CN1566273A - Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof - Google Patents

Abstract

The cracking catalyst containing molecular sieves contains molecular sieves, heat-resistant inorganic oxides and a metal component, the molecular sieves are a mixture of a first zeolite and a second zeolite, the first zeolite is a Y-type zeolite, and the Y-type zeolite is The secondary pore volume accounts for 20-80% of the total pore volume. The second type of zeolite is a zeolite with a molar ratio of silicon oxide to aluminum oxide of more than 20. Based on the total amount of catalyst, the content of the first type of zeolite is 1-50%. % by weight, the content of the second zeolite is 1-40% by weight, the content of heat-resistant inorganic oxide is 2-80% by weight, and the content of clay is 0-80% by weight. In total, the content of the metal component is 0.1-30% by weight, and the metal component basically exists in a reduced valence state. The catalyst can increase the yield of diesel oil and liquefied gas, and has higher desulfurization activity and cracking activity.

Description

A kind of hydrocarbon cracking catalyst containing molecular sieve and preparation method thereof

Technical field

The present invention relates to a hydrocarbon cracking catalyst and its preparation method, more specifically, to a hydrocarbon cracking catalyst containing molecular sieves and its preparation method.

Background technique

The market has a great demand for diesel oil and liquefied gas (LPG). Therefore, it is hoped that more diesel oil and more liquefied gas can be obtained through the catalytic cracking process at the same time. A hydrocarbon cracking catalyst capable of obtaining more liquefied gas.

CN 1307087A discloses a catalyst for catalytic cracking of petroleum, the catalyst contains 50-80% by weight carrier, 10-50% by weight of Y-type molecular sieve, and 3-15% by weight of shape-selective molecular sieve, said The relative crystallinity of Y-type molecular sieve is 70-90%, and its secondary pore volume accounts for 20-80% of the total pore volume. The catalyst can increase the yield of catalytic cracking diesel oil and liquefied gas in a refinery.

On the other hand, due to environmental considerations, the requirements for fuel oil standards are constantly increasing worldwide. Take China as an example. In 1999, the State Bureau of Quality Supervision formulated the "Control Standard for Hazardous Substances in Motor Gasoline". According to the requirements of this standard, the sulfur content of finished gasoline should be less than 800ppm. In fact, more than 90% of the sulfur in finished gasoline comes from FCC gasoline. Correspondingly, the heavy tendency of catalytic cracking raw materials is becoming more and more serious, and the proportion of Middle East crude oil with higher sulfur content in the crude oil of Chinese refineries is also increasing. Therefore, it is necessary to develop Cracking catalyst with cracking activity and desulfurization performance.

US6,036,847 and its family patent EP0,798,362A2 disclose a hydrocarbon fluid catalytic cracking process, wherein the hydrocarbon feed is cracked in a cracking zone in the absence of external hydrogen addition, and comprises All particles of catalyst particles are continuously circulated in a hydrocarbon cracking zone and a catalyst regeneration zone. Wherein, all the granules contain another kind of granule, which has a lower activity of cracking hydrocarbon oil than the catalyst granules, and the activity is based on the fresh granules. The particles consist essentially of titanium oxide and an inorganic oxide other than titanium oxide. The non-titanium oxide inorganic oxide contains a Lewis acid selected from the group consisting of the following elements and their compounds: nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead , bismuth, boron, aluminum (not alumina) and germanium, the Lewis acid supported on alumina. Due to the use of this titanium oxide-containing additive, the sulfur content in the cracked product FCC gasoline is reduced.

US5,376,608 discloses a cracking catalyst composition with desulfurization effect, which composition contains (A) zeolite/molecular sieve dispersed in an inorganic oxide matrix, (b) alumina component containing Lewis acid, the The alumina component contains 1-50% by weight of a Lewis acid selected from the group consisting of nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron A group of elements and oxides of aluminum (non-alumina) and gallium.

WO 99/49001A1 discloses a composition for reducing the sulfur content of hydrocarbon components, the composition contains a hydrotalcite (Hydrotalcite) material impregnated with a Lewis acid, the composition may also contain An FCC catalyst. The Lewis acids include elements and compounds of transition metals, especially zinc, copper, nickel, cobalt, iron and manganese.

WO 01/21733 A1 discloses a process for the catalytic cracking of hydrocarbon feedstocks containing organosulfur compounds in the presence of a thermally regenerated cracking catalyst comprising a product sulfur reducing component containing an oxidation state greater than Zero metal components, which include metal compounds or complexes of the 3rd period of the periodic table, group VB, group VIIB, group VIII, group IIB, group IVA, such as vanadium, zinc, iron, cobalt, Metal compounds or complexes of manganese and gallium. The component for reducing product sulfur includes molecular sieves containing the above-mentioned metal components in the pore structure, and also includes the above-mentioned metal components dispersed in any position of the catalyst carrier, such as in a porous oxide carrier.

WO 01/21732 A1 discloses a process for reducing the sulfur content of cracked petroleum fractions, which comprises catalytically cracking petroleum fractions at elevated temperatures and in the presence of a cracking catalyst and an additive to reduce the sulfur content of the product to obtain Liquid cracking products with lower sulfur content. Wherein, the additive for reducing the sulfur content of the product contains a vanadium-containing non-molecular sieve carrier, and the non-molecular sieve carrier can be an organic or inorganic carrier, and the preferred carrier is an amorphous or subcrystalline inorganic oxide, such as alumina, silicon oxide , clay or their mixtures.

CN1281887A discloses a method for reducing the sulfur content of catalytic cracking petroleum distillates, the method includes catalytic cracking petroleum raw material fractions at high temperature and in the presence of a product desulfurization catalyst to prepare liquid cracked products with low sulfur content. The desulfurization catalyst contains a porous molecular sieve containing metal components inside the porous structure. The porous molecular sieve can be a large-pore zeolite, that is, a zeolite with a pore diameter of at least 0.7 nanometers, such as Y-type zeolite, rare earth Y-type zeolite (REY), ultra-stable Y zeolite (USY), L zeolite, Beta zeolite, mordenite , ZSM-18 zeolite. The molecular sieve can also be a mesoporous zeolite, that is, a zeolite with an orifice diameter greater than 0.56 and less than 0.7 nanometers, such as Pentasil zeolite, ZSM-5 zeolite, ZSM-22, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 Zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite. The molecular sieve can also be a non-zeolite molecular sieve, such as silicates with different silicon-to-aluminum ratios (such as metallosilicate, titanosilicate), metalloaluminates (such as germaniumaluminates), metal phosphoric acid Salt metallophosphates, aluminophosphates aluminophosphates, metalloaluminophosphates, metal integrated silicoaluminophosphates (MeAPSO and ELAPSO), silicoalumino-phosphates (SAPO), gallogermanates (gallogermanates) and their combination.

CN1261618A discloses a desulfurization method of catalytic cracking petroleum fractions, the method comprises catalytic cracking of petroleum raw material fractions containing organic sulfur compounds under high temperature, in the presence of cracking catalysts and product desulfurization catalysts, to produce liquid cracked products with low sulfur content. The product desulfurization catalyst contains a porous molecular sieve, the molecular sieve contains a first metal component and a second metal component, the first metal component is located inside the pore structure of the molecular sieve and its oxidation state is greater than zero, and the second metal component includes At least one rare earth element inside the pore structure of the molecular sieve. The first metal component is selected from metals of the fourth period of the periodic table and metals of groups IIB, VB, IIIA, and VIII, especially vanadium, zinc, iron, and gallium.

Although the desulfurization activity of the catalyst disclosed in the above prior art has been improved, on the one hand, the yield of diesel oil and liquefied gas is low when using the above catalyst, and on the other hand, its desulfurization performance needs to be improved. Since the above-mentioned catalysts are all dried, calcined and/or hydrothermally treated during the preparation process, there is no reduction process, and the metal components contained in the above-mentioned catalysts all exist in their highest oxidation state.

CN1382199A discloses a kind of adsorbent composition, and this composition is made up of bimetallic accelerator and granular carrier, and described bimetallic accelerator basically exists with reducing valence state, and its existing amount can under desulfurization condition, from cracking Sulfur removal from gasoline. The bimetallic accelerator is selected from any two or more of cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony and vanadium. The support consists of zinc oxide in combination with any suitable inorganic and organic supports. The inorganic carrier includes silica, silica gel, alumina, clay, aluminum silicate, silica-alumina, titanium oxide, zirconium oxide, zinc aluminate, zinc titanate, zinc silicate, calcium aluminate, calcium silicate , magnesium silicate, magnesium aluminate, magnesium titanate, synthetic and natural zeolites. The composition is used as an adsorbent for sulfur removal from cracked gasoline and diesel fuel, rather than as a cracking catalyst.

The purpose of the present invention is to provide a new molecular sieve-containing cracking catalyst that can increase the yield of diesel oil and liquefied gas and has higher desulfurization performance.

The inventors of the present invention have found that if a metal component in a reduced state is introduced into the cracking catalyst, not only the desulfurization performance of the cracking catalyst can be improved, but also, unexpectedly, the cracking activity of the cracking catalyst can be significantly improved, and then by using an appropriate zeolite group points, can also significantly increase the yield of diesel and liquefied petroleum gas.

The catalyst provided by the invention contains molecular sieves, heat-resistant inorganic oxides and a metal component, with or without clay, wherein the molecular sieves are a mixture of a first zeolite and a second zeolite, and the first zeolite It is a Y-type zeolite, the secondary pore volume of this Y-type zeolite accounts for 20-80% of the total pore volume, the second zeolite is a zeolite with a molar ratio of silicon oxide to aluminum oxide of more than 20, based on the total amount of catalyst, The content of the first zeolite is 1-50% by weight, the content of the second zeolite is 1-40% by weight, the content of heat-resistant inorganic oxide is 2-80% by weight, and the content of clay is 0-80% by weight, Based on the metal oxide in the highest valence state, the content of the metal component is 0.1-30% by weight, and the metal component basically exists in a reduced valence state, and it is selected from the group IIIA non-aluminum metals of the periodic table of elements, IVA One or more of Group metals, Group VA metals, Group IB metals, Group IIB metals, Group VB metals, Group VIB metals, Group VIIB metals, and Group VIII non-noble metals.

The preparation method of the catalyst provided by the invention comprises contacting the composition containing metal component compound, molecular sieve, refractory inorganic oxide and clay with the atmosphere containing reducing gas, the temperature and time of the contact are sufficient to make the metal The average valence state of the component is lower than its highest oxidation state, the molecular sieve is a mixture of the first zeolite and the second zeolite, the first zeolite is Y-type zeolite, and the secondary pore volume of the Y-type zeolite accounts for 20-80% of the total pore volume, the second zeolite is a zeolite with a molar ratio of silicon oxide to aluminum oxide of more than 20, and the metal component is selected from Group IIIA non-aluminum metals, Group IVA metals, Group VA metals of the Periodic Table of Elements One or more of metals, Group IB metals, Group IIB metals, VB group metals, VIB group metals, VIIB group metals, and VIII group non-noble metals. The content of each component in the composition is contained in the final catalyst. The total amount is based on 1-50% by weight of the first zeolite, 1-40% by weight of the second zeolite, 2-80% by weight of heat-resistant inorganic oxides, 0-80% by weight of clay and the highest valence The metal component is 0.1-30% by weight based on the oxide of the metal.

Compared with the prior art, the catalyst provided by the invention can increase the yield of diesel oil and liquefied gas, has higher desulfurization activity, and unexpectedly has higher cracking activity.

For example, the content of Y-type zeolite provided by the present invention is 24% by weight, the content of ZRP-1 zeolite is 6% by weight, the content of alumina is 31% by weight, the content of rare earth oxide is 1.5% by weight, and the content of MgO is 1.5% by weight. % by weight, the content of kaolin is 35% by weight, in _Co2O3 , the cobalt content is 1% by _weight , and the average valence state of cobalt is +1.5 or zero valence (the average valence state of cobalt is equal to the highest valence state of cobalt Catalyst with a ratio of 0.5 or 0), (after steam aging at 800°C/4 hours, deactivation and then reduction), when the reaction temperature is 480°C, the weight hourly space velocity is 16 hours ^-1 , and the weight ratio of agent to oil is 4.0 Under the conditions, the sulfur content is 2.0% by weight, the distillation range is 329-550 DEG C vacuum gas oil catalytic cracking, the conversion rate is as high as 76.4-77.1% by weight, the yield of liquefied gas is as high as 19.6-20.1% by weight, and the yield of diesel oil is as high as As high as 16.5-16.9% by weight, the sulfur content in the gasoline product is only 414.7-486.5 mg/liter. And adopt the same zeolite content, the cobalt-free cracking catalyst and the content of each component are all the same, but the valence state of cobalt is its highest valence state (+2 valence) catalyst, under the same conditions, the same feedstock oil is processed Catalytic cracking, the conversion rate is only 74.8-75.9% by weight, the yield of liquefied gas is only 16.7-17.6% by weight, the yield of diesel oil is only 16.0-16.3% by weight, and the sulfur content in gasoline products is as high as 673.4-762.9 mg/L .

Detailed ways

According to the catalyst provided by the present invention, based on the total amount of the catalyst, the content of the first zeolite is 1-50% by weight, the content of the second zeolite is 1-40% by weight, and the content of the heat-resistant inorganic oxide is 2-50% by weight. 80% by weight, the content of clay is 0-80% by weight, based on the metal oxide in the highest valence state, the content of metal components is 0.1-30% by weight. Preferably, based on the total amount of the catalyst, the content of the first zeolite is 10-50% by weight, the content of the second zeolite is 1-30% by weight, and the content of the heat-resistant inorganic oxide is 5-60% by weight , the content of clay is 5-60% by weight, and the content of the metal component is 0.5-20% by weight based on the metal oxide in the highest valence state. More preferably, based on the total amount of the catalyst, the content of the first zeolite is 10-50% by weight, the content of the second zeolite is 3-20% by weight, and the content of the heat-resistant inorganic oxide is 10-50% by weight. % by weight, the content of the clay is 15-60% by weight, based on the metal oxide in the highest valence state, the content of the metal component is 0.5-20% by weight.

The first zeolite is Y-type zeolite, and the secondary pore volume of the Y-type zeolite accounts for 20-80% of the total pore volume, preferably accounts for 25-70% of the total pore volume. The definition and measurement method of the secondary pore volume are described in detail in CN1307087A.

The Y-type zeolite whose secondary pore volume accounts for 20-80% of the total pore volume can be a commercially available Y-type zeolite that meets this condition, and can be prepared by a conventional hydrothermal calcination method. Preferably, it is prepared by the method disclosed in CN1307087A. Although Y-type zeolite with higher crystallinity (70-90%) prepared according to the method disclosed in CN1307087A is preferred, this does not mean that Y-type zeolite with lower crystallinity is not available. In fact, if the crystallinity of the Y-type zeolite is low, the purpose of the present invention can also be achieved by adding more of the Y-type zeolite.

The second zeolite is a zeolite having a molar ratio of silica to alumina of 20 or more. Zeolites having a molar ratio of silica to alumina of 20-500, more preferably 25-100 are preferred. The second zeolite can be selected from zeolites with MFI structure, zeolites with MFI structure containing phosphorus, rare earth and/or alkaline earth metals, Beta zeolite, Beta zeolite containing phosphorus, rare earth and/or alkaline earth metals, mordenite, One or more of mordenite containing phosphorus, rare earth and/or alkaline earth metal. It is preferably one or more of zeolite with MFI structure, zeolite with MFI structure containing phosphorus and/or rare earth, Beta zeolite, and Beta zeolite containing phosphorus and/or rare earth metal. Examples of the zeolite having the MFI structure include ZSM-5 zeolite, ZSM-8. Examples of zeolite with MFI structure containing phosphorus, rare earth and/or alkaline earth metal include ZSM-5 zeolite containing phosphorus, rare earth and/or alkaline earth metal, ZSM-8 zeolite containing phosphorus, rare earth and/or alkaline earth metal, disclosed in CN1194181A Phosphorus-containing zeolites with MFI structure (ZRP zeolites).

The reduced valence state means that the average valence state of the metal is zero valence or higher than zero valence and lower than its highest oxidation state. Preferably, the ratio of the average valence state of the metal to its highest valence state is 0-0.95, and more preferably, the ratio is 0.1-0.7.

The highest valence state of the metal mentioned here refers to the highest oxidation state of the metal in the metal oxide that can exist stably after sufficient oxidation. For example, the highest oxidation state of non-aluminum metals in Group IIIA of the periodic table is generally +3 (such as gallium); the highest oxidation state of IVA metals is generally +4; the highest oxidation state of VA metals is generally +5; The highest oxidation state of group IB metals is generally +2 (such as copper) or +1 (such as silver); the highest oxidation state of IIB group metals is generally +2; the highest oxidation state of VB group metals is generally +5 ;The highest oxidation state of VIB metals is generally +6; the highest oxidation state of VIIB metals is generally +4 (such as manganese) or +7 (such as rhenium); the highest oxidation state of VIII non-noble metals is generally + 3 valence (such as iron or cobalt) or +2 valence (such as nickel).

The method for determining the average valence state of the metal is as follows:

Accurately weigh about 0.4 gram of catalyst, put it into the sample cell of the TPD/R/O analysis tester, pass into the mixed gas of hydrogen and nitrogen with a hydrogen content of 5% by volume, and the flow rate of hydrogen is 20 ml/min, and the sample The pool is heated from room temperature to 1000 °C at a rate of 10 °C/min, and the catalyst in the sample pool is subjected to temperature-programmed reduction, and the TPR characteristic peaks of the metal components on the catalyst before and after reduction are measured respectively, and the TPR of the metal is calculated according to the following formula Average Valence:

β _M = β _M ′-2f(A ₁ -A)/N

Among them: β _M is the average valence state of the metal component M in the catalyst, β _M ′ is the highest valence state of the metal component M in the catalyst; A is the TPR characteristic of the metal M in the catalyst in which the metal component M exists in a reduced valence state Peak area; _A1 is the TPR characteristic peak area of metal M in the catalyst that metal component M exists with the highest oxidation state; N is the content (unit is mole) of metal component M in the catalyst; f is correction factor, its determination method As follows: Accurately weigh about 6.5 mg of CuO and put it into the sample cell of the above-mentioned TPD/R/O analysis tester. Under the above-mentioned conditions, measure the TPR characteristic peak area K ₂ where CuO is completely reduced. Calculate hydrogen consumption (mole) K ₁ , f is the ratio of hydrogen consumption to TPR characteristic peak area, ie f=K ₁ /K ₂ , and the unit of f is mole/TPR characteristic peak area.

Since the positions of the TPR characteristic peaks of each metal are different, even if the catalyst contains more than two metal components, the TPR characteristic peaks of each metal can be determined.

The metal component is selected from the group IIIA non-aluminum metals, IVA group metals, VA group metals, IB group metals, IIB group metals, VB group metals, VIB group metals, VIIB group metals, and VIII group non-noble metals in the periodic table of elements. one or several. The Group IIIA non-aluminum metals include gallium, indium, and thallium. The Group IVA metals include germanium, tin, and lead. The Group VA metals include antimony and bismuth. The group IB metals include copper and silver. The Group IIB metals include zinc and cadmium. The VB group metals include vanadium, niobium, and tantalum. The VIB group metals include chromium, molybdenum, and tungsten. The Group VIIB metals include manganese, technetium, rhenium. The Group VIII non-noble metals include iron, cobalt and nickel. The metal component is preferably one or more of gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, nickel, more preferably One or more of gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, and cobalt.

The metal component may exist in the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay at the same time, or in the mixture of the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay. Among any two, it may also be present in any one of the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay.

According to a particular embodiment of the invention, said metal component, in particular when said metal component is vanadium, nickel and/or iron, is present in a refractory inorganic oxide and/or clay.

According to another particular embodiment of the invention, said metal component, especially when said metal component is iron, is present in the first zeolite and/or in the second zeolite.

The type of the heat-resistant inorganic oxide is selected from one or more of the heat-resistant inorganic oxides used as cracking catalyst substrates and binder components, such as alumina, silica, amorphous silica-alumina, zirconia One or more of titanium oxide and boron oxide. Preferably one or more of alumina, silica, amorphous silica-alumina, zirconia, and titania. These refractory inorganic oxides are known to those skilled in the art.

The clay is selected from one or more clays used as active components of cracking catalysts, such as kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, retort, seafoam One or more of stone, attapulgite, hydrotalcite, and bentonite. A more preferred clay is kaolin. These clays are well known to those skilled in the art.

The catalyst provided by the present invention can also and preferably contain alkaline earth metals, and the alkaline earth metals can be present in the first zeolite, the second zeolite, heat-resistant inorganic oxides and clay at the same time, and can also be present in the first zeolite, Any two of the second zeolite, the heat-resistant inorganic oxide and the clay may also be present in any one of the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay. Based on the total amount of the catalyst, the content of the alkaline earth metal group is 0-5% by weight in terms of oxides. The alkaline earth metals exist in the form of alkaline earth metal compounds, such as alkaline earth metal oxides and alkaline earth metal salts. The alkaline earth metal is selected from one or more of beryllium, magnesium, calcium, strontium and barium, preferably magnesium and/or calcium.

The catalyst provided by the present invention may also contain rare earth metals, and the rare earth metals exist in the form of metals and/or compounds (such as oxides of rare earth metals, salts of rare earth metals). The rare earth metal can be present in the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay at the same time, or can be present in any of the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay. Of the two, it may also exist in any one of the first zeolite, the second zeolite, heat-resistant inorganic oxides and clays. The rare earth metal is selected from one or more of the lanthanide and actinide rare earth metals, preferably lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium , one or more of lutetium, more preferably lanthanum, cerium, lanthanum-rich mixed rare earth metals or cerium-rich mixed rare earth metals. Based on the total amount of the catalyst, the content of the rare earth metal is 0-50% by weight, preferably 0-15% by weight.

The catalyst provided by the invention may also contain phosphorus in the form of phosphorus compounds, such as phosphorus oxides and/or phosphates. The phosphorus can exist in the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay at the same time, or in any two of the first zeolite, the second zeolite, the heat-resistant inorganic oxide and the clay. Among the species, it may also exist in any one of the first zeolite, the second zeolite, heat-resistant inorganic oxides and clays. Based on the total amount of the catalyst, the phosphorus content is 0-15% by weight, preferably 0-8% by weight, based on elemental phosphorus.

In an embodiment of the present invention, if the rare earth metal and/or phosphorus is used to prepare the catalyst, the first zeolite or the second zeolite itself contains, and the content of the first zeolite or the second zeolite is The content of rare earth metals and/or phosphorus in the first zeolite or the second zeolite, phosphorus and rare earth metals are not calculated separately and are not given separately.

According to the catalyst preparation method provided by the present invention, the atmosphere containing reducing gas refers to pure reducing gas or an atmosphere containing reducing gas and inert gas.

Examples of said pure reducing gas include one or more of hydrogen, carbon monoxide and hydrocarbons containing 1-5 carbon atoms, preferably hydrogen, carbon monoxide, methane, ethane, propane, butane and various One or more of isomers, pentane and its various isomers.

The inert gas refers to a gas that does not chemically interact with the composition or the metal compound, such as one or more of Group O gases in the periodic table of elements, nitrogen, and carbon dioxide.

Examples of the atmosphere containing reducing gas and inert gas include hydrogen, carbon monoxide, a mixture of one or more of hydrocarbons containing 1-5 carbon atoms and one or more of inert gases, in refineries dry air.

In the atmosphere containing the reducing gas, the concentration of the reducing gas is not particularly limited, as long as the amount of the reducing gas used can reduce the metal. Preferably, in the reducing gas-containing atmosphere, the reducing gas content is at least 10% by volume, more preferably 50% by volume.

The contacting temperature and contacting time are sufficient to reduce the ratio of the average valence state of the metal component to its highest valence state to 0-0.95, preferably 0.1-0.7. Generally speaking, the contact temperature may be 100-900°C, preferably 400-700°C, and the contact time may be 0.1 second to 10 hours, preferably 1 second to 5 hours. The contacting may be static contacting, that is, in a closed container, an atmosphere containing a reducing gas is brought into contact with the composition. The contacting may also be dynamic contacting, ie passing the reducing gas-containing atmosphere through the bed of the composition. The contacting pressure is not limited, and it can be carried out under normal pressure, or under higher or lower than normal pressure. The amount of the atmosphere containing reducing gas is not less than 5 milliliters of reducing gas per gram of catalyst per hour, preferably not less than 10 milliliters of reducing gas per gram of catalyst per hour, more preferably 100-2000 milliliters of reducing gas per gram of catalyst per hour.

The content of each component in the composition is preferably such that the final catalyst contains, based on the total amount of the catalyst, 10-50% by weight of the first zeolite, 1-30% by weight of the second zeolite, and 5-60% by weight of the resistant Thermal inorganic oxides, 5-60% by weight of clay and 0.5-20% by weight of metal components, based on the oxide of the metal in the highest valence state. The content of each component in the composition is more preferably such that the final catalyst contains, based on the total amount of the catalyst, 10-50% by weight of the first zeolite, 3-20% by weight of the second zeolite, and 10-50% by weight The refractory inorganic oxide includes 15-60% by weight of clay and 0.5-20% by weight of metal components based on the oxide of the metal in the highest valence state.

The composition containing metal component compound, molecular sieve, heat-resistant inorganic oxide and clay can be prepared by any one or several methods described below. These methods are all conventional methods.

one of the methods

(1) a. impregnating the first zeolite and/or the second zeolite, the heat-resistant inorganic oxide, the precursor of the heat-resistant inorganic oxide and/or the clay with a solution containing the metal component compound, and then drying or not dry; b. or the solution containing the metal component compound is mixed with the first zeolite and/or the second zeolite, the refractory inorganic oxide, the precursor of the refractory inorganic oxide and/or clay, and then Drying or non-drying; c. or physically mixing said metal component compound with the first zeolite and/or the second zeolite, refractory inorganic oxide, precursor of refractory inorganic oxide and/or clay; d. or mix the solution containing the metal component compound with the first zeolite and/or the second zeolite, refractory inorganic oxide, precursor of refractory inorganic oxide and/or clay, add the metal Precipitating agent for component compounds, depositing said metal component into a first zeolite and/or a second zeolite, a refractory inorganic oxide, a precursor of a refractory inorganic oxide and/or a clay, dry or not Drying; e. or the solution containing said metal component compound is mixed with the first zeolite and/or the second zeolite, refractory inorganic oxide, precursor of refractory inorganic oxide and/or clay, will obtain The slurry is prepared into a colloid; f. or the metal component compound that is insoluble in water is mixed with the first zeolite and/or the second zeolite, a heat-resistant inorganic oxide, a precursor of a heat-resistant inorganic oxide, and/or Mix clay and deionized water, prepare the obtained slurry into a colloid, dry or not dry;

(2) The first zeolite and/or the second zeolite, the heat-resistant inorganic oxide, the precursor of the heat-resistant inorganic oxide and/or clay to be introduced into the metal component compound, or the mixture, or colloid Slurry with deionized water and the first zeolite and/or the second zeolite, the heat-resistant inorganic oxide, the precursor of the heat-resistant inorganic oxide and/or clay without metal component compounds, and prepare a solid content of 10 - 60% by weight, preferably 20-50% by weight, of slurry, drying the resulting slurry, calcined or not.

Method 2

Beat the first zeolite, the second zeolite, the heat-resistant inorganic oxide and/or the precursor of the heat-resistant inorganic oxide, clay and deionized water to prepare a solid content of 10-60% by weight, preferably 20- 50% by weight slurry, drying the resulting slurry, calcined or not, and then impregnating the dried solid with a solution containing the metal component compound, or mixing the solution of the metal component compound with the dried solid , then, dried, roasted or not.

Method three

Slurry the first zeolite, the second zeolite, the heat-resistant inorganic oxide and/or the precursor of the heat-resistant inorganic oxide, clay, deionized water and the metal component compound to prepare a solid content of 10-50 % by weight, preferably 20-50% by weight of the slurry, the resulting slurry is dried, calcined or not.

If the catalyst also contains alkaline earth metals, the above method can be used to introduce alkaline earth metals alone or simultaneously with the introduction of the above metal components, and only the alkaline earth metal compounds are used to replace the compounds of the above metal components. The alkaline earth metal may also be contained in the commercially available first zeolite and/or the second zeolite itself.

If the catalyst also contains rare earth metals and/or phosphorus, the above method can be used to introduce the rare earth metals and/or phosphorus alone or simultaneously with the introduction of the above metal components, but replace the above metal components with rare earth metal compounds and/or phosphorus compounds compounds. The rare earth metal and/or phosphorus may also be contained in the first type of zeolite and/or the second type of zeolite (such as type Y zeolite or ultrastable Y zeolite containing rare earth and/or phosphorus).

Wherein, the methods and conditions of the drying after the introduction of the metal component compound and the drying of the slurry are well known to those skilled in the art, for example, the drying methods may be air drying, oven drying, blast drying, and spray drying. The drying method of the slurry is preferably a spray drying method. The drying temperature can be from room temperature to 400°C, preferably 100-350°C. The roasting after drying the slurry and the roasting conditions after impregnating the metal compound are also well known to those skilled in the art. Generally speaking, the roasting after drying the slurry and the roasting temperature after impregnating the metal compound are both 400-700°C. The temperature is preferably 450-650°C, and the calcination time is at least 0.5 hours, preferably 0.5-100 hours, more preferably 0.5-10 hours.

The precursor of the heat-resistant inorganic oxide refers to one or several substances that can form the heat-resistant inorganic oxide during the preparation process of the cracking catalyst. Precursors such as alumina may be selected from hydrated aluminas (eg pseudo-boehmite) and/or alumina sols. The precursor of silicon oxide can be selected from one or more of silica sol, silica gel and water glass. The precursor of amorphous silica-alumina can be selected from one or more of silica-alumina sol, a mixture of silica sol and alumina sol, and silica-alumina gel. The precursors of other refractory inorganic oxides can be selected from their hydroxides, such as zirconium, titanium hydroxides, boric acid.

The metal component compound can be a water-soluble compound of the metal, or a poorly water-soluble and/or water-insoluble compound, such as Group IIIA non-aluminum metals of the Periodic Table of the Elements, Group IVA metals, VA One or more of the nitrates, chlorides, hydroxides, and oxides of Group metals, Group IB metals, Group IIB metals, VB group metals, VIB group metals, VIIB group metals, and VIII non-noble metals, especially One or more of the nitrates, chlorides, hydroxides, and oxides of gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, and cobalt.

The alkaline earth metal compound can be a water-soluble compound of an alkaline earth metal, or a poorly water-soluble and/or water-insoluble compound, such as chlorides, nitrates, hydroxides, and oxides of alkaline earth metals one or more of.

The rare earth metal compound can be a water-soluble compound of a rare earth metal, or a poorly water-soluble and/or water-insoluble compound, such as chlorides, nitrates, hydroxides, and oxides of rare earth metals. one or more of.

The phosphorus compound can be a water-soluble compound of the phosphorus, or a water-insoluble and/or water-insoluble compound, such as phosphoric acid, phosphorous acid, ammonium phosphate, alkali metal phosphate, One or more of phosphorus oxide and aluminum phosphate.

The catalyst provided by the invention can be used alone as an FCC catalyst to produce diesel and liquefied gas, and simultaneously reduce gasoline and diesel, especially the sulfur content in gasoline. The catalyst provided by the invention can also be used as a desulfurization aid mixed with various cracking catalysts to reduce gasoline and diesel oil, especially the sulfur content in gasoline. When the catalyst provided by the invention was used as a desulfurization aid, the ratio of the catalyst provided by the invention contained in the catalyst mixture was determined according to the sulfur content in the raw oil and the required sulfur content of the gasoline product. Usually, the catalyst provided by the invention The catalyst comprises at least 0.1% by weight of the catalyst mixture, preferably at least 1% by weight, more preferably at least 5% by weight, most preferably at least 10% by weight. In addition, as a cracking catalyst additive, the catalyst provided by the invention can also be mixed with other additives, such as a combustion enhancer, a sulfur transfer catalyst, an octane booster, etc., and used in combination with an existing cracking catalyst.

Regardless of whether the catalyst provided by the present invention is used as a main catalyst or an auxiliary agent, the conditions used are the conventional reaction conditions of the general hydrocarbon cracking process, such as a reaction temperature of 400-700°C, preferably 450-600°C, and a weight hourly space velocity of 10- 120 hours ^-1 , preferably 10-80 hours ^-1 , and the weight ratio of agent to oil is 1-20, preferably 3-15. It can also be used in deep catalytic cracking process or catalytic cracking process.

The catalyst provided by the invention can be used as a main catalyst for catalytic cracking of sulfur-free hydrocarbon oil, so as to improve the conversion rate of hydrocarbon oil and produce diesel oil and liquefied gas. The catalyst provided by the invention can also be used as a main catalyst or an auxiliary agent for catalytic cracking of sulfur-containing hydrocarbon oil, so as to increase the conversion rate of the hydrocarbon oil, produce diesel oil and liquefied gas, and simultaneously reduce the sulfur content in cracked products. The hydrocarbon oil is selected from petroleum and various petroleum fractions, especially petroleum and various petroleum fractions with a boiling range greater than 330°C, such as sulfur-containing or sulfur-free atmospheric residue, vacuum residue, vacuum wax oil , atmospheric gas oil, straight-run gas oil, propane light/heavy deoiling and coker gas oil, and hydrotreated atmospheric residue, vacuum residue, vacuum gas oil, one of atmospheric gas oil or several.

The following examples will further illustrate the present invention.

Unless otherwise specified in the examples, the kaolin used is produced by Suzhou Kaolin Company, and its solid content is 76% by weight; the pseudo-boehmite used is produced by Shandong Zibo 501 Factory, and its solid content is 62% by weight; the aluminum sol used is Qilu catalyst Factory produced, its Al ₂ O ₃ content is 21% by weight; the silica sol used is produced by Qilu Catalyst Factory, its SiO ₂ content is 27% by weight; all compounds are chemically pure.

The cracking activity of zeolite in the fresh cracking catalyst is very high. In actual industrial production, the catalyst is recycled. After a period of reaction of the fresh catalyst, its activity reaches a relatively stable level. Deactivation to the level corresponding to industrial balancers can be achieved by deactivating the zeolite in the catalyst through hydrothermal aging. In the following examples of the present invention, there is an aging catalyst step before reduction. This step is added for the convenience of judging the activity of the catalyst, rather than that the preparation method of the catalyst provided by the present invention needs to have this aging step. In fact, in industrial production, this aging step is unnecessary.

Example 1

This example illustrates the catalyst provided by the invention and its preparation method.

(1) 1000 grams (dry basis weight) of NaY type zeolite ( _Na2O content is 14% by weight, produced by Zhoucun Catalyst Factory of Qilu Petrochemical Company) with a unit cell constant of 2.473 nanometers and 20 liters of concentration is 5% by weight ( NH ₄ ) ₂ SO ₄ aqueous solution was ion-exchanged at 60°C for 0.5 hours, filtered, and the filter cake was washed with deionized water until there were no acid radicals, and dried at 120°C to obtain NH ₄ NaY zeolite, whose Na ₂ O content was measured to be 4.9 weight%.

900 grams (dry basis weight) of the NH ₄ NaY type zeolite prepared above were soaked in 1000 grams of silica sol (SiO Content is ₁₂ % by weight, commercial product of Beijing Changhong Chemical Plant) for 30 minutes, then dried at 120 ° C for 2 hours, An NH ₄ NaY zeolite containing 10% by weight of SiO ₂ was obtained.

800 grams (dry basis weight) of the above-prepared NH ₄ NaY zeolite containing SiO ₂ were roasted for 16 hours at 650° C. in a water vapor atmosphere, and then the product obtained was washed with deionized water equivalent to 20 times the weight of the solid, and heated at 120° C. drying to obtain Y-type zeolite A1. The composition of A1, unit cell constant, relative crystallinity and specific surface area and the percentage of secondary pore volume accounted for total pore volume are as follows (defining the crystallinity of raw material NaY type zeolite is 100%, the relative crystallinity of the zeolite that obtains is relative For the crystallinity of raw material NaY type zeolite, the measuring method of relative crystallinity is referring to "Petrochemical Analysis Method (RIPP Test Method)" PP414-415, edited by Yang Cuiding etc., Science Press, 1990; Sodium oxide, aluminum oxide and silicon oxide The content is measured by X-ray fluorescence spectrometry, the unit cell constant is measured by X-ray diffraction method, and the specific surface and pore volume are measured by low-temperature nitrogen adsorption BET method):

Zeolite number A1 unit cell constant, nanometer 2.450 relative crystallinity, % 82 specific surface area, ^m2 /g 648 total pore volume, ml/g 0.388 micropore volume, ml/g 0.273 secondary pore volume, ml/g 0.115 secondary Pore volume/total pore volume, % 30 Chemical composition, wt% Na ₂ O 4.1 _{Al 2} O ₃ 22.8 SiO ₂ 73.1

(2) Mix 34.0 kilograms of pseudo-boehmite and 170 kilograms of deionized water evenly, add 4.0 kilograms of rare earth chloride RECl _x (produced by Baotou Rare Earth Factory in Inner Mongolia, after the rare earth chloride is baked at 800 ° C for one hour The measured rare earth oxide (RE ₂ O ₃ ) content was 46% by weight, and the dry basis content of each component was La ₂ O ₃ 24.5% by weight, CeO ₂ 6.0% by weight, Pr ₂ O ₃ 6.0% by weight, Nd ₂ O ₃ 9.5% by weight), under stirring, add 4.0 kg of concentrated hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) with a concentration of 36% by volume, and the resulting mixture is heated to 70° C. and aged for 1.5 hours to obtain the aged pseudo-thin Diaspore. Based on the dry basis of the aged pseudo-boehmite, the rare earth metal content is 8.0% by weight in terms of rare earth oxides.

(3) kaolin, the above-mentioned pseudo-boehmite containing rare earth metals, aluminum sol, a magnesium chloride aqueous solution with a concentration of 10% by weight, a cobalt nitrate aqueous solution with a concentration of 30% by weight, the above-mentioned Y-type zeolite A1, and a zeolite with an MFI structure (Industrial grade is ZRP-1, based on element phosphorus, phosphorus content is 2.0% by weight, rare earth oxide content is 1.0% by weight, wherein, lanthanum oxide content is 0.53% by weight, cerium oxide content is 0.13% by weight, other rare earth oxide content of SiO 2 and Al 2 O 3 is 0.34% by weight, Na ₂ O content is less than 0.1% by weight, the molar ratio of SiO ₂ to Al ₂ O ₃ is 60 (produced by Qilu Catalyst Factory) and deionized water are mixed uniformly. The amount of deionized water was such that the resulting slurry had a solids content of 25% by weight. The amount of kaolin, pseudo-boehmite after aging, alumina sol, Y-type zeolite, ZRP-1 _zeolite , cobalt nitrate aqueous solution and magnesium chloride aqueous solution is such that the dry basis weight of kaolin, _Al2O3 , Y-type zeolite dry basis weight, ZRP The weight ratio of -1 zeolite dry basis weight (including phosphorus and rare earth contained therein), Co ₂ O ₃ , rare earth oxide (RE ₂ O ₃ , excluding rare earth contained in ZRP-1 zeolite) and MgO is 35.0 :31.0:24.0:6.0:1.0:1.5:1.5.

The resulting slurry was spray dried at 150°C, calcined at 550°C for 1 hour, and aged at 800°C with 100% steam for 4 hours. 200 grams of the obtained catalyst are loaded into a fixed-bed reduction reactor, and at a temperature of 400° C., a hydrogen gas with a flow rate of 1000 ml/min is introduced, and the hydrogen gas is contacted with the solid for 0.5 hours, and the temperature of the reactor is lowered to room temperature , unload the reduced solid to obtain the catalyst C1 provided by the present invention. The composition of catalyst C1 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 1.

The catalyst composition is obtained by calculation, and the content of the metal component is calculated as the oxide of the highest oxidation state of the metal component. Wherein, in Table 1 and the following tables, the content of ZRP-1 zeolite includes phosphorus and rare earth contained therein, and the content of said rare earth oxide does not include the content of rare earth contained in ZRP-1 zeolite.

Example 2

This example illustrates the catalyst provided by the invention and its preparation method.

The catalyst was prepared according to the method of Example 1, except that the temperature at which the solid was contacted with hydrogen was 500° C., and the contact time was 3 hours to obtain the catalyst C2 provided by the present invention. The composition of catalyst C2 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 1.

Example 3

This example illustrates the catalyst provided by the invention and its preparation method.

3.0 kg (dry basis weight) of kaolin was impregnated with 3.64 kg of 10% by weight cobalt nitrate hexahydrate aqueous solution, dried at 120°C and calcined at 600°C for 1 hour to obtain kaolin containing 2.78% by weight of Co ₂ O ₃ .

The catalyst was prepared according to the method of (3) in Example 1, except that kaolin containing 2.78% by weight of Co ₂ O ₃ was used instead of the kaolin described in Example 1, and cobalt nitrate aqueous solution was not added to obtain catalyst C3 provided by the present invention. The composition of catalyst C3 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 1.

Comparative example 1

This comparative example illustrates a reference catalyst without a metal component and its preparation.

Prepare the catalyst according to the method of Example 1, the difference is that no cobalt nitrate aqueous solution is added, there is no process in which the solid is contacted with hydrogen in a fixed-bed reactor, and kaolin, aged pseudo-boehmite, aluminum sol, Y-type The amount of zeolite A1, ZRP-1 zeolite, magnesium chloride aqueous solution makes the ratio of kaolin dry weight, Al ₂ O ₃ , Y type zeolite dry weight, ZRP-1 zeolite dry weight, RE ₂ O ₃ and the weight of MgO be 35.0 :32.0:24.0:6.0:1.5:1.5. A reference catalyst CB1 with the same content of zeolite, kaolin, RE ₂ O ₃ and MgO and no metal components was obtained. The composition of CB1 is listed in Table 1.

Comparative example 2

This comparative example illustrates a reference catalyst containing the metal component in the highest oxidation state and its preparation. .

The catalyst was prepared as in Example 1, except that there was no process of contacting the solid with hydrogen in a fixed bed reactor to obtain a reference catalyst CB2. The composition of CB2 is listed in Table 1.

Comparative example 3

This comparative example illustrates a reference catalyst containing the metal component in the highest oxidation state and its preparation.

The catalyst was prepared as in Example 3, except that the process of contacting the solid with hydrogen in a fixed-bed reactor was not carried out to obtain the reference catalyst CB3. The composition of CB3 is listed in Table 1.

Table 1 instance number 1 2 3 Comparative example 1 Comparative example 2 Comparative example 3 Catalyst number C1 C2 C3 CB1 CB2 CB3 Molecular sieve type A1/ZRP-1 A1/ZRP-1 A1/ZRP-1 A1/ZRP-1 A1/ZRP-1 A1/ZRP-1 Molecular sieve content, wt% 24.0/6.0 24.0/6.0 24.0/6.0 24.0/6.0 24.0/6.0 24.0/6.0 Types of heat-resistant inorganic oxides Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ Heat-resistant inorganic oxide content, wt% 31.0 31.0 31.0 32.0 31.0 31.0 RE ₂ O ₃ , wt% 1.5 1.5 1.5 1.5 1.5 1.5 MgO, % by weight 1.5 1.5 1.5 1.5 1.5 1.5 Clay type Kaolin Kaolin Kaolin Kaolin Kaolin Kaolin Clay content, wt% 35.0 35.0 35.0 35.0 35.0 35.0 Type of metal component co co co - co co Metal oxide content, wt% 1.0 1.0 1.0 - 1.0 1.0 Average valence state of metal components +1.5 0 +1.5 - +3 +3 The ratio of the average valence state of a metal component to its highest valence state 0.5 0 0.5 - 1 1 Distribution of metal components Evenly distributed in the catalyst Evenly distributed in the catalyst evenly distributed in the clay - Evenly distributed in the catalyst evenly distributed in the clay

Example 4

This example illustrates the catalyst provided by the invention and its preparation method.

(1) 1000 grams (dry basis weight) of NaY type zeolite ( _Na2O content is 14% by weight, produced by Zhoucun Catalyst Factory of Qilu Petrochemical Company) with a unit cell constant of 2.473 nanometers and 20 liters of concentration of 10% by weight ( NH ₄ ) ₂ SO ₄ aqueous solution was ion-exchanged at 60°C for 0.5 hours, filtered, and the filter cake was washed with deionized water until there were no acid radicals, and dried at 120°C to obtain NH ₄ NaY zeolite, whose Na ₂ O content was measured to be 3.7 weight%.

900 grams (dry basis weight) of the NH ₄ NaY type zeolite prepared above are soaked in 1000 grams of water glass (SiO ₂ content is 10% by weight, modulus 3.3, Zhoucun Catalyst Factory product) for 30 minutes, then at 120 ℃ of drying After 2 hours, a silicon-impregnated _NH4NaY zeolite containing 8.5 wt% _SiO2 was obtained.

800 grams (dry basis weight) of the NH ₄ NaY zeolite containing SiO ₂ prepared above were roasted in a water vapor atmosphere at 700°C for 8 hours, and then the product obtained was washed with deionized water equivalent to 20 times that of the solid, and dried at 120°C , to obtain Y-type zeolite A2. The composition of A2, unit cell constant, relative crystallinity and specific surface area and the percentage of secondary pore volume to total pore volume are as follows: Zeolite number A2 unit cell constant, nanometer 2.448 relative crystallinity, % 80 specific surface area, ^m2 /g 656 total pore volume, ml/g 0.384 micropore volume, ml/g 0.253 secondary pore volume, ml/g 0.131 secondary Pore volume/total pore volume, % 34 Chemical composition, wt% Na ₂ O 3.3 Al ₂ O ₃ 21.2 SiO ₂ 75.5

(2) prepare aging pseudo-boehmite by the method of (2) in example 1, the difference is that the consumption of rare earth chloride is 6.5 kilograms, take the dry base of the pseudo-boehmite after aging as benchmark, take rare earth Based on oxides, the content of rare earth metals in the aged pseudo-boehmite is 12.4% by weight.

(3) impregnating 3.0 kilograms (dry weight) of kaolin with 3.15 kilograms of zinc nitrate aqueous solutions with a concentration of 7.0% by weight, drying at 120°C, and roasting at 600°C for 1 hour to obtain kaolin containing ZnO 3.1% by weight.

The catalyst is prepared according to the method of (3) in Example 1, except that the above-mentioned ZnO-containing kaolin is used to replace the kaolin described in Example 1, and the cobalt nitrate aqueous solution is not added, and the pseudo-thin water after the aging described in the present example (2) is used Bauxite replaces the aged pseudo-boehmite described in Example 1, replaces Y-type zeolite A1 with Y-type zeolite A2; described ZnO-containing kaolin, aged pseudo-boehmite, aluminum sol, Y-type zeolite A2 , ZRP-1 zeolite and magnesium chloride aqueous solution make the ratio of kaolin dry basis weight, Al ₂ O ₃ , Y type zeolite A2 dry basis weight, ZRP-1 zeolite dry basis weight, ZnO, RE ₂ O ₃ and the weight of MgO to be 25.0: 16.2: 45.0: 10.0: 0.8: 1.0: 2.0; the reducing atmosphere is a mixed gas of hydrogen and carbon monoxide with a hydrogen content of 50% by volume and a carbon monoxide content of 50% by volume, and the flow rate of the mixed gas is 2000 ml/min. The temperature of contacting with the mixed gas is 800° C., and the contacting time is 3 hours to obtain the catalyst C4 provided by the present invention. The composition of catalyst C4 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 2.

Example 5

This example illustrates the catalyst provided by the invention and its preparation method.

(1) prepare aging pseudo-boehmite by the method of (2) in example 1, the difference is that the consumption of rare earth chloride is 6.5 kilograms, take the dry base of the pseudo-boehmite after aging as benchmark, take rare earth Based on oxides, the content of rare earth metals in the aged pseudo-boehmite is 12.4% by weight.

(2) Impregnate 3.0 kg (dry weight) of kaolin with 2.90 kg of ferric nitrate aqueous solution having a concentration of 10% by weight, dry at 120° C., and roast at 600° C. for 2 hours to obtain kaolin containing 3.1% by weight of Fe ₂ O ₃ .

Catalyst is prepared by the method of (3) in embodiment 1, and difference is with above-mentioned containing Fe ₂ O ₃ kaolin replaces the kaolin described in embodiment 1, does not add cobalt nitrate aqueous solution, with the described aging of this example (1) Pseudo-boehmite replaces the pseudo-boehmite after the aging described in example 1, replaces Y- _type zeolite A1 with Y-type zeolite A2, uses ZSM-5 zeolite (SiO ₂ and Al ₂ O mol ratio is 62, Na ₂ O content is 0.08% by weight, produced by Qilu Catalyst Factory) to replace ZRP-1 zeolite; the kaolin containing Fe ₂ O ₃ , pseudo-boehmite after aging, aluminum sol, Y-type zeolite A2, ZSM-5 zeolite And the consumption of magnesium chloride aqueous solution makes kaolin dry basis weight, Al ₂ O ₃ , Y type zeolite A2 dry basis weight, ZSM-5 zeolite dry basis weight, Fe ₂ O ₃ , RE ₂ O ₃ and the ratio of the weight of MgO is 25.0: 16.2: 45.0: 10.0: 0.8: 1.0: 2.0; the reducing atmosphere is a mixed gas of hydrogen and carbon monoxide with a hydrogen content of 50% by volume and a carbon monoxide content of 50% by volume, and the flow of the mixed gas is 1200 ml/min. The gas contact temperature is 600° C., and the contact time is 0.5 hour to obtain the catalyst C5 provided by the present invention. The composition of catalyst C5 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 2.

Example 6

This example illustrates the catalyst provided by the invention and its preparation method.

(1) 1000 grams (dry basis weight) of NaY type zeolite ( _Na2O content is 14% by weight, produced by Zhoucun Catalyst Factory of Qilu Petrochemical Company) with a unit cell constant of 2.473 nanometers and 20 liters of concentration is 5% by weight ( NH ₄ ) ₂ SO ₄ aqueous solution was ion-exchanged at 60°C for 0.5 hours, filtered, and the filter cake was washed with deionized water until there were no acid radicals, and dried at 120°C to obtain NH ₄ NaY zeolite, whose Na ₂ O content was measured to be 4.9 weight%.

Soak 900 g (dry basis weight) of the above-prepared NH ₄ NaY zeolite in 2000 ml of 0.5 M ammonium fluorosilicate solution for 30 minutes, and then dry at 120° C. for 2 hours to obtain NH ₄ containing 5.6% by weight of SiO ₂ NaY zeolite.

800 grams (dry basis weight) of the SiO _- containing NH ₄ NaY zeolite prepared above were roasted in a steam atmosphere at 750°C for 4 hours, then washed with deionized water equivalent to 20 times the weight of the solid, and baked at 120°C. dry to obtain Y-type zeolite A3. The composition of A3, unit cell constant, relative crystallinity and specific surface area and the percentage of secondary pore volume to total pore volume are as follows: Zeolite number A3 unit cell constant, nanometer 2.449 relative crystallinity, % 78 specific surface area, ^m2 /g 626 total pore volume, ml/g 0.372 micropore volume, ml/g 0.234 secondary pore volume, ml/g 0.138 secondary Pore volume/total pore volume, % 37 Chemical composition, wt% Na ₂ O 3.8 Al ₂ O ₃ 22.7 SiO ₂ 73.5

(2) prepare aging pseudo-boehmite by the method of (2) in example 1, the difference is that the consumption of rare earth chloride is 9.0 kilograms, take the dry base of the pseudo-boehmite after aging as benchmark, take rare earth In terms of oxides, the content of rare earth metals in the aged pseudo-boehmite is 16.4% by weight.

(3) immerse 2.925 kilograms (dry basis weight) of kaolin and 0.075 kilograms of titanium dioxide mixtures with 3.36 kilograms of concentration of copper nitrate aqueous solution of 20 weight percent, 120 ℃ of oven dry, 600 ℃ of roasting 2 hours, obtain containing CuO 8.68 weight percent, TiO ₂ 2.3% by weight kaolin.

Catalyst is prepared by the method of (3) in embodiment 1, difference is with above-mentioned containing CuO and TiO The kaolin that replaces embodiment ₁ described kaolin, do not add cobalt nitrate and magnesium chloride aqueous solution, aging described in present example (2) Pseudo-boehmite after replacement replaces the pseudo-boehmite after aging described in example 1, replaces Y-type zeolite A1 with Y-type zeolite A3; Described containing CuO and _TiO Kaolin, aged pseudo-boehmite The amount of bauxite, aluminum sol, Y-type zeolite A3, and ZRP-1 zeolite is such that the dry basis weight of kaolin, TiO ₂ , Al ₂ O ₃ , Y-type zeolite A3 dry basis weight, ZRP-1 zeolite dry basis weight, CuO and RE ₂ O The ratio of the weight is 39.0: 1.0: 24.0: 25: 5: 3.8: 2.2; The reducing atmosphere is a mixture of hydrogen _and carbon monoxide with a hydrogen content of 50% by volume and a carbon monoxide content of 50% by volume, and the flow rate of the mixture is 1000 ml/min, the temperature at which the solid is contacted with the mixed gas is 400° C., and the contact time is 0.5 hour to obtain the catalyst C6 provided by the present invention. The composition of catalyst C6 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 2.

Example 7

This example illustrates the catalyst provided by the invention and its preparation method.

1000 grams (dry basis weight) of ultra-stable Y-type zeolite (Na ₂ O content is 0.8% by weight, produced by Zhoucun Catalyst Factory of Qilu Petrochemical Company) with a unit cell constant of 2.443 nm and 20 liters of Na ₂ with a concentration of 5% by weight The SO ₄ aqueous solution was ion-exchanged at 60° C. for 0.5 hours, filtered, and the filter cake was washed with deionized water until there were no acid radicals, and dried at 120° C. to obtain HNaY zeolite, whose Na ₂ O content was measured to be 4.5% by weight.

900 g (dry basis weight) of the above-prepared HNaY zeolite was soaked in 100 g of _SiO content of 5.0% by weight in dimethyl silicon aqueous solution for 30 minutes, then dried at 120°C for 2 hours to obtain 4.5% by weight _of SiO HNaY zeolites.

With 800 grams (dry basis weight) above-mentioned preparation containing SiO _The HNaY zeolite roasted 10 hours in 600 ℃ of water vapor atmospheres, then use the product that is equivalent to 20 times of solid weight to wash the product that obtains, 120 ℃ of oven dry, Y-type zeolite A4 was obtained. The composition of A4, unit cell constant, relative crystallinity and specific surface area and the percentage of secondary pore volume to total pore volume are as follows: Zeolite number A4 unit cell constant, nanometer 2.438 relative crystallinity, % 75 specific surface area, ^m2 /g 588 total pore volume, ml/g 0.354 micropore volume, ml/g 0.168 secondary pore volume, ml/g 0.186 secondary Pore volume/total pore volume, % 53 Chemical composition, wt% Na ₂ O 4.0 Al ₂ O ₃ 19.8 SiO ₂ 76.2

(2) Prepare aged pseudo-boehmite according to the method of (2) in Example 1, except that no rare earth chloride is added to obtain aged pseudo-boehmite.

(3) Impregnate 3.0 kg (dry weight) of kaolin with 3.2 kg of manganese nitrate aqueous solution with a concentration of 5.0% by weight, dry at 120° C., and roast at 550° C. for 2 hours to obtain kaolin containing 2.63% by weight of MnO ₂ .

Prepare catalyst by the method for (3) in embodiment 1, difference is with above-mentioned containing MnO Kaolin replaces the kaolin described in embodiment ₁ , does not add cobalt nitrate aqueous solution, with the pseudo thin film after aging described in present example (2) Boehmite replaces the aged pseudo-boehmite described in example ₁ , replaces A1 with Y-type zeolite A4; The consumption of ZRP-1 zeolite and magnesium chloride aqueous solution makes kaolin dry basis weight, Al ₂ O ₃ , Y type zeolite A4 dry basis weight, ZRP-1 zeolite dry basis weight MnO ₂ and the ratio of the weight of MgO is 37.0: 25.5: 28.0: 7.0: 1.0: 1.5; the reducing atmosphere is a mixture of hydrogen and propane with a hydrogen content of 80% by volume and a propane content of 20% by volume, the flow of the mixed gas is 1500 ml/min, and the temperature at which the solid contacts with the mixed gas is 500 °C, the contact time was 1 hour, and the catalyst C7 provided by the present invention was obtained. The composition of catalyst C7 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 2.

Table 2 instance number 4 5 6 7 Catalyst number C4 C5 C6 C7 Molecular sieve type A2/ZRP-1 A2/ZSM-5 A3/ZRP-1 A4/ZRP-1 Molecular sieve content, wt% 45.0/10.0 45.0/10.0 25.0/5.0 28.0/7.0 Types of heat-resistant inorganic oxides Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ /TiO2 Al ₂ O ₃ Heat-resistant inorganic oxide content, wt% 16.2 16.2 24.0/1.0 25.5 RE ₂ O ₃ , wt% 1.0 1.0 2.2 0 MgO, % by weight 2.0 2.0 0 1.5 Clay type Kaolin Kaolin Kaolin Kaolin Clay content, wt% 25.0 25.0 39.0 37.0 Type of metal component Zn Fe Cu mn Metal oxide content, wt% 0.8 0.8 3.8 1.0 Average valence state of metal components 1.4 2.0 0.6 1.5 The ratio of the average valence state of a metal component to its highest valence state 0.70 0.67 0.3 0.38 Distribution of metal components evenly distributed in the clay evenly distributed in the clay Distributed in clay and refractory inorganic oxides evenly distributed in the clay

Example 8

This example illustrates the catalyst provided by the invention and its preparation method.

(1) prepare aging pseudo-boehmite by the method of (2) in example 1, the difference is that the consumption of rare earth chloride is 6.5 kilograms, take the dry base of the pseudo-boehmite after aging as benchmark, take rare earth Based on oxides, the content of rare earth metals in the aged pseudo-boehmite is 12.4% by weight.

(2) impregnating 3.0 kg (dry basis weight) of kaolin and 0.5 kg (dry basis weight) of diatoms with 3.22 kilograms of ammonium molybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .6H ₂ O) aqueous solution with a concentration of 5.0% by weight The mixture of soil (solid content is 85.0% by weight, produced by Huali diatomite factory in Shengzhou City, Zhejiang Province), dried at 120°C, then impregnated with 2.25 kg of 2.0% by weight silver nitrate aqueous solution, dried at 120°C, and dried at 600°C Calcined for 2 hours, a mixture of kaolin and diatomaceous earth containing 3.58% by weight of MoO ₃ and 0.90% by weight of Ag ₂ O was obtained.

The catalyst is prepared according to the method of (3) in Example 1, except that the above-mentioned kaolin containing MoO ₃ and Ag ₂ O is used to replace the kaolin described in Example 1, without adding cobalt nitrate aqueous solution, and using the aging described in the present example (1) The pseudo-boehmite after replacing the aged pseudo-boehmite described in Example 1; the kaolin containing MoO ₃ and Ag ₂ O, the aged pseudo-boehmite, aluminum sol, Y-type zeolite A1, The dosage of ZRP-1 zeolite and magnesium chloride aqueous solution is to make kaolin dry basis weight, Al ₂ O ₃ , Y-type zeolite A1 dry basis weight, ZRP-1 zeolite dry basis weight, MoO ₃ , Ag ₂ O, RE ₂ O ₃ and MgO The weight ratio is 32.0: 19.0: 35.0: 10.0: 1.2: 0.3: 1.0: 1.5; the reducing atmosphere is a mixture of nitrogen and hydrogen with a hydrogen content of 50% by volume, and the flow rate of the mixed gas is 2500 ml/min. The contact temperature of the mixed gas is 650° C., and the contact time is 1 hour to obtain the catalyst C8 provided by the present invention. The composition of catalyst C8 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 3.

Example 9

This example illustrates the catalyst provided by the invention and its preparation method.

(1) prepare aging pseudo-boehmite by the method of (2) in example 1, the difference is that the consumption of rare earth chloride is 5.4 kilograms, take the dry basis of the pseudo-boehmite after aging as benchmark, take rare earth In terms of oxides, the content of rare earth metals in the aged pseudo-boehmite is 10.5% by weight.

(2) Under stirring, the mixture of 3.0 kg (dry basis weight) of kaolin and 0.08 kg of magnesia is impregnated with 2.96 kg of concentration of ammonium metavanadate (NH ₄ VO ₃ ) aqueous solution of 2.0% by weight, and dried at 120°C to obtain The slurry was calcined at 550° C. for 2 hours to obtain kaolin containing 2.6% by weight of MgO and 1.5% by weight of V ₂ O ₅ .

The catalyst is prepared according to the method of (3) in Example 1, except that the above-mentioned kaolin containing MgO and V ₂ O ₅ is used to replace the kaolin described in Example 1, without adding cobalt nitrate aqueous solution and magnesium chloride aqueous solution, using the present example (2) The aged pseudo-boehmite replaces the aged pseudo-boehmite described in Example 1, and replaces A1 with Y-type zeolite A2; the kaolin containing MgO and V ₂ O ₅ , the aged pseudo-boehmite The amount of boehmite, aluminum sol, Y-type zeolite A2, and ZRP-1 zeolite is such that the dry basis weight of kaolin, magnesium oxide, Al ₂ O ₃ , Y-type zeolite A2 dry basis weight, and ZRP-1 zeolite dry basis weight V ₂ The weight ratio of O ₅ and RE ₂ O ₃ is 39.0: 1.0: 23.0: 28.0: 7.0: 0.6: 1.4; the temperature at which the solid is in contact with hydrogen is 550°C, the flow rate of hydrogen is 1000 ml/min, and the contact time is After 1 hour, the catalyst C9 provided by the present invention was obtained. The composition of catalyst C9 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 3.

Example 10

This example illustrates the catalyst provided by the invention and its preparation method.

Use 2.74 kilograms of concentrations to impregnate the mixture of 3.0 kilograms (dry basis weight) of kaolin and 0.86 kilograms (dry basis weight) of pseudo-boehmite in 40% by weight gallium chloride aqueous solution, dry at 120°C, and roast at 600°C for 2 hours to obtain Mixture of kaolin and alumina containing _{Ga2O3 13.1} % by weight.

Mix the mixture of kaolin and alumina containing _Ga2O3 , silica sol, calcium chloride aqueous solution and deionized water, then add Y-type zeolite A3 and ZSM-5 zeolite (specifications are the same as _in Example 5), mix uniformly, The consumption of deionized water makes _the solid content of the obtained slurry be 25% _by weight, and the consumption of the mixture of kaolin and alumina, silica sol, Y type zeolite A3, ZSM-5 zeolite and calcium chloride aqueous solution The ratio of kaolin dry basis weight, alumina, silicon oxide, Y-type zeolite A3 dry basis weight, ZSM-5 zeolite dry basis weight, Ga ₂ O ₃ and the weight of CaO is 35.0: 10: 11.7: 28: 7: 6.8: 1.5.

The resulting slurry was spray dried at 150°C, calcined at 550°C for 2 hours, and aged at 800°C with 100% steam for 8 hours. 200 grams of the obtained solid is packed into a fixed-bed reduction reactor, and at a temperature of 600° C., a hydrogen gas with a flow rate of 3000 ml/min is introduced, and the hydrogen gas is contacted with the solid for 2 hours, so that the temperature of the reactor is lowered to room temperature , unload the reduced solid to obtain the catalyst C10 provided by the invention. The composition of catalyst C10 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 3.

Example 11

This example illustrates the catalyst provided by the invention and its preparation method.

3.1 kilograms of concentrations are 6.0% by weight of stannous chloride SnCl ₂ aqueous solution, 0.6 kilograms (dry basis weight) of silica sol and 3.0 kilograms (dry basis weight) of kaolin are mixed uniformly, 120 ℃ of oven dry, 550 ℃ of roasting 3 hours, obtain Mixture of kaolin and silica containing 4.0% by weight of _SnO2 .

Containing _SnO The mixture of kaolin and silicon oxide, aluminum sol, and deionized water are mixed homogeneously, then add Y type zeolite A4 and ZSM-5 zeolite (specification is the same as embodiment 5), mix homogeneously, the consumption of deionized water makes The solid content of the slurry that arrives is 25% by weight, and the consumption that contains _SnO The mixture of kaolin and silicon oxide, aluminum sol, Y type zeolite A4, ZSM-5 zeolite makes kaolin dry basis weight, aluminum oxide, silicon oxide, Y type The weight ratio of zeolite A4 dry basis weight, ZSM-5 zeolite dry basis weight and SnO ₂ is 40.0:20.0:8.0:25:5:2.0. The resulting slurry was spray dried at 150°C, calcined at 550°C for 2 hours, and aged at 800°C with 100% steam for 8 hours.

200 g of the obtained solid is packed into a fixed-bed reduction reactor, and at a temperature of 650° C., a hydrogen gas with a flow rate of 1000 ml/min is introduced, and the hydrogen gas is contacted with the solid for 1 hour, and the temperature of the reactor is lowered to room temperature , unload the reduced solid to obtain the catalyst C11 provided by the invention. The composition of catalyst C11 and the type, distribution, average valence state and the ratio of the average valence state to its highest valence state are listed in Table 3.

table 3 instance number 8 9 10 11 Catalyst number C8 C9 C10 C11 Molecular sieve type A1/ZRP-1 A2/ZRP-1 A3/ZSM-5 A4/ZSM-5 Molecular sieve content, wt% 35.0/10.0 28.0/7.0 28.0/7.0 25.0/5.0 Types of heat-resistant inorganic oxides Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ /SiO ₂ Al ₂ O ₃ /SiO ₂ Heat-resistant inorganic oxide content, wt% 19.0 23.0 10/11.7 20/8.0 RE ₂ O ₃ , wt% 1.0 1.4 0 0 MgO, % by weight 1.5 1.0 0 0 CaO,,wt% 0 0 1.5 0 Clay type Kaolin + diatomaceous earth Kaolin Kaolin Kaolin Clay content, wt% 32.0 39.0 35.0 40.0 Type of metal component Mo/Ag V Ga sn Metal oxide content, wt% 1.2/0.3 0.6 6.8 2.0 Average valence state of metal components 3.0/0 2.3 1.5 2.2 The ratio of the average valence state of a metal component to its highest valence state 0.5/0 0.46 0.5 0.55 Distribution of metal components evenly distributed in the clay Evenly distributed in clay and inorganic oxides Distributed in clay and inorganic oxides Distributed in clay and inorganic oxides

Example 12-22

The following examples illustrate the catalytic performance of the catalysts provided by the present invention.

On a small fixed-bed reaction device, catalysts C1-C11 provided by the present invention were used to catalytically crack sulfur-containing vacuum gas oils with a boiling range of 329-550°C listed in Table 4, and the catalyst loading was 4.0g. The reaction conditions and reaction results are listed in Tables 5-7. The sulfur content in the cracked product was determined by gas chromatography-atomic emission spectrometry on a HP 6890GC-G2350A AED gas chromatography-atomic emission spectrometer.

Wherein, the ratio of agent to oil refers to the weight ratio of the catalyst to the feedstock oil.

Comparative example 4-6

The following comparative examples illustrate the catalytic performance of the reference catalysts.

The same raw oil was subjected to catalytic cracking according to the method of Example 12, except that the catalysts used were reference catalysts CB1, CB2 and CB3 respectively. The reaction conditions and results are listed in Table 5.

Table 4 Raw oil name atmospheric residue Decompression wax oil Density (20℃), g/cm3 0.8906 0.9154 Viscosity, mm2/s 50℃ - 34.14 100°C 24.84 6.96 Asphaltenes, % by weight 0.8 0.0 Kang's carbon residue, wt% 4.3 0.18 S, weight % 0.13 2.0 Distillation range, ℃ IBP 282 329 10% 370 378 50% 553 436 90% - 501 95% - 518 FBP - 550

table 5 instance number 12 13 14 Comparative example 4 Comparative example 5 Comparative example 6 Catalyst number C1 C2 C3 CB1 CB2 CB3 Reaction temperature, °C 500 500 500 500 500 500 Weight hourly space velocity, hour ^-1 16 16 16 16 16 16 Agent to oil ratio 6.0 6.0 6.0 6.0 6.0 6.0 Conversion, % by weight 77.1 76.4 76.8 75.9 75.4 74.8 Product yield, weight % dry gas 1.8 1.7 1.9 1.5 1.4 1.4 liquefied gas 18.7 18.6 19.1 16.6 15.7 15.9 gasoline 50.8 50.4 50.0 52.3 52.6 51.8 diesel fuel 16.8 16.9 16.5 16.3 16.0 16.1 heavy oil 6.1 6.7 6.7 7.8 8.6 9.1 Coke 5.8 5.7 5.8 5.5 5.7 5.7 Sulfur content in gasoline, mg/L 424.3 486.5 414.7 762.9 691.7 673.4

The result explanation of table 5, is identical with zeolite content, does not contain the catalyst of metal component and each component content is identical, just described metal component is compared with the catalyzer that oxidation state exists, the catalyst provided by the present invention has higher cracking Higher activity, higher diesel and liquefied gas yield, and higher desulfurization activity.

Table 6 instance number 15 16 17 18 Catalyst number C4 C5 C6 C7 Reaction temperature, °C 480 480 500 500 Weight hourly space velocity, hour ^-1 16 16 16 16 Agent to oil ratio 5 5 6 6 Conversion, % by weight 80.9 80.4 75.3 78.3 Product yield, weight % dry gas 2.5 2.4 1.6 2.6 liquefied gas 23.4 22.8 18.5 20.3 gasoline 48.5 48.8 49.8 49.4 diesel fuel 13.3 13.6 17.6 15.1 heavy oil 5.8 6.0 7.1 6.6 coke 6.5 6.4 5.4 6.0 Sulfur content in gasoline, mg/L 536.9 558.4 436.4 451.5

Table 7 instance number 19 20 twenty one twenty two Catalyst number C8 C9 C10 C11 Reaction temperature, °C 500 500 520 520 Weight hourly space velocity, hour ^-1 16 16 20 20 Agent to oil ratio 5.0 5.0 5.0 5.0 Conversion, % by weight 79.5 78.9 75.3 71.5 Product yield, weight % dry gas 2.9 2.7 2.0 1.6 liquefied gas 20.2 19.8 18.1 17.2 gasoline 50.0 50.2 49.6 47.6 diesel fuel 14.2 14.6 16.9 19.3 heavy oil 6.3 6.5 7.8 9.2 coke 6.4 6.2 5.6 5.1 Sulfur content in gasoline, mg/L 426.3 418.2 527.6 494.0

Instances 23-25

The following examples illustrate the catalytic performance of the catalysts provided by the present invention.

On the small-scale fixed fluidized bed reactor, adopt catalyst C1, C4 and C11 that the present invention provides, to the mixed oil that the atmospheric residue content shown in Table 4 is 20% by weight and vacuum wax oil content is 80% by weight. Catalytic cracking, catalyst loading 90 grams. The reaction conditions and reaction results are listed in Table 8.

Table 8 instance number twenty three twenty four 25 Catalyst number C1 C4 C11 Reaction temperature, °C 520 500 500 Weight hourly space velocity, hour ^-1 16 16 16 Agent to oil ratio 5.0 5.0 6.0 Conversion, % by weight 75.3 77.9 70.9 Product yield, weight % gas 18.8 21.6 18.1 gasoline 50.5 49.4 47.3 diesel fuel 17.4 15.4 18.8 heavy oil 7.3 6.7 10.3 Coke 6.0 6.9 5.5 Sulfur content in gasoline, mg/L 420.8 524.1 482.6

Claims (31)

1. A hydrocarbon cracking catalyst containing molecular sieves, the catalyst contains molecular sieves, heat-resistant inorganic oxides and a metal component, with or without clay, characterized in that the molecular sieves are the first zeolite and the second A mixture of two zeolites, the first zeolite is Y-type zeolite, the secondary pore volume of the Y-type zeolite accounts for 20-80% of the total pore volume, the second zeolite is the molar ratio of silicon oxide to aluminum oxide is more than 20 Zeolite, based on the total amount of catalyst, the content of the first zeolite is 1-50% by weight, the content of the second zeolite is 1-40% by weight, the content of heat-resistant inorganic oxide is 2-80% by weight, clay The content is 0-80% by weight, based on the metal oxide in the highest valence state, the content of the metal component is 0.1-30% by weight, and the metal component basically exists in a reduced valence state, which is selected from the element One or more of Group IIIA non-aluminum metals, IVA group metals, VA group metals, IB group metals, IIB group metals, VB group metals, VIB group metals, VIIB group metals, and VIII group non-noble metals. 2. The catalyst according to claim 1, characterized in that, based on the total catalyst amount, the content of the first zeolite is 10-50% by weight, the content of the second zeolite is 1-30% by weight, heat-resistant The content of the inorganic oxide is 5-60% by weight, the content of the clay is 5-60% by weight, and based on the metal oxide in the highest valence state, the content of the metal component is 0.5-20% by weight. 3. The catalyst according to claim 2, characterized in that, based on the total catalyst amount, the content of the first zeolite is 10-50% by weight, the content of the second zeolite is 3-20% by weight, heat-resistant The content of the inorganic oxide is 10-50% by weight, the content of the clay is 15-60% by weight, and based on the metal oxide in the highest valence state, the content of the metal component is 0.5-20% by weight. 4. The catalyst according to claim 1, characterized in that the secondary pore volume of the Y-type zeolite accounts for 25-70% of the total pore volume. 5. The catalyst according to claim 1 or 4, characterized in that the relative crystallinity of the Y-type zeolite is 70-90%. 6. The catalyst according to claim 1, characterized in that the second zeolite is a zeolite with a molar ratio of silicon oxide to aluminum oxide of 20-500. 7. Catalyst according to claim 1 or 6, is characterized in that, described second zeolite is selected from the zeolite with MFI structure, the zeolite with MFI structure containing phosphorus, rare earth and/or alkaline earth metal, Beta zeolite, One or more of Beta zeolite and mordenite containing phosphorus, rare earth and/or alkaline earth metal, and mordenite containing phosphorus, rare earth and/or alkaline earth metal. 8. The catalyst according to claim 1, characterized in that the ratio of the average valence state of the metal to its highest valence state is 0-0.95. 9. The catalyst according to claim 8, characterized in that the ratio of the average valence state of the metal to its highest valence state is 0.1-0.7. 10. The catalyst according to claim 1, 8 or 9, wherein the metal is selected from gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, One or more of manganese, iron, cobalt and nickel. 11. The catalyst according to claim 10, wherein the metal is selected from one or more of gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, and cobalt. 12. The catalyst according to claim 1, wherein the heat-resistant inorganic oxide is selected from one or more of alumina, silicon oxide, amorphous silica-alumina, zirconia, titanium oxide, and boron oxide . 13. The catalyst according to claim 1, wherein the clay is selected from the group consisting of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, retortite, sepiolite, attapulgite One or more of rod stone, hydrotalcite and bentonite. 14. The catalyst according to claim 1, characterized in that the catalyst further contains alkaline earth metal, based on the total amount of the catalyst, the content of the alkaline earth metal is 0-5% by weight. 15. The catalyst according to claim 14, characterized in that the alkaline earth metal is magnesium and/or calcium. 16. The catalyst according to claim 1, characterized in that the catalyst further contains a rare earth metal, based on the total amount of the catalyst, the content of the rare earth metal is 0-50% by weight. 17. The catalyst according to claim 16, characterized in that, based on the total amount of the catalyst, the content of the rare earth metal is 0-15% by weight in terms of oxides. 18. The catalyst according to claim 16 or 17, characterized in that the rare earth metal is selected from lanthanum, cerium, lanthanum-rich misch metal or cerium-rich misch metal. 19. The catalyst according to claim 1, characterized in that the catalyst further contains phosphorus, based on the total amount of the catalyst, in terms of elemental phosphorus, and the content of said phosphorus is 0-15% by weight. 20. The catalyst according to claim 18, characterized in that, based on the total amount of the catalyst, the phosphorus content is 0-8% by weight in terms of elemental phosphorus. 21. The preparation method of catalyst according to claim 1, characterized in that, the method comprises contacting the composition containing metal component compound, molecular sieve, heat-resistant inorganic oxide and clay with an atmosphere containing reducing gas, the contacting temperature and contacting The time is sufficient to make the average valence state of the metal component lower than its highest oxidation state, the molecular sieve is a mixture of a first zeolite and a second zeolite, the first zeolite is a Y-type zeolite, and the Y-type The secondary pore volume of zeolite accounts for 20-80% of the total pore volume. The second zeolite is a zeolite with a molar ratio of silicon oxide to aluminum oxide of more than 20, and the metal component is selected from Group IIIA non-aluminum metals of the periodic table of elements. , IVA group metals, VA group metals, IB group metals, IIB group metals, VB group metals, VIB group metals, VIIB group metals, VIII group non-noble metals, the content of each component in the composition is The final catalyst contains, based on the total amount of the catalyst, 1-50% by weight of the first zeolite, 1-40% by weight of the second zeolite, 2-80% by weight of heat-resistant inorganic oxide, 0-80% by weight Based on the clay and the oxide of the metal in the highest valence state, 0.1-30% by weight of the metal component. 22. The method according to claim 21, characterized in that the atmosphere containing reducing gas refers to pure reducing gas or an atmosphere containing reducing gas and inert gas. 23. The method according to claim 22, characterized in that the pure reducing gas is selected from one or more of hydrogen, carbon monoxide and hydrocarbons containing 1-5 carbon atoms. 24. The method according to claim 22, characterized in that, the atmosphere containing reducing gas and inert gas is selected from one or more of hydrogen, carbon monoxide, hydrocarbons containing 1-5 carbon atoms and inert One or more mixtures of gases, dry gas in refineries. 25. The method of claim 21, wherein the contacting temperature and contacting time are sufficient to reduce the ratio of the average valence state of the metal component to its highest valence state to 0-0.95. 26. The method of claim 25, wherein the contacting temperature and contacting time are sufficient to reduce the ratio of the average valence state of the metal component to its highest valence state to 0.1-0.7. 27. The method according to claim 21, characterized in that the contacting temperature is 100-900°C, and the contacting time is 0.1 second to 10 hours. 28. The method according to claim 21, characterized in that the amount of the reducing gas-containing atmosphere is not less than 5 milliliters of reducing gas per gram of catalyst per hour. 29. The method according to claim 21, characterized in that, the content of each component in the composition makes the final catalyst contain, based on the catalyst total amount, 10-50% by weight of the first zeolite, 1-30% by weight % of the second zeolite, 5-60% by weight of refractory inorganic oxides, 5-60% by weight of clay and 0.5-20% by weight of metal components based on the oxide of the highest valence metal. 30. The method according to claim 29, characterized in that, the content of each component in the composition makes the final catalyst contain, based on the catalyst total amount, 10-50% by weight of the first zeolite, 3-20% by weight % of the second zeolite, 10-50% by weight of heat-resistant inorganic oxide, 15-60% by weight of clay and 0.5-20% by weight of metal component based on the oxide of the highest valence metal. 31. A hydrocarbon cracking catalyst containing molecular sieves, the catalyst contains molecular sieves, heat-resistant inorganic oxides and a metal component, with or without clay, characterized in that the catalyst adopts any one of claims 21-30 prepared by the method described in the item.