numbers in the figure represent the number of carbon atoms in normal paraffin. Patent applicant Toa Fuel Industry Co., Ltd.゛9'] V-Hano

Claims (1)

[Scope of Claims] 1) A method for producing LCGO by catalytic cracking of gas oil, wherein (1) a matrix component consisting of an inorganic oxide, (2) a rare earth metal, hydrogen and an alkaline earth metal is used as a catalyst. A zeolite consisting of faujasite At least one of TSZ, mordenite, or ferrierite ion-exchanged with ions of at least one element selected from metals, hydrogen, nickel, cobalt, and platinum group elements,
A method for producing a low pour point LCGO, characterized by using a catalyst consisting of three zeolite components having a pore diameter of about 7 Å or less. 2) The inorganic oxide matrix of (1) is composed of at least one selected from silica and alumina, silica-alumina gel, and clay. Method for producing low pour point LCGO. 3) The method for producing a low pour point LCGO according to claim 1, wherein the faujasite zeolite in (2) has hydrogen and/or rare earth metal cations. 4) The pore size of the zeolite component in (3) is about 4.3 to about 7.
3. The method for producing a low pour point LCGO according to claim 1, wherein the LCGO is .ANG. 5) SiO_2/Al_2O of the zeolite component in (3)
The low pour point LCGO of claim 4, wherein the _3 molar ratio is in the range of about 10 to about 150.
manufacturing method. 6) The inorganic oxide matrix component (1) is about 35 to about 94.5% by weight, the faujasite type zeolite component (2) is about 5 to about 50% by weight, and the zeolite component (3) is about 0%. The method for producing low pour point LCGO according to any one of claims 1 to 5, characterized in that the content is .5 to 15% by weight. 7) Catalytic cracking reaction conditions include reaction temperature of about 450 to about 650
℃, reaction pressure is normal pressure to about 7 kg/cm^2G, catalyst/oil weight ratio is about 1 to about 25, oil contact time is about 0.5 seconds to about 1
The method for producing low pour point LCGO according to claim 1, characterized in that the time is 0 minutes.