CN1311906C - Cracking catalyst for hydrocarbon and preparation method - Google Patents

Abstract

A hydrocarbon cracking catalyst, the catalyst contains alumina and molecular sieves, with or without clay, characterized in that the alumina is η-alumina and/or χ-alumina, or η-alumina and/or Or a mixture of χ-alumina and γ-alumina, the catalyst also contains phosphorus and alkaline earth metals, based on the total amount of the catalyst, the content of η-alumina and/or χ-alumina is 0.5-50% by weight, γ - the content of aluminum oxide is 0-50% by weight, the content of molecular _sieve is 10-70% by weight, the content of clay is 0-75% by weight, calculated as _P2O5 , the content of phosphorus is 0.1-4% by weight, according to In terms of oxides, the content of alkaline earth metal is 0.1-4% by weight, and the molecular sieve is Y-type zeolite. The catalyst has a strong ability to resist heavy metal pollution, and the catalyst is used to catalyze hydrocarbon oil, and among cracking products, the quality of gasoline is improved.

Description

A kind of hydrocarbon cracking catalyst and preparation method thereof

technical field

The invention relates to a hydrocarbon cracking catalyst and a preparation method thereof.

Background technique

The heavy and inferior tendency of catalytic cracking feedstock oil is becoming more and more serious. Metal pollutants such as nickel, vanadium, and iron contained in the feedstock will deposit on the surface of the catalyst, causing catalyst poisoning and deactivation, thereby deteriorating the selectivity and lightening the catalyst. The yield of quality oil decreased, while the yield of hydrogen and coke increased. This requires the cracking catalyst and cracking process to have a strong ability to resist heavy metal pollution, so as to achieve the purpose of producing more light oil (gasoline and diesel).

For FCC gasoline, olefins, aromatics and isoparaffins are the main contributors to the octane number. Due to environmental protection requirements, it is necessary to reduce the olefin content in FCC gasoline. In order to make up for the loss of gasoline octane value caused by the decrease of olefin content, it is necessary to increase the content of isoparaffins and aromatics in gasoline, which requires the development of gasoline with lower olefin content and higher content of aromatics and isoparaffins. Hydrocarbon cracking catalyst and cracking process.

CN1055301C discloses a kind of cracking catalyst of prolific isomeric olefins and gasoline, the catalyst is composed of 5-70% by weight of pseudo-boehmite and aluminum sol according to the weight ratio of 1:9 to 9:1 composite aluminum-based aluminum The binder is composed of 5-65% by weight of clay and 23-50% by weight _of molecular sieve, the molecular sieve is 15-82% by weight of Y-type zeolite and the remaining phosphorus content (calculated as _P2O5 ) is 0 - 10% by weight of a mixture of rare earth-containing pentasilite and/or HZSM-5 zeolite.

CN1072201A discloses a hydrocarbon conversion catalyst for producing high-octane gasoline and olefins. The catalyst consists of 10-40% by weight of ZSM-5, three zeolites of REY and high-silicon Y and a balance of fully synthetic carriers or containing 10 - Semi-synthetic carrier composition of 40% by weight of silicon and/or aluminum binder, in which ZSM-5 fraction zeolite is present in an amount of 3-50% by weight, and REY and high-silica Y zeolites in an amount of 12-75% by weight each.

CN1085825A discloses a catalyst for producing high-octane gasoline, propylene, and butene. The catalyst consists of 10-40% by weight of ZRP zeolite, three zeolites of REY and high-silicon Y and the balance of fully synthetic carriers or The semi-synthetic carrier composition contains 10-40% by weight of silicon and/or aluminum binder, wherein the content of ZRP zeolite is 3-50% by weight, and the content of REY and high-silica Y zeolite is 12-75% by weight each.

CN1325940A discloses a phosphorus-containing hydrocarbon cracking catalyst, which is composed of 10-60% by weight of Y-type zeolite or Y-type zeolite and MFI structure zeolite and/or Beta zeolite, 0-75% by weight of clay, 10-60% by weight The composition consists of two kinds of alumina by weight, 0.1-7.0% by weight of phosphorus in terms of P ₂ O ₅ and 0-20% by weight of rare earth in terms of RE ₂ O ₃ . The two aluminas are derived from pseudo-boehmite and alumina sol respectively. The catalyst has high conversion capacity of heavy oil, and the content of olefins in the product gasoline is low.

CN1354224A discloses a catalytic cracking catalyst for producing isoparaffin gasoline, propylene and isobutane, the catalyst is composed of 0-70% by weight of clay, 5-90% by weight of inorganic oxide and 1-50% by weight of Molecular sieves, wherein the molecular sieves are (1) 20-75% by weight of high-silicon Y-type zeolite with a silicon-aluminum ratio of 5-15 and a rare earth content of 8-20% by weight based on RE ₂ O ₃ and (2) 20- 75% by weight of high silicon Y-type zeolite with a silicon-aluminum ratio of _16-50 , a rare earth content of 2-7% by weight based on _RE2O3 and (3) 1-50% by weight of beta zeolite or mordenite or ZRP zeolite mixture.

Alumina is a common component of cracking catalysts. In the prior art, alumina mostly comes from alumina monohydrate and alumina sol, wherein alumina monohydrate includes boehmite and pseudoboehmite, and during the roasting process of catalyst preparation, boehmite, pseudoboehmite Both the alumina stone and the alumina sol are transformed into γ-alumina, and the alumina contained in the catalyst described in the above-mentioned prior art is γ-alumina.

Alumina can also be derived from alumina trihydrate. Alumina trihydrate includes α-alumina trihydrate, β-alumina trihydrate (or called gibbsite) and gibbsite. During the catalyst preparation process, α-alumina trihydrate is transformed into χ-alumina, β-alumina trihydrate is transformed into η-alumina. Nozohydrite only exists in nature and cannot be obtained through artificial synthesis. CN1388214 discloses a preparation method of a fluidized cracking catalyst, the method is to dry the cracking catalyst component mixture containing clay, alumina and molecular sieves, the catalyst contains 1.5-55% by weight from β-alumina trihydrate of alumina. The catalyst has strong heavy oil cracking activity and good light oil selectivity, but it cannot reduce the olefin content in gasoline, and the ability to resist heavy metal pollution is not enough.

Contents of the invention

The purpose of the present invention is to provide a new catalyst for hydrocarbon cracking, which has a strong ability to resist heavy metal pollution. When the catalyst is used to catalyze hydrocarbon oil, the content of olefins in gasoline is relatively low in cracked products.

In the prior art, although there are examples of introducing alumina trihydrate in the preparation of cracking catalysts, the purpose is only to improve the cracking ability of the catalyst, but has no effect on the quality of gasoline in the cracking products. The inventors of the present invention unexpectedly found that even for feedstock oils with high heavy metal content such as nickel, vanadium, iron, etc., aluminum oxide formed from alumina trihydrate, phosphorus and alkaline earth metals, especially β-trihydrate, are simultaneously introduced into the cracking catalyst. The alumina formed by alumina hydrate, namely η-alumina, phosphorus and alkaline earth metals, has produced a special synergistic effect. While producing more light oil, it can also improve the quality of gasoline, and it is also effective in catalytic cracking of nickel, vanadium, iron The catalyst still has high cracking activity when the hydrocarbon oil with high content of heavy metals is used.

The catalyst provided by the invention contains alumina and molecular sieves, with or without clay, wherein the alumina is η-alumina and/or χ-alumina, or η-alumina and/or χ-alumina combined with A mixture of γ-alumina, the catalyst also contains phosphorus and alkaline earth metals, based on the total amount of the catalyst, the content of η-alumina and/or χ-alumina is 0.5-50% by weight, and the content of γ-alumina is 0-50% by weight, 10-70% by weight _of molecular sieve, 0-75% by weight of sticky, calculated as _P2O5 , 0.1-4% by weight of phosphorus, calculated as oxide, alkaline earth The metal content is 0.1-4% by weight, and the molecular sieve is Y-type zeolite.

The preparation method of the catalyst provided by the invention comprises drying and roasting the slurry containing aluminum compound, molecular sieve and water, containing or not containing clay, wherein the aluminum compound is capable of forming η-alumina and/or χ-alumina Aluminum compound, or can form the mixture of the aluminum compound of η-alumina and/or χ-alumina and the aluminum compound that can form γ-alumina, also add the compound of phosphorus and alkaline earth metal before roasting, each component The amount used makes the final catalyst contain, based on the total amount of the catalyst, 0.5-50% by weight of η-alumina and/or χ-alumina, 0-50% by weight of γ-alumina, and 10-70% by weight of molecular sieves , 0-75% by weight of clay, calculated as P ₂ O ₅ , 0.1-4% by weight of phosphorus, calculated as oxides, 0.1-4% by weight of alkaline earth metal, and the molecular sieve is Y-type zeolite.

The catalyst provided by the invention has strong ability to resist heavy metal pollution, and the catalyst is used to catalyze hydrocarbon oil, and the quality of gasoline among cracking products is improved. Shown in, when the catalyst catalytic cracking hydrocarbon oil provided by the present invention after being polluted with heavy metals such as nickel, vanadium and iron, catalyst still has higher cracking activity and higher light oil yield, has lower olefin in gasoline content and higher aromatic and isoparaffin content.

Detailed ways

According to the catalyst provided by the present invention, preferably, the content of η-alumina and/or χ-alumina is 5-25% by weight, the content of γ-alumina is 0-40% by weight, and the content of molecular sieve is 20-25%. 50% by weight, the content of clay is 0-60% by weight, the content of phosphorus is 0.2-3% by weight based on P ₂ O ₅ , and the content of alkaline earth metal is 0.2-2.5% by weight based on oxides.

Wherein, the molecular screening is from Y-type zeolite, such as one of HY zeolite, Y-type zeolite containing phosphorus, iron and/or rare earth, ultra-stable Y zeolite, ultra-stable Y zeolite containing phosphorus, iron and/or rare earth or several, preferably one or more of phosphorus, iron and/or rare earth-containing Y-type zeolite, ultra-stable Y zeolite, phosphorus, iron and/or rare-earth-containing ultra-stable Y zeolite.

The alkaline earth metal is selected from one or more of beryllium, magnesium, calcium, strontium and barium, preferably one or more of magnesium, calcium and barium.

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. More preferably, the clay is one or more of kaolin, montmorillonite, diatomite, retort clay, sepiolite, and attapulgite. These clays are well known to those skilled in the art.

According to the preparation method of the catalyst provided by the invention, the aluminum compound is an aluminum compound capable of forming η-alumina and/or χ-alumina, or an aluminum compound capable of forming η-alumina and/or χ-alumina and mixtures of aluminum compounds capable of forming gamma-alumina.

The aluminum compound that can form η-alumina and/or χ-alumina can be any aluminum compound that can form η-alumina and/or χ-alumina in the catalyst preparation process, preferably α-trihydrate Alumina and/or β-alumina trihydrate, more preferably β-alumina trihydrate.

The aluminum compound capable of forming γ-alumina may be any aluminum compound capable of forming γ-alumina during the catalyst preparation process, preferably boehmite, pseudoboehmite and/or aluminum sol.

The phosphorus and alkaline earth metal compound can be added in any step before roasting, as can be added to the aluminum-containing compound, molecular sieve and water, containing or not in the slurry of clay, or the aluminum-containing compound, molecular sieve and water, containing Or dry the clay-free slurry, then introduce phosphorus and alkaline earth metal compounds step by step or together by impregnation method, and then roast. In the catalyst of the present invention, the phosphorus content does not include the phosphorus originally contained in the molecular sieve.

The phosphorus compound includes various phosphorus compounds, such as one or more of phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymeric phosphoric acid, polymeric phosphate, metaphosphoric acid, metaphosphate species, preferably phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, hexameta One or several kinds of potassium phosphate. More preferably, it is one or more of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate.

The alkaline earth metal compound includes various soluble alkaline earth metal compounds, such as beryllium chloride, magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, calcium nitrate, calcium acetate, strontium chloride, strontium nitrate, strontium acetate, barium chloride , barium nitrate, barium acetate, preferably one or more of magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, calcium nitrate, calcium acetate, barium chloride, barium nitrate, barium acetate .

The amount of each component is such that the final catalyst contains, based on the total amount of the catalyst, 0.5-50% by weight of η-alumina and/or χ-alumina, 0-50% by weight of γ-alumina, 10-70 Molecular sieve in weight %, clay in 0-75 weight %, phosphorus in 0.1-4 weight % in P ₂ O ₅ , alkaline earth metal in 0.1-4 weight % in oxide. Preferably, the components are used in amounts such that the final catalyst contains 5-25% by weight of η-alumina and/or χ-alumina, 0-40% by weight of γ-alumina, and 20-50% by weight of molecular sieves , 0-60% by weight of clay, 0.2-3% by weight of phosphorus in terms of P ₂ O ₅ , and 0.2-2.5% by weight of alkaline earth metals in terms of oxides.

The drying and roasting conditions are conventional cracking catalyst drying and roasting conditions, such as the drying temperature is room temperature-200 ° C, preferably 80-180 ° C, the roasting temperature is greater than 200 to 750 ° C, preferably 300-600 ° C °C, the firing time is at least 0.1 hour, preferably 0.1-10 hours, more preferably 0.3-4 hours. The drying method can adopt various existing drying methods, such as drying, air drying, spray drying, preferably drying or spray drying.

The catalyst provided by the invention is suitable for catalytic cracking of petroleum and its various fractions, especially for petroleum with high content of heavy metals such as nickel, vanadium and iron, and petroleum fractions with a boiling point greater than 330°C, such as atmospheric residue, One or more of vacuum residue, vacuum gas oil, atmospheric gas oil, straight-run gas oil, propane light/heavy deoiling and coker gas oil are subjected to catalytic cracking to produce high-quality gasoline.

The use conditions of the catalyst provided by the present invention are conventional cracking reaction conditions. Generally speaking, the cracking conditions include that the reaction temperature is 350-700° C., preferably 400-650° C., the catalyst-to-oil ratio (the weight ratio of the catalyst to the hydrocarbon oil ) is 1-20, preferably 2-15.

The following examples will further illustrate the present invention.

In the example, the alumina content of the β-alumina trihydrate used is 64% by weight (produced by Shandong Aluminum Industry Research Institute); the alumina content of pseudo-boehmite is 62% by weight (produced by Shandong Aluminum Corporation); The alumina content of the sol is 21.6% by weight (produced by Qilu Catalyst Factory); the solid content of kaolin is 76% by weight (produced by China Kaolin Company); the solid content of montmorillonite is 80% by weight (produced by Zhongxiang County Iron Mine Factory in Hubei) The compound containing phosphorus is chemically pure; the compound containing alkaline earth metal is chemically pure; REY zeolite is a kind of Y-type zeolite containing rare earth (the content of rare earth oxide is 18.5% by weight, wherein, La ₂ O ₃ accounts for rare earth oxide 53.2% by weight of rare earth oxides, CeO ₂ accounts for 13.0% by weight of rare earth oxides, Pr ₆ O ₁₁ accounts for 13.0% by weight of rare earth oxides, Nd ₂ O ₃ accounts for 20.8% by weight of rare earth oxides, Na ₂ O content is 1.6% by weight , the silicon-aluminum ratio is 5.4, produced by Qilu Catalyst Factory); DASY _0.0 zeolite is a kind of ultra-stable Y zeolite ( _Na2O content is 1.0% by weight, and the silicon-aluminum ratio is 6.8, produced by Qilu Catalyst Factory); DASY _2.0 zeolite is a A rare earth-containing ultrastable Y zeolite (the content of rare earth oxides is 1.8% by weight, wherein La ₂ O ₃ accounts for 53.2% by weight of rare earth oxides, CeO ₂ accounts for 13.0% by weight of rare earth oxides, Pr ₆ O ₁₁ accounts for 13.0% by weight of the rare earth oxide, _Nd2O3 accounts for 20.8% by weight of the rare earth oxide, _Na2O content is 1.2% by _weight , and the silicon-aluminum ratio is 6.8, produced by Qilu Catalyst Factory); DM-4 zeolite is a kind of Ultrastable Y zeolite of rare earth (the content of rare earth oxide is 3.4% by weight, wherein, La ₂ O ₃ accounts for 53.2% by weight of rare earth oxide, CeO ₂ accounts for 13.0% by weight of rare earth oxide, Pr ₆ O ₁₁ accounts for rare earth oxide 13.0% by weight of rare earth oxides, Nd ₂ O ₃ accounts for 20.8% by weight of rare earth oxides, Na ₂ O content is 2.1% by weight, and the silicon-aluminum ratio is 6.2 (produced by Qilu Catalyst Factory). The above-mentioned silicon-aluminum ratio refers to the molar ratio of silicon oxide to aluminum oxide.

Example 1-6

The following examples illustrate the catalysts provided by the invention and their preparation.

Mix β-alumina trihydrate or β-alumina trihydrate with pseudo-boehmite, molecular sieves, phosphorus compounds and water (sometimes clay) for slurry, and spray-dry the obtained slurry to form a diameter of 40-150 microns particles and calcined to obtain catalysts C ₁ -C ₆ provided by the invention. Wherein, the catalyst was prepared according to the method of Example 6, and the pseudo-boehmite described in Example 5 was replaced with aluminum sol to obtain catalyst C ₆ . The amount of β-alumina trihydrate and pseudo-boehmite, the type and amount of clay, the type and amount of molecular sieve, the type and amount of phosphorus compound and alkaline earth metal compound are listed in Table 1-5 respectively. The spray drying temperature, calcination temperature and time are listed in Table 6. The compositions of catalysts C ₁ -C ₆ are listed in Table 7.

Comparative example 1

This comparative example illustrates a reference catalyst free of phosphorus and alkaline earth metals and its preparation.

The catalyst was prepared according to the method of Example 1, except that phosphorus and alkaline earth metal compounds were not added, and the amount of clay was different to obtain a reference catalyst CB ₁ . The amount of β-alumina trihydrate and pseudo-boehmite, the type and amount of clay, and the type and amount of molecular sieve are listed in Table 1-3 respectively. The spray drying temperature, calcination temperature and time are listed in Table 6. The composition of reference catalyst CB ₁ is listed in Table 7.

Comparative example 2

This comparative example illustrates a reference catalyst without χ or η-alumina and its preparation.

The catalyst was prepared according to the method of Example 1, except that pseudo-boehmite was used instead of β-alumina trihydrate to obtain a reference catalyst CB ₂ . The amount of pseudo-boehmite, the type and amount of clay, the type and amount of molecular sieve, the type and amount of phosphorus and alkaline earth metal compounds are listed in Table 1-5 respectively. The spray drying temperature, calcination temperature and time are listed in Table 6. The composition of reference catalyst CB ₂ is listed in Table 7.

Table 1

Instance number   Dosage of β-alumina trihydrate, kg   Dosage of pseudo-boehmite/alumina sol, kg 1 34.4 - Comparative example 1 34.4 - Comparative example 2 - 35.5/0 2 31.3 25.8/0 3 39.1 54.8/0 4 15.6 29.0/0 5 23.4 29.0/0 6 23.4 0/83.3

Table 2

Instance number Types of molecular sieves Molecular sieve dosage, kg 1 DASY _0.0 +REY 20+5 Comparative example 1 DASY _0.0 +REY 20+5 Comparative example 2 DASY _0.0 +REY 20+5 2 DASY _2.0 48 3 DASY _0.0 +REY 26.6+12 4 REY 20 5 DM-4 30 6 DM-4 30

table 3

Instance number Clay type Amount of clay, kg 1 Kaolin 67.2 Comparative example 1 Kaolin 69.7 Comparative example 2 Kaolin 67.2 2 Kaolin 16.8 3 - 4 Montmorillonite 63.4 5 Kaolin 47.0 6 Kaolin 47.0

Table 4

Instance number Types of Phosphorus Compounds Phosphorus compound dosage, kg 1   Diammonium hydrogen phosphate 1.3 Comparative example 1 - - Comparative example 2   Diammonium hydrogen phosphate 1.3 2 Hexametaphosphate 2.2 3 Ammonium phosphate 4.2 4 Ammonium phosphate 0.7 5   Ammonium dihydrogen phosphate 0.8 6   Ammonium dihydrogen phosphate 0.8

table 5

Instance number Types of Alkaline Earth Metal Compounds Amount of alkaline earth metal compound, kg 1 Magnesium chloride hexahydrate 6.1 Comparative example 1 - - Comparative example 2 Magnesium chloride hexahydrate 6.1 2 Magnesium Sulfate Heptahydrate 10.5 3 Calcium nitrate 1.1 4 Calcium acetate monohydrate 3.1 5 Barium acetate monohydrate 1.4 6 Barium acetate monohydrate 1.4

Table 6

Instance number Drying temperature, ℃ Calcination temperature, ℃ Roasting time, hours 1 110 500 1 Comparative example 1 110 500 1 Comparative example 2 110 500 1 2 120 350 3.5 3 120 600 0.5 4 120 450 0.8 5 160 550 1.5 6 90 550 1.5

Table 7

instance number Catalyst number η-alumina content, wt% γ-alumina content, wt% Molecular sieve content, wt% Clay content, wt% P ₂ O ₅ content, wt% Alkaline earth metal oxides type Content, wt% 1 C ₁ 22.0 0 25.0 51.1 0.7 Magnesium 1.2 Comparative example 1 CB ₁ 22.0 0 25.0 53.0 0 0 Comparative example 2 CB ₂ 0 22.0 25.0 51.1 0.7 Magnesium 1.2 2 C ₂ 20.0 16.0 48.0 12.8 1.5 Magnesium 1.7 3 C ₃ 25.0 34.0 38.6 0 2.0 calcium 0.4 4 C ₄ 10.0 18.0 20.0 50.7 0.3 calcium 1.0 5 C ₅ 15.0 18.0 30.0 35.7 0.5 barium 0.8 6 C ₆ 15.0 18.0 30.0 35.7 0.5 Barium 0.8

Example 7-12

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

Contaminate the catalysts C ₁ -C ₆ with nickel, vanadium, and iron respectively, that is, impregnate the kerosene solution containing nickel naphthenate and vanadium naphthenate for 1 hour, dry at 120°C, and then impregnate the catalyst with ferric chloride aqueous solution for 1 hour , dried at 120°C, calcined at 550°C for 4 hours, and finally aged at 800°C with 100% steam for 8 hours to contaminate the catalyst with 4000ppm of nickel, 1500ppm of vanadium and 3000ppm of iron. On a small-scale fluidized bed reaction device, catalytic cracking was carried out on the raw material oil shown in Table 8 with the above-mentioned polluted catalysts C ₁ -C ₆ , and the loading amount of the catalyst was 90 grams. The reaction conditions and reaction results are listed in Table 9.

Among them, conversion rate = dry gas yield + liquefied gas yield + gasoline yield + coke yield; light oil = gasoline yield + diesel yield. Gasoline refers to the fraction with a distillation range of C ₅ -221°C, diesel oil refers to the fraction with a distillation range of 221-343°C, liquefied gas refers to the fraction from C ₃ to C ₄ , and dry gas refers to the fraction from H ₂ to C ₂ .

Comparative example 3-4

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

The catalyst is polluted by the method of example 7, and under the same conditions, the same stock oil is carried out catalytic cracking, and difference is that used catalyst is the reference catalyst CB1 and CB2 that comparative example 1 and comparative example 2 prepare respectively, reaction Conditions and reaction results are listed in Table 9.

Table 8

Raw oil density (20°C), g/ ^cm3 carbon residue, % by weight Refraction (70°C) Viscosity (80°C), ^mm2 /s Viscosity (100°C), ^mm2 /s Freezing point, °C Aniline point, °C   Atmospheric residual oil 0.89775.141.488423.6113.724497.7 Elemental composition, weight % CHSN 86.8912.770.130.21   Four components, % by weight Saturated aromatic hydrocarbon colloid asphaltenes 62.723.012.71.6  Distillation range, °C initial boiling point/5% 10%/30% 50%/60% 283/350374/432477/511 Characteristic factor 12.3

Table 9

instance number 7 Comparative example 3 Comparative example 4 8 9 10 11 12 Catalyst number C ₁ CB ₁ CB ₂ C ₂ C ₃ C ₄ C ₅ C ₆ Reaction temperature, ℃ 510 510 510 460 530 490 500 500 Agent oil ratio 5.0 5.0 5.0 6.0 3.5 4.5 5.5 5.5 Weight hourly space velocity, hour ^-1 26.0 26.0 26.0 30.0 28.0 24.0 24.0 24.0 Conversion rate, % by weight 71.5 68.4 66.7 77.8 74.9 72.4 73.3 72.8 Light oil, % by weight 63.0 59.0 57.1 66.2 64.7 64.2 65.8 65.5 Product composition, wt% dry gas 2.1 1.4 1.3 1.7 1.9 1.0 1.5 1.2 Liquefied gas 15.9 14.2 13.2 16.3 15.8 16.1 16.0 16.5 gasoline 48.8 45.2 44.0 53.5 51.2 49.5 50.6 50.0 diesel fuel 14.2 13.8 13.1 12.7 13.5 14.7 15.2 15.5 Coke 4.7 7.6 8.2 6.3 6.0 5.8 5.2 5.1 unconverted heavy oil 14.3 17.8 20.2 9.5 11.6 12.9 11.5 11.7 Gasoline composition, weight % olefins aromatics isoparaffins 32.527.224.4 35.625.423.8 36.723.223.5 27.330.426.1 29.227.427.0 31.629.323.4 29.728.627.2 30.327.926.5

As can be seen from the results of Table 9, the same stock oil is carried out to catalytic cracking, compared with using the reference catalyst, although using the catalyst provided by the present invention pollutes higher levels of heavy metal impurities, the conversion rate and light oil yield All of them have been greatly improved, and the content of olefins in gasoline has been significantly reduced, and the content of aromatics and isoparaffins in gasoline has been increased.

Claims (11)

1. A hydrocarbon cracking catalyst, the catalyst contains alumina and molecular sieves, with or without clay, characterized in that, the alumina is η-alumina and/or χ-alumina, or η-alumina And/or a mixture of χ-alumina and γ-alumina, the catalyst also contains phosphorus and alkaline earth metals, based on the total amount of the catalyst, the content of η-alumina and/or χ-alumina is 0.5-50% by weight , the content of γ-alumina is 0-50% by weight, the content _of molecular sieve is 10-70% by weight, the content of clay is 0-75% by weight, and the content of phosphorus is 0.1-4% by weight based on _P2O5 , based on oxides, the content of alkaline earth metal is 0.1-4% by weight, and the molecular sieve is Y-type zeolite. 2. catalyzer according to claim 1 is characterized in that, the content of η-alumina and/or χ-alumina is 5-25% by weight, the content of γ-alumina is 0-40% by weight, the content of molecular sieve The content is 20-50% by weight, the content of clay is 0-60% by _weight , the content of phosphorus is 0.2-3% by _weight , and the content of alkaline earth metal is 0.2-2.5% by weight. . 3. The catalyst according to claim 1 or 2, characterized in that, said molecule is selected from HY zeolite, Y-type zeolite containing phosphorus, iron and/or rare earth, ultrastable Y zeolite, containing phosphorus, iron and/or One or more rare earth ultrastable Y zeolites. 4. Catalyst according to claim 3, is characterized in that, described molecule is selected from Y type zeolite, ultrastable Y zeolite, phosphorus, iron and/or rare earth containing phosphorus, iron and/or rare earth ultrastable Y One or several types of zeolites. 5. The catalyst according to claim 1, characterized in that the alkaline earth metal is selected from one or more of magnesium, calcium and barium. 6. The catalyst according to claim 1 or 2, characterized in that, the clay is selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite , attapulgite, hydrotalcite, bentonite in one or more. 7. the preparation method of claim 1 catalyst, this method comprises will contain aluminum compound, molecular sieve and water, contain or do not contain the slurry drying of clay and roast, it is characterized in that, described aluminum compound can form η-alumina and/or Or aluminum compounds of χ-alumina, or a mixture of aluminum compounds capable of forming η-alumina and/or χ-alumina and aluminum compounds capable of forming γ-alumina, with addition of phosphorus and alkaline earth metals before firing Compounds, the amount of each component is such that the final catalyst contains, based on the total amount of the catalyst, 0.5-50% by weight of η-alumina and/or χ-alumina, 0-50% by weight of γ-alumina, 10 - 70% by weight of molecular sieves, 0-75% by weight of clay, calculated as _P2O5 , _0.1-4 % by weight of phosphorus, calculated as oxides, 0.1-4% by weight of alkaline earth metals, said molecular sieve is Y type Zeolite. 8. The method according to claim 7, characterized in that, the aluminum compound capable of forming η-alumina and/or χ-alumina is α-alumina trihydrate and/or β-alumina trihydrate; The aluminum compound capable of forming γ-alumina is boehmite, pseudoboehmite and/or aluminum sol. 9. The method according to claim 7, wherein the phosphorus compound is selected from the group consisting of phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymeric phosphoric acid, polymeric phosphate, metaphosphoric acid, One or more of metaphosphates. 10. The method according to claim 9, wherein the phosphorus compound is selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium tripolyphosphate , One or more of sodium hexametaphosphate. 11. The method according to claim 7, wherein the alkaline earth metal compound is selected from magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, calcium nitrate, calcium acetate, barium chloride, barium nitrate, barium acetate one or more of.