A catalytic cracking aid and its preparation method, catalytic cracking catalyst and catalytic cracking reaction method

Abstract

The present invention relates to a catalytic cracking aid and a preparation method thereof, a catalytic cracking catalyst and a catalytic cracking reaction method. Based on the total weight of the catalytic cracking aid, the catalytic cracking aid comprises 1-40% by weight of ABO 3 ABO type oxide, 1-10 wt% of alkali metal tungstate, 10-40 wt% of a first binder and 20-60 wt% of a first carrier; wherein the ABO 3 The content of the type oxide is measured by weight of copper oxide, A includes rare earth metal elements and / or alkaline earth metal elements; B includes copper element. The catalyst promoter contains ABO containing copper element 3 Type oxides and alkali metal tungstates, when applied to catalytic cracking reactions, have a significant exothermic effect and reduce the poisoning effect on catalytic cracking catalysts.

Description

Technical Field

[0001] The present disclosure relates to the field of catalytic cracking, and in particular, to a catalytic cracking aid and a preparation method thereof, a catalytic cracking catalyst and a catalytic cracking reaction method. Background Art

[0002] The catalytic cracking unit is the core equipment of the secondary processing of the refinery. It is a process that converts the distillate oil or residual oil obtained from the atmospheric and vacuum tower into fuels such as liquefied gas, gasoline, diesel, or chemical raw materials such as ethylene, propylene, butene, BTX, etc. under the action of catalysts and high temperature. The catalyst is not only the reaction active center of the catalytic cracking reaction, but also the heat and mass transfer carrier of the catalytic cracking regeneration system. The catalyst enters the reactor from the high-temperature regenerator and brings in a large amount of heat, which promotes the occurrence of catalytic cracking reaction. The coke generated by the reaction is loaded on the surface of the catalyst. Then, when entering the regenerator, it burns with oxygen in the air to generate a large amount of heat, completing the transfer and generation of heat.

[0003] Catalytic cracking is an endothermic reaction. The reaction heat of the fluidized catalyst reaction in existing refineries is provided by the catalyst. The process is that the catalytic cracking catalyst with a higher temperature enters the cracking reactor and contacts with the hydrocarbon oil for reaction. The hydrocarbon oil absorbs the heat of the catalyst to undergo a cracking reaction and forms coke on the catalyst. After the reaction, the catalyst with a lowered temperature is stripped and then burned and regenerated in the regenerator. The regenerated catalyst has a higher temperature and is recycled. However, the heat capacity of the catalyst is limited, resulting in limited heat provided to the reaction part. The existing technology usually increases the circulation amount of the catalyst to ensure the degree of reaction (usually to ensure the outlet temperature of the reactor).

[0004] In order to provide more heat during the catalytic cracking reaction, some studies have been conducted to add heat-generating materials to the catalyst. However, the existing heat-generating materials cannot achieve good heat generation effects while maintaining good product distribution. Summary of the invention

[0005] The purpose of the present disclosure is to provide a catalytic cracking aid and a preparation method thereof, a catalytic cracking catalyst and a catalytic cracking reaction method. The catalytic cracking aid has a good exothermic effect and can reduce the poisoning effect on the catalytic cracking catalyst. Using it in a catalytic cracking reaction can increase the reaction temperature and have a better distribution of cracking products.

[0006] In order to achieve the above-mentioned object, the first aspect of the present disclosure provides a catalytic cracking aid, which comprises, based on the total weight of the catalytic cracking aid, 1-40 weight % of ABO3 type oxide, 1-10 weight % of alkali metal tungstate, 10-40 weight % of a first binder and 20-60 weight % of a first carrier in terms of weight percentage;

[0007] Wherein, the content of the ABO3 type oxide is measured by weight of copper oxide, A includes rare earth metal elements and / or alkaline earth metal elements; and B includes copper element.

[0008] Optionally, the B has Cu x B 1 1-x Chemical composition, x is 0.2-1, B 1 Including one or more of titanium, manganese, cobalt, nickel and iron;

[0009] Optionally, the alkali metal tungstate includes one or more of sodium tungstate, potassium tungstate and lithium tungstate.

[0010] Optionally, the first carrier comprises one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;

[0011] The first binder includes one or more of aluminum oxide, silicon oxide and aluminum phosphate.

[0012] Optionally, based on the weight of copper element, the low-valent copper on the surface of the catalytic cracking aid accounts for more than 70% of the total weight of the surface copper element, and the low-valent copper is +1-valent copper.

[0013] A second aspect of the present disclosure provides a catalytic cracking catalyst, which comprises a catalytic cracking main agent and the catalytic cracking auxiliary agent described in the first aspect of the present disclosure.

[0014] Optionally, based on the total weight of the catalytic cracking main agent, the catalytic cracking main agent comprises, in terms of mass percentage, 10-40 wt % of a molecular sieve, 30-60 wt % of a second carrier and 20-40 wt % of a second binder;

[0015] The molecular sieve includes one or more of a FAU structure molecular sieve, an MFI structure molecular sieve and a BEA structure molecular sieve;

[0016] The second carrier comprises one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;

[0017] The second binder includes one or more of aluminum oxide, silicon oxide and aluminum phosphate.

[0018] Optionally, the weight ratio of the catalytic cracking aid to the catalytic cracking main agent is 1:(1-40).

[0019] The third aspect of the present disclosure provides a method for preparing the catalytic cracking aid according to the first aspect of the present disclosure, the method comprising the following steps:

[0020] S1, mixing ABO3 type oxide, alkali metal tungstate, a third binder and a first carrier to obtain a mixed slurry;

[0021] S2, drying and then calcining the mixed slurry;

[0022] Wherein, based on the total dry weight of the mixed slurry, the mixed slurry includes 1-40 weight % of ABO3 type oxide, 1-10 weight % of alkali metal tungstate, 10-40 weight % of the third binder and 20-60 weight % of the first carrier in terms of weight percentage, the content of the ABO3 type oxide is calculated by the weight of copper oxide, and the content of the third binder is calculated by the weight of the metal oxide;

[0023] A includes rare earth metal elements and / or alkaline earth metal elements; B includes copper elements.

[0024] Optionally, the third binder includes one or more of aluminum sol, silica sol, phosphate aluminum sol and peptized pseudo-boehmite, and the solid content of the third binder is 20-90% by weight, calculated as metal oxide.

[0025] Optionally, the method further comprises: before step S1, preparing the ABO3 type oxide, wherein the method for preparing the ABO3 type oxide comprises one or more of a coprecipitation method, a sol-gel method and a complex method;

[0026] Optionally, the calcination conditions are: temperature of 500-900° C. and time of 2-20 h.

[0027] A fourth aspect of the present disclosure provides a method for catalytic cracking reaction, the method comprising:

[0028] Contacting the crude oil with the catalytic cracking catalyst described in the second aspect of the present disclosure in a catalytic cracking reactor to carry out a catalytic cracking reaction;

[0029] The temperature of the catalytic cracking reaction is 450-650°C, and the catalyst-oil ratio is 5-20.

[0030] Optionally, the method further comprises:

[0031] a. Separating the mixed oil obtained from the catalytic cracking reaction to obtain reaction oil gas and spent catalytic material containing spent catalyst and reduced catalytic cracking aid;

[0032] b. allowing the catalytic material to be regenerated to enter a regenerator for regeneration treatment to obtain a regenerated catalytic material comprising a regenerated catalyst and an oxidized catalytic cracking aid;

[0033] c. returning the regenerated catalytic material to the catalytic cracking reactor for continued use or returning the regenerated catalytic material to the catalytic cracking reactor for continued use after reduction pretreatment.

[0034] Optionally, the method further comprises: before the contacting, performing reduction pretreatment on the catalytic cracking aid or the catalytic cracking catalyst;

[0035] Optionally, the reduction pretreatment includes: contacting the catalytic cracking aid or the catalytic cracking catalyst with a reducing gas, the time of the reduction pretreatment is 0.5-5 minutes, the temperature of the reduction pretreatment is 650-750°C; the reducing gas includes one or more of hydrogen, ethylene and methane.

[0036] Optionally, based on the weight of copper element, the low-valent copper on the surface of the catalytic cracking aid after the reduction pretreatment accounts for more than 70% of the total weight of the surface copper element, and the low-valent copper is +1-valent copper.

[0037] Through the above technical scheme, the catalytic cracking aid disclosed in the present invention uses copper-containing ABO3-type oxide and alkali metal tungstate as heating materials, and self-heats through the cycle of copper element oxidation-reduction reaction to provide heat for the catalytic cracking reaction, wherein the copper-containing ABO3-type oxide has a stable structure and is not easy to lose, and the alkali metal tungstate can make it have a higher heating capacity. In addition, the catalytic cracking aid disclosed in the present invention has a large calorific value and a small poisoning effect on the catalytic cracking catalyst. When applied to the catalytic cracking reaction, it does not affect the catalytic effect of the catalytic cracking reaction catalyst.

[0038] The present invention provides a catalytic cracking method, which can improve the depth of cracking reaction (higher conversion rate) without increasing the catalyst-oil ratio, and has good product distribution, such as lower coke yield and higher gasoline and liquefied gas yield.

[0039] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:

[0041] Figure 1 ABO3 type oxide LaCu in one embodiment of the present application x Mn 1-x XRD diffraction pattern of O3. DETAILED DESCRIPTION

[0042] The specific implementation of the present disclosure is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present disclosure, and is not used to limit the present disclosure.

[0043] The first aspect of the present disclosure provides a catalytic cracking aid, which comprises, based on the total weight of the catalytic cracking aid, 1-40 weight percent of an ABO3 type oxide, 1-10 weight percent of an alkali metal tungstate, 10-40 weight percent of a first binder, and 20-60 weight percent of a first carrier in terms of weight percentage;

[0044] Wherein, the content of the ABO3 type oxide is measured by weight of copper oxide, A includes rare earth metal elements and / or alkaline earth metal elements; and B includes copper element.

[0045] The catalytic cracking aid disclosed in the present invention uses copper-containing ABO3 type oxide and alkali metal tungstate as heat-generating materials, and self-heats through the cycle of redox reaction to provide heat for the catalytic cracking reaction. The copper-containing ABO3 type oxide has a stable structure and is not easy to lose, which is conducive to the redox reaction of the copper element therein, and provides heat for the catalytic cracking reaction. The alkali metal tungstate can make the aid have a higher heat-generating capacity.

[0046] In the present disclosure, B has Cu x B 1 1-x Chemical composition, x is 0.2-1, B 1 It includes one or more of titanium, manganese, cobalt, nickel and iron. Preferably, x is 0.3-0.7.

[0047] In the present disclosure, the alkali metal tungstate includes one or more of sodium tungstate, potassium tungstate and lithium tungstate, preferably sodium tungstate.

[0048] In the present disclosure, the first carrier and the second carrier are the same or different, and independently include one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; the first binder and the second binder independently include one or more of alumina, silicon oxide and aluminum phosphate.

[0049] In one embodiment of the present disclosure, the low-valent copper on the surface of the catalytic cracking aid accounts for more than 70% of the total weight of the surface copper element, measured by the weight of the copper element, and the low-valent copper is +1-valent copper. The above content is tested by the XPS method. When the catalytic cracking aid that meets the above low-valent copper content is used in a catalytic cracking reaction, the product distribution is better and the yield of high-value products is high.

[0050] A second aspect of the present disclosure provides a catalytic cracking catalyst, which comprises a catalytic cracking main agent and the catalytic cracking auxiliary agent described in the first aspect of the present disclosure.

[0051] In one embodiment of the present disclosure, based on the total weight of the catalytic cracking main agent, the catalytic cracking main agent includes 10-40 wt% of molecular sieve, 30-60 wt% of the second carrier and 20-40 wt% of the second binder in terms of mass percentage.

[0052] In one embodiment of the present disclosure, the molecular sieve includes one or more of a FAU structure molecular sieve, an MFI structure molecular sieve and a BEA structure molecular sieve. For example, it can be one or more of a Y molecular sieve, a ZSM-5 molecular sieve, and a β molecular sieve. Further, the Y molecular sieve includes one or more of HY, REY, REHY, USY, and a Y molecular sieve containing phosphorus elements and rare earth elements. The ZSM-5 molecular sieve includes one or more of HZSM-5, a ZSM-5 molecular sieve containing phosphorus elements and transition metal elements, and a ZRP molecular sieve, and the transition metal may include one or more of Fe elements, Co elements, Ni elements, Mn elements, Ti elements, Zn elements, Cu elements, Ga elements, and Re elements.

[0053] In one embodiment of the present disclosure, the weight ratio of the catalytic cracking aid to the catalytic cracking main agent is 1:(1-40), preferably 1:(1-25).

[0054] The third aspect of the present disclosure provides a method for preparing the catalytic cracking aid according to the first aspect of the present disclosure, the method comprising the following steps:

[0055] S1, mixing ABO3 type oxide, alkali metal tungstate, a third binder and a first carrier to obtain a mixed slurry;

[0056] S2, drying and then calcining the mixed slurry;

[0057] Wherein, based on the total dry weight of the mixed slurry, the mixed slurry includes 1-40 weight % of ABO3 type oxide, 1-10 weight % of alkali metal tungstate, 10-40 weight % of the third binder and 20-60 weight % of the first carrier in terms of weight percentage, the content of the ABO3 type oxide is calculated by the weight of copper oxide, and the content of the third binder is calculated by the weight of the metal oxide;

[0058] A includes rare earth metal elements and / or alkaline earth metal elements; B includes copper elements.

[0059] In one embodiment of the present disclosure, the third binder includes one or more of aluminum sol, silica sol, phosphate aluminum sol and peptized pseudo-boehmite, and the solid content of the third binder is 20-90% by weight, for example, 20-40% by weight, calculated as metal oxide.

[0060] In one embodiment of the present disclosure, the method further includes: before step S1, preparing ABO3 type oxide, the method for preparing ABO3 type oxide includes one or more of co-precipitation method, sol-gel method and complexation method, which is conventional in the art and will not be elaborated here.

[0061] For example, copper-containing perovskite LaCu x Mn 1-x The preparation method of O3 comprises the following steps:

[0062] (1) dissolving a copper source, a lanthanum source and a manganese source in deionized water at a stirring speed of 400-700 rpm;

[0063] (2) adding citric acid monohydrate thereto, maintaining the same rotation speed, stirring at 35-55° C. for 30-60 min, and adding ethylene glycol to obtain a mixture;

[0064] (3) heating the mixture obtained in step (1) to 80-100° C., stirring until it reaches a sol state, standing for 70-100 hours, and drying at 90-120° C. overnight;

[0065] (4) heat treating the solid obtained in step (3) at 400-500° C. for 3-6 hours;

[0066] (5) calcining the substance obtained in step (4) at 750-1000° C. for 10-15 h to obtain ABO3 type oxide LaCu x Mn 1-x O3.

[0067] In one embodiment of the present disclosure, the calcination conditions are: temperature of 500-900°C, time of 2-20h; preferably, time of 8-15, temperature of 750-850°C.

[0068] In the present disclosure, the method for preparing a catalytic cracking reaction aid further comprises treating the catalytic cracking reaction aid pre-product obtained after roasting with an ammonium sulfate solution, wherein the ratio of ammonium sulfate, the catalytic cracking reaction aid pre-product on a dry basis and water is (0.3-0.7):1:(8-12), and then rinsing with deionized water, filtering, drying and secondary roasting to obtain the catalytic cracking reaction aid. The secondary roasting temperature is 800-1000°C and the time is 8-12h.

[0069] In the present disclosure, the average particle size of the catalytic cracking main agent is 70-90 μm.

[0070] A fourth aspect of the present disclosure provides a method for catalytic cracking reaction, the method comprising:

[0071] Contacting the crude oil with the catalytic cracking catalyst described in the second aspect of the present disclosure in a catalytic cracking reactor to carry out a catalytic cracking reaction;

[0072] The temperature of the catalytic cracking reaction is 450-650°C, and the catalyst-oil ratio is 5-20. Preferably, the temperature is 500-600°C, and the catalyst-oil ratio is 5-15.

[0073] In the present disclosure, the catalytic cracking aid is reduced by the dry gas produced by the catalytic cracking reaction after entering the reactor. The dry gas includes reducing gases such as hydrogen and ethylene. At this time, the copper element in the catalytic cracking aid is converted into a reduced state under the action of the reducing gas.

[0074] In the present disclosure, the catalyst-oil ratio refers to the ratio of the mass of the catalytic cracking catalyst to the mass of the feedstock oil.

[0075] In one embodiment of the present disclosure, the method further comprises:

[0076] a. Separating the mixed oil obtained from the catalytic cracking reaction to obtain reaction oil gas and spent catalytic material containing spent catalyst and reduced catalytic cracking aid;

[0077] b. allowing the catalytic material to be regenerated to enter a regenerator for regeneration treatment to obtain a regenerated catalytic material containing a regenerated catalyst and an oxidized catalytic cracking aid;

[0078] c. Returning the regenerated catalytic material to the catalytic cracking reactor for continued use or returning the regenerated catalytic material to the catalytic cracking reactor for continued use after reduction pretreatment;

[0079] The temperature of the regeneration treatment is 650-750° C. The regeneration treatment includes: introducing oxygen into the regenerator to oxidize the copper element.

[0080] In one embodiment of the present disclosure, the method further comprises: before contacting, performing reduction pretreatment on the catalytic cracking aid or catalytic cracking catalyst. Performing reduction pretreatment can optimize product distribution and increase the yield of high-value products.

[0081] In one embodiment of the present disclosure, the reduction pretreatment includes: contacting the catalytic cracking aid or the catalytic cracking catalyst with a reducing gas, the time of the reduction pretreatment is 0.5-5min, and the temperature of the reduction pretreatment is 650-750°C. The reducing gas includes one or more of hydrogen, ethylene and methane. Further, based on the weight of copper element, the low-valent copper on the surface of the catalytic cracking aid after the reduction pretreatment accounts for more than 70% of the total weight of the surface copper element, and the low-valent copper is +1 valent copper. The above content is tested by XPS method.

[0082] In one embodiment of the present disclosure, the type of feedstock oil used in the catalytic cracking reaction of the present disclosure is conventional in the art and is not specifically required. The feedstock oil may include, for example, hydrotreated oil or Wu-mixed 3, wherein the parameters of the Wu-mixed 3 feedstock oil are listed in the examples.

[0083] In the present disclosure, the content of each component is calculated based on the amount at the time of charging.

[0084] The present invention will be further described below by way of examples, but the present invention is not limited thereto. The instruments and reagents used in the examples and comparative examples of the present invention are commonly used by those skilled in the art unless otherwise specified.

[0085] The FAU structure molecular sieve used in the examples and comparative examples is DASY2.0, and the catalytic cracking main agent is COKC-1, both of which are products of Sinopec Catalyst Company.

[0086] Example 1

[0087] LaCu 0.4 Mn 0.6 O3 is used as an example to illustrate the method of preparing copper-containing perovskite.

[0088] First, prepare copper-containing perovskite. 0.4 Mn 0.6 O3 is used as an example to illustrate the method of preparing copper-containing perovskite.

[0089] (1) 3.94 g (0.016 mol) of copper nitrate trihydrate, 17.65 g (0.041 mol) of lanthanum nitrate hexahydrate, and 8.75 g (0.024 mol) of 50% manganese nitrate were dissolved in 664 g of deionized water at 40° C. under stirring at a speed of 500 rpm;

[0090] (2) adding 34.3 g (0.163 mol) of citric acid monohydrate, maintaining the rotation speed at 500 rpm and the temperature at 40°C, stirring for 30 min, and then adding 10.11 g (0.163 mol) of ethylene glycol;

[0091] (3) heating the mixture obtained in step (2) to 80° C., stirring continuously until a sol is formed, standing for 72 hours, and then drying at 100° C. overnight;

[0092] (4) heat treating the solid obtained in step (3) at 450° C. in a muffle furnace for 3 h;

[0093] (5) The material obtained in step (4) was calcined at 800°C for 12 hours to obtain ABO3 type oxide LaCu 0.4 Mn 0.6 O3.

[0094] On a dry basis, weigh each component according to the ratio shown in Table 1.

[0095] The first carrier kaolin was prepared into a slurry with a solid content of 30 wt% by using decationized water, and stirred evenly. The pH of the slurry was adjusted to 2.5 with hydrochloric acid, and the pH value was maintained. After standing and aging at 50°C for 1 hour, aluminum sol (alumina content of 21.5 wt%) was added and stirred for 1 hour to form a colloid. ABO3 type oxide LaCu 0.4 Mn 0.6 O3 and sodium tungstate form a mixed slurry.

[0096] After continued stirring, the mixed slurry was spray dried to prepare a microsphere catalytic cracking aid precursor. The microsphere catalytic cracking aid precursor was then calcined at 500°C for 1 hour to obtain a catalytic cracking aid pre-product. It was then washed with an ammonium sulfate solution at 60°C (the mass ratio of ammonium sulfate, catalytic cracking aid pre-product on a dry basis and water was 0.5:1:10) until the sodium oxide content was less than 0.25% by weight. After that, it was rinsed with deionized water and filtered, dried, and calcined at 850°C for 10 hours to obtain a catalytic cracking aid Z-31. XPS was used to test the proportion of low-valent copper on the surface of the catalytic cracking aid Z-31 to the total weight of copper elements on the surface area, and the results are listed in Table 2.

[0097] Example 2

[0098] On a dry basis, the catalytic cracking aid Z-32 was prepared according to the ratio shown in Table 1 and the method described in Example 1, except that the ABO3 type oxide was LaCu 0.2 Mn 0.8 O3 and XPS were used to test the ratio of low-valent copper on the surface of catalytic cracking aid Z-32 to the total weight of copper elements on the surface area. The results are listed in Table 2.

[0099] Example 3

[0100] Before entering the reactor, the catalytic cracking aid Z-31 prepared in Example 1 was subjected to reduction pretreatment using 20% ​​hydrogen (the rest being nitrogen) as a reducing gas, and the pre-reduction treatment was performed at 650° C. for 2 minutes to obtain catalytic cracking aid Z-31-1. XPS was used to test the ratio of low-valent copper on the surface of the catalytic cracking aid Z-31-1 to the total weight of copper elements on the surface area, and the results are listed in Table 2.

[0101] Figure 1 The copper-containing ABO3 type oxide LaCu prepared in this application X Mn 1-X The XRD diffraction pattern of O3, X is 0.2, 0.4, and 0.6 respectively. There are obvious diffraction peaks at diffraction angles of 23°, 33°, 47°, and 58° in the XRD spectrum, proving that it has an ABO3 configuration.

[0102] The XRD diffraction instrument model is D5005 X-ray diffractometer from Siemens, Germany, and the experimental conditions are Cu target, Kα radiation, solid detector, tube voltage 40 kV, tube current 40 mA, step scan, step size 0.02, preset time 2 s, and scanning range 5-70.

[0103] The instrument model for testing the proportion of low-priced copper is ESCALab250 X-ray photoelectron spectrometer.

[0104] Embodiment 4-6

[0105] Catalytic cracking aids Z-31, Z-32, Z-31-1 were mixed with a catalytic cracking agent at a weight ratio of 1:19, and aged at 800°C for 12 hours with 100% steam to obtain catalytic cracking catalysts A-31, A-32, and A-31-1. The catalytic cracking agent was a fresh industrial agent (the catalytic cracking agent was COKC-1, a product of Sinopec Catalyst Company). Based on the total weight of the catalytic cracking agent, the catalytic cracking agent contained 28% by weight of alumina, 40% by weight of kaolin, and 32% by weight of a FAU structured molecular sieve. The properties of the catalytic cracking agent are listed in Table 3.

[0106] Table 3

[0107] Analyze Project Industrial freshener Elemental composition, weight % - <![CDATA[Na2O]]> 0.14 <![CDATA[Al2O3]]> 55.7 <![CDATA[SiO2]]> 36.8 <![CDATA[RE2O3,%]]> 2.7 Apparent bulk density / (g / mL) 0.79 Drip hole / (mL / g) 0.37 <![CDATA[BET specific surface area, m 2 / g]]> 237 <![CDATA[Matrix area, m 2 / g]]> 89 <![CDATA[Micropore area, m 2 / g]]> 149 Total pore volume, mL / g 0.18 Micropore volume, mL / g 0.069 Particle size distribution, % - 0-20μm 1.9 0-40μm 17.2 0-80μm 61.7 0-105μm 79.8 0-149μm 94.8 APS 68.3

[0108] Comparative Examples 1-3

[0109] a) On a dry basis, catalytic cracking aids Z-1 to Z-3 were prepared according to the ratios shown in Table 1 and the method of Example 1. XPS was used to test the ratio of low-valent copper on the surface of catalytic cracking aids Z-1 to Z-3 to the total weight of copper elements on the surface area, and the results are listed in Table 2.

[0110] Comparative Examples 4-6

[0111] Catalytic cracking catalysts A-1 to A-3 were prepared by using the catalytic cracking aids prepared in Comparative Examples 1 to 3 respectively and adopting the method of Example 6.

[0112] Comparative Example 7

[0113] Catalytic cracking catalyst D was prepared by the method of Example 1, except that the ABO3 type oxide and the molecular sieve were in the same particle, and the catalytic cracking catalyst contained 10 wt % of LaCu in terms of weight ratio based on the total weight of the catalytic cracking catalyst. 0.4 Mn 0.6 O3, 1 wt% sodium tungstate, 25.4 wt% FAU structure molecular sieve, 27.6 wt% alumina and 36 wt% kaolin.

[0114] Table 1

[0115]

[0116] Test Example 1

[0117] The catalytic cracking catalysts prepared in Examples 6-10 and Comparative Examples 4-7 were subjected to the ACE evaluation of the raw oil. The properties of the evaluated raw oil were as follows:

[0118]

[0119]

[0120] The catalytic cracking reaction catalysts prepared in Examples 4-6 and Comparative Examples 4-7 were fed into a catalytic cracking fixed fluidized bed micro-ACE reactor for catalytic cracking reaction. The reaction starting temperature was set at 530°C, the catalyst-oil ratio was 5, the measurement point of the bed temperature after the reaction was in the middle of the bed of the reactor, and the reaction ended 70s after the feed oil was introduced. The reaction temperature control point was in the middle of the reactor. The reaction temperature changes were recorded and listed in Table 2.

[0121] Table 2

[0122]

[0123] Since the heat generated during the reduction of copper is not included in Table 2, the temperature change value of the reduced additive Z-31-1 is small. In actual production, the heat generated by this part of the reduction can be used.

[0124] The low-valent copper ratio in Table 2 refers to the ratio of +1-valent copper elements on the surface of the catalytic cracking aid to the total amount of copper elements on the surface.

[0125] According to the data in Table 2, when the catalytic cracking aid of the present application containing both copper-containing ABO3 type oxide and alkali metal tungstate as heat-generating materials is used for catalytic cracking reaction, it is better than the catalytic cracking aid not containing copper-containing ABO3 type oxide and / or alkali metal tungstate.

[0126] Test Example 2

[0127] The distribution of catalytic cracking products of catalytic cracking catalysts A-1, A-3, A-31, A-31-1 and D was analyzed by Agilent 6890GC (TCD detector) online composition analysis; liquid products were collected and weighed offline, and simulated distillation analysis and PONA analysis were performed; ACE device was equipped with a CO2 converter and an online CO2 infrared detector for online analysis of the total amount of coke generated; the mass of all products was normalized and the material balance was calculated, and the results are listed in Table 3. Among them, the conversion rate refers to the conversion rate calculated for products other than slurry oil and diesel.

[0128] Table 3

[0129] A-1 A-3 D A-31 A-31-1 Yield / wt% - - - - - Dry gas 4.92 5.18 4.87 5.11 4.99 Liquefied gas 25.54 24.62 22.03 25.01 25.48 Coke 7.29 10.0 13.61 9.52 8.01 gasoline 24.42 22.84 20.31 23.21 24.41 diesel fuel 16.63 15.93 16.27 15.8 15.48 Oil slurry 21.19 21.43 21.75 21.35 21.63 Conversion rate / wt% 62.18 62.64 61.98 62.85 62.89

[0130] According to the data of Tables 2 and 3, the catalytic cracking catalysts A-1, A-2, and A-3 that do not contain ABO3-type oxides and / or alkali metal tungstates as heating materials, although the yield of high-value products such as liquefied gas and gasoline is high, its heating effect is not good; the catalyst A-31-1 that has been pretreated by reduction can maintain a better product distribution while ensuring the heating effect, and the yield of high-value products such as liquefied gas and gasoline is high compared to the catalyst A-31 that has not been pretreated by reduction. According to the data of catalysts A-3 and A-31, it can be seen that under the premise of a considerable heating effect, the amount of heating material added is reduced, thereby reducing its poisoning effect on the catalyst and improving the yield of high-value products. In addition, according to the data of catalyst D, when the heating material and molecular sieve are in different particles, the catalytic performance of the main agent is less affected, the coke is lower, and the yield of high-value products such as liquefied gas and gasoline is higher. Therefore, the heating material and molecular sieve are distributed in different particles, and before the catalytic cracking reaction is carried out, the catalytic cracking aid of the present application is pretreated by reduction to achieve the effect of optimizing the distribution of products while obtaining a higher calorific value.

[0131] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0132] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0133] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A catalytic cracking aid, It is characterized in that Based on the total weight of the catalytic cracking aid, the catalytic cracking aid comprises 1-40 wt % of ABO 3 type oxide, 1-10 wt % of an alkali metal tungstate, 10-40 wt % of a first binder and 20-60 wt % of a first carrier; Wherein, the ABO 3 The content of the type oxide is measured by weight of copper oxide, A includes rare earth metal elements and / or alkaline earth metal elements; B includes copper element; The B has Cu x B 1 1-x Chemical composition, x is 0.2-1, B 1 Including one or more of titanium, manganese, cobalt, nickel and iron; Calculated by the weight of copper element, the low-valent copper on the surface of the catalytic cracking aid accounts for more than 70% of the total weight of the surface copper element, and the low-valent copper is +1-valent copper.

2. The catalytic cracking aid according to claim 1, in, The alkali metal tungstate includes one or more of sodium tungstate, potassium tungstate and lithium tungstate.

3. The catalytic cracking aid according to claim 1, in, The first carrier comprises one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; The first binder includes one or more of aluminum oxide, silicon oxide and aluminum phosphate.

4. A catalytic cracking catalyst, It is characterized in that The catalytic cracking catalyst comprises a catalytic cracking main agent and a catalytic cracking aid as claimed in any one of claims 1 to 3.

5. The catalytic cracking catalyst according to claim 4, in, Based on the total weight of the catalytic cracking main agent, the catalytic cracking main agent comprises 10-40 wt% of a molecular sieve, 30-60 wt% of a second carrier and 20-40 wt% of a second binder in terms of mass percentage; The molecular sieve includes one or more of a FAU structure molecular sieve, an MFI structure molecular sieve and a BEA structure molecular sieve; The second carrier comprises one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; The second binder includes one or more of aluminum oxide, silicon oxide and aluminum phosphate.

6. The catalytic cracking catalyst according to claim 4, in, The weight ratio of the catalytic cracking aid to the catalytic cracking main agent is 1:(1-40).

7. A method for preparing the catalytic cracking aid according to any one of claims 1 to 3, It is characterized in that The method comprises the following steps: S1. ABO 3 The type oxide, the alkali metal tungstate, the third binder and the first carrier are mixed to obtain a mixed slurry; S2, drying and then calcining the mixed slurry; Wherein, based on the total dry weight of the mixed slurry, the mixed slurry comprises 1-40 wt % of ABO 3 ABO type oxide, 1-10 wt% of alkali metal tungstate, 10-40 wt% of a third binder and 20-60 wt% of a first carrier, the ABO 3 The content of the copper oxide is measured by weight of copper oxide, and the content of the third binder is measured by weight of the metal oxide; A includes rare earth metal elements and / or alkaline earth metal elements; B includes copper elements.

8. The method according to claim 7, in, The third binder includes one or more of aluminum sol, silica sol, phosphate aluminum sol and peptized pseudo-boehmite. The solid content of the third binder is 20-90% by weight based on metal oxide.

9. The method according to claim 7, in, The method further comprises: before step S1, preparing the ABO 3 type oxide, preparing the ABO 3 The methods for preparing type oxides include one or more of coprecipitation, sol-gel and complexation.

10. The method according to claim 9, in, The calcination conditions are: temperature of 500-900° C. and time of 2-20 hours.

11. A method for catalytic cracking reaction, It is characterized in that The method includes: Contacting the crude oil with the catalytic cracking catalyst according to any one of claims 4 to 6 in a catalytic cracking reactor to carry out a catalytic cracking reaction; The temperature of the catalytic cracking reaction is 450-650°C, and the catalyst-oil ratio is 5-20.

12. The method according to claim 11, in, The method further includes: a. Separating the mixed oil obtained from the catalytic cracking reaction to obtain reaction oil gas and spent catalytic material containing spent catalyst and reduced catalytic cracking aid; b. allowing the catalytic material to be regenerated to enter a regenerator for regeneration treatment to obtain a regenerated catalytic material comprising a regenerated catalyst and an oxidized catalytic cracking aid; c. returning the regenerated catalytic material to the catalytic cracking reactor for continued use or returning the regenerated catalytic material to the catalytic cracking reactor for continued use after reduction pretreatment.

13. The method according to claim 11, in, The method further comprises: before the contacting, performing reduction pretreatment on the catalytic cracking aid or the catalytic cracking catalyst.

14. The method according to claim 13, in, The reduction pretreatment comprises: contacting the catalytic cracking aid or the catalytic cracking catalyst with a reducing gas, the time of the reduction pretreatment is 0.5-5 minutes, the temperature of the reduction pretreatment is 650-750° C.; the reducing gas comprises one or more of hydrogen, ethylene and methane.

15. The method according to claim 13 or 14, in, Calculated by the weight of copper element, the low-valent copper on the surface of the catalytic cracking aid after the reduction pretreatment accounts for more than 70% of the total weight of the surface copper element, and the low-valent copper is +1-valent copper.

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