CN1200078C - Phosphorus-contained gamma zeolite as cracking catalyst and its preparing process - Google Patents

Abstract

A phosphorus-containing Y-type zeolite cracking catalyst contains phosphorus-containing Y-type zeolite and an aluminum binder, with or without clay, based on the total weight of the catalyst, the content of the phosphorus-containing Y-type zeolite is 10-60% by weight, Based on alumina, the content of the aluminum binder is 10-60% by weight, the content of the clay is 0-75% by weight, and the phosphorus-containing Y-type zeolite contains a phosphorus component and a silicon component , the silicon component is supported by impregnating the zeolite with a silicon compound solution, based on the phosphorus-containing Y-type zeolite, in terms of SiO ₂ , the content of the silicon component is 1-15% by weight, in terms of P ₂ Based on O ₅ , the content of the phosphorus component is 0.1-15% by weight. Compared with conventional phosphorus-containing cracking catalysts, the cracking catalyst has stronger heavy oil conversion capability and better product distribution.

Description

A kind of phosphorus-containing Y-type zeolite cracking catalyst and preparation method thereof

The invention relates to a faujasite hydrocarbon cracking catalyst and a preparation method thereof. More specifically, it relates to a phosphorus-containing Y-type zeolite hydrocarbon cracking catalyst and a preparation method thereof.

The introduction of phosphorus into the Y-type zeolite can improve the catalytic performance of the zeolite, and further improve the catalytic performance of the cracking catalyst containing the Y-type zeolite.

EP252,761A2 discloses a hydrocarbon cracking catalyst comprising (a) a non-zeolitic inorganic oxide matrix and (b) an ultrastable Y-type crystalline zeolite. The zeolite is pretreated by contacting the zeolite with a phosphorus-containing compound for a time sufficient to load the zeolite with an effective amount of phosphorus.

EP397,183 discloses a composition comprising an ion-exchanged NaY zeolite with an _Na2O content of 2-5% by weight and _0.1-4.0 % by weight of phosphorus, calculated as _P2O5 . The preparation method of the composition comprises (a) ion-exchanging and washing an O zeolite to obtain an exchanged Y-type zeolite with a Na ₂ O content of 1-5% by weight, (b) exchanging the Y-type zeolite with a A phosphorus compound solution is mixed and reacted, and the phosphorus compound is selected from a group _consisting of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and sodium dihydrogen phosphate; (c) recovery is based on _P2O5 , and the phosphorus content is 0.1- 4% by weight phosphorus-containing Y-type zeolite product.

In the phosphorus modification method of zeolite, the method of impregnating Y-type zeolite with phosphorus-containing compound solution and obtaining phosphorus-containing Y-type zeolite through hydrothermal treatment is the main method for phosphorus modification of Y-type zeolite. Through such treatment, Y can be removed. Part of the aluminum in the crystal lattice of Y-type zeolite reduces the unit cell of Y-type zeolite, improves the hydrothermal stability of Y-type zeolite, and simultaneously makes phosphorus more effectively combine with zeolite, so that the catalyst containing this phosphorus-containing Y-type zeolite Selectivity has also been somewhat improved. However, after the Y-type zeolite is modified by phosphorus, its crystallinity decreases obviously, which not only causes a large loss of zeolite, but also causes the cracking catalyst containing this phosphorus-containing Y-type zeolite to have poor conversion ability and product distribution of heavy oil.

The purpose of the present invention is to overcome the shortcomings of poor heavy oil conversion ability and poor product distribution of phosphorus-containing Y-type zeolite catalysts in the prior art, and provide a phosphorus-containing Y-type catalyst with strong heavy oil conversion ability and good product distribution. Zeolite cracking catalyst and its preparation method.

The catalyst provided by the invention contains phosphorus-containing Y-type zeolite and aluminum binder, with or without clay, wherein, based on the total weight of the catalyst, the content of the phosphorus-containing Y-type zeolite is 10-60% by weight. In terms of aluminum, the content of the aluminum binder is 10-60% by weight, the content of the clay is 0-75% by weight, and the phosphorus-containing Y-type zeolite contains a phosphorus component and a silicon component, so The silicon component is loaded by impregnating the Y-type zeolite with a silicon compound solution, calculated as _SiO2 and based on the phosphorus-containing Y-type zeolite, the content of the silicon component is 1-15% by weight, in the range of Based on P ₂ O ₅ , the content of the phosphorus component is 0.1-15% by weight.

The preparation method of the catalyst provided by the invention comprises mixing and beating phosphorus-containing Y-type zeolite, clay, aluminum binder and deionized water, and then drying, wherein, the consumption of phosphorus-containing Y-type zeolite, clay, aluminum binder makes the final The catalyst contains 10-60% by weight of phosphorus-containing Y-type zeolite, calculated as alumina, 10-60% by weight of aluminum binder and 0-75% by weight of clay, and the preparation method of the phosphorus-containing Y-type zeolite includes A raw material Y-type zeolite is impregnated with a solution of a phosphorus compound and a silicon compound solution, calculated as SiO ₂ , and the amount of the silicon compound solution is such that the silicon-containing component in the obtained phosphorus-containing Y-type zeolite is 1-15% by weight, with In terms of P ₂ O ₅ , the phosphorus compound solution is used in an amount such that the phosphorus-containing component in the obtained phosphorus-containing Y-type zeolite is 0.1-15% by weight.

According to the catalyst provided by the present invention, based on the total weight of the catalyst, the content of the phosphorus-containing Y-type zeolite is 10-60% by weight, preferably 15-60% by weight, based on alumina, and the content of the aluminum binder is The content is 10-60% by weight, preferably 15-55% by weight, and the content of the clay is 0-75% by weight, preferably 0-60% by weight.

According to the catalyst provided by the present invention, in the phosphorus-containing Y-type zeolite, the content of the silicon component is 1-15% by weight, preferably 5-12% by weight, and the content of the phosphorus component is 0.1-15% by weight. % by weight, preferably 2-10% by weight.

The silicon component is loaded by impregnating the zeolite with a silicon compound solution, and the silicon compound solution is selected from one or more of silicon compound aqueous solutions or organic solutions and liquid silicon compounds, such as silicon One or more of sol, water glass, fluorosilicate aqueous solution, organosilicon compound and their solutions, the preferred silicon compound solution is selected from silica sol, water glass, fluorosilicate aqueous solution, dimethyl silicone oil, One or more of phenylmethyl silicone oils, the more preferred silicon compound solution is selected from silica sol, water glass, ammonium fluorosilicate aqueous solution, phenylmethyl silicone oil 255, phenylmethyl silicone oil 250, phenylmethyl silicone oil 274 , One or more of simethicone oil. The particularly preferred silicon compound solution is selected from one or more of silica sol, water glass and ammonium fluorosilicate aqueous solution.

According to the catalyst provided by the present invention, the phosphorus-containing Y-type zeolite used has a relative crystallinity of not less than 70% after hydrothermal treatment at 550-850° C. for 15 minutes to 5 hours, and the relative crystallinity mentioned in the present invention is provided by the present invention. The percentage value of the crystallinity of phosphorus-containing Y-type zeolite and the crystallinity of NaY raw material (defining its crystallinity is 100%), the measuring method of this relative crystallinity is referring to " petroleum chemical industry analysis method (RIPP test method) " (edited by Yang Cuiding etc. , Science Press, 414-415, published in 1990).

The phosphorus-containing Y-type zeolite used in the catalyst provided by the invention has the following pore distribution. After hydrothermal treatment at 550-850° C. for 15 minutes to 5 hours, the pore volume of the secondary pores of the phosphorus-containing Y-type zeolite accounts for 15-15% of the total pore volume. 75%, preferably 20-60%. The secondary pores refer to pores with a diameter of 20-1000 angstroms except the micropores in the zeolite crystal. The total pore volume is determined by low-temperature nitrogen adsorption method, see "Petrochemical Analysis Method (RIPP Test Method)" (edited by Yang Cuiding et al., Science Press, 424-426, published in 1990). From the adsorption isotherm, the micropore volume of the molecular sieve is determined according to the T plot method, and the total pore volume is subtracted from the micropore volume to obtain the secondary pore volume.

According to the catalyst provided by the present invention, the clay is selected from one or more of clays commonly used in cracking catalysts, such as kaolin, halloysite, montmorillonite, diatomaceous earth, and one or more of cumulated clay , preferably kaolin. The aluminum binder is selected from commonly used aluminum binders for cracking catalysts, preferably pseudoboehmite and/or aluminum sol.

According to the preparation method of the catalyst provided by the present invention, the step of impregnating Y-type zeolite with a silicon-containing compound can be carried out before, after or simultaneously with the step of impregnating phosphorus. The solution impregnated the Y-type zeolite, that is, the steps of impregnating phosphorus and silicon compounds were carried out simultaneously.

The phosphorus-containing compound is selected from various phosphorus compounds commonly used in the field, such as one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate. The silicon-containing compound has been described above. The concentration of the phosphorus compound and silicon compound solution is not important, as long as the phosphorus compound and silicon compound can be uniformly impregnated on the Y-type zeolite, if the solution concentration is low, multiple impregnations can also be performed, but one impregnation is preferred.

The raw material Y-type zeolite can be selected from various Y-type zeolites, such as one or more of NaY, NH ₄ Y, HY zeolite, and ultra-stable Y zeolite, among which, the sodium oxide content is preferably 3-10% by weight. Zeolite Y, such as NaY with a sodium oxide content of 3-10% by weight. The use of a Y zeolite with a high sodium oxide content is more advantageous for the purposes of the present invention, for reasons which will be discussed hereinafter. Therefore, when one or more of NH ₄ Y zeolite, HY, and zeolite ultrastable Y zeolite are used as raw materials, if the sodium content is less than 3-10% by weight, although it can be directly used as the raw material of the present invention, the preferred situation Next, use a solution containing sodium ions to perform ion exchange with the zeolite, so that the zeolite contains 3-10% by weight of sodium oxide.

According to the preparation method of the catalyst provided by the present invention, after impregnating phosphorus and silicon compounds, it is also possible, and preferably, to have a step of hydrothermally treating the Y-type zeolite impregnated with phosphorus and silicon compounds, which step includes, at 550-850°C, Preferably at a temperature of 600-750° C., the Y-type zeolite is contacted with an atmosphere containing water vapor for at least 10 minutes, preferably 15 minutes to 5 hours. The atmosphere containing water vapor can be 100% water vapor, or a mixture of water vapor containing at least 10% water vapor by volume and an inert gas. The inert gas refers to a gas that has no destructive effect on zeolite during the hydrothermal treatment process. , such as one or more of air, nitrogen, oxygen, carbon dioxide gas, and gas of group zero elements in the periodic table. Among them, one or more of air, nitrogen and carbon dioxide are preferred. In the process of hydrothermal treatment, dealumination occurs on zeolite. Since the phosphorus-containing Y-type zeolite used in the catalyst provided by the invention contains silicon components, part of the silicon atoms can migrate to the vacancies formed by the dealumination of Y-type zeolite, and the zeolite is dealuminized. Silicon supplementation, although zeolites with low sodium oxide content can also be used, but in zeolites with high sodium oxide content, the presence of sodium oxide can slow down the dealumination speed of zeolite, so that the speed of silicon atoms entering dealumination vacancies is relatively accelerated. Therefore, Y-type zeolites with a sodium oxide content of 3-10% by weight are preferred. The effect of silicon supplementation keeps the zeolite skeleton structure. Therefore, the hydrothermal treatment not only makes the zeolite produce many secondary pores, but also makes phosphorus and zeolite better combined together, and because of the silicon supplementation effect of the silicon component on the zeolite, the zeolite framework structure It can be complete, has higher crystallinity than the prior art, and overcomes the disadvantage of low crystallinity of phosphorus-containing Y-type zeolite in the prior art after hydrothermal treatment. An increase in relative crystallinity means a reduction in the fraction of zeolite transformed into amorphous silica-alumina, ie a reduction in raw material waste.

According to the preparation method of the catalyst provided by the present invention, the drying of the slurry adopts various existing methods, such as drying, air drying, spray drying and other methods. The drying temperature can be from room temperature to 700°C, preferably from room temperature to 120°C. Drying after washing also adopts conventional methods, and the drying temperature can be from room temperature to 300°C, preferably from room temperature to 120°C.

The purpose of the washing is to remove impurity ions in the catalyst, and the washing method is well known to those skilled in the art. For example, the washing can be done with deionized water, or with a concentration of 0.8-1.2% by weight hydrochloric acid solution, ammonia solution and deionized water containing 0.5-0.8% by weight of ammonia, and the amount of liquid used for each wash is solid 10-20 times.

Due to the use of this special phosphorus-containing Y-type zeolite, the catalyst provided by the invention has better catalytic performance than the prior art, which is manifested in that the catalyst provided by the invention has stronger heavy oil conversion ability and better product distribution. For example, at a reaction temperature of 500°C, an agent-to-oil ratio of 6, and a space velocity of 16 h-1, using a pipe oil as a raw material, the catalyst provided by the invention is evaluated in a small fixed fluidized bed, and the conversion rate Up to 72.4% by weight, light oil yield up to 78.1% by weight, C5 ⁺ gasoline yield up to 55.9% by weight, coke yield up to 5.1% by weight, while under the same conditions, with the same content of existing phosphorus-containing zeolites During catalyst, conversion rate, light oil yield, gasoline yield only have 70.5 weight % respectively, 73.2 weight %, 50.8 weight %, and coke yield then is as high as 7.1 weight %, adopt the catalyst provided by the invention and adopt the existing containing Compared with the catalyst of phosphozeolite, the conversion rate, light oil yield and gasoline yield increased by 2.7%, 6.7% and 10.0% respectively, while the coke yield decreased by 28.2%.

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

Example 1

Preparation of phosphorus-containing Y-type zeolite used in the catalyst provided by the invention.

1. with 100 grams (dry basis weight), the NaY type zeolite (sodium oxide content 14% by weight, produced by Qilu Catalyst Factory) and 2 liters of concentration that the unit cell constant is 2.473 nanometers are 5% by weight NH ₄ Cl aqueous solution at 60 ℃ Perform ion exchange for 0.5 hours, filter, wash the filter cake with deionized water until there is no acid radical, and dry to obtain NH ₄ NaY zeolite, the Na ₂ O content of which is 4.9% by weight.

2. 8.22 grams of diammonium hydrogen phosphate (produced by Beijing Chemical Plant, analytically pure) are dissolved in 20 grams of decationized water and stirred evenly, then added to 80 grams of silica sol (commercial product of Beijing Changhong Chemical Plant, containing 12% by weight SiO ₂ ) to obtain a solution of a phosphorus-containing compound and a silicon compound, impregnate 90 grams of the NH ₄ NaY-type zeolite prepared above with the obtained solution, and then dry at 120° C. to obtain the phosphorus-containing Y-type zeolite used in the catalyst provided by the invention A. The phosphorus and silicon contents of phosphorus-containing Y-type zeolite A are shown in Table 1. The impregnated silicon and phosphorus contents were obtained by calculation.

Comparative Example 1

Reference preparation of phosphorus-containing Y-type zeolite.

1. Prepare NH ₄ NaY zeolite with Na ₂ O content of 3.8% by weight according to the method in 1 of Example 2. Dissolve 7.30 g of diammonium hydrogen phosphate in 100 g of deionized water, impregnate 90 g of the NH ₄ NaY zeolite obtained in step 1 with the obtained diammonium hydrogen phosphate solution, and dry at 120° C. to obtain the reference phosphorus-containing Y-type zeolite A1. The phosphorus content in the reference phosphorus-containing Y-type zeolite A1 is listed in Table 1.

Example 2

Preparation of phosphorus-containing Y-type zeolite used in the catalyst provided by the invention.

1. Perform ion exchange on the same NaY zeolite as in Example 1, except that the concentration of the NH ₄ Cl aqueous solution is 10% by weight, to obtain NH ₄ NaY zeolite with a sodium oxide content of 3.8% by weight.

2. prepare phosphorus-containing zeolite by the method for example 1, difference is that the consumption of diammonium hydrogen phosphate is 4.11 grams, and deionized water consumption is 15 grams, obtains the used phosphorus-containing Y type zeolite B of catalyst provided by the invention. The phosphorus and impregnated silicon contents of phosphorus-containing Y-type zeolite B are listed in Table 1.

Example 3

Preparation of phosphorus-containing Y-type zeolite used in the catalyst provided by the invention.

1. The same NaY zeolite was ion-exchanged according to the method of Example 1 to obtain NH ₄ NaY zeolite with a sodium oxide content of 4.9% by weight.

2. Dissolve 12.33 grams of diammonium hydrogen phosphate in 25 grams of water, mix the resulting diammonium hydrogen phosphate solution with 190 milliliters of 1 mol/liter ammonium fluorosilicate (chemically pure, produced by Beijing Chemical Plant) solution, and use impregnate 90 g of the NH ₄ NaY zeolite obtained in Step 1, and dry at 120° C. to obtain phosphorus-containing Y-type zeolite C used in the catalyst provided by the present invention. The phosphorus and impregnated silicon contents of phosphorus-containing Y-type zeolite C are listed in Table 1.

Example 4

Preparation of phosphorus-containing Y-type zeolite used in the catalyst provided by the invention.

1. 100 grams (dry weight) unit cell constant is 2.446 nanometer ultrastable Y zeolite (Na ₂ O content is 0.8 weight %, Qilu Catalyst Factory produces) and 2 liters of concentrations are 5 weight % Na ₂ SO ₄ aqueous solution Mix, carry out ion exchange at 60° C. for 0.5 hour, filter, wash the filter cake with deionized water until there are no acid radicals, and dry to obtain an ultrastable Y zeolite with a sodium oxide content of 4.6% by weight.

2. Dissolve 8.22 grams of diammonium hydrogen phosphate in 20 grams of deionized water, mix the obtained diammonium hydrogen phosphate solution with 120 ml of 0.5 mol/liter ammonium fluorosilicate solution, and impregnate 90 grams of it with the obtained mixed solution Step 1 The ultrastable Y-type zeolite obtained in the method is dried to obtain phosphorus-containing Y-type zeolite D used in the catalyst provided by the invention. Table 1 shows the contents of phosphorus and impregnated silicon in phosphorus-containing Y-type zeolite D.

Table 1 instance number Zeolite number Phosphorus content, weight % (calculated as P ₂ O ₅ ) Impregnated silicon content, weight % (calculated as SiO ₂ ) 1 A 4.2 9.2 Contrast 1 A1 4.2 - 2 B 2.2 9.4 3 C 6.1 10.6 4 D. 4.4 7.0

Instance 5-8

The following examples illustrate the properties of the phosphorus-containing Y-type zeolites used in the catalysts provided by the present invention after hydrothermal treatment.

The phosphorus-containing Y-type zeolites prepared by examples 1-4 are respectively at different temperatures, roasted for different times in a water vapor atmosphere, measure their relative crystallinity and unit cell constant with X-ray diffraction, and use low-temperature nitrogen adsorption BET The specific surface and pore volume were determined by the method. The results are listed in Table 2.

Comparative example 2

This comparative example illustrates the properties of a reference phosphorus Y zeolite which was hydrothermally treated.

The zeolite was hydrothermally treated according to the method of Example 6, except that the zeolite used was the reference phosphorus-containing Y-type zeolite B1 prepared in Comparative Example 1. The results are listed in Table 2.

Table 2 instance number 5 Comparative example 2 6 7 8 Zeolite number A A1 B C D. Hydrothermal treatment temperature, ℃ 600 650 650 700 750 Hydrothermal treatment time, minutes 20 60 60 90 120 water vapor atmosphere 100% 100% 100% 50%* 100% Relative crystallinity, % 80 60 75 73 70 Unit cell constant, Angstroms 24.59 24.50 24.52 24.50 24.42 Specific surface, ^m2 /g 628 558 602 588 582 Total pore volume, ml/fill 0.369 0.349 0.362 0.344 0.340 Secondary pore volume, ml/g 0.088 0.095 0.100 0.107 0.137 Percentage of secondary pores in total pore volume 23.8 27.2 27.6 31.1 40.3

*A mixture of water vapor and air containing 50% water vapor by volume

As can be seen from the results of Table 2, after high-temperature hydrothermal treatment, compared with the existing phosphorus-containing Y-type zeolite, the relative crystallinity of the phosphorus-containing Y-type zeolite used in the catalyst provided by the invention is greatly improved. After hydrothermal treatment, The relative crystallinity is not less than 70%, while other physical and chemical properties are basically the same. For example, after the phosphorus-containing Y-type zeolite B used in the catalyst provided by the invention is roasted in 100% water vapor at 650°C for 60 minutes, the relative crystallinity is 75%, while the reference phosphorus-containing Y-type zeolite B1 prepared by the prior art , after processing under the same conditions, its relative crystallinity has only 60% respectively, and the relative crystallinity of the phosphorus-containing Y-type zeolite used in the catalyst provided by the invention has improved by 25% compared with the reference phosphorus-containing Y-type zeolite, which means that it is different from the existing Compared with the technology, the present invention loses 25% less zeolite.

Example 9

The preparation of the catalyst provided by the invention.

1. Mix 80 grams of pseudoboehmite (containing Al ₂ O ₃ 34.8% by weight, produced by Shandong Aluminum Factory) and 70 grams of deionized water for beating, then add 23 grams of hydrochloric acid with a concentration of 37% by weight, stir evenly, and heat up to 70° C. and aged for 1.5 hours to obtain aged pseudo-boehmite slurry.

2. the phosphorus-containing Y-type zeolite A prepared by 50 gram (dry basis weight) example 1 was carried out hydrothermal treatment in 100% steam at 500 ℃ for 2 hours, then mixed with 30 gram aluminum sol (containing Al ₂ O ₃ 21 weight %, produced by Qilu Catalyst Factory), 50 grams (solid content 85% by weight) kaolin (produced by Suzhou Kaolin Company) and the above-mentioned aged pseudo-boehmite were mixed evenly. After roasting at 500°C for 2 hours, use 20 times the weight of the dry-based sample to contain HCl 0.84% by weight and NH ₃ ·H ₂ O 0.62% by weight solution, ammonia solution containing NH ₃ ·H ₂ O 0.17% by weight and remove Ionized water is mixed and beaten, washed, filtered, and dried to obtain the catalytic cracking catalyst C1 containing phosphorus-containing Y-type zeolite provided by the present invention. The composition of catalyst C1 is listed in Table 3. The composition of the catalyst was calculated from .

Comparative example 3

This comparative example illustrates the preparation of a reference catalyst.

The catalyst was prepared according to the method of Example 9, except that the phosphorus-containing Y-type zeolite A1 prepared in Comparative Example 1 was used instead of the phosphorus-containing Y-type zeolite A prepared in Example 1 to obtain the reference catalyst CB1. The composition of reference catalyst CB1 is listed in Table 3.

Example 10

The preparation of the catalyst provided by the invention.

Prepare the catalyst as in Example 9, except that the phosphorus-containing Y-type zeolite A prepared in Example 1 is not hydrothermally treated to obtain the catalytic cracking catalyst C2 containing phosphorus-containing Y-type zeolite provided by the present invention. The composition of catalyst C2 is listed in Table 3.

Comparative example 4

This comparative example illustrates the preparation of a reference catalyst.

The catalyst was prepared according to the method of Example 10, except that the phosphorus-containing Y-type zeolite A1 prepared in Comparative Example 1 was used instead of the phosphorus-containing Y-type zeolite A prepared in Example 1 to obtain the reference catalyst CB2. The composition of reference catalyst CB2 is listed in Table 3.

Example 11

The preparation of the catalyst provided by the invention.

1. Mix 70 grams of pseudoboehmite (containing Al ₂ O ₃ 34.8% by weight, produced by Shandong Aluminum Factory) and 70 grams of deionized water for beating, then add 20 grams of hydrochloric acid with a concentration of 37% by weight, stir evenly, and heat up to 70° C. and aged for 1.5 hours to obtain aged pseudo-boehmite slurry.

2. the phosphorus-containing Y-type zeolite B prepared by 50 gram (dry basis weight) example 2 was carried out hydrothermal treatment in 100% steam at 650 ℃ for 1 hour, then mixed with 47.6 gram aluminum sol (containing Al ₂ O ₃ 21 weight %, produced by Qilu Catalyst Factory) and the above-mentioned aged pseudo-boehmite were mixed uniformly. After roasting at 500°C for 2 hours, use 20 times the weight of the dry-based sample containing HCl 0.84% by weight and NH ₃ ·H ₂ O 0.62% by weight solution, NH ₃ ·H ₂ O containing 0.17% by weight ammonia solution Deionized water is mixed and beaten, washed, filtered, and dried to obtain the phosphorus-containing Y-type zeolite catalytic cracking catalyst C3 provided by the present invention. The composition of catalyst C3 is listed in Table 3.

Example 12

The preparation of the catalyst provided by the invention.

1. Mix 60 grams of pseudoboehmite (containing Al ₂ O ₃ 34.8% by weight, produced by Shandong Aluminum Factory) and 70 grams of deionized water for beating, then add 17 grams of hydrochloric acid with a concentration of 37% by weight, stir evenly, and heat up to 70° C. and aged for 1.5 hours to obtain aged pseudo-boehmite slurry.

2. the phosphorus-containing Y-type zeolite prepared by 50 gram (dry weight) example 3 was carried out hydrothermal treatment in 100% steam at 500 ℃ for 2 hours, then with 40 gram aluminum sol (containing Al ₂ O ₂₁ weight % , produced by Qilu Catalyst Factory), 35 grams (solid content 85% by weight) of kaolin (produced by Suzhou Kaolin Company) and the above-mentioned aged pseudo-boehmite were mixed evenly. After roasting at 500° C. for 2 hours, use 20 times the weight of the dry base sample containing HCl 0.84 wt % and NH ₃ H ₂ O 0.62 wt % solution, NH ₃ H ₂ O 0.17 wt % ammonia solution and Deionized water is mixed with beating, washed, filtered, and dried to obtain phosphorus-containing Y-type zeolite catalytic cracking catalyst C4 provided by the present invention. The composition of catalyst C4 is listed in Table 3.

Example 13

The preparation of the catalyst provided by the invention.

1. Mix 40 grams of pseudo-boehmite (containing Al ₂ O ₃ 34.8% by weight, produced by Shandong Aluminum Factory) and 70 grams of deionized water for beating, then add 12 grams of hydrochloric acid with a concentration of 37% by weight, stir evenly, and heat up to 70° C. and aged for 1.5 hours to obtain aged pseudo-boehmite slurry.

2. the phosphorus-containing Y-type zeolite prepared by 50 gram (dry basis weight) example 4 was carried out hydrothermal treatment in 100% steam at 500 ℃ for 2 hours, then mixed with 15 gram aluminum sol (containing Al ₂ O ₃ x 21 weight %, produced by Qilu Catalyst Factory), 50 grams (solid content 85% by weight) kaolin (produced by Suzhou Kaolin Company) and the above-mentioned aged pseudo-boehmite were mixed evenly. After roasting at 500°C for 2 hours, use 20 times the weight of _the dry-based sample to contain 0.84% by weight of HCl and a solution of _0.62 % by weight _{of NH3} . Mix it with deionized water for beating, wash, filter, and dry to obtain the catalyst C5 provided by the present invention. The composition of catalyst C5 is listed in Table 3.

table 3 instance number Catalyst number Catalyst composition, wt% Phosphorous Y-type zeolite Aluminum binder (calculated as alumina) Kaolin 9 C1 39.5 25.0 33.5 Comparative example 3 CB1 39.5 25.0 33.5 10 C2 39.5 25.0 33.5 Comparative example 4 CB2 39.5 25.0 33.5 11 C3 59.3 40.7 - 12 C4 45.9 26.6 27.3 13 C5 45.6 15.6 38.8

Instances 14-15

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

Catalysts C1 and C2 prepared in Example 9 and Example 10 were aged at 800° C. in 100% water vapor for 4 hours respectively, and the pipeline oil delivery shown in Table 4 was used as raw material, and the catalyst was evaluated on a small-scale fixed fluidized bed reactor The catalytic performance of A, the composition of the product analyzed by gas chromatography, the reaction conditions and the reaction results are listed in Table 5.

Among them, conversion rate = dry gas yield + liquefied gas yield + gasoline yield + coke yield

Light oil yield = gasoline yield + diesel yield.

Comparative example 5-6

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

The catalyst is aged by the method of example 14-15 and the catalyst after aging is evaluated, and difference is to replace catalyst C1 and C2 with reference catalyst CB1 and CB2 prepared by comparative example 3 and 4 respectively, reaction condition and reaction result column in Table 5.

Table 4 Density (20℃), g/ ^cm3 0.9044 Kinematic viscosity, mm ² /s50℃100℃ 57.699.96 freezing point, ℃ 40.0 Carbon residue, wt% 2.97 Molecular weight (measured) 390 C ₇ insoluble matter 0.37 C, weight % 85.98 H, weight % 12.86 S, weight% 0.55 Alkaline nitrogen, ppm 1000 Distillation range, °C initial boiling point 5% 10% 30% 50% 70% 90% 243294316395429473530

table 5 instance number 14 Comparative example 5 15 Comparative example 6 catalyst C1 CB1 C2 CB2 Reaction temperature, °C 500 500 500 500 Agent to oil ratio 6 6 6 6 Airspeed, hour ^-1 16 16 16 16 Conversion rate, weight % 72.4 70.5 71.9 69.8 Light oil yield, weight % 78.1 73.2 74.5 71.0 Product composition, wt% H ₂ -C ₂ 1.2 1.5 1.5 1.8 liquefied gas 11.3 13.7 13.7 14.6 gasoline 55.9 50.8 52.9 49.1 diesel fuel 22.2 22.4 21.6 21.9 heavy oil 5.4 7.1 6.5 8.3 Coke 4.0 4.5 3.8 4.3

As can be seen from the results in Table 5, compared with the reference catalyst, the catalyst provided by the invention has higher activity, higher light oil yield, higher gasoline selectivity and lower coke selectivity , which shows that the catalyst provided by the present invention has stronger heavy oil conversion capacity and better product distribution than the prior art.

Instances 16-18

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

The catalysts were aged according to the method of Examples 14-15, and the aged catalysts were evaluated except that catalysts C3, C4 and C5 prepared in Examples 11-13 were used respectively. The reaction conditions and reaction results are listed in Table 6.

Table 6 instance number 16 17 18 catalyst C3 C4 C5 Reaction temperature, °C 500 500 500 Agent to oil ratio 6 6 6 Airspeed, hour ^-1 16 16 16 Conversion rate, weight % 74.8 70.9 72.6 Light oil yield, weight % 76.6 75.9 76.9 Product composition, wt% H ₂ -C ₂ 1.9 1.8 1.5 liquefied gas 12.5 12.0 12.0 gasoline 56.2 53.2 55.0 diesel fuel 20.4 22.7 21.9 heavy oil 4.8 6.4 5.5 Coke 4.2 3.9 4.1

Claims (18)

1. phosphorus-contained gamma-type zeolite as cracking catalyst, this catalyzer contains P-contained Y-zeolite, al binder, contain or argillaceous not, it is characterized in that, with the total catalyst weight is benchmark, the content of described P-contained Y-zeolite is the heavy % of 10-60, in aluminum oxide, the content of described al binder is the heavy % of 10-60, the heavy % of the content 0-75 of described clay, described P-contained Y-zeolite contains a kind of phosphorus component and a kind of silicon components, described silicon components is with in the method load of silicon compound solution dipping y-type zeolite, with SiO ₂Meter and be benchmark with described P-contained Y-zeolite, the content of described silicon components is the heavy % of 1-15, with P ₂O ₅Meter, the content of described phosphorus component are the heavy % of 0.1-15.

2. catalyzer according to claim 1 is characterized in that, the content of described P-contained Y-zeolite is that the content of the heavy % of 15-60, described al binder is the heavy % of 15-55, and the content of described clay is the heavy % of 0-60.

3. catalyzer according to claim 1 is characterized in that, in described P-contained Y-zeolite, the content of described silicon components is the heavy % of 5-12, and the content of described phosphorus component is the heavy % of 2-10.

4. catalyzer according to claim 1 is characterized in that, the solution of described silicon compound is selected from the aqueous solution of silicon compound or organic solution and this as in the silicon compound of liquid one or more.

5. catalyzer according to claim 4 is characterized in that, the solution of described silicon compound is selected from one or more in silicon sol, water glass, the silicofluoride aqueous solution, dimethyl silicone oil, the polymethylphenyl siloxane fluid.

6. catalyzer according to claim 5, it is characterized in that the solution of described silicon compound is selected from one or more in silicon sol, water glass, the ammonium silicofluoride aqueous solution, polymethylphenyl siloxane fluid 255, polymethylphenyl siloxane fluid 250, polymethylphenyl siloxane fluid 274, the dimethyl silicone oil.

7. catalyzer according to claim 6 is characterized in that, the solution of described silicon compound is selected from one or more in silicon sol, water glass and the ammonium silicofluoride aqueous solution.

8. catalyzer according to claim 1 is characterized in that, after 15 minutes to 5 hours, the pore volume of described P-contained zeolite second hole accounts for 15～75% of total pore volume through 550-850 ℃ of hydrothermal treatment consists.

9. catalyzer according to claim 1 is characterized in that, after 15 minutes to 5 hours, the relative crystallinity of described P-contained Y-zeolite is not less than 70% through 550～850 ℃ of hydrothermal treatment consists.

10. claim 1 Preparation of catalysts method, this method comprises mixes making beating with P-contained Y-zeolite, clay, al binder and deionized water, dry, washing and after drying, it is characterized in that, the consumption of described P-contained Y-zeolite, clay, al binder makes the P-contained Y-zeolite that contains the heavy % of 10-60 in the final catalyzer, in aluminum oxide, the clay of the al binder of the heavy % of 10-60 and the heavy % of 0-75, the preparation method of described P-contained Y-zeolite comprises with the solution of P contained compound and silicon compound solution floods a kind of raw material y-type zeolite, with SiO ₂Meter, the consumption of described silicon compound solution make and contain the heavy % of silicon components 1-15 in the P-contained Y-zeolite that obtains, with P ₂O ₅Meter, the consumption of described phosphorus compound solution make and contain the heavy % of phosphorus component 0.1-15 in the P-contained Y-zeolite that obtains.

11. method according to claim 10 is characterized in that, described step with silicon-containing compound dipping y-type zeolite is before soaking the phosphorus step, carry out afterwards or simultaneously.

12. method according to claim 11 is characterized in that, and is described with silicon-containing compound dipping y-type zeolite with soak the phosphorus step and carry out simultaneously.

13. method according to claim 10 is characterized in that, described P contained compound is selected from one or more in phosphoric acid, Secondary ammonium phosphate, primary ammonium phosphate, the ammonium phosphate.

14. method according to claim 10 is characterized in that, described raw material y-type zeolite is that sodium oxide content is the y-type zeolite of the heavy % of 3-10.

15. method according to claim 10, it is characterized in that, after dipping phosphorus and silicon compound, also have a hydrothermal treatment consists dipping to go up the step of the y-type zeolite of phosphorus and silicon compound, this step comprises, under 550-850 ℃ temperature, described y-type zeolite is contacted with a kind of steam-laden atmosphere, be at least duration of contact 10 minutes.

16. method according to claim 15 is characterized in that, described contact temperature is 600-750 ℃, and be 15 minutes to 5 hours duration of contact.

17. method according to claim 15, it is characterized in that, described steam-laden atmosphere is 100% water vapour or contains the water vapour that contains 10 body % water vapour at least and the gas mixture of rare gas element that described rare gas element refers in the hydrothermal treatment consists process zeolite not had the gas of destruction.

18. method according to claim 17 is characterized in that, described rare gas element is selected from one or more in air, nitrogen and the carbonic acid gas.