CN100395029C - Preparation method of cracking catalyst for reducing gasoline olefin content and producing more liquefied gas - Google Patents

Abstract

A method for preparing a cracking catalyst for reducing the olefin content of gasoline and producing more liquefied gas, comprising uniformly mixing clay, deionized water, and a phosphorus-containing compound to prepare a clay slurry, and uniformly mixing molecular sieves, deionized water, phosphorus-containing compounds, and rare earth compounds to prepare To obtain molecular sieve slurry, uniformly mix binder, deionized water and optional inorganic acid to prepare binder slurry; mix uniformly the clay slurry, molecular sieve slurry and binder slurry, and then dry. The cracking catalyst prepared by the method of the present invention has a relatively high yield of liquefied gas, especially a high concentration of propylene in the liquefied gas, and reduces the olefin content in gasoline while maintaining a high gasoline yield and gasoline octane number .

Description

Preparation method of cracking catalyst for reducing gasoline olefin content and producing more liquefied gas

technical field

The invention belongs to a preparation method of a hydrocarbon cracking catalyst.

technical background

With the increasingly stringent environmental protection standards, it is required to reduce the olefin content in gasoline. It is a quick and feasible way to develop a catalyst for reducing the olefin content in catalytic cracking (FCC) gasoline fraction.

With the development of the petrochemical industry, the FCC process is not only an important means to provide light oil, but also a processing method to provide basic organic chemical raw materials such as olefins. For example, propylene is an important raw material for the production of phenol, acetone, acrylic acid, etc. Therefore, It is necessary to develop a catalyst with a higher yield of liquefied gas, especially a higher content of propylene in the liquefied gas.

Increase the yield of liquefied gas in cracked products, especially the yield of propylene in liquefied gas, and reduce the olefin content in gasoline while maintaining a high gasoline yield and octane number. On the one hand, it is necessary to increase low-carbon olefins, and on the other hand, it is necessary to reduce the content of olefins in gasoline.

In recent years, the preparation method of introducing phosphorus into the cracking catalyst has been frequently reported, and its main functions generally fall into the following four categories:

1. It is used to improve the wear index, activity, selectivity and hydrothermal stability of the catalyst. Such as CN1022465C, CN1024504C, CN1062750A, CN1062157A, etc., the precursors of molecular sieves, clay and/or inorganic oxides are mixed uniformly, and after spray drying, the aqueous solution of phosphorus-containing compounds is used for aftertreatment. These methods can improve the wear index of the catalyst, so that the catalyst has Good hydrothermal stability and catalytic activity; USP5110776, USP5378670, EP252761, EP300500, EP397183, WO9421378A, CN1085722C, etc. use phosphorus-containing compounds to treat molecular sieves or directly add silicoaluminophosphate molecular sieves as active components to improve the cracking activity of the catalyst and improve Product selectivity, catalysts prepared by these methods have higher light oil yields and low coke yields.

2. It is used to increase the production of diesel oil. For example, CN1072030C mixes the faujasite and the aqueous solution of the phosphorus-containing compound evenly, dries them, and roasts them at 450-600° C. for 0.5 hour, then mixes the phosphorus-containing faujasite with the aluminum sol and the aged pseudo-boehmite slurry, containing or Does not contain clay.

3. It is used to reduce the olefin content in gasoline. For example, CN1325940A provides a method for preparing a phosphorus-containing molecular sieve cracking catalyst. The molecular sieve is soaked in a phosphorus-containing compound solution, stirred, and then dried. This is repeated one or more times, so that the P ₂ O ₅ content on the molecular sieve is 0.05-10 wt. %, and then mixed with double aluminum binder and clay, dried, washed, filtered and then post-treated with phosphorus-containing compound solution to obtain a catalyst. The catalyst can reduce the olefin content in FCC gasoline fraction, and has good activity and selectivity.

4. Used to produce more low-carbon olefins, maintain or increase the octane number of gasoline. Disclosed as CN1042201C, CN1055301C is prolific C ₃ -C ₅ cracking catalysts of olefins, they can both improve isobutylene, isopentene productive rate, can make gasoline productive rate and gasoline octane number maintain at higher level again; CN1072201A, The disclosed cracking catalysts such as CN1085825A, CN1093101A, CN1098130A are used to improve gasoline octane number and olefin yield.

None of the cracking catalysts prepared by the above prior art can simultaneously reduce the olefin content of gasoline and produce more liquefied gas.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a cracking catalyst, the catalyst prepared by the method will reduce the olefin content of gasoline and simultaneously produce more liquefied gas.

The preparation method of catalyst provided by the invention comprises:

(1), preparation of clay slurry

uniformly mixing clay, deionized water, and a phosphorus-containing compound to prepare a clay slurry, and the amount of the phosphorus-containing compound added is 0.1-5.0% by weight of _P2O5 based on the dry weight of the _catalyst ;

(2), preparation of molecular sieve slurry

Mix molecular sieves, deionized water, phosphorus-containing compounds, and rare earth compounds uniformly to prepare a molecular sieve slurry. The amount _of phosphorus-containing compounds added is 0.1-3.0% by weight based on the dry weight of the catalyst. _P2O5 , the amount of rare earth compounds added 0.1-5.0 wt% RE ₂ O ₃ based on the dry weight of the catalyst;

(3), preparation of binder slurry

uniformly mixing the binder, deionized water and optional inorganic acid to prepare a binder slurry;

(4), mixing of slurry

The above clay slurry, molecular sieve slurry and binder slurry are mixed evenly and then dried.

The cracking catalyst prepared by the method of the present invention has a relatively high yield of liquefied gas, especially a high concentration of propylene in the liquefied gas, and reduces the olefin content in gasoline while maintaining a high gasoline yield and gasoline octane number .

Detailed ways

The preparation method of catalyst provided by the invention comprises:

(1), preparation of clay slurry

Mix the clay, deionized water and phosphorus-containing compound uniformly to prepare a clay slurry, the amount of the phosphorus-containing compound added is 0.1-5.0% by weight based on the dry weight of _the catalyst, preferably 0.3-3.5% by weight of _P2O5 ;

(2), preparation of molecular sieve slurry

Mix the molecular sieve, deionized water, phosphorus-containing compound solution, and rare earth compound uniformly to obtain a molecular sieve slurry, and the amount of the phosphorus-containing compound added is 0.1-3.0% by weight based on the dry weight of the catalyst, preferably 0.3-2.5% by weight of _P2 O ₅ , the amount of the rare earth compound added is 0.1-5.0% by weight, preferably 0.3-4.8% by weight of RE ₂ O ₃ based on the dry weight of the catalyst;

(3), preparation of binder slurry

uniformly mixing the binder, deionized water and optional inorganic acid to prepare a binder slurry;

(4), mixing of slurry

After the clay slurry, the molecular sieve slurry and the binder slurry are uniformly mixed, they are then subjected to conventional drying or spray drying.

The preparation of the clay slurry, the molecular sieve slurry and the binder slurry has no strict sequence, and can be prepared at the same time or in different orders.

The cracking catalyst prepared by the method of _the present invention includes 20-70 wt% clay, 15-50 wt% molecular sieve, 7-45 wt% binder, plus 0.2-8.0 wt% _P2O5 , plus 0.1-5.0 wt% RE ₂ O ₃ , all are calculated by the weight of the catalyst on a dry basis.

The clay is selected from one or a mixture of kaolin, halloysite, montmorillonite, diatomite, bentonite and sepiolite, preferably kaolin.

The molecular screening is selected from one or more mixtures of faujasite, zeolite with MFI structure, mordenite, and beta zeolite, and the faujasite is selected from Y-type zeolite or/and X-type zeolite, wherein Y-type The zeolite is selected from phosphorus-containing Y-type zeolite, REY-type zeolite, phosphorus-containing REY-type zeolite, HY-type zeolite, phosphorus-containing HY-type zeolite, REHY-type zeolite, phosphorus-containing REHY-type zeolite, USY-type zeolite, phosphorus-containing A mixture of one or more of USY zeolite, REUSY zeolite, phosphorus-containing REUSY zeolite; the medium-porous zeolite is selected from zeolites with MFI structure, phosphorus, iron and/or rare earth zeolites with MFI structure One or more mixtures of zeolites.

When multiple molecular sieves such as Y-type zeolite and MFI-structured zeolite are used in the catalyst, the weight ratio of the MFI-structured zeolite to Y-type zeolite should be 0.1-2.7, preferably 0.2-2.5.

In the preparation process of the clay slurry and the molecular sieve slurry, phosphorus-containing compounds are added, and the phosphorus-containing compounds include various phosphorus compounds, such as: phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer One or more of phosphoric acid, polymeric phosphate, metaphosphoric acid, metaphosphate, preferably phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, pyrophosphoric acid One or more of potassium, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, potassium hexametaphosphate. More preferably, it is one or a mixture of phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate. A solution of the above phosphorus-containing compound may also be added during the preparation of the clay slurry and the molecular sieve slurry.

A solution of a rare earth compound is added during the preparation of the molecular sieve slurry, and the rare earth compound is rare earth chloride or/and rare earth nitrate, preferably rare earth chloride.

The binder is selected from one or more of alumina sol, silica sol, pseudoboehmite, silica-alumina sol, modified silica-alumina sol, silica-alumina gel, and modified silica-alumina gel A mixture of aluminum sol, silica sol, pseudo-boehmite or a mixture of several of them.

When the binder contains pseudo-boehmite, it is necessary to add an inorganic acid for acidification, and the inorganic acid is hydrochloric acid, nitric acid or phosphoric acid, preferably hydrochloric acid.

The preparation method provided by the invention has the following characteristics:

1. The cracking catalyst prepared by the method has a relatively high yield of liquefied gas, especially the high concentration of propylene in the liquefied gas, and reduces the olefin content in gasoline while maintaining a high gasoline yield and octane number. The addition of phosphorus in an appropriate amount will cause favorable changes in the surface acidity of molecular sieves and clays, which is the result of the interaction of different states of phosphorus with surface aluminum, the hydrogen transfer performance of the catalyst is moderate, and the coke yield is low.

2. This method is to mix three slurries of clay, molecular sieve and binder to form catalyst slurry. This gelation method makes the gelation method of cracking catalyst more flexible, fast and easy to control; before drying, any catalyst slurry No part needs to be heated and aged, which shortens the preparation time of the catalyst, improves the production efficiency, and reduces energy consumption and production cost.

3. The catalyst prepared by this method can adjust certain physical properties of the catalyst in a wide range while maintaining good anti-wear performance, for example, the bulk specific gravity is 0.60-0.82 g/ml, and the pore volume is 0.25-0.45 ml /gram. The larger pore volume means that the coking tendency of cracked products can be reduced and the product distribution can be improved; the different bulk specific gravity means that the cracking catalyst can be applied to the needs of different catalytic cracking units.

The following examples will further illustrate the present invention, but do not limit the present invention thereby.

In the embodiment, the rare earth content in the catalyst sample is measured by fluorescence analysis method, and the phosphorus content is measured by chemical colorimetry, and the bulk specific gravity, pore volume and wear index adopt "Petrochemical Analysis Method (RIPP Test Method)" respectively (Edited by Yang Cuiding and Gu Kanying, 1990, Science Press) for determination by RIPP31-90, RIPP28-90, and RIPP29-90 methods.

The catalysts used for light oil micro-reaction and fixed fluidized bed evaluation were pre-aged at 800°C and 100% steam for 8 hours or 17 hours.

The evaluation conditions for light oil micro-reaction are: the catalyst is broken into particles with a particle diameter of 420-841 microns, the loading capacity is 5 grams, the reaction raw material is straight-run light diesel oil with a distillation range of 235-337 ° C, and the reaction temperature is 460 ° C. The weight space velocity is 16 h ^-1 , and the agent-to-oil ratio is 3.2.

Light oil micro-reactivity MA=(gasoline yield+gas yield+coke yield below 204°C in the product)/total amount of feed*100%=gasoline yield+gas yield+coke yield below 204°C in the product Rate.

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

Example 1

1.3 kilograms of kaolin (dry basis weight, produced by China Kaolin Co.) was added to 0.3 kilograms of 24% by weight (in terms of ammonium dihydrogen phosphate) in the ammonium dihydrogen phosphate (chemically pure, produced by Beijing Chemical Plant) solution, stirred for 1.5 hours, A kaolin slurry is formed.

Get 1.1 kilograms of pseudo-boehmite (in terms of alumina, produced by Shandong Aluminum Factory), 0.8 kilograms of aluminum sol (in terms of alumina, produced by Qilu Catalyst Factory), 5.6 kilograms of deionized water and 282 milliliters of 36 weight percent hydrochloric acid ( Chemically pure, produced by Beijing Chemical Factory) was mixed and stirred for 1.5 hours, and the binder slurry could be obtained without heating and aging.

Get 1.3 kilograms of REY molecular sieve (RE ₂ O ₃ content 18.5 weight %, Na ₂ O content is 1.6 weight %, silicon-aluminum ratio 5.4, Qilu Catalyst Factory production), 0.4 kilogram ZRP-1 molecular sieve (a kind of phosphorus and rare earth has Zeolite with MFI structure, _Na2O content is 0.1% by weight, silicon-alumina ratio is 25, and the content of rare earth oxide is 1.5% by weight, wherein _La2O3 accounts for 53.2% by weight of rare earth oxide, _CeO2 accounts for 53.2% by weight of rare earth _oxide 13.0% by weight, 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, calculated as elemental phosphorus, the phosphorus content is 1.1% by weight, produced by Qilu Catalyst Factory, the same below) Mix evenly with 2.0 kilograms of deionized water adding 69 grams of phosphoric acid (chemically pure, produced by _Beijing Chemical Plant), then add 114 milliliters of rare earth chloride solution (self-made, RE ₂ O The concentration is 219 grams per liter, and the solid rare earth chloride is made of Produced by Baotou Rare Earth Factory in Inner Mongolia, the content of RE ₂ O ₃ is 46% by weight, and the composition of RE ₂ O ₃ is 53.2% by weight of La ₂ O ₃ , 13.0% by weight of CeO _{2 ,} 13.0% by weight of Pr ₆ O ₁₁ , and 20.8% by weight of Nd ₂ O ₃ %, the same below) and 5 milliliters of ammonia water (chemically pure, produced by Beijing Chemical Plant) to make molecular sieve slurry.

Mix the above three slurries uniformly to obtain the catalyst A1 prepared according to the present invention.

The composition of catalyst A1 is: kaolin 26.4 wt%, pseudoboehmite 22.0 wt%, aluminum sol 16.1 wt%, REY type molecular sieve 25.0 wt%, ZRP-1 molecular sieve 8.0 wt%, plus _{P2O5 2.0} wt%, _{RE2O3 0.5} %. The fixed fluidized bed evaluation results of catalyst A1 are listed in Table 1.

Example 2

1.3 kg of kaolin was added to a solution formed by 0.9 kg of deionized water and 139 g of diammonium hydrogen phosphate (chemically pure, produced by Beijing Chemical Plant), and stirred for 1.5 hours to obtain a binder slurry.

1.1 kg of pseudo-boehmite, 0.8 kg of aluminum sol, 3.6 kg of deionized water and 94 ml of 36% by weight hydrochloric acid were mixed and stirred for 1.5 hours to obtain a binder slurry.

Get 1.3 kg of MOY molecular sieve prepared according to CN1325940A (a kind of Y-type zeolite containing phosphorus and rare earth, _RE2O3 content 8.0 wt%, _Na2O content is 1.3 wt%, phosphorus content 1.1 wt%, silicon-aluminum _ratio 5.6, Qilu catalyst factory production), 0.4 kilograms of ZSP-1 molecular sieves (a kind of MFI type zeolite _containing phosphorus and iron, _Fe2O3 content 2.5 weight%, _{P2O5 4.0} weight%, _Na2O content is 0.1 weight%, Si-alumina ratio 25, produced by Qilu Catalyst Factory), mixed evenly with 2.5 kg of deionized water adding 34.5 g of phosphoric acid, then added 115 ml of rare earth chloride solution and 6 ml of ammonia water to obtain a molecular sieve slurry.

Mix the above three slurries uniformly to obtain the catalyst A2 prepared according to the present invention.

The composition of catalyst A2 is: kaolin 26.0 wt%, pseudoboehmite 22.2 wt%, aluminum sol 16.1 wt%, MOY molecular sieve 25.2 wt%, ZRP-1 molecular sieve 8.0 wt%, plus P ₂ O ₅ 2.0 wt%, RE ₂ O ₃ 0.5% by weight. The fixed fluidized bed evaluation results of catalyst A2 are listed in Table 1.

Comparative example 1

According to the preparation method disclosed in Example 2 of CN1325940A, a comparative catalyst was prepared.

Take 1.3 kg of REY molecular sieve, add 2.8 kg of deionized water and 162 g of ammonium dihydrogen phosphate into a solution, stir for 2 hours and mix well, dry at 120°C for 2 hours, roast in air at 500°C for 3 hours, take out and pulverize .

Take 1.1 kg of pseudo-boehmite, add 7.0 kg of deionized water, hydrochloric acid, stir evenly, and age at 70°C for 2 hours, then mix the above crushed phosphorus-containing REY molecular sieve, 0.4 kg of ZRP-1 molecular sieve, and 1.3 kg of kaolin The aged pseudo-boehmite and 0.8 kg of alumina sol were evenly mixed and calcined at 500° C. for 2 hours.

Process the catalyst according to the third step of its example 2 to obtain comparative catalyst A3.

The composition of comparative catalyst A3 is: 26.5% by weight of kaolin, 22.2% by weight of pseudoboehmite, 16.1% by weight of aluminum sol, 25.2% by weight of Y-type molecular sieve, 8.0% by weight of ZRP-1 molecular sieve, and _2.0 % by weight of _P2O5 . The fixed fluidized bed evaluation results of catalyst A3 are listed in Table 1.

Table 1

Catalyst A1 A2 A3 MA(800℃/8h) 78 76 69 Conversion rate, weight % 83.6 83.7 79.2 Product yield, weight % Liquefied gas 28.7 28.3 25.0 gasoline 43.3 42.8 41.1 diesel fuel 11.8 12.1 11.4 coke 7.6 7.9 8.9 Propylene yield in liquefied gas, weight % 11.2 10.8 9.6 Olefin content in gasoline, weight % 24.2 23.5 30.2

It can be seen from the data in Table 1 that the catalysts A1 and A2 have higher activity levels than the comparative catalyst A3, and the olefin content and coke yield in the gasoline fraction are lower, while the liquefied gas and propylene yields are higher.

Example 3

Add 683 grams of kaolin to a solution formed by 467 grams of deionized water and 53.9 grams of sodium hexametaphosphate (chemically pure, produced by Beijing Chemical Plant), and stir for 1.5 hours to obtain a kaolin slurry.

Get 225 grams of ZRP-1 molecular sieves, 225 grams of REY and 75 grams of DASY _0.0 zeolite (a kind of USY zeolite, _Na O content is 0.98% by weight, silicon-aluminum ratio 6.2, produced by Qilu Catalyst Factory, the same below) and add 600 grams of deionized In the water, 41.8 grams of diammonium hydrogen phosphate, 103 milliliters of rare earth chloride solution and 10 milliliters of ammonia water were added, and stirred to make them evenly mixed to form a molecular sieve slurry.

The above two slurries were uniformly mixed with 210 grams of aluminum sol to obtain catalyst B1 prepared according to the present invention.

The composition of catalyst B1 is: kaolin 45.5 wt%, aluminum sol 14.0 wt%, ZRP-1 molecular sieve 15.0 wt%, REY molecular sieve 15.0 wt%, DASY _0.0 molecular sieve 5.0 wt%, plus RE ₂ O ₃ 1.5 wt%, P ₂ O ₅ 4.0% by weight. The fixed fluidized bed evaluation results of catalyst B1 are listed in Table 2.

Comparative example 2

According to the preparation method disclosed in Example 6 of CN1072201A, a comparative catalyst was prepared.

Take 765 grams of kaolin and add it to 210 grams of aluminum sol and stir evenly to obtain carrier slurry.

225 grams of ZSM-5 (Na ₂ O content 0.2% by weight, silicon-aluminum ratio 60, produced by Qilu Catalyst Factory), 225 grams of REY and 75 grams of DASY _0.0 type zeolite were added to 1100 grams of deionized water, and mixed with the above-mentioned carrier after beating The slurries were mixed, dried, washed and dried to obtain comparative catalyst B2.

The composition of comparative catalyst B2 is: kaolin 51.0 wt%, aluminum sol 14.0 wt%, ZSM-5 molecular sieve 15.0 wt%, REY molecular sieve 15.0 wt%, DASY _0.0 molecular sieve 5.0 wt%. The fixed fluidized bed evaluation results of Comparative Catalyst B2 are listed in Table 2.

Comparative example 3

According to the preparation method disclosed in Example 6 of CN1085825A, a comparative catalyst was prepared.

Take 765 grams of kaolin and add it to 210 grams of aluminum sol and stir evenly to obtain carrier slurry.

225 grams of ZRP-1, 225 grams of REY and 75 grams of DASY _0.0 type zeolite were added to 1100 grams of deionized water, beating homogeneously, mixed with the above-mentioned carrier slurry, dried, washed and dried to obtain comparative catalyst B3.

The composition of comparative catalyst B3 is: kaolin 51.0 wt%, aluminum sol 14.0 wt%, ZRP-1 molecular sieve 15.0 wt%, REY molecular sieve 15.0 wt%, DASY _0.0 molecular sieve 5.0 wt%. The fixed fluidized bed evaluation results of Comparative Catalyst B3 are listed in Table 2.

Table 2

Catalyst B1 B2 B3 MA(800℃/8h) 72 66 67 Conversion rate, weight % 77.7 72.5 72.7 Product yield, weight % Liquefied gas 34.9 30.7 31.4 gasoline 32.8 31.6 31.1 diesel fuel 12.2 11.9 11.6 Coke 7.1 7.9 7.8 Propylene yield in liquefied gas, weight % 12.5 10.6 11.0 Olefin content in gasoline, weight % 25.1 30.6 30.9

From the data in Table 2, it can be seen that the catalyst B1 has a higher activity level than the comparative catalysts B2 and B3, and the olefin content and coke yield in the gasoline fraction are lower, while the liquefied gas and propylene yields are higher.

Example 4

1.8 kg of kaolin was added to a solution formed by 1.2 kg of deionized water and 31.5 g of ammonium phosphate (chemically pure, produced by Beijing Chemical Plant), and stirred for 1.5 hours to obtain a kaolin slurry.

1.0 kg of pseudo-boehmite, 0.5 kg of aluminum sol, 3.4 kg of deionized water and 85 ml of 36% by weight hydrochloric acid were mixed and stirred for 1.0 hour to obtain a binder slurry.

Get 0.15 kilograms of REHY molecular sieves (RE ₂ O ₃ content 3.6 weight %, Na ₂ O content is 4.6 weight %, silicon aluminum ratio 5.6, Qilu Catalyst Factory production), 0.6 kilograms of ZRP-1 molecular sieves, 0.9 kilograms of DASY _2.0 molecular sieves (a kind of REUSY zeolite, _RE2O3 content of 1.5% by weight, _Na2O content of 1.2% by weight, silicon _- aluminum ratio of 6.8, produced by Qilu Catalyst Factory, the same below), mixed evenly with 2.0 kilograms of deionized water adding 73.5 grams of ammonium phosphate, Then add 457 milliliters of rare earth chloride solution to make molecular sieve slurry.

Mix the above three slurries uniformly to obtain the catalyst C1 prepared according to the present invention.

The composition of catalyst C1 is: kaolin 35.0 wt%, pseudoboehmite 20.0 wt%, aluminum sol 10.0 wt%, REHY molecular sieve 3.0 wt%, ZRP-1 molecular sieve 12.0 wt%, DASY _2.0 molecular sieve 17.0 wt%, plus RE ₂ O ₃ 2.0 wt%, P ₂ O ₅ 1.0 wt%. The fixed fluidized bed evaluation results of catalyst C1 are listed in Table 3.

Comparative example 4

According to the preparation method disclosed in Example 6 of CN1055301C, a comparative catalyst was prepared.

Stir 0.5 kg of aluminum sol, 1.9 kg of kaolin and deionized water evenly, then add 1.0 kg of pseudoboehmite, mix evenly, and age at 62°C for 2 hours to obtain a carrier slurry. Take 0.3 kg of ZRP-1, 0.4 kg of ZSM-5, 0.2 kg of REHY and 0.9 kg of DASY _2.0 zeolite respectively and add them into deionized water, make a homogeneous slurry, mix with the above-mentioned carrier slurry, dry, wash and dry to obtain comparative catalyst C2.

The composition of comparative catalyst C2 is: kaolin 37.0 wt%, pseudoboehmite 20.0 wt%, aluminum sol 10.0 wt%, ZRP-1 molecular sieve 6.0 wt%, ZSM-5 molecular sieve 7.0 wt%, REHY molecular sieve 3.0 wt%, DASY _2.0 molecular sieves 17.0% by weight. The fixed fluidized bed evaluation results of Comparative Catalyst C2 are listed in Table 3.

It can be seen from the data in Table 3 that the catalyst C1 has a higher activity level than the comparative catalyst C2, and the olefin content and coke yield in the gasoline fraction are lower, while the liquefied gas and propylene yields are higher.

table 3

Catalyst C1 C2 MA(800℃/8h) 71 67 Conversion rate, weight % 75.2 71.5 Product yield, weight % Liquefied gas 32.5 29.2 gasoline 33.2 30.8 diesel fuel 11.7 11.3 Coke 6.8 7.6 Propylene yield in liquefied gas, weight % 11.8 10.1 Olefin content in gasoline, weight % 26.3 31.2

Example 5

1.6 kg of kaolin was added into a solution formed by 1.2 kg of deionized water and 36 g of sodium hexametaphosphate, and stirred for 1.5 hours to obtain a kaolin slurry.

1.4 kg of pseudo-boehmite, 0.3 kg of aluminum sol, 5.5 kg of deionized water and 239 ml of 36% by weight hydrochloric acid were mixed and stirred for 1.0 hour to obtain a binder slurry.

Take 0.5 kg of DASY _0.0 molecular sieve, 1.0 kg of ZSM-5 molecular sieve, mix with 2.0 kg of deionized water added with 144 g of sodium hexametaphosphate, and then add 799 ml of rare earth chloride solution and 15 ml of ammonia water to make a molecular sieve slurry.

Mix the above three slurries uniformly to obtain the catalyst D1 prepared according to the present invention.

The composition of catalyst D1 is: 31.0 wt% of kaolin, 28.0 wt% of pseudoboehmite, 5.0 wt% of aluminum sol, 10.0 wt% of DASY _0.0 molecular sieve, 20.0 wt% of ZSM-5 molecular sieve, plus _3.5 wt% of _RE2O3 , P ₂ O ₅ 2.5% by weight. The fixed fluidized bed evaluation results of catalyst D1 are listed in Table 4.

Comparative example 5

According to the preparation method disclosed in CN1042201C Example 1, a comparative catalyst was prepared.

Add 1.8 kg of kaolin to 0.3 kg of aluminum sol and 5 kg of deionized water, stir evenly, add 360 ml of hydrochloric acid, then add 1.5 kg of pseudo-boehmite, mix evenly, and age at 60°C for 1 hour to obtain a carrier slurry. Take 0.5 kg of DASY _0.0 and P-ZSM-5 molecular sieve respectively (1 kg of ZSM-5 molecular sieve is added to 10 kg of deionized water, 110 ml of 85% phosphoric acid and 88 ml of ammonia water are added to the water), added to 2 kg of deionized water, ball milled After 30 minutes, it was mixed with the above-mentioned carrier slurry and dried to obtain comparative catalyst D2.

The composition of comparative catalyst D2 is: kaolin 35.0%, pseudoboehmite 30.0% by weight, aluminum sol 5.0% by weight, DASY _0.0 molecular sieve 10.0% by weight, P-ZSM-5 molecular sieve 20.0% by weight. The fixed fluidized bed evaluation results of Comparative Catalyst D2 are listed in Table 4.

Example 6

1.6 kg of kaolin was added to a solution formed by 1.2 kg of deionized water and 336 g of ammonium phosphate, and stirred for 1.5 hours to obtain a kaolin slurry.

Get 1.2 kg of pseudo-boehmite, 0.5 kg of silica sol (produced by Beijing Changhong Chemical Factory, SiO 25 wt%), 5.5 kg of deionized water and 239 ml of 36 wt% _hydrochloric acid and mix and stir for 1.0 hour to obtain a binder slurry .

Get 0.2 kilograms of DASY _0.0 molecular sieves, 0.8 kilograms of ZSM-5 molecular sieves, 0.2 kilograms of beta molecular sieves (Na O content 3.2 weight percent, silicon-aluminum ratio 28, Qilu Catalyst Factory production), mix homogeneously with 2.0 kilograms of deionized water that adds 124 grams of phosphoric acid, Add 1027 milliliters of rare earth chloride solution and 15 milliliters of ammonia water to make molecular sieve slurry.

Mix the above three slurries uniformly to obtain the catalyst E prepared according to the present invention.

The composition of catalyst E is: kaolin 32.5 wt%, pseudoboehmite 24.0 wt%, silica sol 10.0 wt%, DASY _0.0 molecular sieve 4.0 wt%, ZSM-5 molecular sieve 16.0 wt%, β molecular sieve 4.0 wt%, plus RE ₂ O ₃ 4.5% by weight, P ₂ O ₅ 5.0% by weight. The fixed fluidized bed evaluation results of Catalyst E are listed in Table 4.

Table 4

Catalyst D1 D2 E MA(800℃/8h) 64 61 63 Conversion rate, weight % 68.5 65.0 67.4 Product yield, weight % Liquefied gas 35.8 32.5 33.2 gasoline 24.0 22.3 24.7 diesel fuel 8.1 8.3 8.4 coke 6.7 7.4 6.5 Propylene yield in liquefied gas, weight % 13.3 11.9 12.8 Olefin content in gasoline, weight % 27.2 31.0 26.9

It can be seen from the data in Table 4 that the catalyst D1 has a higher activity level than the comparative catalyst D2, and the olefin content and coke yield in the gasoline fraction are lower, while the yield of liquefied gas and propylene is higher; catalyst E also It has a higher activity level, and the olefin content and coke yield in the gasoline fraction are lower, while the liquefied gas and propylene yields are higher.

Example 7

1.7 kg of kaolin was added to a solution formed of 2.1 kg of deionized water and 50 g of ammonium phosphate, and stirred for 1.5 hours to obtain a kaolin slurry.

0.1 kg of pseudo-boehmite, 0.8 kg of aluminum sol, 0.7 kg of deionized water and 2 ml of 36% by weight hydrochloric acid were mixed and stirred for 1.0 hour to obtain a binder slurry.

Get 0.8 kilograms of REHY molecular sieves, 0.4 kilograms of ZRP-5 molecular sieves (a kind of zeolite with MFI structure, Na O content 0.1% by weight, silicon _- aluminum ratio 50, produced by Qilu Catalyst Factory, the same below), and add 34 grams of ammonium phosphate 2.0 kg of deionized water was mixed evenly, and then 457 ml of rare earth chloride solution was added to prepare a molecular sieve slurry.

Mix the above three slurries uniformly to obtain the catalyst F prepared according to the present invention.

The composition of catalyst F is: kaolin 43.5 wt%, pseudoboehmite 3.0 wt%, aluminum sol 20.0 wt%, REHY molecular sieve 20.0 wt%, ZRP-5 molecular sieve 10.0 wt%, plus RE ₂ O ₃ 2.5 wt%, P ₂ O ₅ 1.0% by weight. The physical properties and fixed fluidized bed evaluation results of Catalyst F are listed in Tables 5 and 6, respectively.

Example 8

1.3 kg of kaolin was added to a solution formed by 1.2 kg of deionized water and 33 g of phosphoric acid, and stirred for 1.5 hours to obtain a kaolin slurry.

0.5 kg of pseudo-boehmite, 0.6 kg of aluminum sol, 1.8 kg of deionized water and 6 ml of 36% by weight hydrochloric acid were mixed and stirred for 1.0 hour to obtain a binder slurry.

Get 1.0 kg of REHY molecular sieve, 0.4 kg of ZSP-2 molecular sieve (a kind of MFI type zeolite containing phosphorus and iron, _{Fe2O3 2.5} % by weight, _{P2O5 4.0} % by weight, _Na2O content is 0.1% by weight, silicon Aluminum ratio 50, produced by Qilu Catalyst Factory), mixed evenly with 2.0 kg of deionized water adding 23 g of sodium hexametaphosphate, then adding 457 ml of rare earth chloride solution and 8 ml of ammonia water to make a molecular sieve slurry.

Mix the above three slurries uniformly to obtain the catalyst G prepared according to the present invention.

The composition of catalyst G is: 33.5% by weight of kaolin, 13.0% by weight of pseudoboehmite, 15.0% by weight of aluminum sol, 25.0% by weight of REHY molecular sieve, 10.0% by weight of ZRP-5 molecular sieve, plus 2.5% by weight _{of RE2O3} , P ₂ O ₅ 1.0% by weight. The physical properties and fixed fluidized bed evaluation results of Catalyst G are listed in Tables 5 and 6, respectively.

Example 9

0.7 kg of kaolin was added to a solution formed by 1.3 kg of deionized water, 17 g of phosphoric acid and 17 g of sodium hexametaphosphate, and stirred for 2.0 hours to obtain a kaolin slurry.

0.9 kg of pseudo-boehmite, 0.4 kg of aluminum sol, 3.4 kg of deionized water and 9 ml of 36% by weight hydrochloric acid were mixed and stirred for 1.0 hour to obtain a binder slurry.

Take 1.4 kg of REHY molecular sieve, 0.4 kg of ZRP-5 molecular sieve, mix with 2.0 kg of deionized water added with 30 g of diammonium hydrogen phosphate, and then add 457 ml of rare earth chloride solution and 8 ml of ammonia water to make a molecular sieve slurry.

The above three slurries are uniformly mixed to obtain the catalyst H prepared according to the present invention.

The composition of catalyst H is: kaolin 18.5 wt%, pseudoboehmite 23.0 wt%, aluminum sol 10.0 wt%, REHY molecular sieve 35.0 wt%, ZRP-5 molecular sieve 10.0 wt%, plus RE ₂ O ₃ 2.5 wt%, P ₂ O ₅ 1.0% by weight. The physical properties and fixed fluidized bed evaluation results of Catalyst H are listed in Tables 5 and 6, respectively.

table 5

Example Catalyst Bulk specific gravity, g/ml Pore volume, ml/g Wear index, %/hour 7 F 0.80 0.28 1.8 8 G 0.72 0.37 2.1 9 h 0.61 0.43 3.2

Table 6

Catalyst F G h MA(800℃/8h) 75 73 72 Conversion rate, weight % 80.5 80.4 79.2 Product yield, weight % Liquefied gas 29.7 30.3 30.3 gasoline 39.7 38.6 38.3 diesel fuel 10.5 10.5 10.9 Coke 7.9 8.3 8.7 Propylene yield in liquefied gas, weight % 10.6 11.1 11.4 Olefin content in gasoline, weight % 21.1 23.0 24.0

From the data in Table 6, it can be seen that among the three catalysts F, G, and H, catalyst F has a slightly higher activity level, the olefin content in gasoline is lower, the coke yield is lower, and the yield of liquefied gas and propylene is also higher. Low, while agent H has higher olefin content in gasoline fraction, coke yield, and higher yield of liquefied gas and propylene, and agent G is in the middle.

Claims (15)

1. one kind is reduced the also production of cracking catalyst of voluminous liquefied gas of content of olefin in gasoline, it is characterized in that this method comprises:

(1), the preparation of clay slurry

Clay, deionized water and phosphorus-containing compound are mixed, make clay slurry, the phosphorus-containing compound addition is counted the heavy %P of 0.1-5.0 with the butt weight of catalyst ₂O ₅

(2), the preparation of molecular sieve pulp

Molecular sieve, deionized water, phosphorus-containing compound, rare earth compound are mixed, make molecular sieve pulp, the addition of phosphorus-containing compound is counted the heavy %P of 0.1-3.0 with the butt weight of catalyst ₂O ₅, the addition of rare earth compound is counted the heavy %RE of 0.1-5.0 with the butt weight of catalyst ₂O ₃

(3), the preparation of binding agent slurries

Binding agent, deionized water and optional inorganic acid are mixed, make the binding agent slurries;

(4), the mixing of slurries

Above-mentioned clay slurry, molecular sieve pulp and binding agent slurries are mixed the back drying.

2. method according to claim 1 is characterized in that described clay is selected from one or more the mixture in kaolin, imvite, diatomite, bentonite, the sepiolite.

3. method according to claim 1 is characterized in that one or more the mixture of described molecular screening in faujasite, the zeolite with MFI structure, modenite, β zeolite.

4. method according to claim 3 is characterized in that described faujasite is selected from y-type zeolite or/and X type zeolite.

5. method according to claim 4 is characterized in that described y-type zeolite is selected from one or more the mixture in phosphorous y-type zeolite, REY type zeolite, HY type zeolite, REHY type zeolite, USY type zeolite, the REUSY type zeolite.

6. method according to claim 3 is characterized in that the zeolite of the described MFI of having structure is selected from ZSM-5, the mixture of one or more in the zeolite with MFI structure of one or more among phosphorous, iron, zinc, the rare earth.

7. method according to claim 3 is characterized in that having the zeolite of MFI structure and the weight ratio of y-type zeolite is 0.1-2.7.

8. method according to claim 1 is characterized in that described phosphorus-containing compound is selected from one or more mixtures in phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate.

9. method according to claim 8 is characterized in that described phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium phosphate trimer, the calgon.

10. method according to claim 1 is characterized in that described rare earth compound is that rare earth chloride is or/and nitric acid rare earth.

11. method according to claim 1 is characterized in that described binding agent is selected from one or more the mixture in aluminium colloidal sol, Ludox, boehmite, silicon-aluminum sol, the silica-alumina gel.

12. method according to claim 11 is characterized in that when binding agent contains boehmite, must add inorganic acid and carry out acidifying, described inorganic acid is hydrochloric acid, nitric acid or phosphoric acid.

13. method according to claim 2 is characterized in that described kaolin is halloysite.

14. method according to claim 5, it is characterized in that described REY type zeolite is phosphorous REY type zeolite, described HY type zeolite is phosphorous HY type zeolite, described REHY type zeolite is phosphorous REHY type zeolite, described USY type zeolite is phosphorous USY type zeolite, and described REUSY type zeolite is phosphorous REUSY type zeolite.

15. method according to claim 11 is characterized in that described silicon-aluminum sol is the silicon-aluminum sol of modification, described silica-alumina gel is the silica-alumina gel of modification.