CN100537030C - A catalytic cracking additive for increasing propylene concentration in liquefied gas - Google Patents

Abstract

The present invention relates to a catalyst promoter for raising catalytic cracked liquefied gas propene concentration. Said catalyst promoter composition contains (by wt%) 10-65% of MFI structural zeolite, 0-20% of non-MFI structural zeolite, 0-60% of clay, 15-60% of inorganic oxide adhesive, 0.5-15% of copper additive (CuO) and 2-25% of phosphorus additive (P2O3). Said catalyst promoter can be used in the catalytic cracking process of petroleum hydrocarbon, at the same time of raising catalytic cracked liquefied gas yield and raising catalytic cracked gasoline octane number, it can obviously raise propene concentration in liquefied gas.

Description

A catalytic cracking additive for increasing propylene concentration in liquefied gas

technical field

The invention relates to a catalytic cracking auxiliary agent for increasing the concentration of propylene in catalytic cracking liquefied gas.

Background technique

Propylene is an important organic chemical raw material. With the rapid growth of demand for polypropylene and other derivatives, the world's demand for propylene is also increasing year by year. Fluid catalytic cracking is one of the important production processes for the production of light olefins and propylene. Most catalytic cracking units use catalysts or additives containing zeolite with MFI structure to increase the production of light olefins and propylene.

USP 3,758,403 discloses that adding ZSM-5 zeolite to the catalytic cracking catalyst or using an additive containing ZSM-5 zeolite can increase the octane number of gasoline and increase the yield of C ₃ -C ₄ olefins. For example, after adding 1.5, 2.5, 5 or 10 wt% ZSM-5 zeolite to a conventional catalyst containing 10 wt% REY, the gasoline octane number increases and the yield of light olefins increases.

USP 5,318,696 proposes a hydrocarbon conversion process based on a catalyst composed of a large-pore zeolite and a zeolite with an MFI structure with a silicon-to-aluminum ratio of less than 30. This process produces high-octane gasoline through an improved catalytic cracking process and increases the production of low-carbon Olefins, especially propylene.

USP 5,997,728 discloses a method for catalytic cracking of heavy feedstocks using catalytic cracking aids containing shape-selective zeolites. The additive is formed by adding 12 to 40 weight percent of ZSM-5 zeolite to the amorphous matrix, and the storage capacity in the catalytic cracking system is at least 10 weight percent, and the ratio of ZSM-5 in the catalyst is not less than 3 weight percent %. The method can greatly increase the yield of low-carbon olefins without additionally increasing the yield of aromatics and losing gasoline yield.

After the catalyst containing ZSM-5 zeolite is modified with phosphorus, the cracking activity and stability can be improved.

CN 1049406C discloses a zeolite containing phosphorus and rare earth and having MFI structure, its anhydrous chemical composition is aRE ₂ O ₃ ·bNa ₂ O ·Al ₂ O ₃ ·cP ₂ O ₅ ·dSiO ₂ , where a=0.01～ 0.25, b=0.005-0.02, c=0.2-1.0, d=35-120. The zeolite has excellent hydrothermal activity stability and good low-carbon olefin selectivity when used for high-temperature conversion of hydrocarbons.

CN 1034223C discloses a cracking catalyst for producing low-carbon olefins, which is composed of 0-70% clay, 5-99% inorganic oxides and 1-50% zeolite, and the zeolite is 0-25 wt. % REY or high silicon Y-type zeolite and 75-100% by weight of five-membered ring high silica zeolite containing phosphorus and rare earth. The catalyst has higher hydrothermal activity stability, conversion rate and C ₂ ⁼ ~ C ₄ ⁼ yield than the catalyst with ZSM-5 zeolite as the active component.

USP 5,110,776 discloses a method for preparing a catalyst containing phosphorus-modified ZSM-5 zeolite. In the method, the zeolite is dispersed in the phosphorus-containing compound aqueous solution with a pH value of 2 to 6, then mixed with the base material for beating, spray-dried and shaped. The obtained catalyst does not increase dry gas and coke yield while increasing gasoline octane number.

USP6,566,293 discloses a cracking catalyst for phosphorus-containing modified ZSM-5 zeolite. Said phosphorus-modified ZSM-5 is prepared by dispersing zeolite in an aqueous solution of phosphorus-containing compounds with a pH value above 4.5, making the zeolite load at least 10% by weight of phosphorus (calculated as P ₂ O ₅ ), and then mixing with substrate and non- The MFI structure zeolite component is beaten and spray-dried to shape. The obtained catalyst is used for catalytic cracking and has a relatively high yield of low-carbon olefins.

USP 5,171,921 discloses an improved method for converting C ₃ -C ₂₀ hydrocarbons into C ₂ -C ₅ olefins. The catalyst used in the method contains ZSM-5 zeolite, the silicon-aluminum ratio on the surface of the zeolite is 20-60, the phosphorus content is 0.1-10% by weight, and the phosphorus is introduced and subjected to steam treatment at 500-700 DEG C.

A method for improving the catalytic activity of small and medium pore zeolites is disclosed in USP 6,080,303. This method treats small- and medium-pore zeolites with phosphorus compounds, and then combines the phosphorus-treated zeolites with _AlPO4 gels. The method can improve the activity and hydrothermal stability of the catalyst containing the zeolite.

USP 5,472,594 discloses an FCC process based on a catalyst composed of a large pore zeolite and a phosphorus-containing MFI structure medium pore zeolite. This process can increase the yield of C ₄ , C ₅ olefins and reduce gasoline loss.

USP 2002/0003103 A1 discloses a catalytic cracking process for increasing the yield of propylene. In this process, at least part of the gasoline product is introduced into the second riser to carry out the cracking reaction again, and the catalyst used contains large-pore USY zeolite, medium-pore ZSM-5 zeolite and phosphorus-containing inorganic binder component with cracking performance.

USP 2002/0049133 A1 discloses a catalyst with high zeolite content and high wear resistance for FCC process to increase the yield of low-carbon olefins. The catalyst contains 30-85% by weight of ZSM-5 zeolite, 6-24% by weight of phosphorus (calculated as P ₂ O ₅ ), and less than 10% by weight of Al ₂ O ₃ . The catalyst is especially suitable for increasing the yield of ethylene.

Metal modification of zeolite can also be used to increase the production of light olefins.

CN 1057408A discloses a high-silica zeolite-containing cracking catalyst with high catalytic cracking activity, wherein the high-silica zeolite contains 0.01-3.0 wt% phosphorus, 0.01-1.0 wt% iron or 0.01-10 wt% Aluminum ZSM-5, beta zeolite or mordenite is made by heating the hydrogen type or potassium type ZSM-5 zeolite, beta zeolite or mordenite with a silicon-aluminum ratio greater than 15 to 350-820°C, with a temperature of 0.1-10 hours ^-1 It is obtained after the volumetric space velocity is introduced into an aqueous aluminum halide solution, an aqueous iron halide solution or an aqueous solution of ammonium phosphate salt.

CN 1465527A discloses a zeolite with an MFI structure containing phosphorus and transition metals. The anhydrous chemical expression of the zeolite is (0-0.3) Na ₂ O·(0.5-5) Al ₂ O in terms of the mass of oxides ₃ ·(1.3-10)P ₂ O ₅ ·(0.7-15)M ₂ O ₃ ·(70-97)SiO ₂ , wherein M is selected from one of transition metals Fe, Co and Ni. When the zeolite is applied to the catalytic cracking process of petroleum hydrocarbons, the yield and selectivity of C ₂ -C ₄ olefins can be improved, and the yield of liquefied gas is higher.

At present, for the vast majority of catalytic cracking units, under the premise of the same liquefied gas yield, increasing the propylene concentration in the liquefied gas is an important way to improve the economic benefits of the catalytic cracking unit. The zeolite materials and catalysts disclosed in the prior art are used in the catalytic cracking process. Although they can effectively increase the yield of low-carbon olefins and improve the octane number of catalytic cracking gasoline products, the selection of propylene in the catalytic cracking reaction process The property is low, so the concentration of propylene in the liquefied gas is low.

Contents of the invention

The purpose of the present invention is to provide a catalytic cracking additive for increasing the propylene concentration of catalytic cracking liquefied gas on the basis of the prior art. The concentration of propylene in the gas increases the octane number of catalytic cracked gasoline.

The present inventors have found that, using MFI structure zeolite as an active component, further introducing an appropriate amount of copper additives and an appropriate amount of phosphorus additives, the prepared catalytic assistant is applied to the catalytic cracking process of petroleum hydrocarbons, which can significantly improve the catalytic cracking of liquefied gas. Propylene concentration in .

The invention provides a catalytic cracking additive for increasing the propylene concentration of liquefied gas, which contains 10% to 65% by weight of MFI structure zeolite, 0% to 20% by weight of non-MFI structure zeolite, 0% to 65% by weight based on the weight of the additive. 60% by weight of clay, 15% to 60% by weight of inorganic oxide binders as oxides, 0.5% to 15% by weight of copper additives as CuO and 2% to ₂₅ % by weight as _P2O5 % by weight of phosphorus additives.

The catalyst promoter provided by the invention can significantly improve the selectivity of the catalytic cracking reaction for propylene, thereby significantly increasing the concentration of propylene in the catalytic cracking liquefied gas. For example, the content of copper in the present invention is 2% by weight, the content of phosphorus is 7.5% by weight, the content of ZSM-5 zeolite is 35% by weight, the content of kaolin is 28%, and the content of pseudoboehmite is 27.5% by weight. The weight ratio of 90 is mixed with the industrial balancing agent of the commercial brand MLC-500, and the pipe wax oil mixed with residual oil with a specific gravity of 0.907 is used as the raw material. In a small fixed fluidized bed, the temperature is 500 ° C, and the weight ratio of agent to oil is 5.92 , react under the condition of 16h ^-1 space velocity, the productive rate of propylene is 9.1% by weight, and the concentration of propylene in the liquefied gas is 37.5% by weight; %, the content of kaolin is 30%, and the content of pseudo-boehmite is 27.5% by weight. The copper-free auxiliary agent carries out the catalytic cracking reaction under the same conditions, and the productive rate of propylene is 7.1% by weight. The concentration of propylene in the liquefied gas is 34.7% by weight.

Detailed ways

Based on the weight of additives, the present invention preferably contains 20% to 50% by weight of MFI structure zeolite, 0 to 10% by weight of non-MFI structure zeolite, 10% to 45% by weight of clay, and 25% by weight of oxides. %-50% by weight of inorganic oxide binder, 1-15% by weight of copper additive based on copper oxide, and 5-15% by weight of phosphorus additive based on P ₂ O ₅ .

The MFI structure zeolite of the present invention is selected from one or more of ZSM-5 zeolite, ZRP zeolite and their modified products, preferably the modified MFI structure zeolite containing phosphorus and transition metal disclosed in CN 1465527A, That is, ZSM-5 zeolite is modified by phosphorus and a metal selected from Fe, Co or Ni. Its anhydrous chemical expression is (0~0.3) _Na2O ·(0.5~5) in terms of oxides Al ₂ O ₃ ·(1.3～10)P ₂ O ₅ ·(0.7～15)M _x O _y ·(70～97)SiO ₂ , x represents the atomic number of M, y represents the atomic number of O, M is Fe , Co or Ni; more preferably the anhydrous chemical expression of the MFI structure _zeolite is (0～0.2) _Na2O ·(0.9～3.5) _Al2O3 ·(1.5～ 7) P ₂ O ₅ ·(0.9-10) M _x O _y ·(82-92) SiO ₂ .

The non-MFI structure zeolite in the present invention is selected from one or more conventional zeolites prepared from catalytic cracking catalysts, preferably one or more of Y-type zeolite, beta zeolite or mordenite zeolite. The Y-type zeolite is selected from rare earth-modified Y-type zeolite, phosphorus-modified Y-type zeolite, rare-earth and phosphorus-modified Y-type zeolite, ultra-stable Y zeolite, and rare-earth modified ultra-stable Y zeolite. or several.

The clay described in the present invention is well known to those skilled in the art, and there is no particular limitation. For example, the clay is kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, letronite, diatomite, halloysite , saponite, bentonite or hydrotalcite or one or more. One or more of kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite and letronite are preferred.

The inorganic oxide binder is selected from one or more of the inorganic oxides commonly used as catalytic cracking catalysts or auxiliary substrates and binder components, such as pseudo-boehmite, aluminum sol, and silica-alumina sol , one or more of water glass or phosphate-aluminum sol, preferably one or more of pseudo-boehmite, aluminum sol or phosphate-aluminum sol. When the additive contains aluminum phosphate sol, the phosphorus introduced by the aluminum phosphate sol is regarded as a phosphorus additive.

The catalytic cracking aid of the present invention can be prepared by adding steps of introducing copper additives and phosphorus additives and roasting in the existing cracking catalyst preparation method. For example, the preparation method includes mixing zeolite, clay, and inorganic oxide binders. Beating, spray drying, any steps of slurry preparation before spray drying or steps of introducing copper additives and phosphorous additives by means of impregnation (or chemisorption) and roasting after spray drying. The order of introducing copper and phosphorus is not required, they can be introduced at the same time or separately. If the copper or phosphorus additive is introduced by impregnation or chemical adsorption after spray drying, the introduction should also include the steps of separating the additive from the impregnation solution or adsorption solution, and drying, wherein the drying temperature is from room temperature to 400 ° C. Preferably, it is 100°C to 300°C. The calcination temperature is 400°C-700°C, preferably 450°C-650°C, and the calcination time is 0.5-100 hours, preferably 0.5-10 hours.

If the copper additive is introduced before the spray-drying molding in the additive preparation process, it can be introduced by adding copper-containing compounds to various slurries. Copper-containing compounds are selected from one or more of copper-containing inorganic compounds and organic compounds, such as copper oxides, hydroxides, chlorides, nitrates, sulfates, phosphates, and organic compounds; preferred copper-containing compounds One or more of copper chloride, nitrate, sulfate and phosphate. If the copper additive is introduced after the spray-drying molding of the additive preparation process, the slurry is spray-dried and then impregnated or chemically adsorbed with an aqueous solution of a copper-containing compound, followed by solid-liquid separation (if necessary), drying and roasting, wherein the drying temperature is room temperature to 400°C, preferably 100°C to 300°C, the calcination temperature is 400°C to 700°C, preferably 450°C to 650°C, and the calcination time is 0.5 to 100 hours, preferably 0.5 to 10 hours.

The introduction of the phosphorus additive can adopt one of the following methods or a combination of several methods, but not limited to these methods:

1. Add phosphorus compound to the slurry before the additive is spray-dried and formed;

2. The inorganic oxide binder is introduced into the auxiliary agent. For example, when the inorganic oxide binder contains phosphorus-aluminum sol, phosphorus is brought into the auxiliary agent after roasting, and the phosphorus-aluminum sol can also act as a matrix material and The effect of binding agent, this part phosphorus also belongs to the phosphorus additive of the present invention;

3. Impregnating or chemisorbing phosphorus compounds after spray-drying the additives, followed by solid-liquid separation (if necessary), drying and roasting. The drying temperature is from room temperature to 400°C, preferably from 100°C to 300°C The firing temperature is 400°C to 700°C, preferably 450°C to 650°C, and the firing time is 0.5 hours to 100 hours, preferably 0.5 hours to 10 hours.

The phosphorus compound in the present invention is selected from one or more of various inorganic compounds and organic compounds of phosphorus. The phosphorus compound is one or more of phosphorus oxides, phosphoric acid, phosphate, phosphite, hypophosphite or phosphorus-containing organic compounds. Preferably, the phosphorus compound is one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate or aluminum phosphate sol.

If the phosphorus additive and the copper additive are introduced at the same time, when introduced before spray drying, the copper compound is mixed with the phosphorus compound, made into a slurry or made into a solution and then added to the slurry; when introduced after spray drying, the copper-containing compound is used Impregnation or chemisorption with solutions of phosphorus compounds.

In the auxiliary agent provided by the present invention, the copper additive exists in the form of its oxide, phosphate, phosphite, alkali phosphate, and acid phosphate, and can be present in any possible position of the auxiliary agent, such as The inside of the channel of the zeolite, the surface of the zeolite, and the matrix material, or both exist in the interior of the channel of the zeolite, the surface of the zeolite, and the matrix material. The copper additive is preferably present in the matrix material. At this time, the preparation method is to add a copper-containing compound to the slurry before the additive is spray-dried and formed, so that it first reacts with alumina or a phosphorus-containing compound. The copper-containing compound species in the matrix can be detected by the XRD method.

The phosphorus additive exists in the form of phosphorus compounds (oxides, phosphates, phosphites, alkali phosphates, acid phosphates), and can exist in any possible position of the additive, such as in the pores of zeolite Inside, on the surface of the zeolite, in the matrix material or both inside the pores of the zeolite, on the surface of the zeolite and in the matrix material.

The phosphorus additive in the present invention includes phosphorus introduced by a phosphorus compound added in the slurry, phosphorus introduced by an inorganic oxide binder, and phosphorus introduced by impregnation or chemical adsorption. If the molecular sieve used contains phosphorus, the phosphorus introduced through the molecular sieve is not regarded as the phosphorus additive mentioned in the present invention.

When the catalyst promoter provided by the invention is used in a catalytic cracking process, it can be added to a catalytic cracking reactor alone (for example, as a catalyst for a DCC device), or it can be mixed with a cracking catalyst for use. As an auxiliary agent, the auxiliary agent provided by the present invention accounts for 1% to 25% by weight, preferably 3% to 15% by weight, of the total amount of the FCC catalyst and the auxiliary agent mixture provided by the present invention.

The catalytic assistant provided by the invention is used in the catalytic cracking process, and the hydrocarbon oil cracking conditions are conventional catalytic cracking conditions. Including a reaction temperature of 400°C to 600°C, preferably 450°C to 550°C, a weight hourly space velocity of 10 hours ^-1 to 120 hours ^-1 , preferably 10 hours ^-1 to 80 hours ^-1 , and an agent-to-oil weight ratio of 1 ~20, preferably 3~15.

The catalyst promoter provided by the invention can be used in various existing catalytic cracking reactors, such as fixed bed reactors, fluidized bed reactors, riser reactors, and multi-reaction zone reactors.

The catalytic promoter provided by the present invention can be used for the processing of various hydrocarbon oils, and the hydrocarbon oils are selected from various petroleum fractions, such as crude oil, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, Straight-run gas oil, one or more of propane light/heavy deoiling, coker gas oil and coal liquefaction products. The hydrocarbon oil may contain heavy metal impurities such as nickel and vanadium and impurities such as sulfur and nitrogen. The allowable content of the impurities is that the content of sulfur is not more than 3.0% by weight, and the content of nitrogen is not more than 2.0% by weight. The weight content does not exceed 3000ppm.

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

In the examples and comparative examples, six modified ZSM-5 zeolite samples A ₁ to A ₆ were prepared by the method disclosed in CN1465527A, and its anhydrous chemical expression was determined by X-ray fluorescence spectrometry to determine the elemental composition of the zeolite, and then tested Converted to get.

Sample A ₁ : 0.04Na ₂ O·3.57Al ₂ O ₃ ·4.0P ₂ O ₅ ·2.4Fe ₂ O ₃ ·90.49SiO ₂ .

Sample A ₂ : 0.1Na ₂ O·5.3Al ₂ O ₃ ·1.5P ₂ O ₅ ·1.1Fe ₂ O ₃ ·92SiO ₂ .

Sample A ₃ : 0.03Na ₂ O·2.2Al ₂ O ₃ ·4.9P ₂ O ₅ ·2.1Fe ₂ O ₃ ·90.8SiO ₂ .

Sample A ₄ : 0.1Na ₂ O·0.94Al ₂ O ₃ ·5.1P ₂ O ₅ ·10.1Fe ₂ O ₃ ·84SiO ₂ .

Sample A ₅ : 0.03Na ₂ O·5.1Al ₂ O ₃ ·4.8P ₂ O ₅ ·3.6Co ₂ O ₃ ·86.5SiO ₂ .

Sample A ₆ : 0.1Na ₂ O·5.2Al ₂ O ₃ ·4.5P ₂ O ₅ ·2.0Ni ₂ O ₃ ·88.2SiO ₂ .

Pseudoboehmite is an industrial product produced by Shandong Aluminum Factory, with a solid content of 60% by weight; aluminum sol is an industrial product produced by Sinopec Qilu Catalyst Factory, and its _Al2O3 content is 21.5% by weight; water glass is _produced by Sinopec Qilu Catalyst Factory Industrial product, SiO ₂ content 28.9% by weight, Na ₂ O content 8.9% by weight; Kaolin is special kaolin for cracking catalyst produced by Suzhou Kaolin Company, solid content 78% by weight; ZRP-1 zeolite is conventional MFI structure zeolite produced by Qilu Catalyst Factory ZRP-5 zeolite is an industrial product _{of conventional MFI structure zeolite produced by Qilu Catalyst Factory, wherein P 2 O 5} is _2.5 % by weight , the crystallinity is 85% by weight, and the ratio of silicon to aluminum is 50. DASY- ₂ zeolite is an industrial product of rare earth-containing ultrastable Y zeolite produced by Qilu Catalyst Factory, wherein _RE2O3 content is 1.8 wt%, _Na2O content is 0.9 wt%, relative crystallinity is 55 wt%, unit cell constant a ₀ is 2.454nm.

Examples 1-15 illustrate the preparation of the catalytic promoter provided by the present invention.

Example 1

Preparation of phosphate-aluminum sol: 1.05 kilograms of pseudoboehmite (dry basis) and 3.35 kilograms of decationized water were mixed and beaten for 30 minutes, and 4.9 kilograms of concentrated phosphoric acid (chemically pure, containing 85% by weight of phosphoric acid) were added to the slurry under stirring, and the temperature was raised. to 70°C, and react at this temperature for 45 minutes to produce a colorless and transparent phosphoraluminum sol. The content of P ₂ O ₅ is 30.6% by weight, the content of Al ₂ O ₃ is 10.5% by weight, and pH=1.7.

Take 1.75 kg (dry basis) of A ₁ , 1.4 kg (dry basis) of kaolin and 0.65 kg (dry basis) of pseudoboehmite, mix with 6.2 kg of deionized water and 2.79 kg of aluminum sol for 120 minutes, and add 1 liter of CuCl _{2 ·} 2H ₂ O aqueous solution (which contains 100 g of CuO), and adjust the pH value of the slurry to 3.0 with hydrochloric acid. Continue to beat the mixture for 45 minutes, and then add 1.22 kg of phosphorus-aluminum sol to the mixed slurry. After stirring evenly, the obtained slurry is spray-dried at an inlet temperature of 500°C and an exhaust gas temperature of 180°C to obtain an average particle diameter of 65 micron microspheres. _The microspheres were calcined at 500° C. for _{1 hour} to obtain 35 wt. (calculated as P ₂ O ₅ ) additive ZJ ₁ .

Example 2

Take 1.84 kg (dry basis) of A ₁ , 1.33 kg (dry basis) of kaolin and 0.98 kg (dry basis) of pseudoboehmite, add 7.2 kg of deionized water and 2.79 kg of aluminum sol for beating for 120 minutes, and add 1 liter of An aqueous solution of Cu(NO ₃ ) _2· 6H ₂ O (containing 250 g of CuO) was used to adjust the pH value of the slurry to 2.8 with hydrochloric acid. The mixture was further beaten for 45 minutes, and then the resulting slurry was spray-dried at an inlet temperature of 500° C. and an exhaust gas temperature of 180° C. to obtain microspheres with an average particle diameter of 65 μm. The microspheres were calcined at 500° C. for 1 hour to prepare microspheres containing 36.8 wt % A ₁ , 26.6 wt % kaolin, 31.6 wt % Al ₂ O ₃ and 5.0 wt % Cu additive (calculated as CuO).

Get 1 kg (dry basis) of the obtained microsphere product, add 10 liters of decationized water and 100 grams of diammonium hydrogen phosphate, heat up to 60° C. under stirring, react at this temperature for 20 minutes, vacuum filter the slurry, dry, and then Roasting at 500° C. for 2 hours, prepared 35 wt % A ₁ , 25.3 wt % kaolin, 30 wt % Al ₂ O ₃ , 4.7 wt % Cu additive (calculated as CuO) and 5 wt % phosphorus additive (calculated as P ₂ O ₅ meter) additive ZJ ₂ .

Example 3

Take 1.94 kg (dry basis) of _A1 and 1.91 kg (dry basis) of pseudo-boehmite, add 7.2 kg of decationized water and 2.79 kg of aluminum sol for beating for 120 minutes, add 1 liter of CuCl ₂ 2H ₂ O aqueous solution under stirring (Wherein containing 550 grams of CuO), the pH value of adjusting slurry with hydrochloric acid is 2.5. The mixture was further beaten for 45 minutes, and then the obtained slurry was spray-dried at an inlet temperature of 500° C. and an exhaust gas temperature of 180° C. to obtain microspheres with an average particle diameter of 65 μm. The microspheres were calcined at 500° C. for 1 hour to prepare microspheres containing 38.8 wt % A ₁ , 50.2 wt % Al ₂ O ₃ and 11 wt % Cu additive (calculated as CuO).

Get 1 kg (dry basis) of the obtained microsphere product, add 10 liters of decationized water and 210 grams of diammonium hydrogen phosphate, heat up to 60° C. under stirring, react at this temperature for 20 minutes, vacuum filter the slurry, dry, and then Calcined at 500° C. for 2 hours to obtain 35% by weight of A ₁ , 45.1% by weight of Al ₂ O ₃ , 9.9% by weight of Cu additive (calculated as CuO) and 10% by weight of phosphorus additive (calculated as P ₂ O ₅ ) Auxiliary ZJ ₃ .

Example 4

The preparation method is the same as in Example 1, except that the same amount of ZRP-1 zeolite is used instead of A ₁ zeolite to obtain 35% by weight ZRP-1, 28% by weight kaolin, 27.5% by weight Al ₂ O ₃ , 2% by weight Auxiliary ZJ ₄ of Cu additive (calculated as CuO) and 7.5% by weight phosphorus additive (calculated as P ₂ O ₅ ).

Example 5

The preparation method is the same as in Example 1, except that the same amount of ZRP-5 zeolite is used instead of A ₁ zeolite to obtain 35% by weight ZRP-5, 28% by weight kaolin, 27.5% by weight Al ₂ O ₃ , 2% by weight Auxiliary agent ZJ ₅ of Cu additive (calculated as CuO) and 7.5% by weight phosphorus additive (calculated as P ₂ O ₅ ).

Example 6

Take 1 kg (dry basis) of ZJ ₁ additive, add 10 liters of decationized water and 157 grams of diammonium hydrogen phosphate, heat up to 60°C under stirring, react at this temperature for 20 minutes, vacuum filter and dry the slurry, and then Roasting at 500° C. for 2 hours, prepared 32.38 wt % A ₁ , 25.9 wt % kaolin, 25.4 wt % Al ₂ O ₃ , 1.85 wt % Cu additive (calculated as CuO) and 14.47 wt % phosphorus additive (calculated as P ₂ O ₅ meter) additive ZJ ₆ .

Example 7

Take 1.75 kg (dry basis) of A ₁ , 1 kg (dry basis) of kaolin and 3.46 kg of water glass, add 5 kg of deionized water and beat for 120 minutes, add 1 liter of CuCl _{2 ·} 2H ₂ O aqueous solution (which contains 750 gram CuO), the pH value of slurry is adjusted to 3.0 with hydrochloric acid. Continue beating the mixture for 45 minutes, and then add 1.22 kg of phosphorus-aluminum sol to the mixed slurry. After stirring evenly, the resulting slurry is spray-dried at an inlet temperature of 500°C and an exhaust gas temperature of 180°C to obtain an average particle diameter of 65 micron microspheres. The microspheres were fired at 400°C for 1 hour.

Take 1 kg (dry basis) of the above-mentioned calcined microspheres, add 10 liters of decationized water and 100 grams of ammonium chloride, heat up to 60° C. under stirring, wash at this temperature for 20 minutes, and vacuum filter the slurry. The filter cake was washed again by the same method as above, and dried at 120°C to obtain 35% by weight A ₁ , 20% by weight kaolin, 2.5% by weight Al ₂ O ₃ , 20% by weight SiO ₂ , 15% by weight Auxiliary ZJ ₇ of % Cu additive (calculated as CuO) and 7.5% by weight of phosphorus additive (calculated as P ₂ O ₅ ).

Example 8

The auxiliary agent is prepared according to the method of Example 1, the difference is that the weight of A ₁ is 2.25 kg (dry basis), the weight of kaolin is 0.9 kg (dry basis), and the obtained product contains 45% by weight A ₁ , 18% by weight kaolin, 27.5 Auxiliary agent ZJ ₈ of wt. % Al ₂ O ₃ , 2 wt. % Cu additive (calculated as CuO) and 7.5 wt. % phosphorus additive (calculated as P ₂ O ₅ ).

Example 9

Take 1 kg (dry basis) of A ₁ , 1.85 kg (dry basis) of kaolin and 0.9 kg (dry basis) of pseudo-boehmite, add 7.2 kg of decationized water and 2.79 kg of aluminum sol for beating for 120 minutes, and add 1 liter of An aqueous solution of CuCl _{2 ·} 2H ₂ O (containing 400 g of CuO) was used to adjust the pH value of the slurry to 2.6 with hydrochloric acid. Continue to beat the mixture for 30 minutes, add 465 grams of diammonium hydrogen phosphate, and beat for another 30 minutes, then spray-dry the obtained slurry at an inlet temperature of 500 ° C and an exhaust gas temperature of 180 ° C to obtain an average particle diameter of 65 microns of microspheres. The microspheres were calcined at 500° C. for 1 hour to obtain 20 wt % A ₁ , 37 wt % kaolin, 30 wt % Al ₂ O ₃ , 8 wt % Cu additive (calculated as CuO) and 5 wt % phosphorus additive ( (calculated as P ₂ O ₅ ) additive ZJ ₉ .

Example 10

Auxiliaries were prepared according to the method of Example 9, except that the same weight of A ₂ was used instead of A ₁ to prepare an additive containing 20 wt % A ₂ , 37 wt % kaolin, 30 wt % Al ₂ O ₃ , 8 wt % Cu ( Auxiliary agent ZJ ₁₀ calculated as CuO) and 5% by weight phosphorus additive (calculated as P ₂ O ₅ ).

Example 11

Take 1.25 kg (dry basis) of A ₃ , 1 kg (dry basis) of kaolin and 1.65 kg (dry basis) of pseudo-boehmite, add 7.2 kg of decationized water and 2.79 kg of aluminum sol for beating for 120 minutes, and add 1 liter of An aqueous solution of CuCl _{2 ·} 2H ₂ O (containing 250 g of CuO) was used to adjust the pH value of the slurry to 2.8 with hydrochloric acid. Continue to beat the mixture for 30 minutes, add 465 grams of diammonium hydrogen phosphate, and beat for another 30 minutes, then spray-dry the obtained slurry at an inlet temperature of 500 ° C and an exhaust gas temperature of 180 ° C to obtain an average particle diameter of 65 microns of microspheres. The microspheres were calcined at 500° C. for 1 hour to obtain 25 wt. % A ₃ , 20 wt. % kaolin, 45 wt. % Al ₂ O ₃ , 5 wt. (calculated as P ₂ O ₅ ) additive ZJ ₁₁ .

Example 12

Take 2 kg (dry basis) of A ₄ , 0.75 kg (dry basis) of kaolin and 1.15 kg (dry basis) of pseudoboehmite, add 7.2 kg of decationized water and 2.79 kg of aluminum sol for beating for 120 minutes, and add 1 liter of An aqueous solution of CuCl _{2 ·} 2H ₂ O (containing 250 g of CuO) was used to adjust the pH value of the slurry to 3.0 with hydrochloric acid. Continue to beat the mixture for 30 minutes, add 465 grams of diammonium hydrogen phosphate, and beat for another 30 minutes, then spray-dry the obtained slurry at an inlet temperature of 500 ° C and an exhaust gas temperature of 180 ° C to obtain an average particle diameter of 65 microns of microspheres. The microspheres were calcined at 500° C. for 1 hour to obtain 40 wt _{% A4} , 15 wt % kaolin, 35 wt % _Al2O3 , 5 wt % Cu additive (calculated as CuO) and 5 wt % phosphorus additive ( (calculated as P ₂ O ₅ ) additive ZJ ₁₂ .

Example 13

Take 2.89 kg (dry basis) of _A5 and 1.4 kg (dry basis) of pseudo-boehmite, add 7.2 kg of decationized water and 2.79 kg of aluminum sol for beating for 120 minutes, add 1 liter of CuCl ₂ 2H ₂ O aqueous solution under stirring (wherein containing 105.5 grams of CuO), the pH value of the slurry was adjusted to 3.0 with hydrochloric acid. The mixture was further beaten for 45 minutes, and then the resulting slurry was spray-dried at an inlet temperature of 500° C. and an exhaust gas temperature of 180° C. to obtain microspheres with an average particle diameter of 65 μm. The microspheres were calcined at 500° C. for 1 hour to prepare microspheres containing 57.89 wt % A ₈ , 40 wt % Al ₂ O ₃ and 2.11 wt % Cu additive (calculated as CuO).

Get 1 kg (dry basis) of the obtained microsphere product, add 10 liters of decationized water and 210 grams of diammonium hydrogen phosphate, heat up to 60° C. under stirring, react at this temperature for 20 minutes, vacuum filter the slurry, dry, and then Roasting at 500° C. for 2 hours, prepared 55 wt % A ₅ , 38 wt % Al ₂ O ₃ , 2 wt % Cu additive (calculated as CuO) and 5 wt % phosphorus additive (calculated as P ₂ O ₅ ) Auxiliary ZJ ₁₃ .

Example 14

Take 1.5 kg (dry basis) of A ₆ , 1.5 kg (dry basis) of kaolin and 0.9 kg (dry basis) of pseudoboehmite, add 6.2 kg of decationized water and 2.79 kg of aluminum sol for beating for 120 minutes, and add 1 liter of An aqueous solution of CuCl _{2 ·} 2H ₂ O (containing 125 grams of CuO) was used to adjust the pH value of the slurry to 3.0 with hydrochloric acid. Continue beating the mixture for 45 minutes, and then add 1.22 kg of phosphorus-aluminum sol to the mixed slurry. After stirring evenly, the resulting slurry is spray-dried at an inlet temperature of 500°C and an exhaust gas temperature of 180°C to obtain an average particle diameter of 65 micron microspheres. The microspheres were calcined at 500° C. for 1 hour to obtain 30 wt. % A ₆ , 30 wt. % kaolin, 30 wt. % Al ₂ O ₃ , 2.5 wt. (calculated as P ₂ O ₅ ) additive ZJ ₁₄ .

Example 15

Take 1.75 kg (dry basis) of _A1 , 0.5 kg (dry basis) of DASY-2, 0.9 kg (dry basis) of kaolin and 0.65 kg (dry basis) of pseudoboehmite, with 6.2 kg of decationized water and 2.79 kg of aluminum The sol was mixed and beaten for 120 minutes, and 1 liter of CuCl _{2 ·} 2H ₂ O aqueous solution (containing 100 g of CuO) was added with stirring, and the pH value of the slurry was adjusted to 3.0 with hydrochloric acid. Continue to beat the mixture for 45 minutes, and then add 1.22 kg of phosphorus-aluminum sol to the mixed slurry. After stirring evenly, the obtained slurry is spray-dried at an inlet temperature of 500°C and an exhaust gas temperature of 180°C to obtain an average particle diameter of 65 micron microspheres. The microspheres were calcined at 500°C for 1 hour to obtain additives containing 35% by weight of _A1 , 10% by weight of DASY-2, 18% by weight of kaolin, 27.5% by weight _{of Al2O3} , and 2.0% by weight of Cu additives (calculated as CuO) and 7.5% by weight phosphorus additive (calculated as P ₂ O ₅ ) additive ZJ ₁₅ .

Comparative example 1

This comparative example illustrates the preparation of a reference additive containing A ₁ , a phosphorus additive, and no copper additive.

Get 1.75 kilograms (dry basis) A ₁ , 1.5 kilograms (dry basis) kaolin and 0.65 kilograms (dry basis) pseudo-boehmite, add 7.2 kilograms of decationized water and 2.79 kilograms of aluminum sol beating for 120 minutes, add concentration under stirring 36% by weight of hydrochloric acid, the amount of hydrochloric acid is such that the pH of the slurry is 3.0. Continue beating the mixture for 45 minutes, and then add 1.22 kg of phosphorus-aluminum sol to the mixed slurry. After stirring evenly, the resulting slurry is spray-dried at an inlet temperature of 500°C and an exhaust gas temperature of 180°C to obtain an average particle diameter of 65 micron microspheres. The microspheres were calcined at 500°C for 1 _hour to prepare a _reference additive _{containing 35 wt} . agent CB ₁ .

Comparative example 2

This comparative example illustrates a reference additive with A ₁ , without copper and phosphorous additives and its preparation.

Get 1.75 kilograms (dry basis) A ₁ , 1.5 kilograms (dry basis) kaolin and 1.15 kilograms (dry basis) pseudo-boehmite, add 7.2 kilograms of decationized water and 2.79 kilograms of aluminum sol beating for 120 minutes, add concentration under stirring 36% by weight of hydrochloric acid, the amount of hydrochloric acid is such that the pH of the slurry is 3.0. The mixture was continued beating for 45 minutes. Then, the obtained slurry was spray-dried under the conditions of an inlet temperature of 500° C. and an exhaust gas temperature of 180° C. to obtain microspheres with an average particle diameter of 65 μm. The microspheres were calcined at 500°C for 1 hour to prepare a reference additive CB ₂ containing 35% by weight of A ₁ , 30% by weight of kaolin and 35% by weight of Al ₂ O ₃ .

Comparative example 3

This comparative example illustrates the preparation of a reference aid containing only conventional ZRP-5 zeolite.

The auxiliary agent is prepared according to the method of Comparative Example 2, except that the same weight of ZRP-5 zeolite is used to replace A ₁ to obtain a reference containing 35% by weight of ZRP-5 zeolite, 30% by weight of kaolin and 35% by weight of Al ₂ O ₃ Auxiliary CB ₃ .

Comparative example 4

This comparative example illustrates the preparation of a reference aid containing a conventional ZRP-5 zeolite and a phosphorus additive.

The auxiliary agent is prepared according to the method of Example 1, except that the same weight of ZRP-5 zeolite is used to replace A ₁ to obtain 35% by weight ZRP-5 zeolite, 30% by weight kaolin, 35% by weight Al ₂ O ₃ and 5 weight% % reference additive CB ₄ for phosphorus additives (excluding phosphorus contained in ZRP-5 zeolite).

Comparative example 5

This comparative example illustrates the preparation of a reference additive containing A ₁ , a copper additive, and no phosphorus additive.

Take 1.75 kg (dry basis) of A ₁ , 1.5 kg (dry basis) of kaolin and 0.9 kg (dry basis) of pseudoboehmite, add 6.2 kg of decationized water and 2.79 kg of aluminum sol for beating for 120 minutes, and add 1 liter of An aqueous solution of CuCl _{2 ·} 2H ₂ O (containing 250 grams of CuO therein), the pH value of the slurry is 3.0. The mixture was further beaten for 45 minutes, and the obtained slurry was spray-dried under the conditions of an inlet temperature of 500° C. and an exhaust gas temperature of 180° C. to obtain microspheres with an average particle diameter of 65 μm. The microspheres were calcined at 500°C for 1 hour to prepare the reference additive CB ₅ containing 35 wt% A ₁ , 30 wt% kaolin, 30 wt% Al ₂ O ₃ , 5 wt% Cu additive (calculated as CuO) .

Examples 16-30

The following examples take a fixed fluidized bed reactor as an example to illustrate the cracking reaction effect of the catalytic promoter provided by the present invention.

30 grams of ZJ ₁ -ZJ ₁₅ were subjected to aging treatment for 8 hours at 800° C. and 100% water vapor atmosphere. Different weights of aged ZJ ₁ -ZJ ₁₅ were mixed with different weights of industrial FCC equilibrium catalysts (the industrial grade of FCC equilibrium catalysts is MLC-500, the main properties are shown in Table 1). The catalyst mixture was loaded into the reactor of a small-scale fixed fluidized bed reactor, and the raw oil shown in Table 2 was subjected to catalytic cracking. Table 3, Table 4 and Table 5 give the composition of the catalyst mixture used, the reaction conditions and the reaction results.

Comparative example 6-11

The following comparative examples take a fixed fluidized bed reactor as an example to illustrate the use of reference additives.

The same feedstock oil was subjected to catalytic cracking according to the method in Example 15, except that the catalysts used were 100% industrial FCC equilibrium catalyst, and a mixture of CB ₁ -CB ₅ and industrial FCC equilibrium catalyst. Table 3 shows the composition of the catalyst mixture used, the reaction conditions and the reaction results.

As can be seen from Table 3, Table 4 and Table 5, compared with the reference additive, the catalytic additive provided by the present invention can not only effectively increase the catalytic cracking liquefied gas production rate, improve the octane number of catalytic cracking gasoline, At the same time, the propylene concentration in the catalytic cracking liquefied gas can be significantly increased.

Table 1

Table 2

Claims (9)

1. A catalytic cracking auxiliary agent for increasing the propylene concentration of liquefied gas, based on the weight of the auxiliary agent, containing 10% by weight to 65% by weight of MFI structure zeolite, 0 to 20% by weight of non-MFI structure zeolite, 0 to 60% by weight Weight % of clay, 15% to 60% by weight of inorganic oxide binder in terms of _oxides , 0.5 to 15% by weight of copper additives in terms of CuO and 2 to 25% by weight in terms of _P2O5 % phosphorus additive; wherein, the non-MFI structure zeolite is one or more of Y-type zeolite, beta zeolite, and mordenite. 2. according to the described auxiliary agent of claim 1, it is characterized in that, described auxiliary agent contains the MFI structure zeolite of 20 weight %～50 weight %, the non-MFI structure zeolite of 0～10 weight %, 10 weight %～45 weight % % clay, 25-50 wt% inorganic oxide binder, 1-15 wt% copper additive and 5-15 wt% phosphorus additive. 3. The additive according to claim 1, characterized in that, the MFI structure zeolite is one or more of ZSM-5 zeolite and ZRP zeolite. 4. according to the described auxiliary agent of claim 3, it is characterized in that, described MFI structure zeolite is ZSM-5 zeolite through phosphorus and the zeolite that is selected from the metal modification of one of Fe, Co or Ni, and its anhydrous chemical expression The formula is (0~0.3)Na ₂ O·(0.5~5)Al ₂ O ₃ ·(1.3~10)P ₂ O ₅ ·(0.7~15)M _x O _y ·(70~ 97) SiO ₂ , x represents the atomic number of M, and y represents the atomic number of O. 5. The additive according to claim 4, characterized in that the anhydrous chemical expression of the MFI structure zeolite is (0-0.2) Na ₂ O·(0.9-3.5) Al ₂ O in terms of oxides ₃ ·(1.5-7)P ₂ O ₅ ·(0.9-10)M _x O _y ·(82-92)SiO ₂ . 6. according to the described auxiliary agent of claim 1, it is characterized in that, described Y-type zeolite is Y-type zeolite modified by rare earth, phosphorus-modified Y-type zeolite, rare-earth and phosphorus-modified Y-type zeolite, ultrastable One or several kinds of Y zeolite or ultra-stable Y zeolite modified by rare earth. 7. according to the described auxiliary agent of claim 1, it is characterized in that, described clay is selected from one or the other in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite or accumulite Several kinds. 8. according to the described auxiliary agent of claim 1, it is characterized in that, described inorganic oxide binding agent is selected from one or more of pseudo-boehmite, aluminum sol, silica-alumina sol, water glass or phosphorus aluminum sol kind. 9. The auxiliary agent according to claim 8, characterized in that, the inorganic oxide binder is selected from one or more of pseudo-boehmite, aluminum sol or phosphoraluminum sol.