CN110823750A - Method for evaluating coke rate of heavy oil contact cracking - Google Patents
Method for evaluating coke rate of heavy oil contact cracking Download PDFInfo
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Abstract
The invention relates to a method for evaluating the coke rate of heavy oil contact cracking, which comprises the following steps: (1) placing the contact agent loaded with heavy oil into a crucible of a thermogravimetric analyzer to perform a contact cracking reaction under a contact cracking reaction condition, and performing a regeneration reaction on the obtained carbon deposition spent reagent and oxygen-containing gas under a regeneration condition to obtain a first weight loss of the crucible in the contact cracking reaction process and a second weight loss of the crucible in the regeneration reaction process; (2) calculating the coke rate by adopting the following formula: the char yield is the second weight loss/(first weight loss + second weight loss) × 100 wt%. The method can rapidly measure the coking rate of heavy oil contact cracking.
Description
Technical Field
The invention relates to a method for evaluating the coke rate of heavy oil contact cracking.
Background
Crude oil resources are gradually becoming heavier and poorer worldwide, and the petroleum to be increased in yield is mainly heavy crude oil and heavy synthetic oil. From the analysis of the reserves of crude oil, the low sulfur crude oil accounts for 17 percent, the sulfur-containing crude oil accounts for 37.8 percent and the high sulfur crude oil accounts for 58 percent in the world crude oil, and the high sulfur and heavy crude oil trend of the world crude oil is increasingly serious.
Petroleum is a non-renewable resource and the quality trend is to be heavy and poor, but the development of the world economy requires the production and processing of more petroleum and the provision of more liquid transportation fuels to meet the ever-increasing demands of the economy. To effectively alleviate this contradiction between supply and demand, it is necessary to efficiently utilize petroleum resources. The key point is to use good and poor heavy oil. The inferior heavy oil has the characteristics of high density and viscosity, low H/C atomic ratio, high colloid and asphaltene content, high carbon residue value, high sulfur nitrogen heteroatom and metal content and the like. How to fully utilize and reasonably process the heavy component is a great subject of the refinery process.
The delayed coking can be used for processing various inferior residual oils with high carbon residue value and heavy metal content, the process is simple, the investment and operation cost is low, and the method is a main means for treating inferior heavy oil in China at present. However, the process has high yield of dry gas and coke, the coke/carbon residue value is about 1.5, the liquid product quality is poor, the additional yield value is low, and a large amount of sulfur-containing or high-sulfur petroleum coke (more than 3 percent) which is difficult to utilize is generated, thereby causing environmental pollution.
The Contact Cracking-coke gasification Integrated process RCGT (resin Contact Cracking and CokeGaisification Integrated technology) adopts a catalytic Cracking-like process, and adopts inferior heavy oil containing more metals, colloids and asphaltenes as raw material, such as atmospheric residue, vacuum residue, heavy oil and the like. The process can realize clean production, improve the utilization rate of crude oil and reduce energy consumption. Coke is a low value-added product, and how to reduce the reaction coke rate is a major topic of oil refining workers.
Chinese patent CN205384237U discloses a device for measuring the tendency of heavy oil to form coke. The device includes: the reaction tube is provided with a gas feeding line and a gas discharging line, the top of the reaction tube is provided with a cover body, a first temperature measuring device and a preheating furnace for placing the reaction tube and heating the reaction tube to a specified temperature are arranged in the reaction tube, and the preheating furnace is of an open-close type; and the heating furnace is used for placing and heating the reaction tube heated by the preheating furnace to the reaction temperature. The device can determine the coking tendency of heavy oil in advance.
Chinese patent CN105910944A discloses a device and a method for measuring the tendency of solid-containing heavy raw materials to generate coke by heating. The device comprises a closed box body, wherein a sample pool is arranged in the closed box body, a heater for heating sample oil is arranged outside the sample pool, a heating device which is in a suspension state and provides heat for solid heavy raw materials is arranged inside the sample pool, a sleeve for attaching coke particles is arranged outside the heating device, the top of the sleeve is connected with a weighing device, the weighing device measures the mass of the sleeve of an electric heating rod in real time and the change of the mass of the sleeve of the electric heating rod caused by the heating and coking of reaction raw materials, and the weighing device is connected with a data acquisition module; the data acquisition module is connected with the data processing module, and the data processing module processes the signal number of the balance to obtain the percentage content of the green coke.
The coking rate is of great significance to the whole contact cracking reaction, and the reaction performance of the inferior heavy oil and the contact agent can be known in advance by measuring the coking rate. At present, FFB or a high-temperature reaction kettle device is generally adopted for evaluating the coking rate of contact cracking of the agent and the oil. However, the inferior heavy oil has high boiling point and high viscosity, so that the FFB device is easy to coke and block, and consumes large manpower and material resources. And the material balance is only 80-90%. If a reaction kettle is adopted, the temperature rise of reactants needs longer reaction time, and most or all substances may react in the temperature rise process. These bring inconvenience to the basic research of the contact cracking reaction.
At present, no method for rapidly determining the coking rate of the contact cracking reaction of the inferior heavy oil and the contact agent exists, so that an effective method for rapidly determining the coking rate of the contact cracking is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a method for evaluating the coking rate of heavy oil contact cracking, which can rapidly measure the coking rate of heavy oil contact cracking.
In order to achieve the above object, the present invention provides a method for evaluating the coke rate of heavy oil contact cracking, comprising:
(1) placing the contact agent loaded with heavy oil into a crucible of a thermogravimetric analyzer to perform a contact cracking reaction under a contact cracking reaction condition, and performing a regeneration reaction on the obtained carbon deposition spent reagent and oxygen-containing gas under a regeneration condition to obtain a first weight loss of the crucible in the contact cracking reaction process and a second weight loss of the crucible in the regeneration reaction process; wherein the unit of the first weightlessness and the unit of the second weightlessness are both mg;
(2) calculating the coke rate by adopting the following formula:
the char yield is the second weight loss/(first weight loss + second weight loss) × 100 wt%.
Optionally, the method further includes: sending the gas obtained in the regeneration reaction process into a mass spectrum analyzer for mass spectrum analysis to obtain CO in the regeneration reaction process2Mass spectrum of (2).
Optionally, the heavy oil has carbon residue greater than 15 wt% and a total nickel and vanadium content greater than 100 ppm.
Optionally, the heavy oil is one or more selected from the group consisting of vacuum residue, atmospheric residue, deoiled bitumen, oil sand heavy oil, and natural bitumen.
Optionally, the contact agent comprises a molecular sieve and/or a silica-alumina material;
the molecular sieve is one or more selected from X-type molecular sieve, Y-type molecular sieve, mordenite, ZSM-5 type molecular sieve, pillared clay molecular sieve and SAPO type molecular sieve;
the silicon-aluminum material is one or more selected from amorphous silicon-aluminum, argil, kaolin, montmorillonite, rectorite, illite, chlorite, silicon dioxide, alumina sol and pseudo-boehmite.
Optionally, the preparation step of the heavy oil-loaded contact agent comprises:
dispersing heavy oil by using an organic solvent to obtain a heavy oil dispersion liquid; wherein the organic solvent is dichloromethane and/or toluene, and the weight ratio of the organic solvent to the heavy oil is (10-100): 1;
mixing the contact agent with the heavy oil dispersion and evaporating the organic solvent; wherein the weight ratio of the contact agent to the heavy oil is (1-20): 1, the evaporation temperature is 40-150 ℃ and the time is 10-20 hours.
Optionally, the conditions of the contact cracking reaction include: the reaction is carried out in inert gas, the flow rate of the inert gas is 30-200mL/min, the temperature is 40-800 ℃, the sample loading amount in the crucible is 1-50mg, and the heating rate is 500-.
Optionally, the contact cracking reaction includes a first temperature rise stage, a first heat preservation stage, a second temperature rise stage, a second heat preservation stage, a temperature reduction stage and a third heat preservation stage, each stage is filled with an inert gas, the inert gas is one or more of nitrogen, argon and helium, and the flow rate of the inert gas is 30-200 mL/min;
the initial temperature of the first temperature rise stage is 40-80 ℃, and the temperature rise rate is 20-80 ℃/min;
the temperature of the first heat preservation stage is 100-;
the initial temperature of the second temperature rise stage is 100-;
the temperature of the second heat preservation stage is 400-;
the cooling rate of the cooling stage is 10-80 ℃/min;
the temperature of the third heat preservation stage is 100-.
Optionally, the regeneration reaction conditions include: the temperature is 100-1000 ℃, the oxygen-containing gas comprises oxygen, nitrogen and/or helium, the volume content of the oxygen is 10-50%, and the flow rate of the oxygen-containing gas is 10-200 mL/min.
Optionally, the regeneration reaction includes a regeneration temperature rise stage and a regeneration heat preservation stage;
the initial temperature of the regeneration temperature rise stage is 100-;
the temperature of the regeneration heat preservation stage is 400-.
Optionally, before step (1), the assay method further comprises: measurements were performed on a thermogravimetric analyzer using an empty crucible and a baseline correction file was created.
The method provided by the invention has the advantages that:
1. the functions of the thermogravimetric analyzer and the mass spectrum analyzer are fully utilized, the operation is simple and rapid, the sample consumption is less, the data obtained by adopting the thermogravimetric balance is accurate, the environment is friendly, and the time for testing one sample is short;
2. the coking rate of the contact cracking reaction of the inferior heavy oil and the contact agent can be quickly obtained, and meanwhile, the carbon deposit information of the product can be obtained through mass spectrometry, so that effective reference can be provided for gasification;
3. aiming at the problems that heavy oil has high boiling point and high concentration and is difficult to characterize on a small fixed fluidized bed, the invention develops a new way to use the crucible of a thermogravimetric analyzer as a reactor to carry out heavy oil contact cracking reaction and regeneration reaction, firstly, the heavy oil cannot block a device and a pipeline, and secondly, the weight loss in the cracking reaction and the regeneration reaction can be directly analyzed through a thermogravimetric balance;
4. the coking law of different inferior heavy oil, different contact agents and different reaction temperatures can be evaluated through the coking rate of the reaction of the inferior heavy oil and the contact agent at a certain temperature.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph of the weight loss of contact agent A reacted with vacuum residue in accordance with the present invention in example 1 (time in units of min on the abscissa; percent weight loss in units of% on the ordinate);
FIG. 2 shows CO generated in the regeneration reaction process after the contact agent A reacts with the vacuum residue in example 1 of the present invention2The mass spectrum (abscissa is temperature, unit ℃; ordinate is carbon dioxide signal intensity);
FIG. 3 is a graph of the loss of weight of contact agent B reacted with vacuum residue in accordance with the present invention in example 2 (time in min on the abscissa; percent weight loss in% on the ordinate);
FIG. 4 shows CO generated in the regeneration reaction process after the contact agent B reacts with the vacuum residue in example 2 of the present invention2The mass spectrum (abscissa is temperature, unit ℃; ordinate is carbon dioxide signal intensity);
FIG. 5 is a graph of the loss of weight of contact agent C reacted with vacuum residue in accordance with the present invention in example 3 (time in min on the abscissa; percent weight loss in% on the ordinate);
FIG. 6 shows CO generated in the regeneration reaction process after the contact agent C reacts with the vacuum residue in example 3 of the present invention2The mass spectrum (temperature in abscissa; carbon dioxide signal intensity in ordinate).
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for evaluating the coke rate of heavy oil contact cracking, which comprises the following steps:
(1) placing the contact agent loaded with heavy oil into a crucible of a thermogravimetric analyzer to perform a contact cracking reaction under a contact cracking reaction condition, and performing a regeneration reaction on the obtained carbon deposition spent reagent and oxygen-containing gas under a regeneration condition to obtain a first weight loss of the crucible in the contact cracking reaction process and a second weight loss of the crucible in the regeneration reaction process; wherein the unit of the first weightlessness and the unit of the second weightlessness are both mg;
(2) calculating the coke rate by adopting the following formula:
the char yield is the second weight loss/(first weight loss + second weight loss) × 100 wt%.
The process of the invention also preferably comprises: sending the gas obtained in the regeneration reaction process into a mass spectrum analyzer for mass spectrum analysis to obtain CO in the regeneration reaction process2Mass spectrum of (2).
The invention can measure the weight loss of the contact cracking reaction and the regeneration reaction through a mass spectrum analyzer, thereby measuring the coke rate through a formula, and can also obtain CO in the regeneration reaction process through the mass spectrum analyzer2So as to obtain the carbon deposition information on the spent catalyst. The method has the characteristics of short analysis time, small sample consumption, accurate analysis result and the like, and can be used for quickly evaluating the coke rate of heavy oil contact cracking.
Heavy oils are well known to those skilled in the art in accordance with the present invention, for example, the heavy oil may have greater than 15 weight percent carbon residue, and a total nickel and vanadium content of greater than 100ppm, preferably greater than 120ppm, and more preferably greater than 150ppm, as determined by ASTM D-189 Conn carbon residue test. The heavy oil may be one or more selected from the group consisting of vacuum residue, atmospheric residue, deoiled bitumen, oil sand heavy oil, and natural bitumen.
According to the present invention, the contact agent refers to a catalyst for a contact cracking-coke gasification integrated process, and may generally comprise a molecular sieve and/or a silica-alumina material; the molecular sieve can be one or more selected from X-type molecular sieve, Y-type molecular sieve, mordenite, ZSM-5 type molecular sieve, pillared clay molecular sieve and SAPO type molecular sieve; the silicon-aluminum material can be one or more of amorphous silicon-aluminum, argil, kaolin, montmorillonite, rectorite, illite, chlorite, silica, alumina sol and pseudo-boehmite, and can also comprise components such as a binder, and the contact agent is generally formed by spray drying and has a particle size of 20-200 microns. The contact agents evaluated in the present invention are either commercially available or can be prepared by themselves.
According to the invention, the heavy oil has high melting point of each hydrocarbon fraction, is easy to carbonize, is generally in a solid state at normal temperature, is difficult to be uniformly mixed with the contact agent, and is difficult to enter pores of the contact agent, the contact agent is mixed with the heavy oil in a loading manner, and the preparation step of the heavy oil-loaded contact agent can comprise the following steps: dispersing heavy oil by using an organic solvent to obtain a heavy oil dispersion liquid; wherein, the organic solvent can be dichloromethane and/or toluene, and the weight ratio of the organic solvent to the heavy oil can be (10-100): 1; mixing the contact agent with the heavy oil dispersion and evaporating the organic solvent; wherein, the weight ratio of the contact agent to the heavy oil can be (1-20): 1, the temperature of evaporation can be 40-150 ℃, and the time can be 10-20 hours.
The contact cracking reaction of the present invention cracks heavy oil into gas products and coke under the catalysis of a contact agent, and the conditions of the contact cracking reaction can comprise: the reaction is carried out in an inert gas, wherein the inert gas can be one or more of nitrogen, argon and helium, the flow rate of the inert gas is 30-200mL/min, the temperature is 40-800 ℃, and the loading amount of a crucible is 1-50mg, preferably 10-20 mg. The reaction time of the contact cracking is preferably 2-10s, the heating rate is preferably 500-.
In one embodiment, the contact cracking reaction comprises a first temperature rise stage, a first heat preservation stage, a second temperature rise stage, a second heat preservation stage, a temperature reduction stage and a third heat preservation stage, wherein inert gas is introduced into each stage, the inert gas is one or more of nitrogen, argon and helium, and the flow rate of the inert gas is 30-200 mL/min; the initial temperature of the first temperature rise stage is 40-80 ℃, and the temperature rise rate is 20-80 ℃/min; the temperature of the first heat preservation stage is 100-; the initial temperature of the second temperature rise stage is 100-; the temperature of the second heat preservation stage is 400-; the cooling rate of the cooling stage is 10-80 ℃/min; the temperature of the third heat preservation stage is 100-. The consistency of each evaluation can be ensured by the mode of program heating and cooling.
In the present invention, during the regeneration reaction, the coke obtained from the contact cracking reaction is burned in contact with oxygen, so as to regenerate the spent catalyst, and the conditions of the regeneration reaction may include: the temperature is 100-1000 ℃, the oxygen-containing gas comprises oxygen and nitrogen and/or helium, the volume content of the oxygen is 10-50%, preferably 20-40%, and the flow rate of the oxygen-containing gas is 10-200 mL/min.
In one embodiment, the regeneration reaction comprises a regeneration warming phase and a regeneration holding phase; the initial temperature of the regeneration temperature rise stage is 100-; the temperature of the regeneration heat preservation stage is 400-1000 ℃, preferably 600-900 ℃, and the heat preservation time is 1-10 min. The heating rate is low, slow heating is realized, and the information of carbon deposit species on the contact agent can be obtained.
To overcome the instrumental error, before step (1), the measuring method may further include: measurements were taken at the thermogravimetric analyzer using an empty crucible and a baseline correction file was created that removed the instrument error of the thermogravimetric analyzer.
In order to prevent air from affecting the contact cracking reaction, in step (1), the contact cracking reaction may be performed after evacuation is performed for 1 to 3 times, preferably 2 to 3 times, under an inert atmosphere, so as to reduce the participation of oxygen in the contact cracking reaction.
The following examples will illustrate the process provided by the present invention, but are not intended to limit the invention in any way.
The model of the thermal mass spectrometer used in the embodiment of the invention is STA449F3-QMS 403D.
The preparation method of the contact agents A, B and C used in the embodiment of the invention is as follows:
contact agent A: 5 kg of kaolin (with a solid content of 70 wt%), 7 kg of water and 1 kg of alumina sol (with an alumina content of 21 wt%) were mixed and beaten, and then spray-dried and molded, and the resulting molded microspheres were calcined at 1300 ℃ for 24 hours to obtain a contact agent a.
Contact agent B: SiO available from Qingdao Bangkai high and new technology materials Co Ltd2(particle size 32.9-91.9 microns, micropore volume 0.5-0.9 g/ml) was calcined at 550 ℃ for 4 hours to give contact B.
Contact agent C: taking 100mL of 90gAl2O3Al of/L2(SO4)3Putting the solution into a beaker, dropwise adding ammonia water under the stirring condition until the pH value of the system is 8, and neutralizing and gelling at 55 ℃; 50mL of SiO with a content of 60gSiO were added with stirring2Heating the water glass to 80 ℃ for aging for 4 hours; by NH4Cl solution as precipitate (dry basis): ammonium salt: h2O is 1: 0.8: 15, performing ion exchange on the silicon-aluminum precipitate at 60 ℃ to remove sodium ions in the silicon-aluminum precipitate, repeating the exchange twice, performing each time for 0.5 hour, performing water washing and filtering after each exchange, drying at 120 ℃ for 15 hours, and roasting at 600 ℃ for 3 hours to obtain the contact agent C.
The heavy oil used in the embodiment of the invention is Shijiazhuang slag reduction, victory slag reduction and Qingdao slag reduction, the properties are shown in table 1, and the properties of tower and river slag are shown in table 3.
Example 1
And (3) completely dissolving the shijiazhuang residue-reducing agent by using dichloromethane, and then soaking the shijiazhuang residue-reducing agent on a contact agent A, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent A in a fume hood for 4 hours, and then placing the contact agent A in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent A1 loaded with heavy oil.
A baseline correction file was created with a clean, empty crucible and evacuated 3 times under an inert atmosphere before sample testing. The operating conditions of the thermogravimetric analyzer were as follows:
atmosphere in the reaction stage is N2The flow rate was 100 mL/min. Temperature rising conditions are as follows: heating from 50 deg.C to 150 deg.C at a rate of 50.0 deg.C/min, and maintaining at 150 deg.C for 10 min; heating from 150 deg.C to 540 deg.C at a rate of 1000.0 deg.C/min, and maintaining at 540 deg.C for 10 min; the temperature is reduced from 540 ℃ to 150 ℃ at the cooling rate of 50.0 ℃/min, and the temperature is kept for 2min at 150 ℃.
The atmosphere of the carbon deposit combustion stage is N2+O2In which N is2The flow rate is 70mL/min, O2The flow rate was 30 mL/min. Temperature rising conditions are as follows: the temperature is raised from 150 ℃ to 800 ℃ at the heating rate of 50.0 ℃/min, and the temperature is kept at 800 ℃ for 5 min. The instrument automatically cools down, and the analysis is finished.
Weighing 10.72mg of contact agent A1 loaded with heavy oil in an empty crucible, placing the crucible on a thermogravimetric bracket to perform contact cracking reaction and regeneration reaction in sequence, wherein the burning condition of carbon deposit on the obtained spent agent is detected by mass spectrometry, and the temperature of a capillary connecting the thermogravimetric and mass spectrometry is set to be 280 ℃. The reaction loss chart of the contact agent A1 loaded with heavy oil is shown in figure 1, and CO is generated in the regeneration reaction process2The mass spectrum of the product is shown in FIG. 2, and the coke rate calculated by the reaction weight loss diagram is shown in Table 2.
Example 2
And (3) completely dissolving the residue of the Shijiazhu by using dichloromethane, and then soaking the solution on a contact agent B, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent B in a fume hood for 4h, then placing the impregnated contact agent B in a drying oven for drying at 115 ℃ for 10h to completely evaporate dichloromethane to prepare a heavy oil-loaded contact agent B1, weighing 17.44mg of the heavy oil-loaded contact agent B1 in a crucible, carrying out contact cracking reaction and regeneration reaction under the same conditions as in example 1, wherein the reaction weight loss diagram of the heavy oil-loaded contact agent B1 is shown in FIG. 3, and CO is generated in the regeneration reaction process2The mass spectrum of the reaction is shown in FIG. 4, and the coke rate calculated by the reaction weight loss diagram is shown in Table 2.
Example 3
And (3) completely dissolving the residue of the Shijiazhu by using dichloromethane, and then soaking the solution on a contact agent C, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent C in a fume hood for 4 hours, and then placing the contact agent C in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent C1 loaded with heavy oil. 11.02mg of the heavy oil-loaded contact agent C1 was weighed in a crucible, and subjected to the contact cracking reaction and the regeneration reaction under the same conditions as in example 1, the reaction loss chart of the heavy oil-loaded contact agent C1 is shown in FIG. 5, and CO was present during the regeneration reaction2The mass spectrum of (A) is shown in FIG. 6 byThe coke rate calculated from the reaction weight loss diagram is shown in Table 2.
Example 4
And (3) completely dissolving the victory slag reduction residue by using dichloromethane, and then soaking the dissolved victory slag reduction residue on a contact agent A, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent A in a fume hood for 4 hours, and then placing the contact agent A in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent A2 loaded with heavy oil. 10.12mg of contact agent A2 loaded with a heavy oil was weighed into a crucible, and reacted under the same conditions as in example 1, and the coke rate calculated from the reaction loss chart is shown in Table 2.
Example 5
And (3) completely dissolving the victory slag reduction residue by using dichloromethane, and then soaking the dissolved victory slag reduction residue on a contact agent B, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent B in a fume hood for 4 hours, and then placing the contact agent B in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent B2 loaded with heavy oil. 9.87mg of the contact agent B2 charged with a heavy oil was weighed out into a crucible, and reacted under the same conditions as in example 1, and the coke formation rate calculated from the reaction loss chart is shown in Table 2.
Example 6
And (3) completely dissolving the victory slag reduction residue by using dichloromethane, and then soaking the dissolved victory slag reduction residue on a contact agent C, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent C in a fume hood for 4 hours, and then placing the contact agent C in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent C2 loaded with heavy oil. 10.45mg of contact agent C2 loaded with a heavy oil was weighed into a crucible, and reacted under the same conditions as in example 1, and the coke rate calculated from the reaction loss chart is shown in Table 2.
Example 7
And (3) completely dissolving the residue of the Qingdao by using dichloromethane, and then soaking the Qingdao into a contact agent A, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent A in a fume hood for 4 hours, and then placing the contact agent A in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent A3 loaded with heavy oil. 8.23mg of contact agent A3 loaded with a heavy oil was weighed into a crucible, and reacted under the same conditions as in example 1, and the coke rate calculated from the reaction loss chart is shown in Table 2.
Example 8
And (3) completely dissolving the residue of the Qingdao by using dichloromethane, and then soaking the Qingdao into a contact agent B, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent B in a fume hood for 4 hours, and then placing the contact agent B in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent B3 loaded with heavy oil. 9.67mg of the contact agent B3 charged with a heavy oil was weighed into a crucible, and reacted under the same conditions as in example 1, and the coke rate calculated from the reaction loss chart is shown in Table 2.
Example 9
And (3) completely dissolving the residue of the Qingdao by using dichloromethane, and then soaking the Qingdao into a contact agent C, wherein the weight ratio of the dichloromethane to the contact agent to the heavy oil is 15: 8: 1, then placing the impregnated contact agent C in a fume hood for 4 hours, and then placing the contact agent C in a drying oven for drying at 115 ℃ for 10 hours to completely evaporate dichloromethane, thereby preparing the contact agent C3 loaded with heavy oil. 9.05mg of contact agent C3 loaded with a heavy oil was weighed into a crucible, and reacted under the same conditions as in example 1, and the coke rate calculated from the reaction loss chart is shown in Table 2.
Example 10
The contact agent A and the contact agent C are subjected to contact cracking reaction with the tower river normal slag in a medium-sized fixed fluidized bed device, and the reaction conditions are as follows: the temperature was 540 ℃, the pressure was 0.1MPa, the weight ratio of solvent to oil was 7, the weight ratio of water to oil was 0.2, and the product distribution is shown in table 4.
As can be seen from Table 2, under the same operating conditions, the coke rates of the three types of slag reductions on the different contact agents are as follows: the coking rate of the contact agent A is the lowest, the coking rate of the contact agent C is the highest after the contact agent A is contacted for the second time; the coke rate of the three types of slag reduction on the same contact agent is as follows: the Qingdao has the highest slag reduction, the victory slag reduction is inferior, and the Shijiazhuang has the lowest slag reduction. As can be seen from Table 4, the coke formation rate of contact C was higher on the pilot plant than contact A, indicating that the method of the present invention is capable of well characterizing the coke formation of the contact on the pilot plant.
From FIG. 2, FIG. 24 and 6, it can be seen that the mass spectra of FIGS. 4 and 6 show CO2The signal peak of (A) is normally distributed, and the mass spectrum of FIG. 2 shows CO2The signal peaks of (A) are in a semi-normal distribution, which shows that the coke on the spent catalyst in example 1 is distributed on the surface of the spent catalyst and not in the spent catalyst, and the coke in examples 2-3 enters the pore channels of the spent catalyst.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.
TABLE 1
| Item | Shijiazhuang slag reducing device | Victory slag reduction | Qingdao slag reduction |
| Density (20 ℃ C.) (g. cm-3) | 1.011 | 1.012 | 1.064 |
| Carbon residue value/weight% | 18.62 | 19.4 | 26.3 |
| w (element)/weight% | |||
| C | 86.1 | 85.6 | 84.2 |
| H | 10.6 | 10.92 | 9.77 |
| S | 2.5 | 2.73 | 5.5 |
| N | 0.47 | 0.75 | 0.38 |
| Metal content/(μ g. g)-1) | |||
| Ni | 54.1 | 49.5 | 69.7 |
| V | 68.8 | 51.6 | 230 |
| w (four components)/weight% | |||
| Saturation fraction | 16 | 11.9 | 8.6 |
| Aromatic component | 44.6 | 37.5 | 51.9 |
| Glue | 31.9 | 45.1 | 25.3 |
| Asphaltenes | 7.5 | 5.5 | 14.2 |
TABLE 2
TABLE 3
TABLE 4
The yield of light oil is C5-205 ℃ and 205-350 ℃;
liquid yield + C5-205 ℃ yield + 205-350 ℃ yield + >350 ℃ yield.
Claims (12)
1. A method for evaluating the coking rate of heavy oil contact cracking, which comprises the following steps:
(1) placing the contact agent loaded with heavy oil into a crucible of a thermogravimetric analyzer to perform a contact cracking reaction under a contact cracking reaction condition, and performing a regeneration reaction on the obtained carbon deposition spent reagent and oxygen-containing gas under a regeneration condition to obtain a first weight loss of the crucible in the contact cracking reaction process and a second weight loss of the crucible in the regeneration reaction process; wherein the unit of the first weightlessness and the unit of the second weightlessness are both mg;
(2) calculating the coke rate by adopting the following formula:
the char yield is the second weight loss/(first weight loss + second weight loss) × 100 wt%.
2. The method of claim 1, further comprising: sending the gas obtained in the regeneration reaction process into a mass spectrum analyzer for mass spectrum analysis to obtain CO in the regeneration reaction process2Mass spectrum ofFigure (a).
3. The process of claim 1 wherein the heavy oil has greater than 15 wt% carbon residue and a total nickel and vanadium content greater than 100 ppm.
4. The method of claim 1, wherein the heavy oil is one or more selected from the group consisting of vacuum residue, atmospheric residue, deoiled bitumen, oil sand heavy oil, and natural bitumen.
5. The method of claim 1, wherein the contact agent comprises a molecular sieve and/or a silica-alumina material;
the molecular sieve is one or more selected from X-type molecular sieve, Y-type molecular sieve, mordenite, ZSM-5 type molecular sieve, pillared clay molecular sieve and SAPO type molecular sieve;
the silicon-aluminum material is one or more selected from amorphous silicon-aluminum, argil, kaolin, montmorillonite, rectorite, illite, chlorite, silicon dioxide, alumina sol and pseudo-boehmite.
6. The method of claim 1, wherein the step of preparing the heavy oil-loaded contact agent comprises:
dispersing heavy oil by using an organic solvent to obtain a heavy oil dispersion liquid; wherein the organic solvent is dichloromethane and/or toluene, and the weight ratio of the organic solvent to the heavy oil is (10-100): 1;
mixing the contact agent with the heavy oil dispersion and evaporating the organic solvent; wherein the weight ratio of the contact agent to the heavy oil is (1-20): 1, the evaporation temperature is 40-150 ℃ and the time is 10-20 hours.
7. An assay according to claim 1, wherein the conditions of the contact cracking reaction comprise: the reaction is carried out in inert gas, the flow rate of the inert gas is 30-200mL/min, the temperature is 40-800 ℃, the sample loading amount in the crucible is 1-50mg, and the heating rate is 500-.
8. The method of claim 1, wherein the contact cracking reaction comprises a first temperature rise stage, a first heat preservation stage, a second temperature rise stage, a second heat preservation stage, a temperature reduction stage and a third heat preservation stage, wherein inert gas is introduced into each stage, the inert gas is one or more of nitrogen, argon and helium, and the flow rate of the inert gas is 30-200 mL/min;
the initial temperature of the first temperature rise stage is 40-80 ℃, and the temperature rise rate is 20-80 ℃/min;
the temperature of the first heat preservation stage is 100-;
the initial temperature of the second temperature rise stage is 100-;
the temperature of the second heat preservation stage is 400-;
the cooling rate of the cooling stage is 10-80 ℃/min;
the temperature of the third heat preservation stage is 100-.
9. The method of claim 1, wherein the conditions of the regeneration reaction comprise: the temperature is 100-1000 ℃, the oxygen-containing gas comprises oxygen, nitrogen and/or helium, the volume content of the oxygen is 10-50%, and the flow rate of the oxygen-containing gas is 10-200 mL/min.
10. The method of claim 1, wherein the regeneration reaction comprises a regeneration warm-up phase and a regeneration warm-up phase;
the initial temperature of the regeneration temperature rise stage is 100-;
the temperature of the regeneration heat preservation stage is 400-.
11. The method of claim 1, prior to step (1), the assay method further comprising: measurements were performed on a thermogravimetric analyzer using an empty crucible and a baseline correction file was created.
12. The method according to claim 1, wherein in step (1), the catalytic cracking reaction is performed after evacuation is performed 1 to 3 times under an inert atmosphere.
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