CN111482199A - Olefin cracking catalyst, preparation method thereof and olefin cracking method - Google Patents

Olefin cracking catalyst, preparation method thereof and olefin cracking method Download PDF

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CN111482199A
CN111482199A CN202010337866.7A CN202010337866A CN111482199A CN 111482199 A CN111482199 A CN 111482199A CN 202010337866 A CN202010337866 A CN 202010337866A CN 111482199 A CN111482199 A CN 111482199A
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molecular sieve
catalyst
composite molecular
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CN111482199B (en
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赵亮
孙海玲
高金森
张宇豪
张彬瑞
郝天臻
孟庆飞
李德忠
徐春明
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China University of Petroleum Beijing
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    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
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Abstract

The invention provides an olefin cracking catalyst, a preparation method thereof and an olefin cracking method, wherein the preparation method of the catalyst comprises the step of mixing at least two of SAPO-34, ZSM-5, β and USY molecular sieves which are pretreated according to the mass ratio of 0-30:50-80:0-30:0-50 to obtain a composite molecular sieve, wherein the ZSM-5 molecular sieve, β molecular sieve and USY molecular sieve are respectively subjected to alkali treatment and SAPO-34 molecular sieve is subjected to acid treatment, the composite molecular sieve is further subjected to silanization treatment and nonmetal and metal modification treatment, and finally a matrix and a binder are mixed to obtain the olefin cracking catalyst.

Description

Olefin cracking catalyst, preparation method thereof and olefin cracking method
Technical Field
The invention relates to petrochemical technology, in particular to a preparation method of an olefin cracking catalyst, the catalyst prepared by the method and an olefin cracking method implemented by using the catalyst.
Background
Ethylene is a basic organic feedstock for petrochemical industries, and about 75% of petrochemical products are produced from ethylene. In the case of synthetic materials, the use thereof in large quantities for the production of polyethylene, vinyl chloride and polyvinyl chloride; in the aspect of organic synthesis, the method is widely used for synthesizing various basic organic synthesis raw materials such as ethanol, ethylene oxide, ethylene glycol and the like. In fact, ethylene production has become a measure of the state of the art in the petrochemical industry.
Propylene is an important organic petrochemical basic raw material second to ethylene, and is mainly used for producing polypropylene, phenol, acetone and the like, and other applications also comprise alkylate oil, catalytic polymerization and dimerization, high-octane gasoline blending materials and the like. In recent years, the global propylene consumption has increased dramatically, driven by the rapid growth in demand for downstream derivatives. At the same time, the world's production of propylene is also rapidly evolving.
About 90% of ethylene in China comes from steam cracking, wherein the coproduction of propylene is about 30% and butylene is 20%. With the development of the chemical field, the problems of high energy consumption, high construction cost and the like brought by the traditional steam cracking device are increasingly prominent. The catalytic cracking has the advantages of lower reaction temperature, less steam amount and the like, and the problems of energy consumption and cost are effectively solved.
The catalytic cracking by taking light olefins as raw materials has important practical significance, and analysis has anticipated that the gasoline consumption is gradually increased, the gasoline will keep or decline for a long time in the future, and the conversion of gasoline into chemical products will become the main outlet of future gasoline, including the conversion of gasoline into olefins, the catalytic cracking gasoline in the commodity gasoline in China accounts for as high as about 70 v%, and from the composition, the content of C5-C7 olefins in the Fluid Catalytic Cracking (FCC) gasoline is higher, and the content of C5-C8 olefins in the coking gasoline is higher; on the other hand, the refining enterprises generate a large amount of C4-C5 low-value olefin byproducts, and the efficient utilization of the part of resources can not only solve the practical problem of processing the byproducts faced by the refining enterprises, but also improve the economic benefits of the enterprises.
CN1600757A discloses a process for producing light olefins, particularly propylene, from a hydrocarbon feedstock containing C4-C6 olefins by catalytic cracking of the hydrocarbon feedstock using a ZSM-5/ZSM-11 co-crystallized molecular sieve catalyst to directly obtain a light olefin effluent, but the catalyst conversion is low with yields of ethylene and propylene of 40-50%.
CN104107713A discloses a method for preparing a catalyst for propylene by cracking carbon tetraolefin, wherein a ZSM-5 molecular sieve with a shape index of 3-100% in a range of 20-90%, a transition metal oxide in a range of 0.05-3% and a binder in a range of 18-69% are adopted to prepare the catalyst, the catalyst utilizes the ZSM-5 molecular sieve with a certain shape to improve the diffusion performance of a product, reduce the coking degree of a macromolecular product and improve the stability of the catalyst, and tungsten oxide is adopted for modification to further improve the selectivity of the product propylene. The catalyst is utilized, the reaction temperature is 500 ℃, the reaction pressure is 0.05MPa, and the weight space velocity is 30h-1Under the conditions of (a) conversion of buteneThe conversion rate can reach 78%, the yield of the target product propylene reaches 45%, and the selectivity is 58%.
CN17043873A discloses a preparation method of an olefin catalytic cracking catalyst, which adopts a ZSM-5 molecular sieve with 40-80% of silica-alumina molar ratio of 60-1000 and a binder, the ZSM-5 molecular sieve loads 0.01-5% of rare earth by weight to obtain the catalyst, under the conditions that the reaction temperature is 500-600 ℃, the water/olefin weight ratio is 0.8-2, and the reaction pressure is normal pressure, the conversion rate of the carbon tetraolefin reaches 60-80%, the propylene yield reaches 34%, and the olefin conversion rate is reduced by 10% when the catalyst is used for 800 hours.
Although the conversion rate of olefin and the yield of propylene are improved and the service life of the catalyst is also improved by using the catalyst disclosed in the patent publication, most of the catalysts are only used for catalytic cracking of the carbon-tetraolefin raw material, and the defect of poor ethylene/propylene selectivity still exists, particularly, the difficulty in improving the ethylene selectivity is higher, so that the product yield is low, and the catalytic cracking of gasoline fractions with wider distillation range is more difficult to meet; in addition, these catalytic cracking catalysts are prone to coking, have short life, and have high requirements and investment on regeneration technology.
On the other hand, for a catalytic cracking system mainly based on a carbon four system, when catalyst improvement is considered, a fluidized bed reactor is used for improving a gas-solid contact effect, or a multi-unit coupling process is introduced, so that an effect of improving low-carbon olefin selectivity is achieved, and the method is also an important exploration direction.
Accordingly, there is a need to develop a catalytic cracking catalyst that can preferably overcome the above-mentioned various disadvantages.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an olefin cracking catalyst and a preparation method thereof, wherein the catalyst prepared by the method can be used for catalytic cracking of light olefins, especially olefins in catalytic or coking gasoline fractions, and can solve the problems that the catalyst used in the prior art is difficult to improve the selectivity of ethylene and propylene, and the service life of the catalyst is short.
The invention also provides an olefin catalytic cracking method, and by using the catalyst, the problems that in the prior art, a fluidized bed is required for catalytic cracking, the catalyst is not easy to regenerate, and the process cost is high are solved.
The first aspect of the present invention provides a method for preparing an olefin cracking catalyst, comprising the steps of:
mixing the pretreated SAPO-34 molecular sieve, ZSM-5 molecular sieve, β molecular sieve and USY molecular sieve according to the mass ratio of 0-30:50-80:0-30:0-50 to prepare the composite molecular sieve at least comprising two molecular sieves, wherein the pretreatment comprises that the ZSM-5 molecular sieve, β molecular sieve and USY molecular sieve are respectively treated by alkali, the SAPO-34 molecular sieve is treated by acid, and the concentration of the used acid solution is 0.02-0.1 mol/L;
drying and dehydrating the composite molecular sieve in an inert gas atmosphere and performing silanization treatment, wherein the dosage of a silanization reagent is 0.1-1.0m L/g composite molecular sieve, the composite molecular sieve is dissolved in an anhydrous nonpolar solvent in advance, the composite molecular sieve is dehydrated at high temperature and then undergoes silanization treatment, the silanization treatment temperature is 120 ℃ and 250 ℃ and the treatment time is 0.5-5 hours, the nonpolar solvent is C5-C7 alkane and/or cycloalkane, and the silanization reagent is selected from compounds shown in a general formula (I):
Figure BDA0002467385320000031
wherein R is1Selected from C1-C3 alkyl or phenyl; r2Selected from hydrogen, hydroxyl, C1-C3 alkyl, C1-C3 alkoxy, or phenyl;
sequentially carrying out non-metal element modification and metal element modification on the composite molecular sieve subjected to silanization treatment through impregnation to obtain a modified composite molecular sieve, wherein the loading amounts of the non-metal elements and the metal elements are respectively 0.01-3% based on the mass of the catalyst; the non-metal element is selected from at least one of group VA, group VIA and group VIIIA in the periodic table, and the metal element is selected from at least one of group IA, group IIA, group IB, group VIB, group VIIB, group VIII and lanthanide series in the periodic table;
and mixing and pulping the modified composite molecular sieve, a matrix and a binder, and aging and roasting to obtain the olefin cracking catalyst.
In embodiments of the invention, the SAPO-34 molecular sieve, the ZSM-5 molecular sieve, the β molecular sieve and the USY molecular sieve are used as raw materials for preparing the composite molecular sieve, and the molecular sieve obtained by conventional conversion of the raw materials, such as the HZSM-5 molecular sieve obtained by conventional conversion of the ZSM-5 molecular sieve, are also covered in the range of the molecular sieve raw materials.
In the embodiment of the invention, in order to be suitable for the catalytic cracking of a feedstock of a wider cut section, such as an FCC gasoline or a coker gasoline cut, the cut section generally comprises C4-C5, C5, C5-C6, C6, C6-C7, C7, C5-C7, C5-C9 cuts and the like, or distillate oil mainly comprising C4-C8 cut olefins, when a catalyst is designed and prepared, two or more molecular sieves with different pore sizes can be selected according to the carbon number range of the feedstock cut section, and molecular sieves with different pore structures and properties are added in proper proportion on the basis of ZSM-5 molecular sieves to form a composite molecular sieve feedstock with a multi-stage pore structure.
By controlling the mass ratio and the types of the molecular sieves which are compounded with each other, the catalyst has more excellent olefin yield when being used for catalytically cracking raw oil of different distillation sections, and particularly obtains higher yields of ethylene and propylene.
In the method of the present invention, the selected ZSM-5 molecular sieve and β molecular sieve and/or USY molecular sieve are subjected to an alkali treatment to achieve pore expansion, in the embodiment of the present invention, the alkali treatment can be performed in a conventional manner known to those skilled in the art, such as desilication and pore expansion of the molecular sieve by using a higher alkali solution (e.g., a common alkali solution of 0.4-0.8 mol/L) with a concentration of 0.4 mol/L or more, and then ammonium ion exchange is performed to restore acidity of the molecular sieve, thereby pore expansion of the molecular sieve is achieved without affecting the acid properties of the molecular sieve, which is beneficial to prevent coking of catalyst pores and prolong the catalyst life.
In the embodiment of the present invention, the alkali solution used for carrying out the alkali treatment may be one or two kinds of alkali solutions conventionally used in the art for this purpose, selected from, for example, sodium hydroxide solution, potassium hydroxide solution, ammonia water and the like; the ammonium ion exchange reagent used to carry out the alkali treatment may be one or two reagents conventionally used in the art for this purpose, selected from, for example, ammonium nitrate, ammonium chloride and the like.
In the method of the present invention, the composite molecular sieve may also comprise an acid-treated SAPO-34 molecular sieve, and the SAPO-34 molecular sieve is subjected to acid treatment, also for pore-expanding purposes, the acid treatment uses an acid solution with a concentration of 0.02 to 0.1 mol/L, the acid solution is generally an inorganic acid, such as nitric acid, hydrochloric acid, sulfuric acid and the like, and nitric acid is advantageously selected, and the volume ratio of the molecular sieve to the acid solution in the acid treatment may be 1:1 to 1: 10.
In the invention, the selected molecular sieve after pretreatment (alkali treatment or acid treatment) is mechanically mixed to obtain a uniform mixture, namely the composite molecular sieve.
In a further embodiment of the process of the present invention, the ZSM-5 molecular sieve has a mass content of at least 50%, for example, 50%, 60%, 70% or 75%, based on the mass of the composite molecular sieve. Meanwhile, the proportion of the ZSM-5 molecular sieve to other molecular sieves and the proportion of the molecular sieves in the catalyst are controlled, so that the selectivity of ethylene and propylene of the catalyst can be further optimized, and the yield of ethylene and propylene is increased.
In an embodiment of the present invention, the non-aqueous non-polar solvent is selected from C5-C7 alkanes and/or cycloalkanes, and the non-polar solvent is selected from cyclohexane, n-hexane, 3-methylpentane, n-heptane, etc., and has a suitable molecular size and a suitable boiling point range to facilitate the silylation effect of the present invention.
In the embodiment of the invention, the silanization treatment can realize the regulation and control of the acid amount and the acid distribution of the composite molecular sieve. The pretreated composite molecular sieve is dried and dehydrated and then is subjected to silanization treatment, and moisture in pore channels of the molecular sieve is removed as completely as possible to ensure that the silanization treatment achieves the expected effect. According to the state of the treated molecular sieve, any feasible drying means is adopted, the inert gas purging is used while the drying temperature is controlled, the water can be carried away more conveniently, the surface of the molecular sieve is separated, the rapid drying of the molecular sieve is promoted, and the drying time can be determined according to the specific water content condition of the composite molecular sieve, the drying temperature, the flow rate of the purging gas and other parameters. In general, the drying temperature is adjusted to 350 ℃ and 400 ℃ for 0.5-2 hours, for example, to achieve the desired drying effect. Through drying and dehydration, on one hand, the silanization reagent can be promoted to enter the molecular sieve holes in subsequent treatment, so that the activity of the catalyst is improved, and on the other hand, the side reaction of the silanization reagent when meeting water can be avoided.
In the embodiment of the present invention, the inert gas atmosphere for the silylation treatment is, for example, a nitrogen atmosphere, and may be a helium or argon atmosphere. And (3) performing silanization treatment on the composite molecular sieve subjected to the treatment in the inert gas atmosphere, wherein the composite molecular sieve is continuously kept in the inert gas atmosphere in the process of introducing a silanization reagent solution into the composite molecular sieve and in the period of silanization reaction of the composite molecular sieve. The inert gas atmosphere prevents the silylating agent from undergoing a polycondensation reaction.
In an embodiment of the invention, the silylating agent is used in an amount of 0.1 to 1.0m L/g composite molecular sieve, for example 0.1 to 0.8m L/g composite molecular sieve, or 0.1 to 0.6m L/g composite molecular sieve, or 0.3 to 0.6m L/g composite molecular sieve.
In the embodiment of the invention, the silanization reagent of micromolecule with basically chain-shaped molecular structure and no halogen is used, which is more beneficial to modifying the pore canal of the molecular sieve, and the catalyst has more excellent selectivity of ethylene propylene and avoids environmental pollution caused by introducing halogen while regulating and controlling the acid amount and acid distribution of the molecular sieve. For example, silylating agents meeting the definition set forth can be methyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, methylethylethoxysilane, phenylmethylethoxysilane, and the like, and the silylating agents used are commercially available.
In the embodiment of the invention, the silanization reagent is firstly dissolved in the anhydrous nonpolar solvent, is heated to the set temperature and enters the composite molecular sieve, and can be pumped into a treatment device or a reactor filled with the composite molecular sieve in the specific operation, the volume fraction of the silanization reagent in the nonpolar solvent is 1-50%, generally 1-20%, and the separated solvent after treatment can be recycled.
In the embodiment of the invention, the silanization treatment at a higher temperature is maintained, so that the silanization reagent is in a vaporized state when being brought into the molecular sieve by a solvent, and chemical adsorption in the molecular sieve is ensured, and the silanization treatment temperature is 120-250 ℃, such as 120-200 ℃; the time for the silylation treatment is 0.5 to 5 hours, for example, 1 to 4 hours or 2 to 4 hours.
In the embodiment of the invention, the silanization treatment further comprises heating the composite molecular sieve treated by the silanization reagent to 350-450 ℃ and keeping inert gas purging for 1-3 hours, and/or performing acid washing, wherein the molecular sieve after the silanization reagent modification treatment needs to remove physical adsorbates formed in the silanization reaction process and byproducts possibly generated on the surface, such as silicon oxide, so as to avoid the blocking of the molecular sieve channels, and is further favorable for ensuring the chemical adsorption effect after the silanization treatment.
The element modification of the composite molecular sieve after the silanization treatment is to sequentially modify nonmetal elements and metal elements by an impregnation method to obtain the modified composite molecular sieve. The non-metallic element is selected from at least one element of group VA, group VIA and group VIIIA of the periodic Table, and the loading of the element is 0.01-3 wt% based on the mass of the catalyst, for example, 0.05-3 wt%; the metal element is selected from at least one element of groups IA, IIA, IB, VIB, VIIB, VIII and lanthanide series of the periodic Table, and the loading of the element is 0.01-3 wt%, based on the mass of the catalyst, for example 0.05-2 wt%.
In further embodiments of the invention, the non-metallic elements include one or more of P, S, F and Cl and the metallic elements include one or more of Na, K, Mg, Ca, L a, Ce, Cu, Ag, Ni, Co, Fe, Mn, and Cr.
In the embodiment of the invention, the nonmetal element modification and metal element modification processes which are sequentially carried out on the composite molecular sieve subjected to silanization treatment through impregnation respectively comprise synchronous impregnation or step-by-step impregnation (when more than two elements are modified), the impregnation solution is a soluble salt solution, an isometric impregnation method is generally adopted, the impregnation temperature is 0-50 ℃, the impregnation time is 0.5-5 hours each time, and the aging, drying and roasting are carried out after each impregnation.
In the embodiment of the present invention, in the case of impregnation of, for example, two or more non-metallic elements, a salt containing an element to be supported may be formulated into a mixed solution, co-impregnation, i.e., simultaneous impregnation; or preparing the salt of each non-metal element respectively, impregnating one element, drying and roasting, then impregnating the other element, drying and roasting, namely step-by-step impregnation. In the method of the present invention, the supported metal elements may be impregnated in a similar manner, two or more metal elements being impregnated simultaneously or stepwise.
In an embodiment of the present invention, the non-metallic element and the metallic element are impregnated separately. In an embodiment of the invention, the non-metallic elements are impregnated first, followed by the metallic elements.
In embodiments of the invention, soluble salts comprising non-metals of group VA, VIA and VIIIA include, but are not limited to, phosphates, halates, sulfates, ammonium salts and the like, such as phosphates or halates.
In embodiments of the invention, soluble salts comprising metals of group IA, IIA, IB, VIB, VIIB, VIII and lanthanide series include, but are not limited to, nitrates, halides, sulfates, acetates, ammonium salts and the like, e.g., nitrates or halides.
In embodiments of the invention, equal volumes of impregnation are employed, at impregnation temperatures of 0-50 deg.C, for example 20-40 deg.C; the immersion time is 0.5 to 5 hours, for example 0.5 to 2 hours, per immersion.
In an embodiment of the invention, the aging temperature after each impregnation is from 0 to 50 ℃, e.g. from 20 to 40 ℃, and the aging time is from 6 to 20 hours, e.g. from 6 to 12 hours; drying at 50-160 deg.C, such as 80-130 deg.C, for 4-20 hr, such as 4-12 hr; the roasting temperature is 400-800 ℃, such as 500-700 ℃, and the roasting time is 1-10 hours, such as 2-6 hours.
The specific choice of non-metallic and metallic elements for modification in embodiments of the invention may also be determined by the needs of the catalyst, for example, by the choice of one or more of the non-metallic elements and/or one or more of the metallic elements described above, including in some embodiments at least L a or Ce.
In the method, the modified composite molecular sieve, a matrix and a binder are mixed and pulped, and the olefin cracking catalyst is prepared after aging and roasting. In the actual preparation of the catalyst, the content of the modified composite molecular sieve may be controlled to be 30 to 50% by weight, for example, 40 to 50% by weight, based on the mass of the catalyst.
As with the conventional catalyst preparation process, a proper amount of matrix material can provide a dispersion environment for the carrier and the active ingredients, and increase the mechanical strength of the catalyst and the carbon-containing capacity of the embodiment of the invention, and is also beneficial to preventing the catalyst from coking and deactivating and prolonging the service life of the catalyst. Meanwhile, the required catalyst is finally obtained by utilizing the bonding effect of the binder.
In an embodiment of the present invention, the matrix content is 30 to 60 wt% and the binder content is 10 to 40 wt% based on the mass of the catalyst, and the catalyst is obtained by aging for 4 to 20 hours after pulping, drying and calcining. In particular embodiments of the present invention, the aging time may be, for example, from 6 to 20 hours or from 8 to 20 hours.
In an embodiment of the present invention, the matrix may be selected from one or more of oxides of group IVB elements, kaolin, montmorillonite and pseudo-boehmite, but is not limited thereto; the binder is selected from one or more of silica sol or aluminum sol, nitric acid and sesbania powder, but is not limited thereto.
In an embodiment of the invention, after drying and calcination, monolithic catalyst agglomerates are formed which, upon a pelletizing operation, can be comminuted to a catalyst of a predetermined particle size.
The method also comprises hydrothermal aging treatment of the catalyst, so that the catalyst has more stable activity and is not easy to coke.
In another aspect of the present invention, there is provided an olefin cracking catalyst prepared according to the above-described process of the present invention. The method realizes regulation and control of the pore structure and the acid property of the catalyst by pretreatment, hole expansion allocation and silanization regulation and acid treatment of the molecular sieve raw material and designed modification treatment of non-metallic elements and metallic elements, is suitable for catalytic cracking of light olefin with wider fraction range, and has the advantages of higher olefin conversion rate, higher yield of ethylene and propylene, mild reaction conditions, less coking of the catalyst and long service life, and the loose reaction conditions are favorable for realizing the catalytic cracking in a fixed bed reactor.
In another aspect, the invention provides a method for catalytic cracking of olefins, which employs a fixed bed reactor, and uses the olefin cracking catalyst prepared by the method of the invention, the reaction temperature is 400--1And the diluent used is at least one selected from the group consisting of nitrogen, steam, pyrolysis gas and distillate oil.
The olefin catalytic cracking method provided by the invention can be used for carrying out reaction in a fixed bed by using the olefin cracking catalyst prepared by the method, the olefin conversion rate and the yield of ethylene and propylene products are higher, the reaction can be completed in a simple device with low cost, and the cracking process cost is greatly reduced.
In a further embodiment of the process for the catalytic cracking of olefins according to the invention, the cracked product is separated by condensation to give cracked gas and distillate. The pyrolysis gas can enter a depropenizer and a deethylenizer after being compressed, propylene and ethylene are respectively separated, and the pyrolysis gas rich in C4 and above fractions returns to the fixed bed reactor for secondary pyrolysis, so that the yield of ethylene and propylene is further improved; the distillate oil is an oil-water mixture, and cracked oil is obtained after oil-water separation.
In the embodiment of the olefin catalytic cracking method, the used catalyst can be regenerated in situ, the regeneration temperature is 300-700 ℃, and the regeneration gas comprises two or more of nitrogen, air, water vapor and methanol. The particular catalyst regeneration operation may be carried out in a manner conventional in the art, for example, in three stages.
The technical scheme of the invention has the following effects:
1. the olefin cracking catalyst prepared by the method of the invention is compounded with molecular sieves with different pore diameters in different proportions, has a multi-stage pore channel structure, has a wide range of raw oil application compared with the existing olefin cracking catalyst, and can be particularly used for treating raw oil of each fraction section of catalytic cracking or coking gasoline, such as raw oil mainly comprising C4-C8 fractions.
The catalyst prepared by the method is effectively regulated and controlled in the aspects of pore structure and acidity (acid amount and acid distribution), so that the reaction path of olefin cracking can be controlled, the catalyst is used for catalytic cracking of raw oil, the higher conversion rate of olefin can be realized and can reach more than 70%, the catalyst property can be selected and regulated and controlled to be further improved to about 90%, wherein the propylene yield can reach more than 45%, even can reach 50% or more, the ethylene yield can also reach or exceed 30%, so that the sum of the yields of ethylene and propylene is greatly improved, and the sum of the yields of ethylene and propylene can reach or exceed 80% in most reactions.
On the other hand, the catalyst provided by the invention also has the advantage of longer service life, the service life under continuous operation can reach more than 3 weeks, the continuous production is more facilitated, and the regeneration cost of the catalyst is also reduced.
2. The catalyst and the olefin catalytic cracking method provided by the invention can be used for a fixed bed reactor to carry out catalytic cracking reaction, not only can higher ethylene and propylene conversion rate and yield be obtained, but also the usable reaction device and operation are simple, the catalyst is convenient to regenerate, and the process cost is greatly reduced.
3. The preparation method of the catalyst adopts the silanization reagent without halogen, obtains the catalyst with expected effect, and simultaneously can avoid environmental pollution, thereby having good social benefit.
Drawings
FIG. 1 is a schematic flow diagram of an embodiment of the olefin catalytic cracking process of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments and the accompanying drawings, and it should be understood that the embodiments described herein are some embodiments of the present invention, and not all embodiments.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
The invention is further illustrated below by way of examples, without being limited thereto.
Raw materials
HZSM-5 molecular sieve has a particle size of 0.5-2 μm and a silica-alumina ratio of 25.
The SAPO-34 molecular sieve has micron-sized particle sizes.
β the molecular sieve has micron size and Si/Al ratio of 60.
The USY molecular sieve has micron-sized granularity and a silicon-aluminum ratio of 5.
Example 1
(1) Alkali treatment of HZSM-5 molecular sieve and USY molecular sieve
Adding an HZSM-5 molecular sieve into a 0.5 mol/L NaOH solution to enable the mass ratio of the HZSM-5 molecular sieve to the NaOH solution to be 1: 6 to obtain mixed slurry, heating the mixed slurry in a water bath to about 80 ℃, maintaining the temperature for about 2 hours, filtering out an HZSM-5 molecular sieve filter cake by suction filtration, washing to be neutral, drying the obtained molecular sieve filter cake in an oven at 110 ℃ for 12 hours, and then roasting in a muffle furnace at 550 ℃ for 4 hours.
Using 0.1M NH for the roasted HZSM-5 molecular sieve4NO3And (4) solution treatment. HZSM-5 molecular sieve NH4NO3The mass ratio of the solution is 1: 6, heating in water bath to about 80 ℃, maintaining for 2 hours, filtering out HZSM-5 molecular sieve filter cake after ammonium exchange, washing to be neutral, and then carrying out NH operation again4NO3Solution (0.1M) treatment, two ammonium exchange processes do not bake. Obtaining the HZSM-5 molecular sieve treated by alkali.
And (3) carrying out alkali treatment on the USY molecular sieve according to the method to obtain the alkali-treated USY molecular sieve.
(2) Hybrid HZSM-5 and USY molecular sieves
Mixing the alkali-treated HZSM-5 molecular sieve and the alkali-treated USY molecular sieve in a mass ratio of 3:1 to obtain the HZSM-5/USY composite molecular sieve.
(3) Silanization treated HZSM-5/USY composite molecular sieve
And (3) filling the alkali-treated HZSM-5/USY composite molecular sieve obtained in the step (2) into a reaction tube for olefin cracking, introducing nitrogen at 350 ℃ at a volume flow of 1L/min, purging for 1 hour, and performing high-temperature dehydration and drying on the composite molecular sieve.
And (3) cooling the dehydrated composite molecular sieve to 200 ℃, and pumping a silanization reagent cyclohexane solution with the volume ratio of methyldiethoxysilane to cyclohexane of 1:50 into a composite molecular sieve bed layer under the nitrogen flow of 300m L/min, wherein the pumping flow is 0.1m L/min, and the addition amount of the silanization reagent is 0.5m L methyldiethoxysilane/g of the composite molecular sieve.
After the feeding is finished, the silanization reaction is kept for 2 hours, then the temperature of the system is continuously increased to 400 ℃, nitrogen is continuously introduced, the nitrogen flow is 1L/min, and the physical adsorption product formed in the reaction is removed by high-temperature purging for 1 hour.
Filtering the reaction system after the silanization treatment to recover cyclohexane solvent (the solvent does not participate in the reaction and can be recycled), placing the composite molecular sieve in a muffle furnace to be roasted for 4 hours at 540 ℃, and setting the programHeating up to 4 deg.C/min, adding 0.05 mol/L HNO into the calcined HZSM-5/USY composite molecular sieve3And (3) carrying out acid washing in the solution at the temperature of 80 ℃ for 2 hours, so as to further wash off silicon oxide and prevent pores from being blocked, thereby obtaining the silanized HZSM-5/USY composite molecular sieve.
(4) Modified HZSM-5/USY composite molecular sieve
(4.1) nonmetallic element modified HZSM-5/USY composite molecular sieve
And (3) performing equal-volume impregnation on the silanized HZSM-5/USY composite molecular sieve obtained in the step (3) by using a diammonium hydrogen phosphate solution at room temperature for about 1 hour, wherein the load of P is 1%, aging at room temperature for 12 hours after the impregnation is completed, then drying in an oven at 120 ℃ for 12 hours, then roasting in a muffle furnace at 540 ℃ for 4 hours, and cooling to obtain the non-metal element modified HZSM-5/USY composite molecular sieve.
(4.2) metallic element modified HZSM-5/USY composite molecular sieve
And (3) adding the nonmetal element modified HZSM-5/USY composite molecular sieve obtained in the step (4.1) into a lanthanum nitrate solution, soaking for about 1 hour at room temperature in an equal volume mode, wherein the loading amount of L a is 1%, obtaining a soaking mixture, continuing to age at room temperature for 12 hours after the soaking is completed, then placing the soaked mixture into an oven to dry at 120 ℃ for 12 hours, then placing the dried mixture into a muffle furnace to bake at 540 ℃ for 4 hours, and cooling to obtain the metal element modified HZSM-5/USY composite molecular sieve.
And (4) modifying the non-metal elements in the step (4.1) and modifying the metal elements in the step (4.2) in sequence to obtain the modified HZSM-5/USY composite molecular sieve.
(5) Preparation of HZSM-5/USY composite molecular sieve catalyst
And (3) mixing and pulping the modified HZSM-5/USY composite molecular sieve obtained in the step (4) with kaolin, pseudo-boehmite, titanium dioxide, alumina sol and sesbania powder according to the dry basis mass ratio of 40:30:10:5:14:1, and stirring for 4 hours by adopting an electric mechanical stirrer to obtain a uniform mixture containing the HZSM-5/USY composite molecular sieve, the matrix and the binder.
The homogeneous mixture was aged at room temperature for 12 hours, then dried in an oven at 120 ℃ for 12 hours, and then calcined in a muffle furnace at 540 ℃ for 4 hours. Finally, carrying out hydrothermal aging on the calcined catalyst for 6 hours at the temperature of 600 ℃ in the atmosphere of 100% of water vapor to obtain the catalyst A.
(6) Evaluation of catalytic Effect
Catalyst A was evaluated on a small fixed bed reactor using a catalytically cracked C6-C7 gasoline fraction as a feedstock, and the flow chart is shown in FIG. 1. The evaluation reaction condition is 0.1MPa, and the mass space velocity is 3h-1The reaction time is 12 hours at the temperature of 550 ℃ and the water-oil volume ratio of 0.6.
The flow chart is shown in FIG. 1, the catalyst A prepared in example 1 is charged into a fixed bed reactor, the temperature of the fixed bed reactor is set to 550 ℃, the pressure is set to 0.1MPa, and the mass space velocity of the raw oil feeding is set to 3h-1. The catalytic cracking reaction is carried out in a fixed bed reactor to generate a cracking product, and the cracking product comprises ethylene, propylene, C4 and the fractions above.
The cracked product enters a condenser, part of the cracked product is condensed in the condenser to form an oil-water mixture in a liquid phase form, the oil-water mixture enters an oil-water separation tank for oil-water separation, the separated water phase is treated and recycled in a steam form to be used as a diluent of raw oil, the recycle ratio is 5, and the separated oil phase is cracked oil;
the uncondensed substances of the cracking products in the condenser are led out in a gas phase form, namely cracking gas for separating and recovering ethylene and propylene.
The olefin conversion and the yields of ethylene and propylene were measured without recycling after removing ethylene and propylene (fig. 1 shows a case where a part of the ethylene and propylene can be recycled in actual production), and the results are shown in table 1.
Example 2
A catalyst was prepared following the same procedure as in example 1, except that HZSM-5, USY and SAPO-34 were included in the composite molecular sieve composition.
The method for alkali treatment of the HZSM-5 molecular sieve and the USY molecular sieve is the same as in example 1.
SAPO-34 molecular sieve was added to 0.05 mol/L of HNO3In solution, SAPO-34 molecular sieve HNO3The mass ratio of the solution is 1: 6, obtaining mixed slurryAnd (4) liquid. The mixed slurry was heated in a water bath to about 80 ℃ and maintained at this temperature for about 2 hours. And filtering the SAPO-34 molecular sieve filter cake by suction filtration, and washing to be neutral. The molecular sieve filter cake was dried in an oven at 110 ℃ for 2 hours and then calcined in a muffle furnace at 550 ℃ for 4 hours.
Mixing the HZSM-5 molecular sieve subjected to alkali treatment, the USY molecular sieve subjected to alkali treatment and the SAPO-34 molecular sieve subjected to acid treatment in a ratio of 5:2:1 to obtain the HZSM-5/USY/SAPO-34 composite molecular sieve.
The same operation as in example 1 was repeated to obtain catalyst B.
The catalytic effect of catalyst B was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Example 3
A catalyst was prepared following the same procedure as in example 1, except that the composite molecular sieve composition included HZSM-5 and β molecular sieves.
The same operation as in example 1 was repeated to obtain catalyst C.
The catalytic effect evaluation test of catalyst C was the same as in example 1, and the results are shown in Table 1.
Example 4
A catalyst was prepared according to the same procedure as in example 1, except that the content of the composite molecular sieve in the catalyst was changed. The method specifically comprises the following steps:
in the step (5), "mixing and pulping the modified HZSM-5/USY composite molecular sieve, kaolin, pseudo-boehmite, titanium dioxide, alumina sol and sesbania powder according to the dry basis mass ratio of 30:35:15:5:14: 1.
The rest of the operation was the same as in example 1 to obtain catalyst D.
The catalytic effect evaluation test of catalyst D was the same as in example 1, and the results are shown in Table 1.
Example 5
A catalyst was prepared by following the same procedure as in example 1 except that phenylmethylmethoxysilane was used as the reagent in the silylation treatment.
The rest of the operation was the same as in example 1 to obtain catalyst E.
The catalytic effect of catalyst E was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Example 6
A catalyst was prepared by following the same procedure as in example 1 except that the silylation treatment temperature was different, that is, in step (3), the dehydrated composite molecular sieve was cooled to 120 ℃ to perform silylation treatment.
The rest of the operation was the same as in example 1 to obtain catalyst F.
The catalytic effect of catalyst F was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Example 7
A catalyst was prepared by following the same procedure as in example 1 except that the amount of the silylating agent used was different, that is, in step (3), the amount of the silylating agent added was 0.1m L methyldiethoxysilane/g of the composite molecular sieve.
The same operation as in example 1 was repeated to obtain catalyst G.
The experiment for evaluating the catalytic effect of catalyst G was the same as in example 1, and the results are shown in Table 1.
Example 8
A catalyst was prepared by following the same procedure as in example 1 except that the concentration of the silylating agent cyclohexane solution was varied, i.e., in step (3), a solution of methyldiethoxysilane in cyclohexane in a volume ratio of 1:30 was pumped through the composite molecular sieve bed.
The rest of the operation was the same as in example 1 to obtain catalyst H.
The catalytic effect of catalyst H was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Example 9
A catalyst was prepared by following the same procedure as in example 1 except that the anhydrous nonpolar solvent was used in the preparation of the silylating agent solution, that is, the solvent in step (3) was changed to 3-methylpentane.
The rest of the operation was the same as in example 1 to obtain catalyst I.
The catalytic effect of catalyst I was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Example 10
A catalyst was prepared by following the same procedure as in example 1 except that the elements used for the modification with the nonmetallic elements were different. That is, in the step (4.1), a mixed solution of ammonium dihydrogen phosphate solution and ammonium chloride was used, and an equal volume impregnation method was used, wherein the loading amount of P was 0.8% and the loading amount of Cl was 0.2%.
The rest of the operation was the same as in example 1 to obtain catalyst J.
The catalytic effect of catalyst J was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Example 11
A catalyst was prepared by following the same procedures as in example 1, except that the elements used for the modification of the metal elements were different from each other, that is, in step (4.2), a mixed solution of lanthanum nitrate and magnesium nitrate was used, and an equal volume impregnation method was employed, in which L a was supported at 0.5% and Mg was supported at 0.75%.
The rest of the operation was the same as in example 1 to obtain catalyst K.
The experiment for evaluating the catalytic effect of catalyst K is the same as that of example 1, and the results are shown in Table 1.
Example 12
After 800 hours of catalytic cracking reaction described in example 1, catalyst a was regenerated in situ in the fixed bed reactor to give regenerated catalyst L.
Conditions for in situ regeneration:
the first-stage regeneration temperature is 350 ℃, and the regeneration time is 12 hours; the second-stage regeneration temperature is 450 ℃, and the regeneration time is 12 hours; the three-stage regeneration temperature is 600 ℃, and the regeneration time is 6 hours;
in the regeneration gas, the ratio of nitrogen to air is 9:1, and the flow rate of the regeneration gas is 300m L/min.
The catalytic effect of the catalyst L was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Example 13
The catalytic effect evaluation was carried out using a catalytically cracked C4-C8 gasoline fraction as a raw material and catalyst B, and the other operations were the same as in example 1, and the results are shown in Table 1.
Example 14
A catalyst was prepared by following the same procedure as in example 1 except that the concentration of the silylating agent cyclohexane solution was varied, i.e., in step (3), a solution of methyldiethoxysilane in cyclohexane in a volume ratio of 1:4 was pumped through the composite molecular sieve bed.
The rest of the operation was carried out in the same manner as in example 1 to obtain catalyst L.
The catalytic effect of the catalyst L was evaluated in the same manner as in example 1, and the results are shown in Table 1.
Comparative example 1
A catalyst was prepared by following the same procedure as in example 1, except that the molecular sieve used was only alkali-treated HZSM-5.
The rest of the operation was the same as in example 1 to obtain catalyst M.
The experiment for evaluating the catalytic effect of catalyst M was the same as in example 1, and the results are shown in Table 1.
Comparative example 2
A catalyst was prepared according to the same procedure as in example 1, except that the composite molecular sieve was not subjected to the silylation treatment, that is, step (3) was not performed.
The remaining operation was carried out in the same manner as in example 1 to obtain catalyst N.
The experiment for evaluating the catalytic effect of catalyst N is the same as that of example 1, and the results are shown in Table 1.
Comparative example 3
A catalyst was prepared by following the same procedure as in example 1 except that the silylating agent was changed from methyldiethoxysilane to ethyl orthosilicate.
The rest of the operation was the same as in example 1 to obtain catalyst O.
The experiment for evaluating the catalytic effect of catalyst O was the same as in example 1, and the results are shown in Table 1.
Comparative example 4
A catalyst was prepared by following the same procedure as in example 1 except that the silylation treatment temperature was different, that is, in step (3), the dehydrated composite molecular sieve was cooled to 300 ℃ to perform silylation treatment.
The rest of the operation was the same as in example 1 to obtain catalyst P.
The experiment for evaluating the catalytic effect of catalyst P was the same as in example 1, and the reaction results are shown in Table 1.
Comparative example 5
A catalyst was prepared by following the same procedure as in example 1 except that the amount of the silylating agent used was different, that is, in step (3), the amount of the silylating agent added was 1.2m L methyldiethoxysilane/g of the composite molecular sieve.
The same operation as in example 1 was repeated to obtain catalyst Q.
The experiment for evaluating the catalytic effect of catalyst Q was the same as in example 1, and the results are shown in Table 1.
Comparative example 6
A catalyst was prepared by following the same procedure as in example 1 except that the ratio of HZSM-5 to USY was different, and the alkali-treated HZSM-5 molecular sieve and the alkali-treated USY molecular sieve were mixed in a mass ratio of 2:3 to obtain an HZSM-5/USY composite molecular sieve.
The rest of the operation was the same as in example 1 to obtain catalyst R.
The experiment for evaluating the catalytic effect of catalyst R is the same as that of example 1, and the results are shown in Table 1.
Comparative example 7
A catalyst was prepared by following the same procedure as in example 1 except that the anhydrous nonpolar solvent was used instead of the solvent used for the preparation of the silylation agent solution, that is, the solvent in step (3) was changed to isooctane.
The rest of the operation was the same as in example 1 to obtain catalyst S.
The experiment for evaluating the catalytic effect of catalyst S was the same as in example 1, and the results are shown in Table 1.
Comparative example 8
A catalyst was prepared by following the same procedure as in example 2, except that SAPO-34 in the composite molecular sieve had not been subjected to acid treatment, as in example 2.
The method for alkali treatment of the HZSM-5 molecular sieve and the USY molecular sieve is the same as in example 1.
Mixing the HZSM-5 molecular sieve subjected to alkali treatment, the USY molecular sieve subjected to alkali treatment and the SAPO-34 molecular sieve not subjected to acid treatment in a ratio of 5:2:1 to obtain the HZSM-5/USY/SAPO-34 composite molecular sieve.
The rest of the operation was the same as in example 1 to obtain catalyst T.
The experiment for evaluating the catalytic effect of catalyst T was the same as in example 1, and the results are shown in Table 1.
TABLE 1 evaluation results of catalysts
Figure BDA0002467385320000171
Figure BDA0002467385320000181
Description of the drawings: in the above data, both the conversion and yield of olefins are calculated based on the olefin content of the distillate. Specifically, the method comprises the following steps:
ethylene yield ═ ethylene mass/mass of feed olefin in the feed;
propylene yield-mass of propylene/mass of feed olefin in the feed;
olefin conversion (mass of feed olefin-mass of olefin in liquid phase fraction product × mass percent of olefin in liquid phase fraction product) in feed/mass of feed olefin in feed.
The data in Table 1 show that catalysts A, B, C, D, E, F, G, H, I, J, K and L both achieve better olefin conversion rate and ethylene and propylene yield when used for catalytically cracking raw oil of corresponding fractions, and the evaluation data of the catalytic effect of the regenerated catalyst L show that the catalyst prepared by the method of the invention has good regeneration performance.
Evaluation test of catalyst Life
In the evaluation experiment of the catalyst A, samples were taken every 4 hours, the gas phase composition and the liquid phase composition of the product were measured by a gas chromatograph (agent 6890/7890B), and the conversion of C6-C7 olefins and the yields of ethylene and propylene were calculated. Some results are shown in table 2.
TABLE 2 evaluation results of catalyst Life
Reaction time/hour Olefin conversion/%) Ethylene yield/% Propylene yield/%
12 89.9 34.7 50.3
24 89.9 34.7 50.3
48 89.8 34.8 50.2
100 89.8 34.7 50.3
200 89.8 34.6 50.1
300 89.6 34.8 50.1
400 89.4 34.7 50.2
500 84.5 30.3 45.2
The data in table 2 show that the catalyst of the present invention can be operated continuously for 500 hours, the ethylene and propylene yields are maintained to be substantially stable, and the ethylene/propylene yield and the olefin conversion rate are still maintained at a high level, and the above experimental results are obtained based on the maintenance of the set temperature and pressure (in industrial production, the catalyst can be maintained with high selectivity by properly adjusting the reaction temperature as the reaction progresses), and the catalyst can be expected to have a long service life.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims (10)

1. A preparation method of an olefin cracking catalyst comprises the following steps:
mixing the pretreated SAPO-34 molecular sieve, ZSM-5 molecular sieve, β molecular sieve and USY molecular sieve according to the mass ratio of 0-30:50-80:0-30:0-50 to prepare the composite molecular sieve at least comprising two molecular sieves, wherein the pretreatment comprises that the ZSM-5 molecular sieve, β molecular sieve and USY molecular sieve are respectively treated by alkali, the SAPO-34 molecular sieve is treated by acid, and the concentration of the used acid solution is 0.02-0.1 mol/L;
drying and dehydrating the composite molecular sieve in an inert gas atmosphere and carrying out silanization treatment, wherein the dosage of a silanization reagent is 0.1-1.0m L/g composite molecular sieve, the silanization reagent is pre-dissolved in an anhydrous nonpolar solvent, the treatment temperature is 120-250 ℃, and the treatment time is 0.5-5 hours, the nonpolar solvent is C5-C7 alkane and/or cycloalkane, and the silanization reagent is selected from methylalkoxysilane with the following general formula (I):
Figure FDA0002467385310000011
wherein R is1Selected from C1-C3 alkyl or phenyl; r2Selected from hydrogen, hydroxyl, C1-C3 alkyl, C1-C3 alkoxy, or phenyl;
the silanized composite molecular sieve is subjected to impregnation, and then nonmetal element modification and metal element modification are sequentially carried out to obtain a modified composite molecular sieve, wherein the loading amounts of the nonmetal elements and the metal elements are respectively 0.01-3% based on the mass of the catalyst, the nonmetal elements are selected from at least one of the group VA, the group VIA and the group VA, and the metal elements are selected from at least one of the group IA, the group IIA, the group IB, the group VIB, the group VIIB, the group VIII and the lanthanide series in the periodic table;
and mixing and pulping the modified composite molecular sieve, a matrix and a binder, and aging and roasting to obtain the olefin cracking catalyst.
2. The production method according to claim 1, wherein the content of the modified composite molecular sieve is 30 to 50 wt% based on the mass of the catalyst.
3. The method of claim 1, wherein the silylating agent comprises methyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, methylethylethoxysilane, or phenylmethylethoxysilane.
4. The process according to claim 1 or 3, wherein the non-aqueous, non-polar solvent is selected from the group consisting of C5-C7 alkanes and cycloalkanes.
5. The production method according to any one of claims 1 to 4, wherein the volume fraction of the silylation agent in the nonpolar solvent is 1 to 50%, and the separated solvent after the treatment is recycled.
6. The preparation method according to any one of claims 1 to 5, wherein the silylation treatment further comprises heating the composite molecular sieve treated with the silylation agent to 350-450 ℃ for 1-3 hours under inert gas purge, and/or performing acid washing.
7. The method of claim 1, wherein the non-metallic element comprises one or more of P, S, F and Cl and the metallic element comprises one or more of Na, K, Mg, Ca, L a, Ce, Cu, Ag, Ni, Co, Fe, Mn, and Cr preferably the metallic element comprises at least L a or Ce.
8. The preparation method according to claim 1 or 7, wherein the non-metal element modification and metal element modification processes of the silanized composite molecular sieve sequentially comprise synchronous impregnation or step-by-step impregnation, the impregnation temperature is 0-50 ℃, and aging, drying and roasting are performed after each impregnation.
9. An olefin cracking catalyst prepared according to the process of any one of claims 1 to 8.
10. A method for catalytic cracking of olefins, which comprises using a fixed bed reactor and the olefin cracking catalyst of claim 8, wherein the reaction temperature is 400--1And dilution usedThe agent is at least one selected from nitrogen, steam, cracking gas and distillate oil.
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