CN1142019C - P-contained cracking catalyst for hydrocarbons and its preparing process - Google Patents

Abstract

The present invention relates to a phosphorus-containing hydrocarbon cracking catalyst prepared from 10 to 60 wt% of Y-type molecular sieve or 10 to 60 wt% of Y-type molecular sieve and molecular sieve in an MFI structure and/or beta molecular sieve, 0 to 75 wt% of clay, 10 to 60 wt% of two kinds of aluminum oxide, 0.1 to 7.0 wt% of phosphorus (measured by P2O5) and 0 to 20 wt% of rare earth (measured by RE2O3). The catalyst is obtained by mixing a molecular sieve treated with a phosphorus-containing solution with the clay and a dialuminium binding agent after the molecular sieve treated with the phosphorus-containing solution is mixed with or not mixed with a molecular sieve not treated with a phosphorus-containing solution and by treating the mixture with a phosphorus containing solution after the mixture is calcined at the temperature of 500DEG C or dried in a spraying mode. The catalyst can reduce the content of olefins in a gasoline fraction of products to 20 to 26 wt%.

Description

A phosphorus-containing hydrocarbon cracking catalyst and its preparation

The invention relates to a phosphorus-containing hydrocarbon cracking catalyst and a preparation method thereof, in particular to a phosphorus-containing molecular sieve hydrocarbon cracking catalyst and a preparation method thereof for reducing the olefin content in product gasoline fractions.

Since the mid-1970s, countries around the world have gradually adopted fluid catalytic cracking (FCC) catalysts containing ultra-stable Y molecular sieves (USY) to increase the octane number of catalytic cracked gasoline. This is because USY has the characteristics of low acid center density. It reduces the hydrogen transfer reaction in the FCC process and increases the olefin content in the gasoline fraction, thereby increasing the gasoline octane number, mainly the research octane number. However, as a relatively active hydrocarbon, olefin not only volatilizes into the atmosphere, but also undergoes a photochemical reaction to generate ozone, which seriously pollutes the environment, and its existence will affect the stability of gasoline and the use of engines. Therefore, countries are paying more and more attention to the content of olefins in gasoline, and the gasoline standards of many countries have restricted the content of olefins in gasoline.

More than 80% of my country's gasoline blending components are FCC gasoline, and FCC gasoline has a high olefin content, which is the main reason for the high olefin content in commercial gasoline in my country. Therefore, reducing the olefin content in my country's FCC gasoline fraction is an important and realistic way to reduce the olefin content in my country's commercial gasoline.

In recent years, people have adopted the method of introducing phosphorus into the cracking catalyst to improve the anti-wear strength, activity, selectivity and hydrothermal stability of the catalyst. These methods can basically be divided into three categories:

The first type: the molecular sieve, clay and/or the precursor of high-temperature-resistant inorganic oxide are mixed evenly, and after spray molding, the catalyst is made by post-treatment with an aqueous solution of a phosphorus compound. Such as CN1062750A and CN1062157A. Or use dihydrogen phosphate ions, dihydrogen phosphite ions or ammonium salts to treat the Y-type molecular sieve catalyst made by in-situ conversion of clay to improve its catalytic activity. Such as USP4454241, USP4465780 and USP4504382.

The second type: treat the substrate with phosphorus-containing compounds or use phosphorus-containing compounds as all or part of the substrate, and then add active components to make catalysts. In USP4,584,091, it is reported that alumina is pretreated with phosphorus-containing compounds, and then the phosphorus-containing alumina is mixed with white clay, USY and silica-alumina sol to prepare a catalyst. In USP4873211, it is reported that the specific surface is 50-300 m ² /g aluminum phosphate as the substrate, and the specific surface is 200-1000 m ² /g Y-type molecular sieve added cracking catalyst. However, the cracking catalyst matrix in USP5151394 contains 0.1-5% by weight of boron phosphate.

The third category: treat molecular sieves with phosphorus-containing compounds or directly add silicoaluminophosphate molecular sieves as active components or a part of active components, and then add substrates to make catalysts. As reported in EP300500, at least one silicoaluminophosphate molecular sieve is combined with 0-99% by weight of an inorganic oxide matrix to make a cracking catalyst for the production of high-octane gasoline. The method disclosed in EP397183 is to treat NaY after ammonium exchange with phosphoric acid or its ammonium salt phosphorus-containing compound aqueous solution to obtain a Y-type molecular sieve containing 0.1-4% by weight of phosphorus, and then obtain P-USY through hydrothermal treatment, and then combine with resistant High-temperature inorganic oxide and clay are slurried and spray-dried to prepare the catalyst. The agent has better gasoline selectivity. In USP5110776, it is reported that various molecular sieves (including X, Y, USY, REX, REY, RE-USY, ZSM-5, ZSM-22, etc.) are treated with a phosphate solution, and then mixed with the matrix precursor without drying After beating, it is spray-dried to make a catalyst. The agent has good anti-wear performance and improved gasoline octane number. In WO9421378, 0.5-4% by weight phosphoric acid solution is used to modify molecular sieves such as USY at 20-100° C., supplemented with a kaolin matrix to make a catalyst, which can reduce dry gas and coke. In USP5378670, the exchanged molecular sieves, especially the USY molecular sieves, are sequentially treated with a phosphorus-containing compound, hydrothermally treated, and again treated with a phosphorus-containing compound to obtain a phosphorus-modified molecular sieve. The molecular sieve can improve the cracking activity of the catalyst, gasoline selectivity and reduce the generation of dry gas and coke.

In summary, the purpose of phosphorus modification of catalysts in the prior art is to improve the selectivity and octane number of product gasoline, the hydrothermal stability and anti-wear strength of catalysts, and to improve coke selectivity.

So far, there is no report on the modification of molecular sieves and catalysts with phosphorus to reduce the content of olefins in gasoline.

The object of the present invention is exactly to provide a kind of catalytic cracking catalyst and preparation method thereof that can reduce olefin content in the FCC gasoline fraction on the basis of above-mentioned prior art, and have good activity and selectivity phosphorus-containing molecular sieve type.

The catalyst provided by the invention is composed of 10-60% by weight of Y-type molecular sieve or Y-type molecular sieve and MFI structure molecular sieve and/or β molecular sieve, 0-75% by weight of clay, 10-60% by weight of two kinds of alumina, and 0.1-7.0 wt. % phosphorus as P ₂ O ₅ and 0-20 wt. % rare earth as RE ₂ O ₃ .

Wherein said Y-shaped molecule is selected from one or more mixtures of HY, REY, REHY, USY, REUSY and REDASY. The rare earth content of the rare earth-containing Y-type molecular sieve is 0.5-20% by weight calculated as RE ₂ O ₃ .

The molecular sieve of the MFI structure is selected from ZSM-5 or one or more molecular sieves belonging to the same MFI structure, as disclosed in CN1052290A, CN1058382A, CN1147420A, and CN1194181A.

When multiple molecular sieves are used in the catalyst, the weight ratio of molecular sieves with MFI structure to Y-type molecular sieves should be 0.025-1, preferably 0.1-0.5; the weight ratio of β-type molecular sieves to Y-type molecular sieves should be 0.025-0.8.

The clay mentioned above is the clay commonly used in cracking catalyst substrates, such as kaolin, halloysite, montmorillonite, bentonite and the like.

The two aluminas are a mixture of aluminas derived from pseudoboehmite and alumina sol, respectively. The alumina from pseudo-boehmite accounts for 6-40%, preferably 15-25%, of the weight of the catalyst; the alumina from aluminum sol accounts for 4-20%, preferably 6-12%, of the weight of the catalyst. The pseudo-boehmite may contain 0-40% by weight of rare earth based on the pseudo-boehmite dry basis and calculated as RE ₂ O ₃ .

The catalyst provided by the present invention is prepared according to the following method: Y-type molecular sieve or Y-type molecular sieve and molecular sieve with MFI structure and/or β molecular sieve are treated with phosphorus-containing compound solution one or more times, so that the phosphorus on the molecular sieve When the content reaches the expected value, dry it, and after roasting at 350-750°C for 0.1-8 hours, mix the phosphorus-containing molecular sieve with double aluminum binder and clay, or mix the phosphorus-containing molecular sieve with the above-mentioned molecular sieve and double aluminum that have not been treated with phosphorus solution Binder and clay are mixed, homogenized, roasted at 500°C for 0.5-6 hours or spray-dried, then washed, filtered, post-treated with a phosphorus-containing compound solution, and dried to obtain the phosphorus-containing hydrocarbon cracking catalyst provided by the invention .

The double-aluminum binder is a mixture of pseudo-boehmite and aluminum sol, wherein all or part of the pseudo-boehmite needs to undergo acidification and aging treatment. The specific treatment method is: beat pseudo-boehmite and water, add a rare earth compound or its solution which is calculated as RE ₂ O ₃ and accounts for 0-40% of the weight of pseudo-boehmite, stir evenly, and mix with acid aluminum weight ratio Acidify with 0.15-0.50 hydrochloric acid, and age at 40-90°C for 0.5-5 hours. The method for acidifying and aging treatment of pseudo-boehmite may also be to mix clay and pseudo-boehmite, add water and beat, add rare earth compound or its solution and stir evenly, acidify with hydrochloric acid, and then age. The amount of rare earth added can be adjusted according to whether the Y-type molecular sieve contains rare earth and its content. The rare earth in the slurry should ensure that the rare earth content in the final catalyst reaches a predetermined value.

The above-mentioned method for treating molecular sieves with a phosphorus-containing compound solution is: impregnating the molecular sieve in a phosphorus-containing compound solution with a dry basis weight ratio of 0.5-3.0 and an elemental phosphorus content of 0.05-5.0% at 4-80 ° C or After stirring for 1-8 hours, dry at 100-120°C for 1-10 hours. Repeat this one or more times. The phosphorus content in the molecular sieve after drying is 0.05-10% by weight calculated as P ₂ O ₅ .

The post-treatment process with phosphorus-containing compounds is to stir the obtained roasted or spray-dried product in a phosphorus-containing compound solution with a dry weight ratio of 0.5-4.0 and an elemental phosphorus content of 0.1-2.0% for 1-8 hours or After exchanging and adsorbing with the phosphorus-containing compound solution on the filter, it is dried at 100-120°C for 1-10 hours.

The phosphorus-containing compound is a water-soluble compound of phosphorus, including orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite, aluminum phosphate, etc. Among them, phosphoric acid and its ammonium Salt is the best, and the ammonium salt can also be prepared with phosphoric acid and ammonia water. The concentration of the phosphorus-containing compound solution is 0.05-5.0% by weight as elemental phosphorus.

Compared with other phosphorus-containing catalysts in the prior art, the catalyst provided by the invention has the advantages of high activity stability, high conversion capacity of heavy oil, low olefin content and less coke in the product gasoline when used in catalytic cracking process.

The following examples will further illustrate the catalyst provided by the invention and its preparation method.

In the example, the rare earth content in the sample catalyst was determined by fluorescence analysis, the phosphorus content was determined by chemical colorimetry, and the specific surface and pore volume were determined by low temperature nitrogen adsorption.

The catalysts used for light oil micro-reaction and fixed fluidized bed evaluation were pre-aged at 800°C and 100% steam for 4 hours or 17 hours.

The evaluation conditions of light oil micro-reaction are: 235～335℃ Dagang light diesel oil as raw material, agent-oil ratio 3.2, weight space velocity 16h ^-1 , temperature 460℃.

The evaluation conditions of the fixed fluidized bed are as follows: the reaction temperature is 520°C, the weight space velocity is 20h ^-1 , the catalyst loading is 90g, the catalyst-to-oil ratio is 5, and the reaction raw material is 80% VGO+20% vacuum residue .

The olefin content in gasoline was determined by gas chromatography.

Instance 1

With 32 grams of REHY molecular sieves ( _RE2O3 content 3.4% by weight, _Na2O content 4.5% by weight, silicon _- aluminum ratio is 5.6, produced by Qilu Catalyst Factory) and 43.8 grams of ammonium phosphate of 7.8% by weight (in ammonium phosphate amount) After the (chemically pure) solutions were mixed, they were stirred for 0.5 hours, dried at 120° C. for 2 hours, calcined in air at 480° C. for 40 minutes, taken out and pulverized.

Add 78 grams of water to 41 grams of pseudo-boehmite (solid content 34.8% by weight, produced by Shandong Aluminum Factory), stir well, then weigh 3.0 grams of rare earth chloride (produced by Inner Mongolia Baotou Rare Earth Factory, RE ₂ O ₃ Content 46% by weight, the composition of RE ₂ O ₃ is La ₂ O ₃ 53.2%, CeO ₂ 13.0%, Pr ₆ O ₁₁ 13.0%, Nd ₂ O ₃ 20.8%), dissolved in 10 grams of water, and pseudoboehmite The stone solution was mixed, and after stirring for 10 minutes, 15 grams of 37% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was weighed and added dropwise to the mixed solution, and stirred evenly. The resulting paste was aged at 90°C for 1.5 hours. Combine the crushed phosphorus-containing REHY molecular sieve with 2 grams of MFI structural molecular sieve (Na ₂ O content 3.0% by weight, silicon-aluminum ratio 30, produced by Qilu Catalyst Factory), 39.4 grams of kaolin (solid content 85.0% by weight, industrial product of China Kaolin Company) After mixing, it was mixed evenly with aged pseudo-boehmite and 24 g of aluminum sol (containing 21% by weight of Al ₂ O ₃ , produced by Qilu Catalyst Factory), and then calcined at 500° C. for 2 hours.

Grind the calcined catalyst, pass through a 20-mesh sieve, and wash at 60°C in water, ammonia water, and decationized water, which are 20 times the pH of the dry catalyst, until Na ₂ O < 0.25% , after filtration, the filter cake was treated in a phosphoric acid solution of 0.70% by weight based on elemental phosphorus for 1 hour at 20-80°C, and then dried at 120°C for 2 hours to obtain the phosphorus-containing REHY molecular sieve catalyst A provided by the present invention .

The composition of catalyst A is: 36.9% of kaolin, 15.8% of alumina from pseudoboehmite, 5.6% of alumina from aluminum sol, 34.1% of Y-type molecular sieve, 2.2% of MFI molecular sieve, 2.7% of RE ₂ O ₃ , _{P2O5 2.7} %.

The evaluation results are shown in Table 1.

Comparative example 1

The catalyst was prepared as described in Example 1, except that the calcination in step 1 was in 100% steam. This comparative catalyst is designated A'.

The composition of catalyst A' is: kaolin 36.9%, alumina 21.4%, Y-type molecular sieve 34.1%, MFI structure molecular sieve 2.2%, RE ₂ O ₃ 2.7%, P ₂ O ₅ 2.7%.

The data of the evaluation results are listed in Table 1.

Table 1 catalyst A A' Specific surface, ^m2 /g 229 198 Pore volume, ml/g 0.32 0.27 Slight reaction activity, wt%800℃/4hr800℃/17hr 8267 7962 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 17.451.819.23.620.2 16.249.120.64.224.5

As can be seen from the data in Table 1: Catalyst A has higher activity stability and low coke rate than comparative catalyst A', and has lower olefin content in the gasoline fraction.

Example 2

To 21 grams of REY molecular sieves ( _RE2O3 content is 19.5% by weight, _Na2O content _is 1.6% by weight, silicon-aluminum ratio is 5.4, produced by Changling Catalyst Factory), adding 32 grams of concentration is 4.1% by weight (as diphosphate ammonium hydrogen phosphate) ammonium dihydrogen phosphate (chemically pure) solution, stirred and mixed for 2 hours, dried at 120°C for 2 hours, roasted in air at 500°C for 3 hours, taken out and pulverized.

Take 42.5 grams of pseudo-boehmite, add 100 grams of water and stir evenly, then add 20 grams of HCl, stir evenly, and age the paste at 70° C. for 2 hours. Then the phosphorus-containing REY molecular sieve after the above pulverization, 2 grams of MFI structure molecular sieve (Na ₂ O content 3.0% by weight, silicon-aluminum ratio 30, produced by Qilu Catalyst Factory), 20.1 grams of kaolin, aged pseudo-boehmite and 51.3 After the gram of aluminum sol is mixed evenly, it is baked at 500° C. for 2 hours.

Same as the third step in Example 1, except that the phosphorus-containing solution is an ammonium phosphate solution containing 0.30% by weight of phosphorus, to obtain the phosphorus-containing REY molecular sieve catalyst B provided by the present invention.

The composition of catalyst B is: 25.5% of kaolin, 22.1% of alumina from pseudoboehmite, 16.1% of alumina from aluminum sol, 25.2% of Y-type molecular sieve, 3.0% of MFI structure molecular sieve, 6.0% of RE ₂ O ₃ , _{P2O5 2.0} %.

See Table 2 for the evaluation results.

Comparative example 2

Catalyst is prepared by the method described in example 2, but the phosphorus-containing solution that adds in the 1st step is the ammonium dihydrogen phosphate solution of 7.1% by weight (in ammonium dihydrogen phosphate) of 32 gram concentrations, and roasting is in 100% water steam, and no phosphorus-containing solution was used to treat the filter cake in step 3, the resulting comparative catalyst was denoted as B'.

The composition of catalyst B' is 25.5% of kaolin, 38.2% of alumina, 25.2% of Y-type molecular sieve, 3.0% of MFI structure molecular sieve, 6.0% of RE ₂ O ₃ and 2.0% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 2.

Comparative example 3

According to the preparation method disclosed in Example 3 of USP5110776, a comparative catalyst was prepared.

Get REY molecular sieve (RE ₂ O ₃ content is 19.5 weight %, Na ₂ O content is 1.6 weight %, silicon-aluminum ratio is 5.4, Changling Catalyst Factory produces) 101.4 grams, 0.61 gram dispersant, 11.0 gram ammonium dihydrogen phosphate and 133.8 grams of water were mixed and stirred for 16 hours before an additional 163.8 grams of deionized water was added. In addition, 96.5 grams of kaolin, 385 grams of sodium silicate (containing SiO 26.8% by weight, Na ₂ O 7.8% by weight, produced by Qilu Petrochemical Company Catalyst Factory) and 2134 _grams of water were mixed evenly, and finally the prepared molecular sieve slurry was added, mixed Uniform, dried, washed to no acid ions, repulped, spray-dried to obtain comparative catalyst B".

The composition of catalyst B" is 25.4% of kaolin, 41.2% of silicon oxide, 25.2% of Y-type molecular sieve, 6.1% of RE ₂ O ₃ , and 2.1% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 2.

Table 2 catalyst B B' B" Specific surface, ^m2 /g 238 211 218 Pore volume, ml/g 0.32 0.29 0.29 Slight reaction activity, wt%800℃/4hr800℃/17hr 8367 7860 8163 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 15.849.821.04.019.9 14.847.822.45.423.2 15.648.922.05.222.5

As can be seen from the data in Table 2: Catalyst B has higher activity stability and low coke rate than comparative catalyst B', and has lower olefin content in the gasoline fraction. Catalyst B has higher activity, activity stability and lower coke formation rate and olefin content in gasoline fraction than comparative catalyst B".

Example 3

In 22 grams of USY molecular sieves ( _Na O content is 0.87% by weight, the ratio of silicon to aluminum is 6.8, produced by Qilu Catalyst Factory), adding 30 grams of concentration is 1.85% by weight (in terms of ammonium dihydrogen phosphate) ammonium dihydrogen phosphate solution , Stir and mix for 4 hours, dry at 120°C for 2 hours, bake at 550°C for 30 minutes, take out and pulverize.

Take 26 grams of pseudo-boehmite, add 32 grams of water and stir evenly. After stirring for 10 minutes, add 10.5 grams of HCl dropwise. After stirring evenly, the paste is aged at 70° C. for 1.5 hours. Then the crushed phosphorus-containing USY molecular sieve, 1 gram of MFI structural molecular sieve (Na ₂ O content 3.0% by weight, silicon-aluminum ratio 30, produced by Qilu Petrochemical Company Catalyst Factory), 30 grams of kaolin and the above-mentioned aged pseudo-boehmite and 30 grams of aluminum sol are mixed together, and then roasted at 500 ° C for 2 hours after mixing.

Same as the third step in Example 2, except that the phosphorus-containing solution is an ammonium phosphite solution with 0.15% by weight of elemental phosphorus, to obtain the phosphorus-containing USY molecular sieve catalyst C provided by the present invention.

The composition of catalyst C is: 20.7% of kaolin, 22.3% of alumina from pseudoboehmite, 11.1% of alumina from aluminum sol, 43.4% of Y-type molecular sieve, 1.5% of MFI structure molecular sieve, and 1.0% of P ₂ O ₅ .

The analysis and evaluation results are shown in Table 3.

Comparative example 4

A USY molecular sieve type comparative catalyst, the comparative catalyst C', was prepared as described in EP397183 Examples I-IV.

The composition of the catalyst C' is 20.5% of kaolin, 19.1% of alumina, 45.7% of Y-type molecular sieve, 0.4% of P ₂ O ₅ , and 14.3% of alumina dry powder.

Data on the analysis and evaluation are presented in Table 3.

table 3 catalyst C C' Specific surface, ^m2 /g 252 234 Pore volume, ml/g 0.34 0.32 Slight reaction activity, wt%800℃/4hr800℃/17hr 7867 7662 Heavy oil slightly reversed, weight % Gasoline, light diesel oil, coke, olefin content in gasoline, weight % 16.848.920.83.225.2 15.447.621.54.133.5

As can be seen from the data in Table 3: Catalyst C has higher activity stability and lower coke rate than comparative catalyst C', and has lower olefin content in the gasoline fraction.

Example 4

To 25 grams of REUSY molecular sieves ( _Na2O content is 1.2% by _weight , _RE2O3 content is 1.5% by weight, silicon-aluminum ratio is 6.8, produced by Qilu Catalyst Factory), adding 45 grams of ammonium phosphate, the concentration is 5.1% by weight % ammonium phosphate solution, stirred for 3 hours, dried at 120°C for 2 hours, then calcined in air at 600°C for 2 hours, took out and pulverized.

Take 21.7 grams of pseudo-boehmite, add 42 grams of water and stir evenly, then add 0.37 grams of rare earth chloride, and after stirring for 10 minutes, add 10 grams of HCl dropwise, after stirring evenly, age the paste at 80°C for 1.5 Hour. Then the above pulverized phosphorus-containing REUSY molecular sieve, 3 grams of MFI structure molecular sieve (Na ₂ O content 3.0% by weight, silicon-aluminum ratio 30, produced by Qilu Petrochemical Company Catalyst Factory), 44.6 grams of kaolin and aged pseudo-boehmite and 12 grams of aluminum sol were evenly mixed, and then fired at 500° C. for 4 hours.

Same as the third step of Example 1, except that the phosphorus-containing solution is an ammonium dihydrogen phosphate solution with an elemental phosphorus content of 0.30% by weight, to obtain the phosphorus-containing REUSY molecular sieve catalyst D provided by the present invention.

Catalyst D consists of 48.8% kaolin, 9.8% pseudoboehmite, 3.2% aluminum sol, 31.7% Y-type molecular sieve, 3.9% MFI molecular sieve, 0.7 RE ₂ O ₃ , and 1.9% P ₂ O ₅ .

The analysis and evaluation results are shown in Table 4.

Comparative example 5

Prepare catalyst by the method described in example 4, but do not process molecular sieve with phosphorus-containing solution in the 1st step, other is all with example 4, prepares comparison catalyst D '.

The composition of catalyst D' is: kaolin 49.5%, binder 13.2%, Y-type molecular sieve 32.2%, MFI molecular sieve 3.9, RE ₂ O ₃ 0.7%, P ₂ O ₅ 0.5%.

The relevant analysis and evaluation data are listed in Table 4.

Comparative example 6

Prepare comparative catalyst D " by the method described in example 8 among CN1062750 " (the composition of this comparative catalyst is adjusted in the scope that its patent includes).

The composition of catalyst D" is: kaolin 48.8%, alumina 13.0%, Y-type molecular sieve 31.7%, MFI structure molecular sieve 3.9%, RE ₂ O ₃ 0.7%, P ₂ O ₅ 1.9%.

The relevant analysis and evaluation data are listed in Table 4. Table 4 catalyst D. D' D" Specific surface, ^m2 /g 231 242 240 Pore volume, ml/g 0.32 0.34 0.33 Slight reaction activity, wt%800℃/4hr800℃/17hr 7966 8362 8264 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke Olefin content in gasoline, wt% 16.249.822.93.024.0 17.750.819.04.428.2 16.950.219.64.227.4

As can be seen from Table 4, catalyst D has higher activity stability and lower coke formation rate than comparative catalysts D' and D", and has lower olefin content in the gasoline fraction.

Example 5

With 50 grams of NaY ( _Na O content 11% by weight, silicon-aluminum ratio is 5.6, produced by Changling Catalyst Factory) in 1 liter of 0.15M ammonium chloride solution at 60 ° C for 1 hour, the filter cake after filtration is at 550 °C for 2 hours to obtain HNaY with a Na ⁺ pre-exchange degree of 65%. It was exchanged twice according to the above steps to obtain HY molecular sieve.

23 grams of HY molecular sieves were added with 30 grams of a mixture of phosphoric acid and ammonia water containing 1.7% by weight of phosphorus in terms of elemental phosphorus, and pH 4.5, stirred for 6 hours, dried at 120°C, and then calcined in air at 500°C for 1 hour , take out and crush.

After obtaining the same weight of aged pseudo-boehmite according to the same method in the second step of Example 3, the above-mentioned pulverized phosphorus-containing HY molecular sieve, 2 grams of β molecular sieve ( _Na O content 3.2% by weight, silicon-aluminum ratio 28, Qilu Petrochemical Company Catalyst Factory), 28.5 grams of kaolin, 17.2 grams of aluminum sol and aged pseudo-boehmite were evenly mixed, and then calcined at 500° C. for 1.5 hours.

After the same steps as the third step in Example 1, the phosphorus-containing molecular sieve catalyst E provided by the present invention was obtained.

The composition of catalyst E is: 38.0% of kaolin, 14.2% of alumina from pseudoboehmite, 5.7% of alumina from aluminum sol, 36.1% of Y-type molecular sieve, 3.1% of β zeolite, and 2.9% of P ₂ O ₅ .

The analysis and evaluation results are shown in Table 5.

Comparative Example 7

According to the preparation method disclosed in the example of USP4970183, the HY type comparative catalyst was prepared.

First, 80 grams of NaY ( _Na2O content 11% by weight, silicon-aluminum ratio 5.6, produced by Changling Catalyst Factory) was ion-exchanged with ammonium ion solution to obtain 75 grams of HY molecular sieve, and then it was mixed with 45 grams of 20% by weight ( A mixed solution of H ₃ PO ₄ solution and 50 grams of 20% by weight (NH ₄ ) ₂ SO ₄ solution in terms of phosphoric acid content was stirred and reacted at 90° C. for 0.5 hour, filtered and washed to obtain phosphorus-containing NH ₄ Y, The phosphorus-containing NH ₄ Y was treated in a water vapor atmosphere at 700° C. for 2 hours to obtain phosphorus-containing HY. Then first 40 grams of silica sol (commercial product of Beijing Changhong Chemical Plant, containing 12% SiO ₂ ), 20.4 grams of kaolin, 14 grams of hydrated alumina (solid content 34.8% by weight, produced by Qilu Petrochemical Company Catalyst Factory) were mixed, and then 17.6 1 g of phosphorus-containing HY was mixed with it, dried, washed, and then dried to obtain HY-type comparative catalyst E'.

The composition of catalyst E' is: 38.9% of kaolin, 21.6% of silica-alumina binder, 36.6% of Y-type molecular sieve, and 2.9% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 5.

Comparative example 8

Catalyst is prepared by the method described in example 5, but filter cake is not carried out to add phosphorus post-treatment in the 3rd step, obtains the comparative catalyst E " that contains phosphorus.

The composition of catalyst E" is 38.4% of kaolin, 20.0% of alumina, 36.5% of Y-type molecular sieve, 3.2% of beta zeolite, and 1.9% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 5.

table 5 catalyst E. E' E" Specific surface, ^m2 /g 233 208 238 Pore volume, ml/g 0.30 0.27 0.31 Slight reaction activity, wt%800℃/4hr800℃/17hr 7664 7359 7761 Heavy oil slightly reversed, weight % Gasoline, light diesel oil, coke, olefin content in gasoline, weight % 16.248.119.83.824.8 14.545.822.24.529.2 16.848.819.34.729.3

As can be seen from the data in Table 5: Catalyst E has higher activity stability and lower coke rate than comparative catalysts E' and E", and has lower olefin content in the gasoline fraction.

Example 6

Add 24 _grams of concentration to 8 grams of REHY ( _RE2O3 content is 3.4% by weight, produced by _Changling Catalyst Factory) and 8 grams of REY molecular sieve ( _RE2O3 content is 19.5% by weight, produced by Qilu Petrochemical Company Catalyst Factory) respectively The ammonium dihydrogen phosphate solution was 2.0% by weight (based on the amount of ammonium dihydrogen phosphate), stirred for 5 hours, dried at 120° C. for 2 hours, then calcined in air at 600° C. for 1 hour, taken out and pulverized.

By the method described in the second step of example 3, 20 grams of aging pseudo-boehmite are obtained. Phosphorus-containing REHY and REY molecular sieve (RE ₂ O ₃ 19.5% by weight, produced by Qilu Petrochemical Company Catalyst Factory), 2 grams Molecular sieve with MFI structure (Na ₂ O content 3.2% by weight, silicon-aluminum ratio 33, produced by Changling Catalyst Factory), 30 grams of kaolin, aged pseudo-boehmite and 40 grams of aluminum sol are evenly mixed, and roasted at 500 ° C 2 hours.

The same steps as the third step of Example 1, but the phosphorus-containing solution is diammonium hydrogen phosphate with a concentration of 0.40% by weight in terms of elemental phosphorus, to obtain the phosphorus-containing mixed molecular sieve catalyst F provided by the invention.

The composition of catalyst F is: 35.2% of kaolin, 27.6% of alumina from pseudoboehmite, 11.6% of alumina from aluminum sol, 19.5% of Y-type molecular sieve, 2.8% of MFI structure molecular sieve, 2.5% of RE ₂ O ₃ , P ₂ O ₅ 0.8%.

The relevant analysis and evaluation data are listed in Table 6.

Comparative Example 9

Prepare catalyst by the method described in example 6, but do not add ZSM-5 in the second step, and add REHY more, reach same molecular sieve content, this comparison catalyst F '.

The composition of catalyst F' is: kaolin 35.2%, alumina 39.2%, Y-type molecular sieve 22.2%, RE ₂ O ₃ 2.6%, P ₂ O ₅ 0.8%.

The relevant analysis and evaluation data are listed in Table 6.

It can be seen from the data in Table 6 that catalyst F has higher activity stability and lower coke formation rate than comparative catalyst F', and has lower olefin content in gasoline fraction. Table 6 catalyst f F' Specific surface, ^m2 /g 218 196 Pore volume, ml/g 0.30 0.29 Slight reaction activity, wt%800℃/4hr800℃/17hr 7766 7461 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 17.247.221.14.222.8 16.146.322.05.626.5

Example 7

With 30 grams of REHY molecular sieves ( _RE2O3 content is 3.4% by weight, _produced by Qilu Petrochemical Company Catalyst Factory) and 45.3 grams of elemental phosphorus, 3.0% by weight of diammonium hydrogen phosphate solution after mixing, stirring for 6 hours, at 120 After drying at 650°C for 2 hours in the air, it was taken out and pulverized.

Add 40 g of water to 20 g of pseudo-boehmite, stir evenly, add 7 g of HCl, stir for 30 minutes, and age the acidified pseudo-boehmite at 80° C. for 2 hours. Then, mix the crushed phosphorus-containing REHY molecular sieve, 70.5 grams of kaolin, aged pseudo-boehmite and 14.3 grams of aluminum sol evenly, and then calcined at 500° C. for 2.5 hours.

After the same steps as the third step in Example 2, the molecular sieve catalyst G provided by the present invention was obtained.

The composition of catalyst G is: kaolin 57.6%, alumina from pseudoboehmite 6.7%, alumina from aluminum sol 2.9%, Y-type molecular sieve 27.9%, RE ₂ O ₃ 0.9%, P ₂ O ₅ 4.0% .

The relevant analysis and evaluation data are listed in Table 7.

Comparative Example 10

Prepare catalyst by the method described in example 7, but roasting is in 100% steam in the first step, and do not process filter cake with phosphorous solution in the 3rd step, obtain comparative catalyst G'.

The composition of catalyst G is: kaolin 58.1%, alumina 9.7%, Y-type molecular sieve 28.2%, RE ₂ O ₃ 0.9%, P ₂ O ₅ 3.1%.

The relevant analysis and evaluation data are listed in Table 7.

Table 7 catalyst G G' Specific surface, ^m2 /g 212 205 Pore volume, ml/g 0.28 0.26 Slight reaction activity, wt%800℃/4hr800℃/17hr 7769 7863 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 16.047.620.84.022.2 16.848.020.24.826.4

It can be seen from the data in Table 7 that catalyst G has higher activity stability and lower coke formation rate than comparative catalyst G', and has lower olefin content in gasoline fraction.

Example 8

After mixing 36 grams of USY molecular sieve (Na ₂ O content 0.87% by weight, silicon-aluminum ratio 6.8, produced by Qilu Petrochemical Company Catalyst Factory) with 49.8 grams of 6.5% by weight (in terms of ammonium dihydrogen phosphate) ammonium dihydrogen phosphate solution , continue to stir for 3 hours, dry at 120°C for 2 hours, and then bake in air at 500°C for 1.5 hours, then take it out and pulverize.

Mix 4 grams of molecular sieve with MFI structure (Na ₂ O content 3.0% by weight, silicon-aluminum ratio 30, produced by Qilu Petrochemical Company Catalyst Factory) with 12 grams of 1.1% by weight in terms of elemental phosphorus, and mix the phosphoric acid and ammonia water at pH 4.5 After that, it was stirred for 6 hours, dried at 120° C., calcined at 700° C. in air for 2 hours, and then taken out and pulverized.

Add 230 g of water to 115 g of pseudo-boehmite, stir evenly, then add 41 g of hydrochloric acid in turn, and after stirring for 30 minutes, age the acidified pseudo-boehmite at 50° C. for 2.5 hours. Then the above-mentioned pulverized phosphorus-containing USY molecular sieve, phosphorus-containing MFI molecular sieve, 2 grams of β molecular sieve ( _Na2O content 3.2% by weight, silicon-aluminum ratio 28, produced by Qilu Petrochemical Company Catalyst Factory), aged pseudo-boehmite After the stone and 95 grams of aluminum sol were mixed evenly, they were calcined at 500°C for 3 hours.

The same procedure as step 3 in Example 1, except that the concentration of the phosphorus-containing solution is an ammonium dihydrogen phosphate solution of 0.50% by weight based on elemental phosphorus, to obtain the phosphorus-containing molecular sieve catalyst H provided by the present invention.

The composition of catalyst H is: 38.2% of alumina from pseudoboehmite, 19.0% of alumina from aluminum sol, 34.3% of Y-type molecular sieve, 3.8% of MFI molecular sieve, 1.9% of β zeolite, and 2.8% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 8.

Comparative Example 11

Catalyst is prepared by the method described in example 8, but roasting is in 100% steam in the first step, and filter cake is not processed with phosphorous solution in the 3rd step, obtains comparative catalyst and is denoted as H '.

The composition of the catalyst H' is: 57.5% of alumina, 34.5% of Y-type molecular sieve, 3.8% of MFI molecular sieve, 1.9% of beta zeolite, and 2.2% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 8.

Comparative Example 12

According to the method disclosed in EP252761, 50 grams of USY molecular sieves (Na ₂ O content 0.87% by weight, silicon-aluminum ratio 6.8, produced by Qilu Petrochemical Company Catalyst Factory) were treated in 100% steam at 700°C for 16 hours, and 30% of them were taken. gram, in 1096.3 grams of 6.3% by weight (calculated by the amount of ammonium dihydrogen phosphate) ammonium dihydrogen phosphate solution at 65.6 ° C for 2 hours, filtered, dried, roasted at 538 ° C for 2 hours, and then mixed with 25 weight % 47 g (dry basis weight) of silica-alumina gel of % alumina was mixed to prepare a phosphorus-containing comparative catalyst, denoted as H".

The composition of the catalyst H" is: 59.3% of silicon-alumina binder, 37.9% of Y-type molecular sieve, and 2.8% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 8.

Table 8 catalyst h H' H" Specific surface, ^m2 /g 248 230 232 Pore volume, ml/g 0.34 0.32 0.31 Slight reaction activity, wt%800℃/4hr800℃/17hr 8068 7963 7964 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 17.649.819.94.126.3 16.649.320.85.431.7 17.149.320.25.031.2

It can be seen from the data in Table 8 that catalyst H has higher activity stability and lower coke formation rate than comparative catalysts H' and H", and has lower olefin content in gasoline fraction.

Example 9

In terms of elemental phosphorus, 450ml of diammonium hydrogen phosphate solution containing 100 g _/ liter of phosphorus is added to 2 kilograms (dry weight) of wet unwashed REHY molecular sieves (RE ₂ O The content is 3.4% by weight, Changling catalyst Factory production), mixed and stirred for 8 hours, dried at 100°C for 2 hours, and then calcined in air at 500°C for 2 hours.

Add 4 kg of water to 2.74 kg of pseudo-boehmite in the beating tank, after beating for 30 minutes, add 705 g of 37% by weight hydrochloric acid, stir for 1 hour, age at 85°C for 2 hours, and then add kaolin 1.86 kg, 2 kg of water, 1.14 kg of aluminum sol, beating for 30 minutes.

Add phosphorus-containing rare earth hydrogen Y-type molecular sieve after roasting for 2 hours and 200 grams of MFI structure molecular sieve (Na ₂ O content 3.2% by weight, silicon-aluminum ratio 33, produced by Changling Catalyst Factory), 3 kilograms of water into another beating tank, beating After 2 hours, add it to the beating tank mentioned in the second step, beat and homogenize for another 5 hours, and then spray dry.

Wash the catalyst obtained by spray drying on a filter at 60°C, and treat it with diammonium hydrogen phosphate whose phosphorus-containing solution concentration is 1.0% by weight in terms of elemental phosphorus, filter, and dry at 100°C to obtain the present invention. Phosphorus-containing molecular sieve catalyst I.

The composition of catalyst I is: 30.5% of kaolin, 18.4% of alumina from pseudoboehmite, 4.6% of alumina from aluminum sol, 37.4% of Y-type molecular sieve, 3.9% of MFI molecular sieve, 1.3% of RE ₂ O ₃ , _{P2O5 3.9} %.

The relevant analysis and evaluation data are listed in Table 9.

Comparative Example 13

Catalyst is prepared by the method described in example 9, but the amount of the diammonium hydrogen phosphate solution that adds in the first step is 877ml, and roasting is in 100% steam, and does not use phosphorous solution to filter cake in the 4th step line processing. This comparative catalyst is designated as I'.

The composition of the catalyst I' is: 30.5% of kaolin, 23.0% of alumina, 37.4% of Y-type molecular sieve, 3.9% of MFI structure molecular sieve, 1.3% of RE ₂ O ₃ , and 3.9% of P ₂ O ₅ .

The relevant analysis and evaluation data are listed in Table 9. Table 9 catalyst I I' Specific surface, ^m2 /g 238 203 Pore volume, ml/g 0.30 0.27 Slight reaction activity, wt%800℃/4hr800℃/17hr 8173 7564 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 16.849.220.24.423.1 15.847.221.34.926.8

As can be seen from the data in Table 9, catalyst I has higher activity stability and lower coke rate than comparative catalyst I', and has lower olefin content in the gasoline fraction.

Example 10

Add 400ml of phosphoric acid and ammonia mixed solution containing 150g/l of phosphorus in terms of elemental phosphorus to 2.7 (on a dry basis) kilograms of wetted REHY molecular sieves (RE ₂ O The content is 6.0% by weight, Qilu Petrochemical _Co. , Ltd. Company Catalyst Factory), mixed and stirred for 5 hours, dried at 100°C for 2 hours, and then calcined in air at 500°C for 4 hours.

Add 2 kilograms of kaolin in the beating tank, beating after adding 4 kilograms of water, then add 4.9 kilograms of pseudo-boehmite in the beating tank, after beating for 2 hours, add 1.26 kilograms of 37% by weight hydrochloric acid, after stirring for 1 hour, Aged at 75°C for 2 hours, then added 3.4 kg of aluminum sol, and beat for 1 hour.

Add phosphorus-containing REHY type molecular sieve after roasting for 4 hours and 300 grams of MFI structure molecular sieve (Na ₂ O content 3.0 weight %, silicon-aluminum ratio 30, Qilu Petrochemical Company Catalyst Factory production), 4.5 kilograms of water add another beating tank, beating 2 After 1 hour, add it to the beating tank mentioned in step 2, beat and homogenize for 5 hours, and then spray dry.

The catalyst obtained by spray drying was washed on a filter at 60°C with 1.0% by weight phosphoric acid solution based on elemental phosphorus, filtered, and dried at 100°C to obtain the phosphorus-containing molecular sieve catalyst J provided by the present invention.

The composition of catalyst J is: 23.1% of kaolin, 23.2% of alumina from pseudoboehmite, 9.7% of alumina from alumina sol, 34.5% of Y-type molecular sieve, 4.1% of MFI molecular sieve, 2.2% of RE ₂ O ₃ , _{P2O5 3.2} %.

The relevant analysis and evaluation data are listed in Table 10.

Comparative Example 14

The catalyst was prepared in the same manner as described in Example 10, but the amount of the mixed solution added in the first step was 691 ml, and the filter cake was not treated with the phosphorus-containing solution in the fourth step. This comparative catalyst is designated as J'.

The composition of catalyst J' is: kaolin 23.1%, alumina 32.9%, Y-type molecular sieve 34.5%, MFI molecular sieve 4.1%, RE ₂ O ₃ 2.2%, P ₂ O ₅ 3.2%.

The relevant analysis and evaluation data are listed in Table 10. Table 10 catalyst J J' Specific surface, ^m2 /g 235 209 Pore volume, ml/g 0.31 0.27 800℃/4hr800℃/17hr 7970 7563 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 17.450.119.85.122.6 16.247.822.35.825.8

It can be seen from the data in Table 10 that catalyst J has higher activity stability and lower coke formation rate than comparative catalyst J', and has lower olefin content in gasoline fraction.

Example 11

Add 3.8 kilograms (dry basis weight) of wetted REHY molecular sieve (RE ₂ O ₃ content is 6.0 weight %, Qilu Petrochemical Company Catalyst Factory produces ), mix well, continue stirring for 3 hours, dry at 100°C for 2 hours, and then bake in air at 650°C for 3 hours.

Add 6.5 kg of pseudo-boehmite to the beating tank, then add 10 kg of water, after beating for 2 hours, add 1.67 kg of 37% by weight hydrochloric acid, stir for 2 hours, age at 65°C for 1 hour, and then add to the beating tank Add 12.7 kg of aluminum sol to the tank for beating for 1 hour, then add 4 kg of kaolin for beating for 2 hours.

The phosphorus-containing REHY type molecular sieve after roasting for 3 hours was mixed with 250 grams of MFI structure molecular sieve (Na ₂ O content 3.0 weight percent, silicon-aluminum ratio 30, Qilu Petrochemical Company Catalyst Factory production), 250 grams β molecular sieve (Na ₂ O content 3.2 weight percent %, silicon-aluminum ratio 28, produced by Qilu Petrochemical Company Catalyst Factory), 6.5 kilograms of water into another beating tank, after beating for 3 hours, join in the beating tank mentioned in the second step, beating for homogenization for 4 hours, and then spray dry.

The catalyst obtained by spray drying was washed on a filter with 0.80% by weight phosphoric acid solution based on elemental phosphorus at 60°C, filtered, and dried at 100°C to obtain the phosphorus-containing molecular sieve catalyst K provided by the present invention.

The composition of catalyst K is: 26.4% of kaolin, 17.5% of alumina from pseudoboehmite, 20.7% of alumina from aluminum sol, 27.7% of Y-type molecular sieve, 1.9% of MFI molecular sieve, 1.8% of RE ₂ O ₃ , Beta zeolite 1.9%, P ₂ O ₅ 2.1%.

The relevant analysis and evaluation data are listed in Table 11.

Comparative Example 15

The catalyst was prepared as described in Example 11, except that the molecular sieves were calcined in a 100% steam atmosphere in the first step. The comparative catalyst is designated as K'.

The composition of catalyst K' is: kaolin 26.4%, alumina 38.2%, Y-type molecular sieve 27.7%, MFI structure molecular sieve 1.9%, RE ₂ O ₃ 1.8%, zeolite β 1.9%, P ₂ O ₅ 2.1%.

The relevant analysis and evaluation data are listed in Table 11. Table 11 catalyst K K' Specific surface, ^m2 /g 230 211 Pore volume, ml/g 0.31 0.28 Slight reaction activity, wt%800℃/4hr800℃/17hr 7968 7662 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 16.948.619.65.023.7 16.447.421.85.926.2

It can be seen from the data in Table 11 that catalyst K has higher activity stability and lower coke formation rate than comparative catalyst K', and has lower olefin content in gasoline fraction.

Example 12

In terms of elemental phosphorus, 540ml of phosphoric acid and ammonia mixed solution containing 150g/l of phosphorus is added to 4 kg (in dry basis weight) of wetted REHY (RE ₂ O ₃ content is 3.4% by weight, Changling catalyst Factory production) molecular sieve, mixed and stirred for 2 hours, dried at 100°C for 2 hours, and then calcined in air at 700°C for 2 hours.

Add 4.7 kilograms of kaolin in the beating tank, beating after adding 6 kilograms of water, then add 11.9 kilograms of pseudoboehmite and 724 grams of rare earth chloride in the beating tank, after beating for 3 hours, add 3.1 kilograms of 37% by weight hydrochloric acid , after stirring for 1 hour, aged at 70°C for 2 hours, then added 15.87 kg of aluminum sol, and beat for 1 hour.

The phosphorus-containing REHY molecular sieve after roasting for 2 hours was mixed with 1 kilogram of REHY molecular sieve (RE ₂ O _The content is 3.4 weight percent, produced by Changling Catalyst Factory), 667 grams of MFI structure molecular sieve (Na ₂ O content 3.2 weight percent, silicon-aluminum ratio 33, produced by Changling Catalyst Factory), 7 kg of water was added to another beating tank, after beating for 2 hours, it was added to the beating tank mentioned in the second step, and the beating was homogenized for 5 hours, and then spray-dried.

The catalyst obtained by spray drying was washed on a filter at 60°C with a 1.2% by weight phosphoric acid solution based on elemental phosphorus, filtered, and dried at 100°C to obtain the phosphorus-containing molecular sieve catalyst L provided by the present invention.

The composition of catalyst L is: kaolin 22.4%, alumina from pseudoboehmite 23.1%, alumina from aluminum sol 18.6%, Y-type molecular sieve 27.0%, MFI structure molecular sieve 3.7%, RE ₂ O ₃ 2.8%, _{P2O5 2.4} %.

The relevant analysis and evaluation data are presented in Table 12.

Comparative Example 16

Prepare catalyst by the method described in example 12, but do not process molecular sieve with phosphorus-containing solution in the first step, just replace phosphorus-containing solution with equal amount of water, make comparison catalyst L'.

The composition of the catalyst L' is: kaolin 22.6%, alumina 43.2%, Y-type molecular sieve 27.3%, MFI structure molecular sieve 3.7%, RE ₂ O ₃ 2.8%, P ₂ O ₅ 1.4%.

The relevant analysis and evaluation data are presented in Table 12. Table 12 catalyst L L' Specific surface, ^m2 /g 236 249 Pore volume, ml/g 0.31 0.33 Slight reaction activity, wt%800℃/4hr800℃/17hr 8068 8165 Fixed fluidized bed, wt% Gasoline, light diesel oil, coke, olefin content in gasoline, wt% 17.249.219.94.923.7 17.649.519.36.127.3

It can be seen from the data in Table 12 that catalyst L has higher activity stability and lower coke formation rate than comparative catalyst L', and has lower olefin content in gasoline fraction.

Claims (16)

1. A phosphorus-containing hydrocarbon cracking catalyst, characterized in that: (1) The catalyst consists of 10-60% by weight of ①Y-type molecular sieve, or ②Y-type molecular sieve, MFI structure molecular sieve and β molecular sieve, or ③Y-type molecular sieve and β-type molecular sieve; 0-75% by weight of clay; 10-60% by weight of A mixture of two aluminas _{from pseudoboehmite} and alumina sol, respectively; 0.1-7.0 wt. % phosphorus as _P2O5 and 0-20 wt. % rare earths as _RE2O3 ; (2) Its preparation method is as follows: ①Y-type molecular sieve, or ②Y-type molecular sieve, MFI structure molecular sieve and β molecular sieve, or ③Y-type molecular sieve and β molecular sieve, are treated with phosphorus-containing compound solution, dried, and roasted at 350-750°C for 0.1- After 8 hours, mix it with the double aluminum binder and clay composed of pseudo-boehmite and aluminum sol, or mix it with the above-mentioned molecular sieve and double aluminum binder and clay that have not been treated with phosphorus solution, and make homogeneous Afterwards, it is roasted at 500°C for 0.5-6 hours or spray-dried, washed, filtered, post-treated with a phosphorus-containing compound solution, and dried. 2. The catalyst according to claim 1, wherein said Y-type molecule is selected from one or more mixtures of HY, REY, REHY, USY, REUSY, REDASY. 3. The catalyst according to claim 2, wherein the rare earth content of the rare earth-containing Y-type molecular sieve is 0.5-20% by weight of RE ₂ O ₃ . 4. The catalyst according to claim 1, wherein said molecular sieve with MFI structure is selected from ZSM-5 or one or more molecular sieves belonging to the same MFI structure. 5. The catalyst according to claim 1, characterized in that when multiple molecular sieves are used in the catalyst, the weight ratio of the molecular sieve with the MFI structure to the Y-type molecular sieve is 0.025-1; the weight ratio of the β molecular sieve to the Y-type molecular sieve is 0.025-0.8. 6. The catalyst according to claim 5, characterized in that the weight ratio of molecular sieve with MFI structure to Y-type molecular sieve is 0.1-0.5. 7. The catalyst according to claim 1, characterized in that said clay is selected from kaolin, halloysite, montmorillonite, bentonite. 8. The catalyst according to claim 1, characterized in that said two aluminas from pseudo-boehmite and alumina sol respectively account for 6-40% and 4-20% of the weight of the catalyst. 9. Catalyst according to claim 8, characterized in that the alumina from pseudo-boehmite and alumina sol constitutes 15-25% and 6-12% by weight of the catalyst, respectively. 10. The catalyst according to claim 8 or 9, characterized in that said pseudo-boehmite contains 0-40% of rare earth based on the weight of pseudo-boehmite on a dry basis and calculated as RE ₂ O ₃ . 11. The catalyst according to claim 1, characterized in that all or part of said pseudo-boehmite has undergone the following acidification and aging treatment: making slurry of pseudo-boehmite and water, adding RE ₂ O ₃ 1. The rare earth compound or its solution accounting for 0-40% by weight of pseudo-boehmite is stirred evenly, acidified with hydrochloric acid with a weight ratio of 0.15-0.50 to aluminum, and aged at 40-90° C. for 0.5-5 hours. 12. The catalyst according to claim 1, characterized in that all or part of said pseudo-boehmite has undergone the following acidification and aging treatment: after mixing clay and pseudo-boehmite with water and beating, adding RE A rare earth compound or its solution accounting for 0-40% of the weight of pseudo-boehmite in terms of ₂ O ₃ , stirred evenly, acidified with hydrochloric acid with an acid-aluminum weight ratio of 0.15-0.50, and aged at 40-90°C for 0.5-5 hours . 13. The catalyst according to claim 1, characterized in that the method of treating the molecular sieve with the phosphorus-containing compound solution is: the molecular sieve is mixed with the phosphorus-containing compound whose dry basis weight ratio is 0.5-3.0 and the elemental phosphorus content is 0.05-5.0%. Soak or stir in the solution for 1-8 hours at 4-80°C, then dry at 100-120°C for 1-10 hours, repeat once or more until the phosphorus content in the molecular sieve after drying is 0.05-10 in terms of P ₂ O ₅ Heavy%. 14. The catalyst according to claim 1, characterized in that the post-treatment process with the phosphorus-containing compound solution is that the obtained roasted or spray-dried product has a weight ratio of 0.5 to 4.0 on a dry basis and an elemental phosphorus content of Stir in 0.1-2.0% phosphorus-containing compound solution for 1-8 hours or perform exchange and adsorption with phosphorus-containing compound solution on a filter, then dry at 100-120° C. for 1-10 hours. 15. The catalyst according to any one of claims 1, 13 and 14, characterized in that said phosphorus-containing compound is selected from the group consisting of orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, A mixture of one or more of ammonium phosphite and aluminum phosphate. 16. The catalyst according to any one of claims 1, 13 and 14, characterized in that the concentration of said phosphorus-containing compound solution is 0.05-5.0% by weight of elemental phosphorus.