CN102079996B - Catalytic conversion method for producing high-quality light fuels from crude oil - Google Patents

Abstract

A catalytic conversion method for producing high-quality light fuel from crude oil. Crude oil is contacted with a catalyst with a coarse particle size distribution rich in mesoporous zeolite for reaction in a reactor. Make the reaction to obtain a reaction product containing 12-60% by weight of the raw material oil containing catalytic wax oil, wherein the reaction temperature is 420-600°C, the weight hourly space velocity is 25-100h ^-1 , and the weight ratio of the catalyst to the raw material oil is 1 to 30; the catalytic wax oil is then hydrocracked. The method provides a combination of catalytic conversion of crude oil and hydrocracking, especially when converting inferior crude oil into high-octane gasoline and high cetane diesel, while greatly reducing the yield of dry gas and coke so that Realize efficient utilization of petroleum resources, and reduce catalyst breakage tendency and catalyst consumption.

Description

Catalytic conversion method for producing high-quality light fuel from crude oil

technical field

The invention relates to a method for producing high-quality light fuel by combining catalytic conversion of crude oil and hydrocracking. More specifically, a process for maximizing the production of high octane gasoline and high cetane diesel through catalytic conversion and hydrocracking.

Background technique

Worldwide demand for high-quality diesel is increasing, while demand for fuel oil is decreasing. Although the increase in demand for gasoline and diesel varies from region to region, overall, the growth rate of demand for diesel worldwide will exceed the growth rate of demand for gasoline. Therefore, more catalytic light diesel oil with low cetane number is being used as a blending component of diesel oil. In order to meet the demand for high-quality diesel oil, it is necessary to upgrade the catalytic light diesel oil, or directly produce a large amount of high-quality catalytic light diesel oil through catalytic cracking (FCC).

The production of catalytic cracking gasoline and diesel oil generally uses straight-run vacuum distillate (VGO) as raw material and blends some residues such as atmospheric residue (AR) and vacuum residue (VR). Heavy raw materials such as residual oil contain high content of heavy metals such as residual carbon, sulfur, nitrogen, nickel, and vanadium. In order to improve the feed properties of these catalytic cracking units (FCCU), in addition to decarburization and demetallization by delayed coking or deasphalting, catalytic cracking is more and more used to hydrogenate heavy oil and residual oil to increase the feedstock oil of FCCU. Hydrogenation and deacidification and demetallization to further fully and efficiently utilize crude oil. Hydrogenation and upgrading of FCCU feed consumes a lot of hydrogen, which is limited by the hydrogen source, and the hydrogenation of FCCU feed cannot overcome the disadvantages of catalyst activity and selectivity reduction caused by coke deposition in the conventional riser catalytic cracking process. Aiming at the inherent shortcomings of riser reactors, US4243514 and US4263128 disclose methods for upgrading crude oil fractions or partial fractions, using an inert heat carrier material without cracking activity to absorb the entire fraction or partial fractions of crude oil to remove carbon residue in the raw material and heavy metals, the upgraded raw material is then used as the feed of conventional FCCU for cracking. However, this method has many disadvantages such as poor gasoline properties and high energy consumption.

All in all, the existing FCC gasoline has high olefin content in the light fraction, and the heavy fraction has a low octane number, which affects the quality of gasoline; FCC diesel oil contains more single-ring aromatics, has a low cetane number, and is of poor quality. To meet the increasing demand for motor gasoline, it is necessary to develop a catalytic conversion method for converting heavy feedstocks into high-quality light fuels such as high-octane gasoline and high-cetane diesel, as well as jet fuel.

Contents of the invention

The purpose of the invention is to provide a catalytic conversion method for producing high-quality light fuel from crude oil on the basis of the prior art.

The catalytic conversion method for producing high-quality light fuel from crude oil provided by the invention comprises:

In the catalytic conversion reactor, the pretreated crude oil is used as the feedstock oil to contact with the catalyst of coarse particle size distribution containing large-pore zeolite for reaction in the reactor. It is enough to make the reaction to obtain a reaction product containing 12-60% by weight of the raw material oil containing catalytic wax oil, wherein the weight hourly space velocity is 25-100h ^-1 , the reaction temperature is 420-600°C, and the weight of the catalyst and the raw material oil is The ratio is 1-30. The catalytic wax oil is further hydrocracked.

The reaction temperature is 420-600°C, preferably 450-550°C, more preferably 460-520°C.

The weight hourly space velocity is 30-80h ^-1 , preferably 40-60h ^-1 .

The weight ratio of the catalyst to the raw oil is 1-30, preferably 2-25, more preferably 3-14.

In an embodiment, the reaction pressure is between 0.10 MPa and 1.0 MPa.

The crude oil described in the present invention is selected from or includes a mixture of one or more (including two, the same below) in petroleum-based crude oil and/or other mineral oils, and other mineral oils are coal liquefied oil, oil sand oil, shale One or a mixture of two or more oils.

The crude oil pretreatment process of the present invention refers to conventional crude oil desalination, dehydration, decalcification and other processes, through which most of the salts (such as magnesium chloride, sodium chloride, etc.), water and calcium in the crude oil are removed. The total value of vanadium and nickel in the pretreated crude oil according to the present invention is preferably not more than 30ppm, and its density (20°C) is greater than 0.85g·cm ^-3 , preferably greater than 0.90g·cm ^-3 , more preferably greater than 0.92g • cm ⁻³ .

In a preferred embodiment, the crude oil is selected from or includes petroleum-based crude oil, including paraffinic crude oil, paraffin-intermediate base crude oil, intermediate-paraffinic base crude oil, intermediate base crude oil, intermediate-naphthenic crude oil, naphthenic-intermediate One or more of base crude oil and naphthenic crude oil. The most preferred crude oil is a petroleum base crude oil, more preferably a heavy petroleum base crude oil containing at least 1% by weight bituminous component.

In an embodiment, the catalyst includes zeolite, inorganic oxide and optional clay, and each component accounts for the total weight of the catalyst: 1-50% by weight of zeolite, 5-99% by weight of inorganic oxide, 0-70% by weight of clay %. Wherein the zeolite is a large-pore zeolite and/or an optional medium-pore zeolite, and the large-pore zeolite accounts for 80-100% by weight of the total weight of the zeolite, preferably 90-100% by weight; the medium-pore zeolite accounts for 0-20% by weight of the total weight of the zeolite. % by weight, preferably 0% by weight to 10% by weight. The large-pore zeolite is selected from Y series zeolites, including rare earth Y (REY), rare earth hydrogen Y (REHY), ultra-stable Y obtained by different methods, and high silicon Y. Medium-pore zeolites are selected from ZSM series zeolites and/or ZRP zeolites, and the above-mentioned medium-pore zeolites can also be modified with non-metallic elements such as phosphorus and/or transition metal elements such as iron, cobalt, and nickel. A more detailed description of ZRP Referring to US5,232,675, ZSM series zeolites are selected from one or both of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structure zeolites For more than one mixture, see US3,702,886 for a more detailed description of ZSM-5.

The inorganic oxide as a binder is selected from silicon dioxide (SiO ₂ ) and/or aluminum oxide (Al ₂ O ₃ ). On a dry basis, in the inorganic oxide, silicon dioxide accounts for 50-90 wt%, and aluminum oxide accounts for 10-50 wt%.

Clay as matrix (i.e. carrier) is selected from silica, kaolin and/or halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, retortite, sepiolite, attapulgite, water One or more of talc and bentonite. The catalytic conversion catalysts in each reactor can be the same or different.

The sieving composition of the catalyst of the coarse particle size distribution is as follows: the volume ratio of particles less than 40 microns accounts for all particles is less than 10%, preferably less than 5%; the volume ratio of particles greater than 80 microns accounts for all particles is less than 15% %, preferably less than 10%, and the rest are particles of 40-80 microns.

In a more preferred embodiment, the reactor is selected from one or more of a riser, a fluidized bed of equal linear velocity, a fluidized bed of equal diameter, an upward conveying line, and a descending conveying line Combination, or a combination of two or more reactors of the same type, the combination includes series or/and parallel connection, wherein the riser is a conventional riser with equal diameter or a riser with various forms of reduced diameter.

In a more preferred embodiment, the feedstock oil is introduced into the reactor at one location, or the feedstock oil is introduced into the reactor at more than one location at the same or different heights.

In a more preferred embodiment, the method also includes separating the reaction product from the catalyst, and the catalyst is stripped and coke-regenerated and then returned to the reactor, and the separated products include high-octane gasoline, high cetane Diesel and catalytic wax oils.

In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point not less than 330°C.

In a more preferred embodiment, the hydrogen content of the catalytic wax oil is not lower than 11.5% by weight, preferably not lower than 12% by weight.

Catalytic wax oil hydrocracking is in the presence of hydrogen, in contact with the hydrocracking catalyst, at a reaction pressure of 4.0-16.0MPa, a reaction temperature of 280-450°C, a hydrogen-to-oil volume ratio of 300-2000v/v, and a volume space velocity of 0.1- It can be obtained by hydrocracking under the reaction conditions of 10.0h ^-1 . Hydrocracking tail oil can be returned to the catalytic conversion unit as raw material oil.

The catalytic wax oil hydrocracking catalyst contains one or more active metal components of W, Mo, Ni and Co, and acid cracking components. The weight content of the active metal component in the hydrocracking catalyst is generally 5-50%, usually 15-30%. The hydrocracking catalyst is a middle distillate type hydrocracking catalyst for producing middle distillate oil. The acid cracking active components are generally selected from molecular sieves and amorphous silica-alumina. The types of molecular sieves that are often used include: Y-type molecular sieves, β-type molecular sieves, ZSM-5 type molecular sieves, SAPO series molecular sieves, etc. The hydrocracking catalyst may also contain other refractory inorganic oxides, such as aluminum oxide, silicon oxide, titanium oxide, and composite oxides or mixed oxides of various elements.

The preparation method of the catalytic wax oil hydrocracking catalyst includes molecular sieve preparation and carrier preparation. The preparation of molecular sieves includes the synthesis and modification of molecular sieves. The modification mainly includes metal cation exchange, hydrothermal treatment, liquid phase chemical modification, gas phase chemical modification, etc. The preparation of the carrier includes extrusion method and co-precipitation method.

The best embodiment of the present invention is carried out in a variable-diameter riser reactor. For a more detailed description of the reactor, refer to CN1237477A.

In another embodiment of the present invention, a catalytic conversion method using desalted, dehydrated crude oil as feedstock oil is provided, wherein the feedstock oil is contacted with a catalyst rich in large-pore zeolite in the reactor for reaction , which is characterized by:

(1) The feedstock oil includes difficult-to-crack feedstock oil and easy-to-crack feedstock oil, and the feedstock oil is introduced into the reactor at one position, or introduced into the reactor at more than one position with the same or different heights;

(2) The difficult-to-crack raw material oil is first contacted with a catalyst with a coarse particle size distribution rich in large-pore zeolite in the reactor, or reacted no later than the easy-to-crack raw material oil;

(3) reaction temperature, weight hourly space velocity, catalyst and raw material oil weight ratio are enough to make reaction obtain the reaction product that comprises accounting for 12～60 weight % catalytic wax oils of raw material oil;

(4) The raw catalyst and the reaction oil gas are separated by a cyclone separator; optionally, the raw catalyst enters the stripper, and returns to the reactor after stripping and charring regeneration; the reaction oil gas is separated to obtain gasoline containing high octane number , High cetane number diesel oil, reaction product of catalytic wax oil;

(5) wherein the catalytic wax oil is subjected to hydrocracking to obtain gasoline, high cetane number diesel oil and hydrogenated heavy oil, and the hydrogenated heavy oil is returned to step (1) or / and in step (2).

The difficult-to-crack raw oil is selected from or includes low-quality crude oil, oil slurry, diesel oil, and gasoline with a density (20°C) greater than 0.90 g·cm ^-3, preferably greater than 0.92 g·cm ^-3 , more preferably greater than 0.93 g·cm ^-3 one or a mixture of two or more. The gasoline is selected from or includes one or more of catalytic cracked gasoline obtained by this method, catalytic cracked gasoline from outside the device, straight-run gasoline, coker gasoline, pyrolysis gasoline, thermal cracking gasoline, and hydrogenated gasoline Among them, catalytic cracking gasoline, straight-run gasoline, coker gasoline, thermal cracking gasoline, thermal cracking gasoline, and hydrogenated gasoline are gasoline from outside the unit. The diesel oil is selected from or includes one of catalytic cracking diesel oil, catalytic cracking diesel oil, straight-run diesel oil, coker diesel oil, thermal cracking diesel oil, hydrogenated diesel oil or a mixture of more than one of them, wherein catalytic cracking diesel oil, direct-run diesel oil Distilled diesel, coked diesel, thermally cracked diesel, hydrogenated diesel are diesel from outside this unit.

The crackable feedstock oil is selected from or includes conventionally pretreated petroleum-based crude oil and/or other mineral oils. Among them, the density (20°C) of petroleum-based crude oil is greater than 0.85g·cm ^-3 but not higher than 0.90g·cm ^-3 , which can be selected from paraffin-based crude oil, paraffin-intermediate base crude oil, intermediate-paraffin-based crude oil, and intermediate base crude oil , intermediate-naphthenic crude oil, naphthenic-intermediate base crude oil, and a mixture of two or more of naphthenic crude oils; other mineral oils are one or more of coal liquefied oil, oil sands oil, and shale oil A mixture of two or more.

The reaction conditions for refractory feedstock oil are: reaction temperature 520-650°C, weight hourly space velocity 100-800h ^-1 , reaction pressure 0.10-1.0MPa, weight ratio of catalyst to refractory feedstock oil 30-150, water vapor and refractory feedstock oil The weight ratio of raw material oil is 0.05-1.0.

The reaction conditions of easily crackable feedstock oil are: reaction temperature 420-550°C, weight hourly space velocity 5-100h ^-1 , reaction pressure 0.10-1.0MPa, weight ratio of catalyst to crackable feedstock oil 1.0-30, water vapor and crackable feedstock oil The weight ratio of raw material oil is 0.05-1.0. Preferably, the reaction temperature of the crackable feedstock oil is 450-540°C, and the weight hourly space velocity is 10-90h ^-1 , preferably 20-60h ^-1 . More preferably, the reaction temperature of easily cracked raw oil is 460-520°C, the weight hourly space velocity is 30-50h ^-1 , and the weight ratio of catalyst to raw oil is 3-14.

In this embodiment, the catalyst, reactor, separation of reaction products, etc. are the same as the previous embodiment.

The sieving composition of the catalyst of the coarse particle size distribution is as follows: the volume ratio of particles less than 40 microns accounts for all particles is less than 10%, preferably less than 5%; the volume ratio of particles greater than 80 microns accounts for all particles is less than 15% %, preferably less than 10%, and the rest are particles of 40-80 microns.

In order to increase the ratio of catalyst to oil in the downstream area of the reaction and improve the catalytic activity of the catalyst, hot or cold regenerated catalysts, semi-regenerated catalysts, spent catalysts, and fresh catalysts can be supplemented. The cooled regenerated catalyst and the cooled semi-regenerated catalyst are obtained by cooling the unused catalyst after two stages of regeneration and one stage of regeneration respectively. The carbon content of the regenerated catalyst is less than 0.1% by weight, preferably less than 0.05% by weight. The carbon content of the semi-regenerated catalyst is 0.1% to 0.9% by weight, the best carbon content is 0.15% to 0.7% by weight; the carbon content of the raw catalyst is more than 0.9% by weight, and the best carbon content is 0.9% to 1.2% by weight.

In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point not less than 330°C.

In a more preferred embodiment, the hydrogen content of the catalytic wax oil is not lower than 11.5% by weight, preferably not lower than 12% by weight.

Catalytic wax oil hydrocracking is in the presence of hydrogen, in contact with the hydrocracking catalyst, at a reaction pressure of 4.0-16.0MPa, a reaction temperature of 280-450°C, a hydrogen-to-oil volume ratio of 300-2000v/v, and a volume space velocity of 0.1- It can be obtained by hydrocracking under the reaction conditions of 10.0h ^-1 . Hydrocracking tail oil can be returned to the catalytic conversion unit as raw material oil.

The catalytic wax oil hydrocracking catalyst contains one or more active metal components of W, Mo, Ni and Co, and acid cracking components. The weight content of the active metal component in the hydrocracking catalyst is generally 5-50%, usually 15-30%. The hydrocracking catalyst is a medium oil type hydrocracking catalyst for producing middle distillates. The acid cracking active components are generally selected from molecular sieves and amorphous silica-alumina. The types of molecular sieves that are often used include: Y-type molecular sieves, β-type molecular sieves, ZSM-5 type molecular sieves, SAPO series molecular sieves, etc. The hydrocracking catalyst may also contain other refractory inorganic oxides, such as aluminum oxide, silicon oxide, titanium oxide, and composite oxides or mixed oxides of various elements.

This technical solution organically combines the catalytic conversion of desalted crude oil and catalytic wax oil hydrocracking to maximize the production of light fuel oil, especially high-octane gasoline and high cetane diesel, from desalted crude oil, thereby realizing Efficient use of petroleum resources. Compared with the prior art, the present invention has the following technical effects:

1. The crude oil processing process provided by the present invention cancels equipment such as heating furnaces and atmospheric and vacuum distillation towers in the conventional crude oil distillation process, which can reduce equipment investment and equipment anticorrosion costs.

2. The catalytic conversion of pretreated crude oil in the present invention has a good effect on removing carbon residue from crude oil, and does not produce coke, asphalt and other by-products.

3. The catalytic conversion of crude oil in the present invention has a good demetallization effect on crude oil, and the demetallization rate can approach or reach more than 95%. Metals in crude oil, especially heavy metals, are deposited on the catalyst through fluidized catalytic conversion; and the present invention uses light components in crude oil to replace part of the water vapor lifting medium, so that the catalyst can be evenly distributed, and the heavy metals on the catalyst can be mixed with light hydrocarbons at high temperature. When the reaction occurs, the heavy metal loses part of its activity and is passivated to a certain extent, thereby inhibiting the harmful effect of the heavy metal on the catalyst, significantly increasing the yield of light oil, and significantly reducing the yield of oil slurry, thereby improving the utilization efficiency of petroleum resources. .

4. The yield of diesel oil is obviously increased, and the cetane number of diesel oil is obviously increased.

5. In the case of increasing the gasoline yield, the gasoline octane number is obviously improved; and the dry gas yield and coke are obviously reduced.

6. The operating cycle of the hydrocracking unit has been significantly improved.

7. Due to the more uniform particles of the catalyst, the local temperature distribution during the regeneration process is also more uniform, and the tendency of the catalyst to break is correspondingly reduced.

8. The catalyst consumption is reduced, and the catalyst content in the oil slurry is reduced.

Description of drawings

The accompanying drawing is a schematic flow diagram of the basic flow chart of the catalytic conversion method for producing high-quality light fuel from crude oil provided by the present invention.

Detailed ways

The method provided by the present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereto.

The accompanying drawing is a schematic flow diagram of the basic flow chart of the catalytic conversion method for producing high-quality light fuel from crude oil provided by the present invention.

The method provided by the present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereto.

The embodiment of the present invention is carried out in a variable-diameter riser reactor, and for a more detailed description of the reactor, refer to CN1237477A.

Its technological process is as shown in the accompanying drawing:

The pre-lift medium enters from the bottom of the riser reactor 2 through the pipeline 1, and the regenerated catalyst from the pipeline 16 accelerates upward along the riser under the lifting effect of the pre-lift medium, and the difficult-to-crack raw oil passes through the pipeline 3 and the atomized catalyst from the pipeline 4 The steam is injected into the bottom of the riser 2 reaction zone I and mixed with the existing flow in the riser reactor, and the difficult-to-crack raw material oil undergoes cracking reaction on the hot catalyst and accelerates upward. Easily cracked raw oil such as light petroleum-based crude oil is injected into the middle and upper part of reaction zone I of riser 2 through pipeline 5 together with atomized steam from pipeline 6, and is mixed with the existing flow in the riser reactor. A cracking reaction occurs on the catalyst containing a certain amount of carbon, and accelerates upwards to enter the reaction zone II to continue the reaction. The generated oil gas and deactivated catalyst enter the cyclone separator in the settler 8 through the pipeline 7 to realize the deactivation of the catalyst. Separation from the oil and gas, the oil and gas enter the gas collection chamber 9, and the catalyst fine powder is returned to the settler by the material leg. The spent catalyst in the settler flows to stripping section 10 where it contacts steam from line 11. The oil and gas stripped out from the unborn catalyst enters the gas collection chamber 9 after passing through the cyclone separator. The stripped standby catalyst enters the regenerator 13 through the inclined pipe 12, the main air enters the regenerator through the pipeline 14, burns off the coke on the standby catalyst, and regenerates the deactivated standby catalyst, and the flue gas enters the flue gas through the pipeline 15. machine. The regenerated catalyst enters the riser through the inclined pipe 16.

The reaction product oil and gas in the gas collection chamber 9 passes through the large oil and gas pipeline 17, and then enters the subsequent separation system 18. The separated propylene is drawn out through the pipeline 102, the separated propane is drawn out through the pipeline 103, and the carbon tetrahydrocarbons are drawn out through the pipeline 104 for catalytic cracking. The dry gas is drawn out through the pipeline 101, and the catalytically cracked gasoline is drawn out through the pipeline 105. According to production requirements, the distillate with a distillation range of 180-260°C is returned to the riser 2 through the line 106 and can also be output as catalytic diesel oil with a distillation range of 260-330°C. The distillate can be drawn out through the pipeline 107, and can also be drawn together with the catalytic wax oil (≥330°C) and enter the hydrocracking unit 19 through the pipeline 108, and the separated light components can be drawn out through the pipeline 201, and the hydrocracked light components can be produced according to production needs. Separated as light components to obtain jet fuel, high cetane number diesel oil, etc., can also be used as heavy components and return to the bottom of riser 2 reaction zone 1 through pipeline 202 together with hydrogenated heavy oil.

The following examples will further illustrate the present invention, but do not limit the present invention thereby. The raw oil used in the examples and comparative examples is crude oil after desalting and dehydration pretreatment, and its properties are listed in Table 1 respectively.

The catalytic conversion catalyst preparation method used in the embodiment is briefly described as follows:

1) Dissolve 0.20kg of NH ₄ Cl in 10kg of water, and add 1.0kg (dry basis) of the crystallization product ZRP-1 zeolite (produced by Qilu Petrochemical Company Catalyst Factory, SiO ₂ /Al ₂ O ₃ =30, rare earth content RE ₂ O ₃ =2.0% by weight), exchanged at 90°C for 0.5h, filtered to obtain a filter cake; added 40gH ₃ PO ₄ (concentration 85%) and 45gFe(NO ₃ ) ₃ dissolved in 0.90kg of water, and the filter cake Mixing impregnation and drying; followed by calcination at 550°C for 2 hours to obtain a phosphorus- and iron-containing MFI structure mesoporous zeolite, whose elemental analysis chemical composition is

0.1Na ₂ O 5.1Al ₂ O ₃ 2.4P ₂ O ₅ 1.5Fe ₂ O ₃ 3.8RE ₂ O ₃ 88.1SiO ₂ .

2), configuration 200 liters of silicon dioxide concentration is 155kg/m ³ water glass solution and 100 liters of free acid is 148kg/m ³ , Al ₂ O ₃ content is 20kg/m ³ acidified aluminum sulfate solution, above-mentioned two These solutions enter the rapid mixer to react at the same time to obtain silica sol.

Use 25kg of decationized water to beat the kaolin slurry obtained by beating 45kg of polyhydrate kaolin (industrial product of Suzhou China Clay Company, solid content 71.6% by weight); mix the above-mentioned prepared silica sol with the kaolin slurry, and beat for 1 hour. Then add 5.5kg pseudo-boehmite (industrial product of Shandong Aluminum Works, _Al2O3 content is 33% by weight), mixed with _45kg deionized water for beating for 30 minutes, then adding 2.5 liters of concentration is 31% by weight of hydrochloric acid ( Acid/Al ₂ O ₃ molar ratio is 0.2), the pH is adjusted to 2-4, stirred evenly, and aged at 60-70° C. for 1 hour to obtain a silica-kaolin-alumina mixed sol.

3), the phosphorus-containing and iron-containing MFI structure mesoporous zeolite (dry basis is 2.0kg) prepared in step 1) and DASY zeolite (industrial product of catalyst factory of Qilu Petrochemical Company, unit cell constant is 2.445～2.448nm, dry basis is 22.5kg) was added to the silica-kaolin-alumina mixed sol obtained in step 2), stirred evenly, spray-dried to shape, washed with ammonium dihydrogen phosphate solution (phosphorus content: 1m%), washed away free Na ⁺ , and dried That is, a catalytic cracking catalyst sample with a diameter of 20-120 microns is obtained, and the composition of the catalyst is 2% by weight of phosphorus- and iron-containing MFI structure mesoporous zeolite, 22% by weight of DASY zeolite, and 32% by weight of pseudo-boehmite in silica content stone, 5% by weight of aluminum sol and the balance of kaolin.

4) The prepared catalyst is aged at 800° C. and 100% water vapor. The properties of the aged catalyst are listed in Table 2, and its code name is MDCO-1. Part of the aging agent is then analyzed to remove fine particles and particles larger than 100 microns. Particles, to obtain a catalyst with a coarse particle size distribution, its code name is MDCO-2, and its properties are listed in Table 2.

Catalyzed wax oil hydrocracking catalyst HCC, the preparation of its carrier is with 75g pseudo-boehmite (Shandong Aluminum Works industrial product, Al ₂ O The content is ₃₃ weight %), 100gDASY zeolite (Qilu Petrochemical Company Catalyst Factory industrial product, The unit cell constant is 2.445-2.448nm, the dry basis is 22.5kg), 5gH ₃ PO ₄ (concentration 85%) and an appropriate amount of binder are mixed evenly, extruded, dried at 120°C for 3hrs, calcined at 500°C for 4hrs, and crushed into The particles are the granular DASY-Al ₂ O ₃ carrier. Weigh ammonium metatungstate ((NH ₄ ) ₂ W ₄ O ₁₃ ·18H ₂ O, chemically pure) and nickel nitrate (Ni(NO ₃ ) ₂ ·18H ₂ O, chemically pure), and prepare a 200 mL solution with water. Add the solution to 50 grams of DASY-Al ₂ O ₃ carrier, impregnate at room temperature for 3 hours, use ultrasonic wave to treat the impregnation solution for 30 minutes during the impregnation process, cool, filter, and dry in a microwave oven for about 15 minutes. The composition of the catalyst is: 30.0% by weight of WO ₃ , 3.1% by weight of NiO, 4.5% by weight of P ₂ O ₅ , 38% by weight of alumina and the balance of SiO ₂ . The properties of the wax oil hydrocracking catalyst HCC are listed in Table 2.

Example 1

This example illustrates the production of a large amount of high-quality gasoline by catalytic conversion and hydrocracking reaction using the method provided by the present invention.

This embodiment is tested according to the flow process of accompanying drawing, and catalyzer is MDCO-2, and raw material oil A is directly used as the easily crackable raw material oil of catalytic cracking, is tested on the medium-sized device by riser reactor, and easy crackable raw material oil enters reaction zone In the middle and upper part of I, the difficult-to-crack raw oil enters the bottom of reaction zone I. At the bottom of reaction zone I, the refractory feedstock oil is under the conditions of reaction temperature 580°C, weight hourly space velocity 240h ^-1 , weight ratio of catalytic cracking catalyst to refractory feedstock oil 30, and weight ratio of water vapor to refractory feedstock oil 0.20 Carry out cracking reaction; in the middle and upper part of the reaction zone I, the easily crackable raw material oil is at a reaction temperature of 510°C and a weight hourly space velocity of 90h ^-1 , the weight ratio of the catalytic cracking catalyst to the easily crackable raw material oil is 10, and the weight ratio of water vapor to the easily crackable raw material oil is The cracking reaction is carried out under the condition that the ratio is 0.15. In reaction zone II, reactant stream oil gas undergoes cracking reaction at reaction temperature of 495°C, weight hourly space velocity of 30h ^-1 , and weight ratio of water vapor to crackable feedstock oil of 0.15. The reaction product oil gas and the catalyst to be produced are separated in the settler, and the products are cut according to the distillation range in the separation system, so as to obtain propylene, gasoline, fractions with a distillation range of 180-250°C, diesel oil with a distillation range of 250-330°C and distillate Catalytic wax oil with temperature greater than 330°C. The distillate with a distillation range of 180-250°C is recycled back to the catalytic conversion unit as easily cracked raw material oil. The catalytic wax oil is hydrocracked again, using the hydrocracking catalyst HCC, and the catalyst is processed under the reaction conditions of hydrogen partial pressure 12.0MPa, reaction temperature 385°C, hydrogen-oil volume ratio 1300v/v, volume space velocity 1.0h ^-1 Hydrocracking, the hydrocatalytic wax oil after hydrogenation is cut according to the distillation range, so as to obtain jet fuel with a distillation range of 180-250°C, diesel oil with a distillation range of 250-330°C and hydrogenated catalytic wax oil above 330°C Distillate and other products, the hydrogenated catalytic wax oil fraction greater than 330°C is recycled to the above-mentioned medium-sized catalytic conversion unit, and enters the bottom of the reaction zone I of the riser reactor as a difficult-to-crack feed oil for re-cracking. The operating conditions and product distribution are listed in Table 3.

It can be seen from Table 3 that the raw material oil A in Example 1 was converted by catalytic conversion, the yield of catalytic wax oil was 31.58% by weight, the hydrogen content was 12.98% by weight, the nickel and vanadium were only 0.2 μg·g ^-1 , and the carbon residue was only 0.44% by weight; Feed oil A is through catalytic conversion and hydrocracking, and gasoline yield is 41.35% by weight, and its research method octane number (RON) is as high as 91.48, and motor method octane number (MON) is 85; Diesel oil yield is 26.05% by weight, cetane number 56; yield of jet fuel 17.74% by weight; total yield of light oil 85.14% by weight. The dry gas yield was 1.01% by weight, and the coke yield was 2.28% by weight.

Comparative example 1

Comparative example is to use stock oil A directly as the raw material of catalytic cracking, and the stock oil of test and test procedure and method are identical with embodiment 1, just the catalyst that adopts is changed into catalyst MDCO-1 by the MDCO-2 of embodiment 1. The operating conditions and product distribution are listed in Table 3.

As can be seen from Table 3, with respect to embodiment 1, the catalytic wax oil productive rate of comparative example 1 is low 0.98 weight %, and its hydrogen content is low 0.12 weight %, and residual charcoal is high 0.02 weight %; And light oil The total yield is low, 84.13% by weight; the yield of dry gas is 1.25% by weight and the yield of coke is 2.98% by weight, and the yield of dry gas and coke has increased significantly.

Example 2

This example illustrates the situation of mass production of high-quality diesel oil by catalytic conversion and hydrocracking reaction using the method provided by the present invention.

This embodiment is the same as the test device of Example 1, with MDCO-2 as the catalyst, feed oil B is directly used as the refractory feed oil of catalytic conversion, and the test is carried out on a medium-sized device with a riser reactor, and the refractory feed oil enters The bottom of the reaction zone I reacts, and the easy-to-crack raw oil enters the upper part of the reaction zone I to react. At the bottom of the reaction zone I, the refractory feedstock oil is under the conditions of reaction temperature 520°C, weight hourly space velocity 300h ^- 1, weight ratio of catalytic conversion catalyst to refractory feedstock oil 90, and weight ratio of water vapor to refractory feedstock oil 0.20 Carry out cracking reaction; in the middle and upper part of the reaction zone I, the easily crackable raw material oil is at a reaction temperature of 480°C and a weight hourly space velocity of 120h ^-1 , the weight ratio of the catalytic conversion catalyst to the easily crackable raw material oil is 30, and the weight ratio of water vapor to the easily crackable raw material oil is The cracking reaction is carried out under the condition that the ratio is 0.15; in addition, a supplementary part of the raw catalyst that has been stripped from the stripping section enters the bottom of the reaction zone II to reduce the temperature and reaction weight hourly space velocity of the reaction zone II. In reaction zone II, oil and gas undergo cracking reaction under the conditions of reaction temperature 470°C, weight hourly space velocity 20h ^-1 , and weight ratio of water vapor to easily cracked raw material oil 0.15. Oil gas and catalyst to be charred are separated in settler, and the product is The separation system is cut according to the distillation range to obtain propylene, some C4 hydrocarbons and gasoline, diesel with a distillation range of 180-330°C and catalytic wax oil with a distillation range >330°C. The catalytic wax oil is then hydrocracked, under the reaction conditions of hydrogen partial pressure 15.0MPa, reaction temperature 420°C, hydrogen oil volume ratio 1500v/v, volume space velocity ^0.5h The hydrogenated catalytic wax oil after hydrogenation is cut according to the distillation range, so as to obtain jet fuel at 150-240 °C, diesel oil at 240-330 °C and hydrogenated catalytic wax oil fractions greater than 330 °C, etc. The wax oil fraction is recycled back to the above-mentioned medium-sized catalytic conversion unit, and enters the middle and upper part of the reaction zone I of the catalytic conversion unit as easy-to-crack feed oil for re-cracking. The operating conditions and product distribution are listed in Table 4.

It can be seen from Table 4 that the catalytic conversion of raw material B in Example 2 yielded 40.23% by weight of catalytic wax oil, only 0.2 μg·g ^-1 of nickel and vanadium, and only 0.81% by weight of carbon residue. After catalytic conversion of feedstock oil B and catalytic wax oil hydrocracking, the yield of diesel oil was 46.23% by weight, and the cetane number was 54; the yield of gasoline was 29.12% by weight, and its research octane number (RON) was as high as 90.52. The method octane number (MON) was 84; the yield of jet fuel was 10.31% by weight; the total yield of light oil was 85.66% by weight; the yield of dry gas was 0.91% by weight; the yield of coke was 2.79% by weight.

Comparative example 2

In this comparative example, raw material oil B is directly used as a refractory raw material for catalytic cracking. The raw material oil, test steps and methods of the test are exactly the same as in Example 2, except that the catalyst used is changed from MDCO-2 in the embodiment to catalyst MDCO-1. . The operating conditions and product distribution are listed in Table 4.

As can be seen from Table 4, with respect to embodiment 2, comparative example 2 light oil total yield is low, is 84.44 weight %; Dry gas yield 1.13 weight %; Coke yield 3.58 weight %; Dry gas yield and coke Yield increased significantly.

Table 1

Example 1 Comparative Example 1 Example 2 Comparative Example 2 Raw oil number A B Raw oil properties Density (20℃), g·cm ^-3 0.9010 0.9330 Sulfur content, μg g ^-1 8000 4300 Nitrogen content, μg g ^-1 4100 2100 Aromatics, weight % 12.5 31.2 C, weight % 86.26 86.23 H, weight% 12.20 12.69 Carbon residue, wt% 6.4 7.2 Metal content, μg g ^-1 Nickel 26.0 18.7 Vanadium 1.0 1.2 Sodium 420 560 calcium 78.5 80.4 Acid value, mgKOH·g ^-1 1.55 11.45 Distillate composition (ASTM D-1160) IBP～200℃ 7.5 2.5 200～350℃ 17.6 9.0 350～500℃ 27.5 27.0 ＞500℃ 47.4 61.5

Table 2

catalyst MDCO-1 MDCO-2 HCC Particle size type Regular particle size Coarse particle size Chemical composition, wt% Aluminum oxide 8.5 8.4 44 sodium oxide 0.29 0.27 ＜0.1 iron oxide 1.0 1.0 - Nickel oxide - - 5.6 Tungsten oxide - - 24.3 rare earth 0.9 1.0 - Apparent density, kg/ ^m3 765 754 912 Pore volume, ml/g 0.28 0.26 0.35 Specific surface area, ^m2 /g 117 114 326 Wear index, weight % h ^-1 1.4 1.3 0.52 Sieve composition, wt% 0～40 microns 22.4 9.1 - 40～80 microns 54.0 76.4 - >80 microns 23.6 14.5 -

table 3

Example 1 Comparative example 1 Raw oil number A A Catalytic conversion unit Catalyst MDCO-2 MDCO-1 Riser outlet temperature, ℃ 490 490 Riser reaction zone II Reaction temperature, ℃ 500 500 Heavy hourly space velocity, h ^-1 20 20 Water vapor/feed oil weight ratio 0.15 0.15 Riser reaction zone I Average temperature, ℃ 640/550 640/550 Agent oil ratio, m/m 90/30 90/30 Heavy hourly space velocity, h ^-1 300/120 300/120 Water vapor/feed oil weight ratio 0.20/0.15 0.20/0.15 Catalytic wax oil Yield, weight % 31.58 30.6 Hydrogen content, weight % 12.98 12.86 Nickel + vanadium, μg g ^-1 0.2 0.2 Carbon residue, wt% 0.44 0.46 Hydrocracking unit Catalyst HCC HCC Hydrogen partial pressure, MPa 18.0 18.0 Reaction temperature, ℃ 450 450 Hydrogen oil volume ratio, v/v 1500 1500 Volumetric space velocity, h ^-1 0.5 0.5 Product distribution, weight % dry gas 1.01 1.25 Liquefied gas 11.57 11.64 Propylene and carbon tetraolefins 4.38 4.37 gasoline 41.35 41.25 jet fuel 17.74 17.42 diesel fuel 26.05 25.46 Coke 2.28 2.98 Gasoline properties Research octane number RON 91.48 91.56 Motor octane number MON 85 85 Diesel properties Density (20℃), g·cm ^-3 0.8152 0.8146 Freezing point, ℃ -4 -4 cetane number 56 56

Table 4

Example 2 Comparative example 2 Raw oil number B B Catalytic conversion unit Catalyst MDCO-2 MDCO-1 Riser outlet temperature, ℃ 475 475 Riser reaction zone II Reaction temperature, ℃ 480 480 Heavy hourly space velocity, h ^-1 30 30 Water vapor/feed oil weight ratio 0.15 0.15 Riser reaction zone I Average temperature, ℃ 550/510 550/510 Agent oil ratio, m/m 60/10 60/10 Heavy hourly space velocity, h ^-1 180/60 180/60 Water vapor/feed oil weight ratio 0.20/0.15 0.20/0.15 Catalytic wax oil Yield, weight % 40.23 38.56 Hydrogen content, weight % 11.84 11.67 Nickel + vanadium, μg g ^-1 0.2 0.2 Carbon residue, wt% 0.81 0.84 Hydrocracking unit Catalyst HCC HCC Hydrogen partial pressure, MPa 10.0 10.0 Reaction temperature, ℃ 350 350 Hydrogen oil volume ratio, v/v 500 500 Volumetric space velocity, h ^-1 1.5 1.5 Product distribution, weight % dry gas 0.91 1.13 Liquefied gas 10.64 10.85 Propylene and carbon tetraolefins 4.70 4.79 gasoline 29.12 28.34 jet fuel 10.31 10.26 diesel fuel 46.23 45.84 coke 2.79 3.58 Gasoline properties Research octane number RON 90.52 90.34 Motor octane number MON 84 83 Diesel properties Density (20℃), g·cm ^-3 0.8274 0.8268 Freezing point, ℃ -6 -6 cetane number 54 54

Claims (21)

1. the catalysis conversion method of producing high-quality light fuels from crude oil, it is characterized in that crude oil contacts and reacts with the catalyzer that contains the thick size distribution of large pore zeolite in reactor, it is characterized in that temperature of reaction, the oil gas residence time, catalyzer are enough to make to react obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil with stock oil weight ratio, wherein said weight hourly space velocity is 25～100h ^-1, described temperature of reaction is 420～600 ℃, described catalyzer and stock oil weight ratio are 1～30; Catalytic wax oil is further hydrocracking again; Described large pore zeolite is selected from Y-series zeolite, comprise one or more in Rare Earth Y, rare earth hydrogen Y, super steady Y, high silicon Y, the size composition of the catalyzer of described thick size distribution is to be less than volume ratio that the particle of 40 microns accounts for all particles lower than 10%, is greater than volume ratio that the particle of 80 microns accounts for all particles lower than 15%; Described crude oil be selected from paraffinic crude, paraffin-intermediate base crude oil, Medium-paraffin base crude oil, intermediate base crude oil, in one or more in m-naphthenic base crude, cycloalkanes-intermediate base crude oil, naphthenic base crude; Described crude oil is through desalination, dehydration pre-treatment, and in the crude oil after processing, vanadium, nickel total value are not more than 30ppm, and its density is greater than 0.85g.cm ^-3; Described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % of zeolite 1～50, the heavy % of inorganic oxide 5～99, the heavy % of clay 0～70, its mesolite is large pore zeolite and/or optional mesopore zeolite, and large pore zeolite accounts for 80-100 heavy % of zeolite gross weight.

2. according to the method for claim 1, it is characterized in that described temperature of reaction is 450～550 ℃, weight hourly space velocity is 30～80h ^-1, the weight ratio of catalyzer and stock oil is 2～25.

3. according to the method for claim 2, it is characterized in that described temperature of reaction is 460～520 ℃, weight hourly space velocity is 40～60h ^-1, the weight ratio of catalyzer and stock oil is 3～14.

4. according to the method for claim 1, the size composition that it is characterized in that the catalyzer of described thick size distribution is to be less than volume ratio that the particle of 40 microns accounts for all particles lower than 5%.

5. according to the method for claim 1, the size composition that it is characterized in that the catalyzer of described thick size distribution is to be greater than volume ratio that the particle of 80 microns accounts for all particles lower than 10%.

6. according to the method for claim 1, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the two or more combinations of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.

7. according to the method for claim 1, it is characterized in that in described reactor, or in the position of more than one identical or different height, described stock oil is introduced in reactor.

8. according to the method for claim 1, it is characterized in that described method also comprises carries out separated by reaction product with catalyzer, catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises stop bracket gasoline, high hexadecane value diesel oil and catalytic wax oil.

9. according to the method for claim 1, it is characterized in that described catalytic wax oil is that initial boiling point is not less than the cut of 330 ℃, catalytic wax oil hydrogen richness is not less than 11.5 heavy %.

10. according to the method for claim 1, it is characterized in that catalytic wax oil hydrocracking is under hydrogen exists situation, contact with hydrocracking catalyst, at reaction pressure 4.0～16.0MPa, 280～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～10.0h ^-1reaction conditions react.

The catalysis conversion method of 11. producing high-quality light fuels from crude oils, is characterized in that the method comprises the following steps:

(1) stock oil comprises difficult cracking stock oil and easy cracking stock oil, a position, described stock oil is introduced in reactor, or in the position of more than one identical or different height, described stock oil is introduced in reactor;

(2) difficult cracking stock oil in reactor first be rich in the catalyzer contact reacts of the thick size distribution of large pore zeolite, or be not later than easy cracking stock oil and react;

(3) temperature of reaction, weight hourly space velocity, catalyzer are enough to make to react obtain comprising the reaction product that accounts for stock oil 12-60 heavy % catalytic wax oil with stock oil weight ratio;

(4) reclaimable catalyst is separated by cyclonic separator with reaction oil gas; Optionally, reclaimable catalyst enters stripper, Returning reactor after stripping, coke burning regeneration; Reaction oil gas is isolated to the reaction product that comprises stop bracket gasoline, high hexadecane value diesel oil, catalytic wax oil;

(5) wherein catalytic wax oil, through hydrocracking, obtains gasoline, high hexadecane value diesel oil and hydrogenation heavy oil, and described hydrogenation heavy oil is oily or/and easy cracking stock oil turns back to step (1) or/and in step (2) as difficult cracking stock;

Described large pore zeolite is selected from Y-series zeolite, comprise one or more in Rare Earth Y, rare earth hydrogen Y, super steady Y, high silicon Y, the size composition of the catalyzer of described thick size distribution is to be less than volume ratio that the particle of 40 microns accounts for all particles lower than 10%, is greater than volume ratio that the particle of 80 microns accounts for all particles lower than 15%.

12. according to the method for claim 11, it is characterized in that described difficult cracking stock grease separation certainly or comprises that density is greater than 0.90gcm ^-3crude oil with poor quality, slurry oil, diesel oil, gasoline in one or more mixture.

13. according to the method for claim 11, it is characterized in that described easy cracking stock grease separation from or comprise paraffinic crude, paraffin-intermediate base crude oil, Medium-paraffin base crude oil, intermediate base crude oil, in one or more in m-naphthenic base crude, cycloalkanes-intermediate base crude oil, naphthenic base crude.

14. according to the method for claim 13, it is characterized in that described crude oil density after desalination, processed is not more than 0.90gcm ^-3.

15. according to the method for claim 11, it is characterized in that the reaction conditions of difficult cracking stock oil is: 520～650 ℃ of temperature of reaction, weight hourly space velocity 100～800h ^-1, reaction pressure 0.10～1.0MPa, catalyzer and difficult cracking stock oil weight ratio 30～150, the weight ratio of water vapor and difficult cracking stock oil is 0.05～1.0.

16. according to the method for claim 11, it is characterized in that the reaction conditions of easy cracking stock oil is: 420～550 ℃ of temperature of reaction, weight hourly space velocity 5～100h ^-1, reaction pressure 0.10～1.0MPa, catalyzer and the easy weight ratio 1～30 of cracking stock oil, water vapor is 0.05～1.0 with the easy weight ratio of cracking stock oil.

17. according to the method for claim 11, and the temperature of reaction that it is characterized in that easy cracking stock oil is 450～540 ℃, and weight hourly space velocity is 10～90h ^-1, catalyzer and stock oil weight ratio are 3～14.

18. according to the method for claim 12, and the temperature of reaction that it is characterized in that easy cracking stock oil is 460～520 ℃, weight hourly space velocity 30～50h ^-1.

19. according to the method for claim 11, it is characterized in that described catalytic wax oil is that initial boiling point is not less than the cut of 330 ℃, and catalytic wax oil hydrogen richness is not less than 11.5 heavy %.

20. according to the method for claim 11, and the size composition that it is characterized in that the catalyzer of described thick size distribution is to be less than volume ratio that the particle of 40 microns accounts for all particles lower than 5%.

21. according to the method for claim 11, and the size composition that it is characterized in that the catalyzer of described thick size distribution is to be greater than volume ratio that the particle of 80 microns accounts for all particles lower than 10%.