CN116023979A - Catalytic cracking reaction method, catalytic cracking reaction auxiliary agent, preparation method of catalytic cracking reaction auxiliary agent and catalytic cracking catalyst - Google Patents
Catalytic cracking reaction method, catalytic cracking reaction auxiliary agent, preparation method of catalytic cracking reaction auxiliary agent and catalytic cracking catalyst Download PDFInfo
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Abstract
The present disclosure relates to a method for catalytic cracking reaction, a catalytic cracking reaction auxiliary agent, a preparation method thereof and a catalytic cracking catalyst, wherein raw oil is contacted with the catalytic cracking auxiliary agent and a catalytic cracking main agent in a catalytic cracking reactor to perform catalytic cracking reaction; wherein, based on the total weight of the catalytic cracking auxiliary agent, the catalytic cracking auxiliary agent comprises 20 to 60 weight percent of a first carrier, 10 to 40 weight percent of a first binder and 1 to 40 weight percent of copper-containing oxide according to weight percent. The method uses the catalytic cracking auxiliary agent which takes the copper-containing oxide as the heating material, and the catalytic cracking auxiliary agent can perform self-heating through self-oxidation reduction of copper, so as to provide heat for catalytic cracking reaction, improve the temperature of the catalytic cracking reaction, improve the yield of high-value products, and avoid the damage of the catalyst caused by the fact that the molecular sieve and the heating material are positioned on the same particle.
Description
Technical Field
The present disclosure relates to the field of catalytic cracking, and in particular, to a catalytic cracking reaction method, a catalytic cracking reaction auxiliary agent, a preparation method thereof, and a catalytic cracking catalyst.
Background
The catalytic cracking device is a core device for secondary processing of a refinery, and is used for converting distillate oil or residual oil raw oil obtained by an atmospheric and vacuum tower into liquefied gas, gasoline, diesel oil and other fuels or ethylene, propylene, butylene, BTX and other chemical raw materials under the action of a catalyst and high temperature. The catalyst is not only the reactive center of the catalytic cracking reaction, but also the heat and mass transfer carrier of the catalytic cracking reverse-recycling system. The catalyst is introduced into the reactor from a high-temperature regenerator to bring in a large amount of heat, so that catalytic cracking reaction is promoted to occur, and coke generated by the reaction is loaded on the surface of the catalyst. And then the air enters the regenerator to be burnt with oxygen in the air to generate a large amount of heat, so that heat transfer and generation are completed.
With the heavy and poor quality of the processed raw materials, the oil refining device is required to transform to chemical industry. The reaction conditions are more severe. However, the heat capacity of the catalyst is limited, resulting in limited heat supplied to the reaction part, so that it is difficult to further increase the reaction temperature; at the same time, in order to transfer more heat, the agent-oil ratio is increased, and the adverse effects are brought about. For this reason, there is a study on using a heat generating material to increase the conversion depth without increasing the agent-to-oil ratio.
So far, the prior heating material cannot obtain satisfactory reaction effect when being used for catalytic cracking.
Disclosure of Invention
The purpose of the present disclosure is to provide a catalytic cracking reaction method, a catalytic cracking reaction auxiliary agent, a preparation method thereof, and a catalytic cracking catalyst, wherein the catalytic cracking auxiliary agent has a higher heating value, and avoids catalyst damage caused by the fact that a molecular sieve and a heating material are in the same particle.
To achieve the above object, a first aspect of the present disclosure provides a method of catalytic cracking reaction, the method comprising:
the raw oil is contacted with a catalytic cracking auxiliary agent and a catalytic cracking main agent in a catalytic cracking reactor to carry out catalytic cracking reaction;
wherein, based on the total weight of the catalytic cracking auxiliary agent, the catalytic cracking auxiliary agent comprises 20 to 60 weight percent of a first carrier, 10 to 40 weight percent of a first binder and 1 to 40 weight percent of copper-containing oxide according to weight percent.
Optionally, the first carrier comprises one or more of kaolin, montmorillonite, kieselguhr, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;
the first binder comprises one or more of aluminum oxide, silicon oxide and aluminum phosphate;
the copper-containing oxide is copper oxide and/or cuprous oxide.
Optionally, the method further comprises: before the contact, the catalytic cracking auxiliary is subjected to reduction pretreatment to obtain a reduced catalytic cracking auxiliary;
optionally, the reduction pretreatment includes: contacting the catalytic cracking auxiliary agent with reducing gas, wherein the time of the reduction pretreatment is 0.5-3min, and the temperature of the reduction pretreatment is 650-700 ℃; the reducing gas comprises one or more of hydrogen, ethylene and methane.
Optionally, the low-valence copper on the surface of the catalytic cracking auxiliary in the reduced state accounts for more than 70% of the total weight of the surface copper element, and the low-valence copper is +1-valence copper.
Optionally, the temperature of the catalytic cracking reaction is 450-650 ℃, and the catalyst-oil ratio is 5-20;
the weight ratio of the catalytic cracking auxiliary agent to the catalytic cracking main agent is 0.01-0.5.
Optionally, the method comprises:
separating reaction oil gas and a spent catalytic material from a product mixture obtained by catalytic cracking reaction, and carrying out regeneration treatment on the spent catalytic material to obtain a regenerated catalytic material;
optionally, the regeneration process includes the steps of:
a. enabling the to-be-regenerated catalytic material to enter a regenerator for regeneration treatment to obtain regenerated catalytic material containing regenerated catalyst and oxidation state catalytic cracking auxiliary agent;
b. and returning the regenerated catalytic material to the catalytic cracking reactor for continuous use or returning the regenerated catalytic material to the catalytic cracking reactor for continuous use after reduction.
A second aspect of the present disclosure provides a catalytic cracking catalyst comprising catalytic particles and exothermic particles;
the heat-generating particles comprise, in weight percent, 20-60% by weight of a second carrier, 10-40% by weight of the second binder, and 1-40% by weight of a copper-containing oxide, based on the total weight of the heat-generating particles.
Optionally, the catalytic particles comprise, in weight percent, 10-40 weight percent molecular sieve, 30-60 weight percent third support, and 20-40 weight percent third binder, based on the total weight of the catalytic particles;
optionally, the molecular sieve comprises one or more of a FAU structure molecular sieve, an MFI structure molecular sieve and a BEA structure molecular sieve;
the copper-containing oxide comprises copper oxide and/or cuprous oxide;
the second binder and the third binder are the same or different and each independently comprise one or more of aluminum oxide, silicon oxide and aluminum phosphate;
the second carrier and the three carriers are identical or different and respectively and independently comprise one or more of kaolin, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;
optionally, the weight ratio of the exothermic particles to the catalytic particles is 0.01-0.5.
A third aspect of the present disclosure provides a catalytic cracking reaction auxiliary comprising, in weight percent, 20-60% by weight of a fourth support, 10-40% by weight of a fourth binder, and 1-40% by weight of a copper-containing oxide, based on the total weight of the catalytic cracking reaction auxiliary.
Optionally, the copper-containing oxide comprises copper oxide and/or cuprous oxide;
the fourth carrier comprises one or more of kaolin, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;
the fourth binder comprises one or more of aluminum oxide, silicon oxide and aluminum phosphate.
Optionally, the low-valence copper on the surface of the catalytic cracking reaction auxiliary agent accounts for more than 70% of the total weight of the surface copper element by weight of the copper element, and the low-valence copper is +1-valence copper.
A fourth aspect of the present disclosure provides a method of preparing a catalytic cracking reaction aid according to the third aspect of the present disclosure, the method comprising the steps of:
s1, mixing a copper-containing substance, a fifth binder and a fourth carrier to obtain mixed slurry;
s2, spray drying and roasting the mixed slurry;
wherein the mixed slurry comprises, by weight percent, 1-40% of the copper-containing substance, 1-40% of a fifth binder and 20-60% of a fourth carrier, based on the total weight of the dry basis of the mixed slurry, the copper-containing substance being based on the weight of copper oxide, the fifth binder being based on the weight of metal oxide, and the copper-containing substance comprising a copper-containing oxide and/or a copper salt.
Optionally, the copper-containing oxide comprises copper oxide and/or cuprous oxide;
the copper salt comprises one or more of copper sulfate, copper chloride, copper nitrate and copper carbonate;
the fifth binder comprises one or more of aluminum sol, silica sol, phosphorus aluminum sol and peptized pseudo-boehmite, and the solid content of the fifth binder is 20-90 wt% based on metal oxide.
Optionally, the firing conditions are: the temperature is 500-700 ℃ and the time is 2-5h.
Through the technical scheme, the catalytic cracking method adopts the catalytic cracking auxiliary agent which takes the copper-containing oxide as the heating material, and the catalytic cracking auxiliary agent can perform self-heating through self-oxidation reduction, so that heat is provided for the catalytic cracking reaction, the catalytic cracking reaction temperature is improved, and the yield of high-value products is improved. Compared with a method that the copper-containing oxide and the molecular sieve are in the same particle, the method avoids direct contact between the alkaline copper-containing oxide and the acidic molecular sieve, can ensure higher heating value, and simultaneously avoids damage to the molecular sieve, thereby avoiding influence on catalytic activity of the catalyst.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a graph of H2-TPR for catalytic cracking reaction aid Z-15-1 of example 6 of the present application.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides a method of catalytic cracking reactions, the method comprising:
the raw oil is contacted with a catalytic cracking auxiliary agent and a catalytic cracking main agent in a catalytic cracking reactor to carry out catalytic cracking reaction;
wherein, based on the total weight of the catalytic cracking auxiliary agent, the catalytic cracking auxiliary agent comprises 20 to 60 weight percent of a first carrier, 10 to 40 weight percent of a first binder and 1 to 40 weight percent of copper-containing oxide according to weight percent.
In the present disclosure, the catalytic cracking aid is reduced by a dry gas generated by a catalytic cracking reaction after entering the reactor, wherein the dry gas includes a reducing gas such as hydrogen and ethylene, and at this time, copper elements in the catalytic cracking aid are converted into a reduced state under the action of the reducing gas.
In one embodiment of the present disclosure, the method further comprises: before contact, the catalytic cracking auxiliary agent is subjected to reduction pretreatment to obtain a reduced catalytic cracking auxiliary agent; the reduction pretreatment comprises the following steps: the catalytic cracking auxiliary agent is contacted with reducing gas, the time of the reduction pretreatment is 0.5-3min, and the temperature of the reduction pretreatment is 650-700 ℃; the reducing gas comprises one or more of hydrogen, ethylene and methane. When the catalytic cracking auxiliary agent subjected to reduction pretreatment is applied to catalytic cracking reaction, the optimization of product distribution is facilitated, and the yield of high-value products is further improved.
In the present disclosure, the reduced copper on the surface of the catalytic cracking aid represents 70% or more of the total weight of the surface copper element, based on the weight of the copper element, and the reduced copper is +1 copper. When the catalytic cracking auxiliary agent with the low-valence copper content is used for catalytic cracking reaction, the product distribution is good, and the high-value product yield is high. The above contents were tested by XPS.
In one embodiment of the present disclosure, the catalytic cracking reaction temperature is 450-650 ℃, preferably 500-600 ℃; the ratio of the agent to the oil is 5-20, preferably 5-15; the weight ratio of the catalytic cracking auxiliary agent to the catalytic cracking reaction catalyst is 0.01-0.5; preferably 0.01-0.2.
In the present disclosure, the catalyst-to-oil ratio refers to the mass ratio of the sum of the masses of the catalytic cracking main agent and the catalytic cracking auxiliary agent to the raw oil.
In one embodiment of the present disclosure, the weight ratio of the catalytic cracking aid to the catalytic cracking host is 0.01 to 0.5.
In one embodiment of the present disclosure, the method comprises:
and separating reaction oil gas and a spent catalytic material from a product mixture obtained by the catalytic cracking reaction, and carrying out regeneration treatment on the spent catalytic material to obtain a regenerated catalytic material.
In one embodiment of the present disclosure, the regeneration process includes the steps of:
a. enabling the to-be-regenerated catalytic material to enter a regenerator for regeneration treatment to obtain regenerated catalytic material containing regenerated catalyst and oxidation state catalytic cracking auxiliary agent;
b. returning the regenerated catalytic material to the catalytic cracking reactor for continuous use;
wherein the temperature of the regeneration treatment is 650-750deg.C, preferably 670-730 deg.C.
In the present disclosure, the method of regeneration treatment may be, for example, to introduce oxygen into the regenerator to oxidize copper elements in the catalytic material to be regenerated.
In the present disclosure, the kind of the feedstock oil used for the catalytic cracking reaction is conventional in the art, and no specific requirement is made. The feedstock oil may include, for example, one or more of hydrotreated oil, atmospheric residue, hydrogenated residue, coker gas oil, and vacuum residue, and specifically, the feedstock oil may be hydrogenated residue.
A second aspect of the present disclosure provides a catalytic cracking catalyst comprising catalytic particles and exothermic particles;
the heat-generating particles comprise, in weight percent, 20-60% by weight of a second carrier, 10-40% by weight of the second binder, and 1-40% by weight of a copper-containing oxide, based on the total weight of the heat-generating particles.
In one embodiment of the present disclosure, the catalytic particles comprise 10 to 40 weight percent molecular sieve, 30 to 60 weight percent third support, and 20 to 40 weight percent third binder, based on the total weight of the catalytic particles.
In one embodiment of the present disclosure, the weight ratio of exothermic particles to catalytic particles is 0.01-0.5, preferably 0.01-0.2.
In one embodiment of the present disclosure, the molecular sieve comprises one or more of a FAU structural molecular sieve, an MFI structural molecular sieve, and a BEA structural molecular sieve. For example, the catalyst can be one or more of a Y molecular sieve, a ZSM-5 molecular sieve and a beta molecular sieve. Further, the Y molecular sieve includes one or more of a HY, REY, REHY, USY and a phosphorus element and rare earth element containing Y molecular sieve. The ZSM-5 molecular sieve comprises one or more of HZSM-5, ZSM-5 molecular sieve containing phosphorus element and transition metal element, and ZRP molecular sieve, and the transition metal can comprise one or more of Fe element, co element, ni element, mn element, ti element, zn element, cu element, ga element and Re element.
In the present disclosure, the catalytic particles have an average particle size of 70 to 90 μm.
A third aspect of the present disclosure provides a catalytic cracking reaction auxiliary comprising, in weight percent, 20-60% by weight of a fourth support, 10-40% by weight of a fourth binder, and 1-40% by weight of a copper-containing oxide, based on the total weight of the catalytic cracking reaction auxiliary.
The catalytic cracking reaction auxiliary agent disclosed by the invention takes copper-containing oxide as a heating material, and self-heats through the circulation of the following oxidation-reduction reaction, so as to provide heat for the catalytic cracking reaction.
2Cu+O 2 →2CuO ΔH＝-156KJ/mol＝1914J/g
CuO+2H 2 →Cu+2H 2 O ΔH＝-95KJ/mol＝1190J/g
In one embodiment of the present disclosure, the low-valence copper on the surface of the catalytic cracking reaction auxiliary comprises more than 70% of the total weight of the surface copper element, based on the weight of the copper element, and the low-valence copper is +1 valence copper. The above contents were tested by XPS.
A fourth aspect of the present disclosure provides a method of preparing a catalytic cracking reaction aid as described in the third aspect of the present disclosure, the method comprising the steps of:
s1, mixing a copper-containing substance, a fifth binder and a fourth carrier to obtain mixed slurry;
s2, drying and roasting the mixed slurry;
wherein the mixed slurry comprises, by weight percent, 1-40% of the copper-containing substance, 1-40% of a fifth binder and 20-60% of a fourth carrier, based on the total weight of the dry basis of the mixed slurry, the copper-containing substance being based on the weight of copper oxide, the fifth binder being based on the weight of metal oxide, and the copper-containing substance comprising a copper-containing oxide and/or a copper salt.
In the present disclosure, the copper-containing oxide includes copper oxide and/or cuprous oxide; the copper salt comprises one or more of copper sulfate, copper chloride, copper nitrate and copper carbonate; preferably, the copper-containing species comprises copper sulfate and/or copper chloride. Further, no matter what copper-containing material is selected, the copper element exists mainly in the form of copper oxide after drying and roasting.
In one embodiment of the present disclosure, the fifth binder comprises one or more of an aluminum sol, a silica sol, a phosphoalumina sol, and peptized pseudo-boehmite, and the solids content of the fifth binder is 20 to 90 wt%, for example, 20 to 40 wt%, on a metal oxide basis.
In one embodiment of the present disclosure, the conditions of firing are: the temperature is 500-700 ℃ and the time is 2-5h.
In the present disclosure, the method for preparing a catalytic cracking reaction aid further comprises treating a catalytic cracking aid pre-product obtained after calcination with an ammonium sulfate solution, the ratio of ammonium sulfate, the catalytic cracking aid pre-product on a dry basis, to water being (0.3-0.7): 1: (8-12), leaching with deionized water, filtering, drying and secondary roasting to obtain the catalytic cracking reaction auxiliary agent. The temperature of the secondary roasting is 600-800 ℃ and the time is 3-6h.
In the present disclosure, the first carrier, the second carrier, the third carrier, and the fourth carrier are the same or different, and each independently includes one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite; the first binder, the second binder, the third binder and the fourth binder are the same or different and each independently comprise one or more of aluminum oxide, silicon oxide and aluminum phosphate.
The catalytic cracking host used in the first aspect of the present disclosure is conventional in the art, e.g., has the same composition and structure as the catalytic particles of the second aspect of the present disclosure.
The present invention will be further illustrated by the following examples, but the present invention is not limited thereto, and the apparatus and reagents used in the examples and comparative examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.
In the present disclosure, the content of the carrier, the content of the binder, and the content of the copper-containing oxide are calculated as the charge amounts.
The FAU structure molecular sieve used in the examples and the comparative examples is DASY2.0, the catalytic cracking main agent is COKC-1, and the above products are all made by China petrochemical catalyst company.
Examples 1 to 4
The components were weighed in the proportions shown in table 1 on a dry basis and catalytic cracking reaction auxiliaries were prepared as follows.
The fourth carrier kaolin is prepared into slurry with 30 weight percent of solid content by using decationizing water, the slurry is stirred uniformly, the pH value of the slurry is adjusted to 2.5 by hydrochloric acid, the pH value is kept, standing and aging are carried out for 1 hour at 50 ℃, then aluminum sol (with the alumina content of 21.5 weight percent) is added, the mixture is stirred for 1 hour to form colloid, and copper chloride is added to form mixed slurry.
And (3) after continuing stirring, spray drying the mixed slurry to prepare the microsphere catalytic cracking reaction auxiliary precursor. And then roasting the microsphere catalytic cracking reaction auxiliary precursor for 1 hour at 500 ℃ to obtain a catalytic cracking reaction auxiliary pre-product. And washing with an ammonium sulfate solution at 60 ℃ (the mass ratio of ammonium sulfate, catalytic cracking reaction auxiliary pre-product and water is 0.5:1:10 on a dry basis) until the sodium oxide content is less than 0.25 wt%. And then leaching with deionized water, filtering, drying, and roasting at 650 ℃ for 3 hours to obtain the catalytic cracking reaction auxiliary Z-12 to Z-15. The proportion of low-valence copper on the surface of the catalytic cracking reaction auxiliaries Z-12 to Z-15 to the total weight of the surface area copper element was tested by XPS, and the results are shown in Table 2.
Example 5
The components were weighed in accordance with the proportions shown in Table 1 on a dry basis, and a catalytic cracking reaction auxiliary Z-16 was prepared in accordance with the procedure of example 1, except that copper sulfate was used instead of copper chloride as the copper-containing substance. The proportion of low-valence copper on the surface of the catalytic cracking reaction auxiliary Z-16 to the total weight of the surface area copper element was tested by XPS, and the results are shown in Table 2.
Example 6
Before entering a reactor, the catalytic cracking reaction auxiliary Z-15 prepared in the example 4 is reduced by adopting hydrogen (the rest is nitrogen) with the mass fraction of 20% as reducing gas, and the catalytic cracking reaction auxiliary Z-15-1 is obtained by pre-reducing treatment for 2min at the temperature of 650 ℃. The proportion of low-valence copper on the surface of the catalytic cracking reaction auxiliary Z-15-1 to the total weight of the surface area copper element was tested by XPS, and the results are shown in Table 2. FIG. 1 is a graph of H2-TPR for catalytic cracking reaction aid Z-15-1 of example 6.
Wherein the measuring instrument of the H2-TPR graph is ChemBet Pulsar TPR/TPD manufactured by Micromertics corporation of America. The testing method comprises the following steps: the sample mass is 10mg, the sample is put in a U-shaped quartz tube, the temperature is increased to 200 ℃ in He gas at 10 ℃/min, the temperature is kept constant for 30min at 200 ℃, then the temperature is reduced to 100 ℃, reducing gas is introduced, and the gas flow rate is 120cm 3 And/min, heating to 1000 ℃ at a speed of 10 ℃/min.
The model of the low-cost copper proportion test instrument is ESCALab250 type X-ray photoelectron spectrometer.
Examples 7 to 12
And respectively mixing the catalytic cracking reaction auxiliary agents Z-12 to Z-16 and Z-15-1 with the catalytic cracking main agent according to the weight ratio of 1:19, and ageing with 100% water vapor at 800 ℃ for 12 hours to obtain catalytic cracking catalysts A-12 to A-16 and A-15-1. The catalytic cracking main agent is an industrial fresh agent, and comprises 28 weight percent of alumina, 40 weight percent of kaolin and 32 weight percent of FAU structure molecular sieve based on the total weight of the catalytic cracking main agent, and the properties of the catalytic cracking main agent are listed in table 3.
Comparative example 1
The components were weighed in accordance with the proportions shown in Table 1 on a dry basis, and a catalytic cracking reaction auxiliary Z-1 was prepared in accordance with the procedure of example 1, except that the main catalytic cracking reaction agent of comparative example 1 did not contain copper-containing substances. The proportion of low-valence copper on the surface of the catalytic cracking reaction auxiliary Z-1 to the total weight of the surface area copper element was tested by XPS, and the results are shown in Table 2.
TABLE 1
Comparative example 2
Catalytic cracking catalyst D was prepared by the method of example 1, except that the copper-containing oxide was in the same particle as the molecular sieve, and the catalytic cracking catalyst contained 1% by weight of copper-containing oxide, 30.4% by weight of FAU structure molecular sieve, 27.6% by weight of alumina, and 41% by weight of kaolin, based on the total weight of the catalytic cracking catalyst. The proportion of low-valence copper on the surface of the catalytic cracking catalyst D to the total weight of the surface area copper element was tested by XPS and the results are shown in Table 2.
Comparative example 3
A catalytic cracking catalyst A-1 was prepared by the method of example 7, except that the catalytic cracking aid Z-1 prepared in comparative example 1 was used as a catalytic cracking aid.
TABLE 3 Table 3
| Analysis item | Industrial fresh agent |
| Elemental composition, weight percent | - |
| Na 2 O | 0.14 |
| Al 2 O 3 | 55.7 |
| SiO 2 | 36.8 |
| RE2O 3 ，％ | 2.7 |
| Apparent bulk/(g/mL) | 0.79 |
| Drip hole/(mL/g) | 0.37 |
| BET specific surface, m 2 /g | 237 |
| Matrix area, m 2 /g | 89 |
| Micropore area, m 2 /g | 149 |
| Total pore volume, mL/g | 0.18 |
| Micropore volume, mL/g | 0.069 |
| Particle size distribution, percent | - |
| 0-20μm | 1.9 |
| 0-40μm | 17.2 |
| 0-80μm | 61.7 |
| 0-105μm | 79.8 |
| 0-149μm | 94.8 |
| APS | 68.3 |
Test example 1
The catalytic cracking reaction catalysts A-12 to A-16, A-15-1, A-1, and D prepared above were subjected to raw oil ACE evaluation. The properties of the raw oil were evaluated as shown in table 4 below.
TABLE 4 Table 4
The catalytic cracking catalysts prepared in examples 7 to 12 and comparative examples 2 and 3 were fed into a catalytic cracking fixed fluidized bed micro-reverse ACE reactor to perform catalytic cracking reaction. Wherein the initial temperature of the reaction is set to 530 ℃, the catalyst-to-oil ratio is 5, the measuring point of the bed temperature after the reaction is positioned in the middle of the bed of the reactor, and the reaction is finished 70s after the raw oil is introduced. The reaction temperature control point is arranged in the middle of the reactor. The reaction temperature changes are recorded and are listed in table 2.
TABLE 2
Since the heat generated during the reduction of copper elements is not taken into account in Table 2, the temperature change of Z-15-1 of the reduced auxiliary is small, and the heat generated by the partial reduction can be used in actual production.
The low copper ratio in table 2 refers to the ratio of the surface +1 valent copper of the catalytic cracking aid to the total surface copper element.
As can be seen from the data in table 2, the catalytic cracking reaction auxiliary agent using the copper-containing oxide as the heat generating material of the present application was used for catalytic cracking reaction, and the heat generating effect was remarkable as compared with the catalytic cracking reaction auxiliary agent without the copper-containing oxide when the molecular sieve was in different particle form.
Test example 2
The distribution of the catalytic cracking products of the catalytic cracking catalysts A-1, A-15-1 and D is analyzed, and the analysis method is Agilent 6890GC (TCD detector) online analysis composition; the liquid product is weighed off-line after being collected, and simulated distillation analysis and PONA analysis are carried out; ACE device with CO 2 Converter and on-line CO 2 The infrared tester is used for analyzing the total coke generation amount on line; the material balance was normalized for all product qualities and the results are shown in Table 5. Wherein the conversion is referred toIs the calculated conversion of products other than slurry and diesel.
TABLE 5
| Catalyst numbering | A-1 | A-15 | A-15-1 | D |
| Auxiliary numbering | Z-1 | Z-15 | Z-15-1 | - |
| Yield/wt% | - | - | - | - |
| Dry gas | 4.92 | 5.18 | 4.65 | 5.62 |
| Liquefied gas | 25.54 | 22.62 | 24.36 | 19.63 |
| Coke | 7.29 | 11.58 | 8.34 | 16.57 |
| Gasoline | 24.42 | 22.24 | 23.86 | 18.9 |
| Diesel oil | 16.63 | 15.93 | 17.18 | 17.45 |
| Slurry oil | 21.19 | 22.46 | 21.61 | 21.83 |
| Conversion per wt% | 62.18 | 61.62 | 61.21 | 60.72 |
As can be seen from the data in tables 2 and 5, the catalytic cracking catalyst A-1 containing no copper oxide, although the yield of high value products such as liquefied gas and gasoline is high, its heating effect is poor; compared with the catalyst A-15 which is not subjected to reduction pretreatment, the catalyst A-15-1 which is subjected to reduction pretreatment can maintain good product distribution and higher yield of high-value products such as liquefied gas, gasoline and the like while ensuring heating effect. In addition, according to the data of the catalyst D, when the heating material and the molecular sieve are in different particles, the influence on the catalytic performance of the main agent is smaller, the coke generation is lower, and the yield of high-value products such as gasoline, liquefied gas and the like is higher. Therefore, before the catalytic cracking reaction, the catalytic cracking reaction auxiliary agent is subjected to reduction pretreatment, and the heating material and the molecular sieve are in different particles, so that the effect of optimizing the product distribution while keeping higher heating value can be achieved.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (14)
1. A method of catalytic cracking reactions, the method comprising:
the raw oil is contacted with a catalytic cracking auxiliary agent and a catalytic cracking main agent in a catalytic cracking reactor to carry out catalytic cracking reaction;
wherein, based on the total weight of the catalytic cracking auxiliary agent, the catalytic cracking auxiliary agent comprises 20 to 60 weight percent of a first carrier, 10 to 40 weight percent of a first binder and 1 to 40 weight percent of copper-containing oxide according to weight percent.
2. The method of claim 1, wherein the first carrier comprises one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite;
the first binder comprises one or more of aluminum oxide, silicon oxide and aluminum phosphate;
the copper-containing oxide is copper oxide and/or cuprous oxide.
3. The method of claim 1, wherein the method further comprises: before the contact, the catalytic cracking auxiliary is subjected to reduction pretreatment to obtain a reduced catalytic cracking auxiliary;
optionally, the reduction pretreatment includes: contacting the catalytic cracking auxiliary agent with reducing gas, wherein the time of the reduction pretreatment is 0.5-3min, and the temperature of the reduction pretreatment is 650-700 ℃; the reducing gas comprises one or more of hydrogen, ethylene and methane.
4. A process according to claim 3, wherein the reduced catalytic cracking promoter surface has a low copper content of greater than 70% by weight of the total surface copper element, based on the weight of copper element, the low copper being +1 copper.
5. The method according to claim 1, wherein the catalytic cracking reaction temperature is 450-650 ℃ and the catalyst to oil ratio is 5-20;
the weight ratio of the catalytic cracking auxiliary agent to the catalytic cracking main agent is 0.01-0.5.
6. A method according to claim 1 or 3, wherein the method comprises:
separating reaction oil gas and a spent catalytic material from a product mixture obtained by catalytic cracking reaction, and carrying out regeneration treatment on the spent catalytic material to obtain a regenerated catalytic material;
optionally, the regeneration process includes the steps of:
a. enabling the to-be-regenerated catalytic material to enter a regenerator for regeneration treatment to obtain regenerated catalytic material containing regenerated catalyst and oxidation state catalytic cracking auxiliary agent;
b. and returning the regenerated catalytic material to the catalytic cracking reactor for continuous use or returning the regenerated catalytic material to the catalytic cracking reactor for continuous use after reduction.
7. A catalytic cracking catalyst, characterized in that the catalytic cracking catalyst comprises catalytic particles and exothermic particles;
the heat-generating particles comprise, in weight percent, 20-60% by weight of a second carrier, 10-40% by weight of the second binder, and 1-40% by weight of a copper-containing oxide, based on the total weight of the heat-generating particles.
8. The catalytic cracking catalyst of claim 7, wherein the catalytic particles comprise, in weight percent, based on the total weight of the catalytic particles, 10-40 weight percent molecular sieve, 30-60 weight percent third support, and 20-40 weight percent third binder;
optionally, the molecular sieve comprises one or more of a FAU structure molecular sieve, an MFI structure molecular sieve and a BEA structure molecular sieve;
the copper-containing oxide comprises copper oxide and/or cuprous oxide;
the second binder and the third binder are the same or different and each independently comprise one or more of aluminum oxide, silicon oxide and aluminum phosphate;
the second carrier and the three carriers are identical or different and respectively and independently comprise one or more of kaolin, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;
optionally, the weight ratio of the exothermic particles to the catalytic particles is 0.01-0.5.
9. A catalytic cracking reaction auxiliary agent, which is characterized in that the catalytic cracking reaction auxiliary agent comprises 20-60 weight percent of a fourth carrier, 10-40 weight percent of a fourth binder and 1-40 weight percent of copper-containing oxide by taking the total weight of the catalytic cracking reaction auxiliary agent as a reference.
10. The catalytic cracking reaction aid of claim 9, wherein the copper-containing oxide comprises copper oxide and/or cuprous oxide;
the fourth carrier comprises one or more of kaolin, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite;
the fourth binder comprises one or more of aluminum oxide, silicon oxide and aluminum phosphate.
11. The catalytic cracking reaction auxiliary according to claim 9, wherein the low valence copper on the surface of the catalytic cracking reaction auxiliary is 70% or more of the total weight of the surface copper element, based on the weight of the copper element, and the low valence copper is +1 valence copper.
12. A process for preparing a catalytic cracking reaction aid according to any one of claims 9-11, characterized in that the process comprises the steps of:
s1, mixing a copper-containing substance, a fifth binder and a fourth carrier to obtain mixed slurry;
s2, spray drying and roasting the mixed slurry;
wherein the mixed slurry comprises, by weight percent, 1-40% of the copper-containing substance, 1-40% of a fifth binder and 20-60% of a fourth carrier, based on the total weight of the dry basis of the mixed slurry, the copper-containing substance being based on the weight of copper oxide, the fifth binder being based on the weight of metal oxide, and the copper-containing substance comprising a copper-containing oxide and/or a copper salt.
13. The method of claim 12, wherein the copper-containing oxide comprises copper oxide and/or cuprous oxide;
the copper salt comprises one or more of copper sulfate, copper chloride, copper nitrate and copper carbonate;
the fifth binder comprises one or more of aluminum sol, silica sol, phosphorus aluminum sol and peptized pseudo-boehmite, and the solid content of the fifth binder is 20-90 wt% based on metal oxide.
14. The method of claim 12, wherein the firing conditions are: the temperature is 500-700 ℃ and the time is 2-5h.
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