CN102031147B - Catalytic conversion method for producing diesel and propylene in high yield - Google Patents

Abstract

A catalytic conversion method for producing diesel oil and propylene. The feedstock oil is contacted with a catalyst for reaction in a reactor. The reaction temperature, weight hourly space velocity, and weight ratio of the catalyst to the feedstock oil are sufficient to allow the reaction to obtain 12 to 60% by weight of the feedstock oil. The reaction product of the catalytic wax oil, the catalytic wax oil enters the hydrocracking unit for further processing, and the obtained catalytic wax oil hydrocracking tail oil is used as the raw material of the multi-production diesel unit. Through the organic combination of catalytic cracking, hydrocracking and multi-production diesel process, through selective cracking and isomerization of alkanes, alkyl side chains and other hydrocarbons in the catalytic feedstock, while minimizing the aromatics in the feedstock entering the diesel fraction , and avoid other components in the product to generate aromatics through aromatization and other reactions and remain in the diesel fraction. While the raw materials are converted into high-cetane diesel and propylene, the yield of dry gas and coke is greatly reduced, so as to achieve Efficient use of petroleum resources.

Description

Process for Catalytic Conversion of Prolific Diesel and Propylene

technical field

The invention belongs to the catalytic conversion method of hydrocarbon oil in the absence of hydrogen, more specifically, it is a catalytic conversion method for converting heavy feedstock into high cetane number diesel oil and propylene.

Background technique

At present, the global demand for high-quality gasoline is increasing day by day, and the technology for producing high-quality gasoline is developing rapidly, while the technology for producing high-cetane diesel is developing relatively slowly. Although the demand for gasoline and diesel varies from region to region, overall, the growth rate of global demand for diesel will gradually exceed the growth rate of demand for gasoline. The cetane number of diesel produced by traditional catalytic cracking process is relatively low, so it is often used as a blending component of diesel. In order to meet the demand of high-quality diesel oil, it is necessary to upgrade the catalytic light diesel oil.

In the prior art, methods for upgrading catalytic light diesel mainly include hydrotreating and alkylation. CN1289832A also discloses a method for upgrading catalytic cracking diesel oil by hydrotreating. Under hydrogenation conditions, the raw materials are sequentially passed through a single-stage hydrorefining catalyst and a hydrocracking catalyst in series without intermediate separation. The method increases the cetane number of the product diesel fraction by more than 10 units compared with the raw material, and significantly reduces the sulfur and nitrogen contents.

CN1900226A discloses a catalytic cracking co-catalyst and its preparation method for prolific diesel oil production. Adding a certain amount of the co-catalyst can increase the diesel yield of the FCC catalytic unit and improve Product distribution, but the method does not mention the improvement of diesel properties.

Propylene and other low-carbon olefins are important organic chemical raw materials, and propylene is a synthetic monomer for products such as polypropylene and acrylonitrile. With the rapid growth of demand for derivatives such as polypropylene, the demand for propylene is also increasing year by year. The demand in the world propylene market has increased from 15.2 million tons 20 years ago to 51.2 million tons in 2000, with an average annual growth rate of 6.3%. It is estimated that the demand for propylene will reach 86 million tons by 2010, with an average annual growth rate of about 5.6%.

The methods for producing propylene are mainly steam cracking and catalytic cracking (FCC), wherein steam cracking uses naphtha and other light oils as raw materials to produce ethylene and propylene through thermal cracking, but the yield of propylene is only about 15% by weight, while FCC Heavy oil such as vacuum gas oil (VGO) is used as raw material. At present, 61% of the world's propylene comes from steam cracking to produce ethylene by-products, 34% comes from refinery FCC to produce gasoline and diesel by-products, and a small amount (about 5%) is obtained from propane dehydrogenation and ethylene-butene metathesis.

If the petrochemical industry follows the traditional route of steam cracking to produce ethylene and propylene, it will face several major constraints such as shortage of light raw material oil, insufficient production capacity and high cost.

FCC has been paid more and more attention due to its advantages such as wide adaptability of raw materials and flexible operation. In the United States, almost 50% of the propylene market demand comes from FCC units. The improvement technology of catalytic cracking to increase the production of propylene is developing rapidly.

US4,422,925 discloses a variety of methods for contacting and converting hydrocarbons with different cracking properties with thermally regenerated catalysts. The hydrocarbons described in the method contain at least one gaseous alkane feedstock and one liquid hydrocarbon feedstock. The method is based on different The hydrocarbon molecules have different cracking properties, and the reaction zone is divided into multiple reaction zones for cracking reactions to produce more low-molecular-weight olefins.

CN1279270A discloses a kind of catalytic conversion method of prolific diesel oil and liquefied gas, this method is to carry out in a riser or fluidized bed reactor with four sections, gasoline feedstock, conventional cracking feedstock and reaction terminator are injected into different positions, The method can simultaneously increase the yield of liquefied gas and diesel oil. However, the dry gas and coke yields of this method are relatively high.

For a long time, those skilled in the art believed that the higher the conversion rate of heavy oil catalytic cracking, the better. However, after creative thinking and repeated experiments, the inventor found that the conversion rate of heavy oil catalytic cracking is not as high as possible. When the conversion rate reaches a certain level, the increase of the target product is small, but the yield of dry gas and coke is greatly increased.

In order to efficiently utilize low-quality heavy oil resources and meet the growing demand for light fuel oil, it is necessary to develop a catalytic conversion method for converting heavy oil feedstocks into large quantities of clean diesel and propylene.

Contents of the invention

The purpose of the present invention is to provide a method for converting heavy oil into high cetane number diesel oil and propylene based on the prior art. It is mainly through selective cracking and isomerization of alkanes, alkyl side chains and other hydrocarbons in the catalytic raw material, while minimizing the aromatics in the raw material entering the diesel fraction, and avoiding other components in the product through aromatization, etc. The reaction generates aromatics and remains in the diesel fraction. While the cracked raw materials are converted into high-cetane diesel and propylene, the yield of dry gas and coke is greatly reduced, thereby realizing the effective utilization of petroleum resources.

In one embodiment of the present invention, a kind of catalytic conversion method is provided, wherein feedstock oil is reacted in contact with catalyst in reactor, it is characterized in that reaction temperature, weight hourly space velocity, catalyst and feedstock oil weight ratio are enough to make reaction A reaction product comprising 12-60% by weight of the raw material oil containing catalytic wax oil is obtained, wherein the weight hourly space velocity is 25-100 h ^-1 , the reaction temperature is 450-600°C, and the weight ratio of the catalyst to the raw material oil is 1 ~30; The catalytic wax oil enters the hydrocracking unit for further processing, and the obtained hydrocracking tail oil is used as the raw material for the multi-production diesel unit.

In a more preferred embodiment, the reaction temperature is 450-600°C, preferably 460-580°C, more preferably 480-540°C.

In a more preferred embodiment, the weight hourly space velocity is 30 to 80 h ^-1 , preferably, 40 to 60 h ^-1 .

In a more preferred embodiment, the weight ratio of catalyst to feedstock oil is 1-30, preferably 2-25, more preferably 3-14.

In a more preferred embodiment, the reaction pressure is between 0.10 MPa and 1.0 MPa.

In a more preferred embodiment, the feedstock oil is selected from or includes petroleum hydrocarbons and/or other mineral oils, wherein petroleum hydrocarbons are selected from vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum One or more mixtures of residue oil and atmospheric residue oil, and other mineral oils are one or more mixtures of coal liquefied oil, oil sand oil, and shale oil.

In a more preferred 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, and 0% by weight of clay. ~70% by weight, wherein the zeolite is a medium-pore zeolite and optionally a large-pore zeolite, and the medium-pore zeolite accounts for 51-100% by weight of the total weight of the zeolite, preferably 70-100% by weight. The large-pore zeolite accounts for 0-49% by weight of the total weight of the zeolite, preferably 0-30% by weight. The medium-pore zeolites are selected from ZSM series zeolites and/or ZRP zeolites, and the large-pore zeolites are selected from Y series zeolites.

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 further includes separating the reaction product from the catalyst, and the catalyst is stripped and charred and regenerated and then returned to the reactor, and the separated products include propylene, diesel oil and catalytic wax oil.

In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point of not less than 260° C., and a hydrogen content of not less than 10.5% by weight.

In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point of not less than 330° C., and a hydrogen content of not less than 10.8% by weight.

The reaction system of a hydrocracking unit usually includes a refining reactor and a cracking reactor, both of which are fixed-bed reactors. The refining reactor is usually filled with a hydrotreating catalyst, which is supported on amorphous alumina or/and silicon The VIB group or/and VIII group non-noble metal catalyst on the aluminum support; the hydrocracking catalyst is the VIB group or/and VIII group non-noble metal catalyst supported on the Y-type zeolite molecular sieve. Wherein the VIB group non-noble metal is molybdenum and/or tungsten, and the VIII group non-noble metal is one or more of nickel, cobalt and iron.

The process conditions of the hydrocracking are: hydrogen partial pressure 4.0-20.0MPa, reaction temperature 280-450°C, volume space velocity 0.1-20h ^-1 , hydrogen-oil ratio 300-2000v/v.

In a more preferred embodiment, the diesel prolific unit is a diesel prolific catalytic cracking unit.

In a more preferred embodiment, the reaction temperature of the catalytic cracking unit that produces diesel oil is 400-650°C, preferably 430-500°C, more preferably 430-480°C; the oil and gas residence time is 0.05-5 seconds, preferably, 0.1-4 seconds; the reaction pressure is 0.10MPa-1.0MPa.

In a more preferred embodiment, the prolific diesel catalyst comprises zeolites, inorganic oxides, clays. On a dry basis, each component accounts for the total weight of the catalyst: 5-60 wt% of zeolite, preferably 10-30 wt%; 0.5-50 wt% of inorganic oxide; 0-70 wt% of clay. Wherein the zeolite is used as the active component and is selected from large-pore zeolites. The large-pore zeolite refers to one or more mixtures of the group of zeolites composed of rare earth Y, rare earth hydrogen Y, ultrastable Y obtained by different methods, and high silicon Y.

Inorganic oxides as substrates are 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 is used as a binder, selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, retort clay, sepiolite, attapulgite, hydrotalcite, bentonite or Several kinds.

In a more preferred embodiment, the multi-production diesel reactor is selected from one or a combination of riser, fluidized bed with equal linear velocity, fluidized bed with equal diameter, upward conveying line, and descending conveying line More than one 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 equal-diameter riser or various forms of reduced-diameter riser.

In a more preferred embodiment, the hydrocracked tail oil is introduced into the productive diesel reactor at one location, or the hydrocracked tail oil is introduced into the productive diesel reactor at more than one location of the same or different heights inside the device.

In a more preferred embodiment, the method for producing more diesel oil also includes separating the reaction product and the catalyst for producing more diesel oil, and the catalyst for producing more diesel oil is returned to the reactor for more producing diesel oil after stripping and coke regeneration, and the product after separation Includes high cetane diesel and propylene.

In another embodiment of the present invention, a catalytic conversion method is provided, wherein the feedstock oil is reacted in contact with a catalyst in a reactor, characterized in that

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

(2) The re-cracked raw oil reacts in the reactor no later than the cracked raw 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 weight hourly space velocity of the cracked raw oil is 5-100h ^-1 ;

(5) The catalytic wax oil enters the catalytic wax oil hydrocracking unit;

(6) The hydrocracking tail oil obtained by hydrocracking is used as a raw material for a multi-production diesel unit.

In a more preferred embodiment, the re-cracked raw oil is selected from or includes one or a mixture of dry gas, liquefied gas, and gasoline.

In a more preferred embodiment, the cracked feed oil is selected from or includes petroleum hydrocarbons and/or other mineral oils, wherein petroleum hydrocarbons are selected from vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, One or more mixtures of pressure residue oil and atmospheric pressure residue oil, and other mineral oils are one or more mixtures of coal liquefied oil, oil sand oil, and shale oil.

In a more preferred 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, and 0% by weight of clay. ~70% by weight, wherein the zeolite is a medium-pore zeolite and optionally a large-pore zeolite, and the medium-pore zeolite accounts for 51-100% by weight of the total weight of the zeolite, preferably 70-100% by weight. The large-pore zeolite accounts for 0-49 wt% of the total weight of the zeolite, the medium-pore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and the large-pore zeolite is selected from Y series zeolite.

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 reaction conditions for re-cracking feedstock oil are: reaction temperature 600-750°C, weight hourly space velocity 100-800h ^-1 , reaction pressure 0.10-1.0MPa, catalyst to re-cracking feedstock oil weight ratio 30 ~150, the weight ratio of steam to re-cracked feedstock oil is 0.05~1.0.

In a more preferred embodiment, the reaction conditions for cracking feedstock oil are: reaction temperature 450-600°C, weight hourly space velocity 5-100h ^-1 , reaction pressure 0.10-1.0MPa, weight ratio of catalyst to cracked feedstock oil 1.0-30 , the weight ratio of steam to cracked raw oil is 0.05-1.0.

In a more preferred embodiment, the reaction temperature of the cracked raw oil is 460-580°C, the weight hourly space velocity is 10-90h ^-1 , preferably 20-60h ^-1 , more preferably 30-50h ^-1 , the catalyst and the raw material The oil weight ratio is 3-14.

In a more preferred embodiment, the method also includes separating the reaction product and the catalyst, and the catalyst is stripped and coke-regenerated and then returned to the reactor, and the separated products include propylene, high cetane number diesel oil and catalytic wax Oil.

In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point of not less than 260° C., and a hydrogen content of not less than 10.5% by weight.

In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point of not less than 330° C., and a hydrogen content of not less than 10.8% by weight.

The reaction system of a hydrocracking unit usually includes a refining reactor and a cracking reactor, both of which are fixed-bed reactors. The refining reactor is usually filled with a hydrotreating catalyst, which is supported on amorphous alumina or/and silicon The VIB group or/and VIII group non-noble metal catalyst on the aluminum support; the hydrocracking catalyst is the VIB group or/and VIII group non-noble metal catalyst supported on the Y-type zeolite molecular sieve. Wherein the VIB group non-noble metal is molybdenum and/or tungsten, and the VIII group non-noble metal is one or more of nickel, cobalt and iron.

The process conditions of the hydrocracking are: hydrogen partial pressure 4.0-20.0MPa, reaction temperature 280-450°C, volume space velocity 0.1-20h ^-1 , hydrogen-oil ratio 300-2000v/v.

In a more preferred embodiment, the diesel prolific unit is a diesel prolific catalytic cracking unit.

In a more preferred embodiment, the reaction temperature of the catalytic cracking unit producing diesel oil is 400-650°C, preferably 430-500°C, more preferably 430-480°C. The oil-gas residence time is 0.05-5 seconds, preferably 0.1-4 seconds. The reaction pressure is 0.10MPa～1.0MPa.

In a more preferred embodiment, the prolific diesel catalyst comprises zeolites, inorganic oxides, clays. On a dry basis, each component accounts for the total weight of the catalyst: 5-60 wt% of zeolite, preferably 10-30 wt%; 0.5-50 wt% of inorganic oxide; 0-70 wt% of clay. Wherein the zeolite is used as the active component and is selected from large-pore zeolites. The large-pore zeolite refers to one or more mixtures of the group of zeolites composed of rare earth Y, rare earth hydrogen Y, ultrastable Y obtained by different methods, and high silicon Y.

Inorganic oxides as substrates are 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 is used as a binder, selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, retort clay, sepiolite, attapulgite, hydrotalcite, bentonite or Several kinds.

In a more preferred embodiment, the multi-production diesel reactor is selected from one or a combination of riser, fluidized bed with equal linear velocity, fluidized bed with equal diameter, upward conveying line, and descending conveying line More than one 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 equal-diameter riser or various forms of reduced-diameter riser.

In a more preferred embodiment, the hydrocracked tail oil is introduced into the productive diesel reactor at one location, or the hydrocracked tail oil is introduced into the productive diesel reactor at more than one location of the same or different heights inside the device.

In a more preferred embodiment, the method for producing more diesel oil also includes separating the reaction product and the catalyst for producing more diesel oil, and the catalyst for producing more diesel oil is returned to the reactor for more producing diesel oil after stripping and coke regeneration, and the product after separation Includes high cetane diesel and propylene.

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.

Methods such as separating propylene from the reaction product are the same as methods well known to those of ordinary skill in the art; cuts greater than 250°C or 260°C (or fractions greater than 330°C) are used as feed oil for catalytic cracking units, or greater than 250°C or 260°C The catalytic wax oil (or catalytic wax oil greater than 330°C) hydrocracking method adopts a catalytic wax oil hydrocracking unit.

The technical scheme organically combines catalytic cracking, catalytic wax oil hydrocracking and other processes to maximize the production of high-cetane number diesel oil and low-carbon olefins, especially propylene, from heavy raw materials with low hydrogen content. Compared with the prior art, the present invention has the following technical effects:

1. While producing more diesel oil, the yield of propylene and the selectivity of propylene in liquefied petroleum gas are greatly increased;

2. The yield of diesel oil is obviously increased, and the cetane number of diesel oil is obviously improved;

3. In the case of a substantial increase in propylene yield and diesel oil yield, the dry gas yield and coke are significantly reduced;

4. The yield of light oil is significantly increased, and the yield of oil slurry is significantly reduced, so that the utilization efficiency of petroleum resources is improved;

5. The operating cycle of the hydrotreating unit has been significantly improved.

Description of drawings

The Figure is a schematic representation of one embodiment of the invention.

The accompanying drawings are intended to illustrate the invention schematically and not to limit it.

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 thereby.

The accompanying drawing is a schematic diagram of a first embodiment of the invention.

Its technological process is as follows:

The pre-lift medium enters from the bottom of the riser reactor 2 through the pipeline 1, the regenerated catalyst from the pipeline 16 accelerates upward along the riser under the lifting effect of the pre-lift medium, and the re-cracked raw oil passes through the pipeline 3 and the atomized catalyst from the pipeline 4 The steam is injected into the bottom of the reaction zone I of the riser 2 and mixed with the existing flow in the riser reactor, and the re-cracking raw material undergoes cracking reaction on the hot catalyst and accelerates upward. The cracked raw material oil is injected into the middle and lower part of the reaction zone I of the riser 2 through the pipeline 5 together with the atomized steam from the pipeline 6, and is mixed with the existing flow of the riser reactor, and the cracked raw material is generated on a lower catalyst containing a certain carbon Cracking reaction, and accelerate upward movement into 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, realize the separation of the catalyst and the oil gas, and the oil gas enters the gas collection In chamber 9, the catalyst fine powder is returned to the settler by the dipleg. 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 oil and gas in the gas collection chamber 9 enters the subsequent separation system 18 through the large oil and gas pipeline 17, the separated propylene is drawn out through the pipeline 19, and the separated propane is drawn out through the pipeline 28; while the C4 hydrocarbons are drawn out through the pipeline 20, they can also be returned Riser 2; Catalytic cracking dry gas is drawn out through pipeline 21; Catalytic cracking gasoline is drawn out through pipeline 27, and gasoline fraction with a preferred distillation range less than 65-110°C is drawn out through pipeline 22 as re-cracking raw material and returned to the reactor; Diesel fraction is drawn out through pipeline 29 , the heavy diesel oil fraction can also be drawn together with the catalytic wax oil into the hydrocracking unit; the catalytic wax oil raw material is drawn to the hydrocracking unit 24 through the pipeline 23, and the separated hydrocracking product is split through the pipeline 25, and hydrocracked Tail oil is sent to prolific diesel unit 27 via pipeline 26. The oil and gas generated by the multi-production diesel plant can enter the fractionation system 18 through the oil and gas pipeline 28 or/and enter other fractionation systems for separation. The distillation range of each fraction is adjusted according to the actual needs of the refinery.

The following examples will further illustrate the method, but the method is not limited thereby.

The raw material oil used in the embodiment is VGO, and its properties are as shown in Table 1.

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

Catalyst CAT-MP preparation method

1) Dissolve 20g NH ₄ Cl in 1000g water, add 100g (dry basis) 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), after exchanging at 90°C for 0.5h, filter the filter cake; add 4.0g H ₃ PO ₄ (concentration 85%) and 4.5g Fe(NO ₃ ) ₃ to dissolve in 90g water, and mix with the filter cake Impregnation and drying; followed by roasting 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), with 250kg decationized water, 75.4kg polyhydrate kaolin (industrial product of Suzhou China Clay Company, solid content 71.6% by weight) is beaten, then add 54.8kg pseudoboehmite (industrial product of Shandong Aluminum Plant, solid content 63% by weight) ), adjust its pH to 2-4 with hydrochloric acid, stir evenly, leave it to age at 60-70°C for 1 hour, keep the pH at 2-4, lower the temperature below 60°C, add 41.5Kg aluminum sol (Qilu Petrochemical company catalyst factory product, Al ₂ O ₃ content is 21.7% by weight), stirred for 40 minutes to obtain mixed slurry.

3), the phosphorus-containing and iron-containing MFI structure mesoporous zeolite (dry basis is 22.5kg) prepared in step 1) and DASY zeolite (industrial product of Qilu Petrochemical Company Catalyst Factory, unit cell constant is 2.445～2.448nm, dry basis is 2.0kg) was added to the mixed slurry obtained in step 2), stirred evenly, spray-dried to form, washed with ammonium dihydrogen phosphate solution (phosphorus content is 1% by weight), washed away free Na ⁺ , and dried to obtain a catalytic cracking catalyst sample CAT-MP, the composition of the catalyst is 18% by weight of MFI structure mesoporous zeolite containing phosphorus and iron, 2% by weight of DASY zeolite, 28% by weight of pseudo-boehmite, 7% by weight of aluminum sol and the balance of kaolin.

The prolific diesel catalyst preparation method used in the embodiment is briefly described as follows:

Preparation method of catalyst CAT-MD

1), configuration 2 liters of silicon dioxide concentration is the water glass solution of 155g/l and ₁ liter of free acid is 148g/L, Al ₂ O Content is the acidified aluminum sulfate solution of 20g/L, above-mentioned two kinds of solutions enter fast simultaneously Mixer reaction to obtain silica sol.

2) Add 465 g of kaolin (Suzhou Kaolin Company, solid content: 80% by weight) to the silica sol prepared above, and beat for 1 hour to obtain kaolin-silica sol.

3), Pseudo-boehmite containing 124g of Al ₂ O ₃ (Shandong Aluminum Factory, Al ₂ O ₃ content is 33% by weight) and 450g deionized water were mixed and beaten for 30 minutes, and then 25 ml of 31% by weight was added. Hydrochloric acid (acid/ _Al2O3 molar ratio is 0.2) peptization, continue beating for 2 _hours , then add 656g molecular sieve content and be that 32% by weight of ground DASY0.0 molecular sieve slurry (produced by Qilu Catalyst Factory, unit cell constant is 2.445nm ), beating for 30 minutes to obtain a mixed slurry of pseudo-boehmite and molecular sieve.

4), mix the kaolin-silica sol slurry prepared above with the mixed slurry of pseudo-boehmite and molecular sieve prepared above and beat for 10 minutes to obtain a catalyst slurry, and spray-dry the obtained slurry to a diameter of 20 to 120 microns, silicon oxide For granules with a content of 29.9% by weight, a kaolin content of 35.9% by weight, an alumina content of 13.9% by weight, and a molecular sieve content of 20.3% by weight, the drying temperature is 180°C. Wash with deionized water until no sodium ions are detected, and dry at 150°C to obtain the prepared catalyst CAT-MD.

The trade names of the hydrorefining catalyst and the hydrocracking catalyst used in the examples are RN-2 and RT-1 respectively, both of which are produced by Changling Catalyst Factory of Sinopec Catalyst Company.

Example 1

This embodiment is tested according to the flow process of accompanying drawing, and cracked raw material oil A is directly used as the raw material of catalytic cracking, adopts catalyst CAT-MP, is tested on the medium-sized device of riser reactor, and cracked raw material enters the middle and upper part of reaction zone I, D Olefin enters the bottom of reaction zone I as a re-cracking raw material. At the bottom of reaction zone I, the re-cracked raw material is at a reaction temperature of 610°C, a weight hourly space velocity of 175h ^-1 , a weight ratio of catalytic cracking catalyst to raw material of 70, and a weight ratio of water vapor to raw material The cracking reaction is carried out under the condition of a ratio of 0.20; in the middle and upper part of the reaction zone I, the catalytic raw material is at a reaction temperature of 530°C and a weight hourly space velocity of 40h ^-1 , the weight ratio of catalytic cracking catalyst to raw material is 4, and the weight ratio of water vapor to raw material is 0.15 The cracking reaction is carried out under the conditions. In the reaction zone II, the oil gas is cracked at the reaction temperature of 480°C and the weight ratio of water vapor to raw material is 0.15. The oil gas and the catalyst to be charred are separated in the settler, and the product is separated in the separation system Process cutting to obtain propylene, butene, gasoline, diesel and catalytic wax oil fractions. The catalytic wax oil is sent to the hydrocracking unit for treatment. The reaction system of the hydrocracking unit includes two reactors, a refining reactor and a cracking reactor. Under the reaction conditions of 0.95/1.2h ^-1 , hydrotreating is carried out, and the hydrocracking tail oil after hydrogenation is sent to a diesel catalytic cracking unit for catalytic conversion. The operating conditions and product distribution are listed in Table 2.

It can be seen from Table 2 that the yield of propylene is as high as 13.10% by weight, the yield of diesel oil is 11.36% by weight, the cetane number of diesel oil is as high as 52, and that of jet fuel is 13.33% by weight.

Table 1

Raw material type A Density (20℃), kg/ ^m3 858.6 Kinematic viscosity (100°C), ^mm2 /s 4.9 Carbon residue, wt% 0.03 Total nitrogen, wt% 0.05 Sulfur, wt% 0.06 Carbon, weight % 86.3 Hydrogen, weight % 13.64 Heavy metal content, ppm Nickel ＜0.1 Vanadium ＜0.1 Distillation range, ℃ initial boiling point 290 10% 372 30% 415 50% 440 70% 470 90% 502 end point -

Table 2

Example 1 Raw oil number A Catalytic cracking unit Catalyst CAT-MP operating conditions Riser reaction zone II Reaction temperature, ℃ 480 Water vapor/feed oil weight ratio 0.15 Riser reaction zone I Average temperature, ℃ 610/530 Agent oil ratio, m/m 70/4 Heavy hourly space velocity, h ^-1 175/40 Water vapor/feed oil weight ratio 0.2/0.15 Hydrocracking unit Hydrogen partial pressure, MPa 17.9/17.4 Reaction temperature, ℃ 374/371 Volumetric space velocity, h ^-1 0.95/1.2 Prolific Diesel Catalytic Cracking Unit Catalyst CAT-MD Reaction temperature, ℃ 480 Agent oil ratio, m/m 3 Product distribution, m% dry gas 4.65 Liquefied gas 36.96 Propylene 13.10 gasoline 29.33 jet fuel 13.33 diesel fuel 11.36 coke 4.65 loss 0.50 Total 100.78 Diesel cetane number 52

Claims (43)

1. A method for the catalytic conversion of prolific diesel oil and propylene, wherein the feed oil is reacted in contact with a catalyst in a reactor, characterized in that the reaction temperature, weight hourly space velocity, catalyst and feed oil weight ratio are sufficient to make the reaction obtain Oil 12-60% by weight is the reaction product of catalytic wax oil, wherein the weight hourly space velocity is 25-100h ^-1 , the reaction temperature is 450-600°C, the weight ratio of the catalyst to the raw oil is 1-30, and the catalytic The wax oil enters the hydrocracking unit for further processing, and the obtained hydrocracking tail oil is used as the raw material of the multi-production diesel unit; the hydrocracking process conditions are: hydrogen partial pressure 4.0-20.0MPa, reaction temperature 280-450°C, volume empty The speed is 0.1-20h ^-1 , the hydrogen-to-oil ratio is 300-2000v/v, and the hydrocracking catalyst is a VIB group or/and VIII group non-noble metal catalyst supported on a Y-type zeolite molecular sieve. 2. according to the method for claim 1, it is characterized in that said raw material oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, and wherein petroleum hydrocarbon is selected from vacuum gas oil, normal pressure gas oil, coker gas oil, deasphalted One or more mixtures of oil, vacuum residue, and atmospheric pressure residue, and other mineral oils are one or more mixtures of coal liquefied oil, oil sands oil, and shale oil. 3. according to the method for claim 1, it is characterized in that described catalyzer comprises zeolite, inorganic oxide compound and optional clay, and each component accounts for catalyst gross weight respectively: 1～50 weight % of zeolite, 5～99 weight % of inorganic oxide compound %, clay 0-70% by weight, wherein the zeolite is medium-pore zeolite and optional large-pore zeolite, medium-pore zeolite accounts for 51-100% by weight of the total weight of zeolite, and large-pore zeolite accounts for 0-49% by weight of the total weight of zeolite , the medium pore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and the large pore zeolite is selected from Y series zeolite. 4. according to the method for claim 1, it is characterized in that said reactor is selected from the one in riser, the fluidized bed of equal linear velocity, the fluidized bed of equal diameter, uplink conveying line, descending conveying line or A combination of more than one type, or a combination of two or more reactors of the same type, including series or/and parallel connection, where the riser is a conventional riser with equal diameter or a riser with various forms of reduced diameter . 5. The method according to claim 1, characterized in that the feedstock oil is introduced into the reactor at one location, or at more than one location at the same or different heights. 6. The method according to claim 1, characterized in that the reaction temperature is 460-580°C, the weight hourly space velocity is 30-80h ^-1 , and the weight ratio of catalyst to raw oil is 2-15. 7. The method according to claim 1, characterized in that the reaction temperature is 480-540°C. 8. The method according to claim 1, characterized in that the weight hourly space velocity is 40-60h ^-1 . 9. The method according to claim 1, characterized in that the weight ratio of catalyst to feed oil is 3-14. 10. The method according to claim 1, characterized in that the reaction is carried out at a pressure of 0.10 MPa to 1.0 MPa. 11. according to the method for claim 1, it is characterized in that described method also comprises that reaction product and catalyzer are separated, and catalyzer is returned reactor after stripping, burnt regeneration, and the product after separation comprises propylene, high cetane number Diesel and catalytic wax oils. 12. The method according to claim 1, characterized in that said catalytic wax oil is a fraction with an initial boiling point of not less than 260° C. and a hydrogen content of not less than 10.5% by weight. 13. The method according to claim 12, characterized in that said catalytic wax oil is a fraction with an initial boiling point of not less than 330° C. and a hydrogen content of not less than 10.8% by weight. 14. According to the method for claim 1, it is characterized in that the catalytic cracking unit for producing diesel oil is adopted in the multi-production diesel unit. 15. The method according to claim 1, characterized in that the reaction temperature of the catalytic cracking unit producing diesel oil is 400-650° C., the oil-gas residence time is 0.05-5 seconds, and the reaction pressure is 0.10 MPa-1.0 MPa. 16. According to the method of claim 14, it is characterized in that the catalyst used in the high-production diesel unit comprises zeolite, inorganic oxides, clay, and on a dry basis, each component accounts for the total catalyst weight: zeolite 5 to 60% by weight; Inorganic oxide 0.5% to 50% by weight; clay 0% to 70% by weight, wherein zeolite is selected from large-pore zeolite as the active component, and the large-pore zeolite refers to rare earth Y, rare earth hydrogen Y, and different methods. One or more mixtures of this group of zeolites composed of ultra-stable Y and high-silicon Y. 17. according to the method for claim 16, it is characterized in that described inorganic oxide is as substrate, is selected from silica and/or aluminum oxide; When inorganic oxide is silicon dioxide and aluminum oxide, with dry Based on the inorganic oxide, silicon dioxide accounts for 50 to 90% by weight, and aluminum oxide accounts for 10 to 50% by weight. 18. according to the method for claim 16, it is characterized in that described clay is used as binding agent, is selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite , attapulgite, hydrotalcite, bentonite in one or more. 19. according to the method for claim 1, it is characterized in that the used reactor of described prolific diesel oil plant is selected from the riser, the fluidized bed of equal linear velocity, the fluidized bed of equal diameter, ascending conveying line, descending conveying line A combination of one or more of them, or a combination of two or more of the same reactor, the combination includes series or/and parallel connection, where the riser is a conventional equal-diameter riser or various forms Reduced diameter riser. 20. The method according to claim 1, characterized in that said hydrocracking tail oil is introduced into the productive diesel reactor at one position, or said hydrocracking tail oil is introduced at more than one position at the same or different heights Prolific diesel reactor. 21. according to the method for claim 1, it is characterized in that described method also comprises that reaction product and prolific diesel catalyst are separated, and prolific diesel catalyst is returned to prolific diesel reactor after stripping, charred regeneration, separated Products include high cetane diesel and propylene. 22. A catalytic conversion method, wherein the raw oil is reacted in contact with the catalyst in the reactor, characterized in that (1) The feedstock oil includes re-cracked feedstock oil and cracked feedstock oil, the feedstock oil is introduced into the reactor at one position, or the feedstock oil is introduced into the reactor at more than one position with the same or different heights; (2) The re-cracked raw oil reacts in the reactor no later than the cracked raw oil; (3) The weight ratio of reaction temperature, weight hourly space velocity, catalyst and feedstock oil is enough to make reaction obtain and comprise the reaction product that comprises 12～60 weight % of cracked feedstock oil catalytic wax oil; (4) The weight hourly space velocity of the cracked raw oil is 5-100h ^-1 ; (5) The catalytic wax oil enters the hydrocracking unit; (6) The hydrocracking tail oil obtained by hydrocracking is used as a raw material for a multi-production diesel unit. 23. The method according to claim 22, characterized in that the re-cracked raw oil is selected from or includes one or a mixture of oil slurry, diesel oil, gasoline, and hydrocarbons with 4-8 carbon atoms. 24. According to the method for claim 22, it is characterized in that the cracked raw oil is selected from or includes petroleum hydrocarbons and/or other mineral oils, wherein petroleum hydrocarbons are selected from vacuum gas oil, atmospheric gas oil, coker gas oil, degassing One or more mixtures of asphalt oil, vacuum residue oil, and atmospheric pressure residue oil, and other mineral oils are one or more mixtures of coal liquefied oil, oil sand oil, and shale oil. 25. according to the method for claim 22, it is characterized in that described catalyzer comprises zeolite, inorganic oxide compound and optional clay, and each component accounts for catalyst gross weight respectively: 1～50 weight % of zeolite, 5～99 weight % of inorganic oxide %, clay 0-70% by weight, wherein the zeolite is medium-pore zeolite and optional large-pore zeolite, medium-pore zeolite accounts for 51-100% by weight of the total weight of zeolite, and large-pore zeolite accounts for 0-49% by weight of the total weight of zeolite , the medium pore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and the large pore zeolite is selected from Y series zeolite. 26. according to the method for claim 22, it is characterized in that said reactor is selected from riser, the fluidized bed of equal linear velocity, the fluidized bed of equal diameter, the one in the ascending conveying line, descending conveying line or A combination of more than one type, or a combination of two or more reactors of the same type, including series or/and parallel connection, where the riser is a conventional riser with equal diameter or a riser with various forms of reduced diameter . 27. The method according to claim 22, characterized in that the reaction conditions for re-cracking feedstock oil are: reaction temperature 600-750°C, weight hourly space velocity 100-800h ^-1 , reaction pressure 0.10-1.0MPa, catalyst and re-cracking feedstock oil The weight ratio of water vapor to re-cracked feedstock oil is 0.05-1.0. 28. The method according to claim 22, characterized in that the reaction conditions for cracking feedstock oil are: reaction temperature 450-600°C, weight hourly space velocity 5-100h ^-1 , reaction pressure 0.10-1.0MPa, weight of catalyst and cracked feedstock oil The ratio is 1.0-30, and the weight ratio of steam to cracked raw oil is 0.05-1.0. 29. The method according to claim 22, characterized in that the reaction temperature of the cracked raw oil is 460-560°C. 30. The method according to claim 22, characterized in that the weight hourly space velocity is 10 to 90 h ^-1 . 31. The method according to claim 22, characterized in that the weight ratio of catalyst to feedstock oil is 1-14. 32. According to the method of claim 22, it is characterized in that the method also includes separating the reaction product and the catalyst, and the catalyst returns to the reactor after stripping and charring regeneration, and the separated products include propylene, high cetane number Diesel and catalytic wax oils. 33. The method according to claim 22, characterized in that said catalytic wax oil is a fraction with an initial boiling point of not less than 260° C. and a hydrogen content of not less than 10.5% by weight. 34. The method according to claim 33, characterized in that said catalytic wax oil is a fraction with an initial boiling point of not less than 330° C. and a hydrogen content of not less than 10.8% by weight. 35. According to the method of claim 22, it is characterized in that the high-production diesel unit adopts a high-production diesel catalytic cracking unit. 36. The method according to claim 22, characterized in that the reaction temperature of the catalytic cracking unit producing diesel oil is 400-650° C., the oil-gas residence time is 0.05-5 seconds, and the reaction pressure is 0.10 MPa-1.0 MPa. 37. According to the method of claim 22, it is characterized in that the catalyst used in the high-production diesel unit includes zeolite, inorganic oxides, clay, and on a dry basis, each component accounts for the total catalyst weight: zeolite 5% to 60% by weight ; Inorganic oxide 0.5% to 50% by weight; clay 0% to 70% by weight, wherein zeolite is selected from large-pore zeolite as an active component, and the large-pore zeolite refers to rare earth Y, rare earth hydrogen Y, different methods One or more mixtures of the group of zeolites formed by the obtained ultrastable Y and high silicon Y. 38. The method according to claim 37, characterized in that said inorganic oxide as substrate is selected from silicon dioxide or aluminum oxide. 39. according to the method for claim 37, it is characterized in that described inorganic oxide is used as matrix, is selected from silicon dioxide and aluminum oxide, and in dry basis, silicon dioxide accounts for 50 to 90 weight % in the inorganic oxide , Al2O3 accounts for 10 to 50% by weight. 40. according to the method for claim 37, it is characterized in that described clay is used as binding agent, is selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite , attapulgite, hydrotalcite, bentonite in one or more. 41. according to the method for claim 22, it is characterized in that the used reactor of described prolific diesel oil plant is selected from riser, the fluidized bed of equal linear velocity, the fluidized bed of equal diameter, ascending conveying line, descending conveying line A combination of one or more of them, or a combination of two or more of the same reactor, the combination includes series or/and parallel connection, where the riser is a conventional equal-diameter riser or various forms Reduced diameter riser. 42. The method according to claim 22, characterized in that said hydrocracked tail oil is introduced into the productive diesel reactor at one location, or said hydrocracked tail oil is introduced at more than one location at the same or different heights Prolific diesel reactor. 43. according to the method for claim 22, it is characterized in that described method also comprises that reaction product and prolific diesel catalyst are separated, and prolific diesel catalyst is returned to prolific diesel reactor after stripping, charred regeneration, separated Products include high cetane diesel and propylene.