CN110824026B - Evaluation method of contact agent for heavy oil contact cracking - Google Patents
Evaluation method of contact agent for heavy oil contact cracking Download PDFInfo
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Abstract
The invention relates to a method for evaluating a contact agent for heavy oil contact cracking, which comprises the following steps: and placing the contact agent loaded with the heavy oil into a sample cup of a thermal cracking instrument, and enabling the heavy oil and the contact agent to carry out contact cracking reaction in the thermal cracking instrument, and sending the obtained gas phase product into a chromatographic column of the gas phase chromatograph through a sample injection needle of the thermal cracking instrument for gas phase chromatographic analysis. The method of the invention can be used for rapid evaluation of the contact agent.
Description
Technical Field
The invention relates to an evaluation method of a contact agent for heavy oil contact cracking.
Background
Crude oil resources are gradually becoming heavier and inferior worldwide, and the oil which is increased in yield will be mainly heavy crude oil and heavy synthetic oil. From analysis of crude oil reserves, the world crude oil has a tendency to become increasingly heavy due to high sulfur content of 17% and 37.8% and 58% of sulfur-containing crude oil and heavy weight.
Petroleum is a non-renewable resource and the trend in quality is to be heavy and inferior, but the development of world economy requires the production of more petroleum and the provision of more liquid transportation fuels to meet the ever-increasing demands of economy. Efficient utilization of petroleum resources is required in order to effectively alleviate this supply and demand contradiction. The key is to use good and bad 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 components is a major topic of the refinery process.
The delayed coking can process various inferior residuum with high carbon residue value and heavy metal content, and has simple process, low investment and operation cost, and is the main means for treating inferior heavy oil in China. However, the process has high dry gas and coke yields, coke/char values of about 1.5, poor liquid product quality, low additional yield, and large amounts of sulfur-containing or high sulfur petroleum coke (> 3%) that are difficult to utilize, causing environmental pollution.
The integrated process RCGT (Resid Contact Cracking and Coke Gasification Integrated Technology) of contact cracking and coke gasification adopts a process similar to catalytic cracking and adopts inferior heavy oil containing more metals, colloid and asphaltene as raw materials, such as normal pressure residual oil, vacuum residual oil, thick oil and the like. The process can realize clean production, improve the utilization rate of crude oil and reduce energy consumption.
The reaction of the evaluation agent and the oil is currently generally carried out using a Fixed Fluidized Bed (FFB) apparatus. However, the low-quality heavy oil has high boiling point and high viscosity, the device is extremely easy to coke and block, large manpower and material resources are consumed, and the material balance is only 80-90%. This brings a lot of inconveniences to the basic research of the contact cracking reaction.
Chinese patent CN101275930B discloses a micro-reactor gas chromatography combined analysis and evaluation system. The system comprises a reactor, and a gas chromatograph with a filling column sample inlet and a split-flow sample inlet, wherein one end of the reactor is connected with the filling column sample inlet of the gas chromatograph through a material inlet transmission pipeline, and the other end of the reactor is connected with the split-flow sample inlet of the gas chromatograph through a material outlet transmission pipeline. The combined analysis and evaluation system can be used for on-line analysis of micro-reaction products and evaluation of initial activity and activity stability of the catalyst.
Chinese patent CN101275932B discloses an online simulated distillation analysis method of pulse micro-reaction products, which comprises the steps of injecting reactants into a filling column sample inlet of a gas chromatograph in a pulse mode, enabling the reactants to enter a reaction tube of the micro-reaction device through a material transmission pipeline, enabling micro-reaction products flowing out of the reaction tube to enter a split sample inlet of the gas chromatograph through another material transmission pipeline, enabling one part of the micro-reaction products to be discharged from a split outlet after being split, enabling the other part of the micro-reaction products to enter a nonpolar capillary chromatographic column, separating the micro-reaction products according to a boiling point sequence under a linear temperature programming condition, enabling the micro-reaction products to enter a detector for detection, and obtaining the simulated distillation range of the micro-reaction products by chromatographic analysis, wherein the mass percent of distillate components and the corresponding temperature correspond to corresponding retention time.
The product, which is generally gaseous at room temperature, is readily amenable to on-line gas chromatographic analysis. However, for complex samples with wide boiling ranges, the components are extremely easy to generate physical and chemical changes such as condensation, leakage, polymerization, cracking and the like in a transmission pipeline, so that the problems of difficult sampling and sample pretreatment, high chromatographic separation analysis difficulty and the like are caused, and the online chromatographic analysis is difficult to realize.
Disclosure of Invention
The invention aims to provide an evaluation method of a contact agent for heavy oil contact cracking, which can be used for rapidly evaluating the contact agent.
In order to achieve the above object, the present invention provides a method for evaluating a contact agent for heavy oil contact cracking, the method comprising:
and placing the contact agent loaded with the heavy oil into a sample cup of a thermal cracking instrument, enabling the heavy oil and the contact agent to carry out contact cracking reaction in the thermal cracking instrument, and sending the obtained gas phase product into a chromatographic column of the gas phase chromatograph through a sample injection needle of the thermal cracking instrument for gas phase chromatographic analysis.
Optionally, the heavy oil has a carbon residue greater than 15 wt%, and the total content of nickel and vanadium is greater than 100ppm.
Alternatively, the heavy oil is one or more selected from the group consisting of vacuum residuum, atmospheric residuum, deoiled asphalt, oil sand heavy oil and natural asphalt.
Optionally, the contact agent comprises a molecular sieve and/or a silica-alumina material;
the molecular sieve is one or more selected from an X-type molecular sieve, a Y-type molecular sieve, mordenite, a ZSM-5 type molecular sieve, a layer column clay molecular sieve and an SAPO type molecular sieve;
the silicon aluminum material is one or more selected from amorphous silicon aluminum, clay, kaolin, montmorillonite, rectorite, illite, chlorite, silicon dioxide, alumina sol and pseudo-boehmite.
Optionally, the preparation step of the heavy oil-loaded contact agent includes:
dispersing heavy oil by adopting an organic solvent to obtain heavy oil dispersion liquid; wherein the organic solvent is methylene dichloride and/or toluene, and the weight ratio of the organic solvent to heavy oil is (10-100): 1, a step of;
mixing the contact agent with the heavy oil dispersion liquid and then evaporating the organic solvent; wherein the weight ratio of the contact agent to the heavy oil is (1-20): 1, the evaporating temperature is 40-150 ℃ and the evaporating time is 10-20 hours.
Optionally, the conditions of the contact cracking reaction include: the method is carried out under inert gas, the flow rate of the inert gas is 3-150mL/min, the temperature is 200-800 ℃, and the sample loading amount in a sample cup is 0.1-5mg.
Optionally, a thermal insulation sleeve is sleeved on the periphery of the sample injection needle, and the temperature of the sample injection needle is kept to be 350-400 ℃.
Optionally, the evaluation method further includes: delivering part of the gas phase product into a chromatographic column, separating the rest part of the gas phase product from the chromatographic column, and delivering the gas phase product into the chromatographic column with a volume ratio of 1: (1-50).
Optionally, the conditions of the gas chromatographic analysis include:
the temperature of the sample inlet is 200-400 ℃, and the flow rate of the chromatographic column is 3-10mL/min;
the control temperature of the column box is as follows: the initial temperature is 30-40 ℃, the heating rate is 5-20 ℃/min, the final temperature is 300-420 ℃, and the final temperature holding time is 3-15min;
the temperature of the detector is 400-430 ℃, the hydrogen flow is 20-40mL/min, the air flow is 300-400mL/min, the tail blowing flow is 10-30mL/min, the EI ion source and the ionization voltage is 70eV.
Optionally, the evaluation method further includes:
C5-C100 normal paraffin mixed sample is sequentially subjected to thermal cracking and gas chromatograph to determine retention time of C12, C20 and C40 normal paraffins and normal paraffins with the highest boiling point which can be detected;
the relative weight content of the gas phase product having a retention time less than the retention time of the C12 normal paraffins, a product having a retention time between the retention times of the C12 and C20 normal paraffins, a product having a retention time between the retention times of the C20 and C40 normal paraffins, and a product having a retention time greater than the retention time of the C40 normal paraffins is obtained bounded by the retention times of the C12, C20, and C40 normal paraffins.
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 take a sample cup of a thermal cracking instrument as a reactor for carrying out heavy oil contact cracking reaction, firstly heavy oil can not block devices and pipelines, secondly the obtained reaction product can be directly introduced into a gas chromatograph for analysis at high temperature, thereby preventing product loss and blocking a transmission pipeline, improving evaluation precision and reducing evaluation errors and sample quantity.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a schematic flow chart of an embodiment of the method of the present invention.
FIG. 2 is a chromatogram of an n-alkane mixed standard (time on the abscissa, minutes, current magnitude on the ordinate, pA) for a test example of the present invention.
FIG. 3 is a chromatogram of the product of the reaction of contact A with vacuum residuum in example 1 of this invention (time on the abscissa, in minutes, current magnitude on the ordinate, in pA).
FIG. 4 is a chromatogram of the product of the reaction of contact B with vacuum residuum in example 2 of this invention (time on the abscissa, in minutes, current magnitude on the ordinate, in pA).
FIG. 5 is a chromatogram of the product of the reaction of contact C with vacuum residuum in example 3 of this invention (time on the abscissa, in minutes, current magnitude on the ordinate, in pA).
Description of the reference numerals
1. Sample cup release button 2 thermal cracking instrument 3 sample cup
4. Thermal cracking chamber 5 thermal insulation sleeve 6 sample injection needle
7. Gas chromatography 8 sample inlet 9 chromatographic column
10. Carrier gas outlet of detector 11
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a method for evaluating a contact agent for heavy oil contact cracking, which comprises the following steps: and placing the contact agent loaded with the heavy oil into a sample cup of a thermal cracking instrument, enabling the heavy oil and the contact agent to carry out contact cracking reaction in the thermal cracking instrument, and sending the obtained gas phase product into a chromatographic column of the gas phase chromatograph through a sample injection needle of the thermal cracking instrument for gas phase chromatographic analysis.
Heavy oils are well known to those skilled in the art in accordance with the present invention, for example, the heavy oil may have a carbon residue of greater than 15 weight percent, and the total nickel and vanadium content may be greater than 100ppm, preferably greater than 120ppm, and more preferably greater than 150ppm, as determined by the ASTMD-189 Conn carbon residue test method. The heavy oil may be one or more selected from the group consisting of vacuum residuum, atmospheric residuum, deoiled asphalt, oil sand heavy oil, and natural asphalt.
According to the present invention, a contact agent refers to a catalyst for a contact cracking-coke gasification integrated process, and may generally include molecular sieves and/or silica-alumina materials; the molecular sieve can be one or more selected from an X-type molecular sieve, a Y-type molecular sieve, mordenite, a ZSM-5 type molecular sieve, a layer column clay molecular sieve and a SAPO type molecular sieve; the silicon aluminum material can be one or more selected from amorphous silicon aluminum, clay, kaolin, montmorillonite, rectorite, illite, chlorite, silicon dioxide, alumina sol and pseudo-boehmite, and can also comprise a binder and other components, wherein the contact agent is generally formed by spray drying and has a particle size of 20-200 microns. The contact agent evaluated by the invention can be purchased commercially or prepared by itself.
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 mix with the contact agent uniformly, and is more difficult to enter into the pore canal of the contact agent. Dispersing heavy oil by adopting an organic solvent to obtain heavy oil dispersion liquid; mixing the contact agent with the heavy oil dispersion liquid and then evaporating the organic solvent; wherein the organic solvent can be methylene dichloride and/or toluene, and the weight ratio of the organic solvent to heavy oil can be (10-100): 1, a step of; the weight ratio of the contact agent to the heavy oil may be (1-20): 1, the evaporating temperature can be 40-150 ℃ and the evaporating time can be 10-20 hours.
The contact cracking reaction of the invention on one hand cracks heavy oil into products such as dry gas, liquefied gas, gasoline, diesel oil and the like under the catalysis of a contact agent, and on the other hand, the products enter a chromatographic column for analysis under the purging of inert gas in a thermal cracking device to obtain the distribution data of reaction products. The conditions of the contact cracking reaction may include: the reaction is carried out under inert gas, wherein the inert gas can be one or more of nitrogen, argon and helium, the flow rate of the inert gas is 3-150mL/min, the temperature is 200-800 ℃, preferably 400-700 ℃, further preferably 500-600 ℃, and the sample loading amount in a sample cup can be 0.1-5mg, preferably 0.2-1mg.
In the invention, the part of the gas phase product obtained by contact cracking is a liquid product at normal temperature, in order to prevent the part of the liquid product from condensing in a sample injection needle and influencing the detection result, as shown in figure 1, the periphery of the sample injection needle is sleeved with a heat preservation sleeve, the temperature of the sample injection needle is kept to be 350-400 ℃, the heat preservation sleeve can comprise an internal heating resistance wire, a sleeve pipe wrapped on the outer side of the heating resistance wire and a thermocouple inserted into the sleeve pipe, the sleeve pipe is sleeved on the periphery of the sample injection needle to give heat to the sample injection needle, the sleeve pipe can be made of asbestos and other materials, the thermocouple is used for measuring the temperature at the position of the sample injection needle, and the heating power of the heating resistance wire can be controlled by a PLC (programmable logic controller) according to the temperature measured by the thermocouple.
According to the present invention, since the amount of the product measured by the column is small and the amount of the product obtained by the contact cracking is large, the evaluation method may further include: delivering part of the gas phase product into a chromatographic column, separating the rest of the gas phase product from the chromatographic column, wherein the volume ratio of the gas phase product delivered into the chromatographic column to the gas phase product of the fractional distillation chromatographic column can be 1: (1-50).
In the present invention, the gas chromatography is well known to those skilled in the art, and may generally include a chromatography column, a detector, a temperature programming control system, etc., the chromatography column of the present invention may be a nonpolar stainless steel chromatography column, hydrocarbons or hydrocarbon fractions having boiling points or boiling ranges of 0 to 688 ℃ may be analyzed, the inside diameter may be 530 μm, the film thickness may be 0.15 μm, the column length may be 5 to 10m, and the detector may be a hydrogen flame ionization detector. The conditions of the gas chromatography analysis may include: the temperature of the sample inlet is 200-400 ℃, and the flow rate of the chromatographic column is 3-10mL/min; the control temperature of the column box is as follows: the initial temperature is 30-40 ℃, the heating rate is 5-20 ℃/min, the final temperature is 300-420 ℃, and the final temperature holding time is 3-15min; the temperature of the detector is 400-430 ℃, the hydrogen flow is 20-40mL/min, the air flow is 300-400mL/min, the tail blowing flow is 10-30mL/min, the EI ion source and the ionization voltage is 70eV.
According to the invention, the distribution of the reaction product can be obtained through a gas chromatographic analysis spectrogram, and the cracking performance of the contact agent can be further evaluated according to the distribution of the product. On industrial plants, the contact cracked products can be generally classified into dry gas, liquefied gas, gasoline, diesel, cycle oil, slurry oil, etc., and in order to correspond to the contact cracked products of the industrial plant, the evaluation method may further include: C5-C100 normal paraffin mixed sample is sequentially subjected to thermal cracking and gas chromatograph to determine retention time of C12, C20 and C40 normal paraffins and normal paraffins with the highest boiling point which can be detected; the relative weight content of the gas phase product having a retention time less than the retention time of the C12 normal paraffins, a product having a retention time between the retention times of the C12 and C20 normal paraffins, a product having a retention time between the retention times of the C20 and C40 normal paraffins, and a product having a retention time greater than the retention time of the C40 normal paraffins is obtained bounded by the retention times of the C12, C20, and C40 normal paraffins. Generally, hydrocarbons with the same carbon number and highest boiling point of normal paraffins are obtained by measuring the retention time of a chromatographic column of the normal paraffins of C5-C100, the limit of the paraffins which can be measured by the chromatographic column can be measured on one hand, the contact cracking products are ensured to be within the limit range, and on the other hand, the gas phase products corresponding to dry gas, liquefied gas and gasoline fractions (the retention time is smaller than the retention time of the normal paraffins of C12), the gas phase products corresponding to diesel oil fractions (the retention time is between the retention time of the normal paraffins of C12 and C20), the gas phase products corresponding to circulating oil (the retention time is between the retention time of the normal paraffins of C20 and C40) and the gas phase products corresponding to slurry oil (the retention time is larger than the retention time of the normal paraffins of C40) can be obtained by taking the retention time of the normal paraffins of C12, C20 and C40 as a boundary, so that the evaluation method is more consistent with the process of industrial devices. Wherein, a certain product relative content = integrated peak area over the product retention period/integrated peak area of all products.
In the invention, all samples are preferably subjected to baseline compensation before the gas chromatography is carried out, so that the drift of peak positions along with the counting rate can be effectively compensated, and the evaluation error is reduced.
Specific embodiments of the present invention will be further described below with reference to the accompanying drawings, but the present invention is not limited thereto.
In fig. 1, a heavy oil-loaded contact sample is placed in a sample cup 3 of a thermal cracker 2, and the sample cup 3 is placed in the upper part of the thermal cracker, where the temperature is 50 ℃. After the temperature of the thermal cracking chamber 4 rises to reach the reaction temperature, the sample cup release button 1 is quickly pressed, so that the sample cup quickly and vertically falls into the thermal cracking chamber to carry out contact cracking reaction, and gas chromatographic analysis is started. The gas phase product enters a sample inlet 8 of the gas chromatograph 7 through a sample injection needle 6 of the cracker. In order to avoid condensation and aggregation of products, the periphery of the sample injection needle is sleeved with a heat preservation sleeve 5, and the temperature of the heat preservation sleeve 5 is 400 ℃. After the product enters the sample inlet, part of the product is shunted out from the carrier gas outlet 11, the rest part of the product enters the chromatographic column 9, the chromatographic column 9 separates the product according to the boiling point sequence under the linear temperature programming condition, and the separated effluent enters the detector 10 for detection so as to obtain a corresponding product chromatogram. The low-quality heavy oil contact cracking contact agent can be rapidly evaluated by calculating the relative weight contents of the gasoline fraction, the diesel fraction and the heavy oil fraction.
The following examples illustrate the methods provided by the present invention, but are not intended to limit the invention in any way.
The model of the thermal cracking instrument used in the embodiment and the test example of the invention is PY-2020iD, and the model of the gas chromatograph is Agilent 7890A.
The preparation methods of the contact agents A, B and C used in the embodiment of the invention are as follows:
contact agent A: 5 kg of kaolin (solid content: 70% by weight), 7 kg of water and 1 kg of alumina sol (alumina content: 21% by weight) 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: will be purchased from Qingdao Cooki high technology materials Co., ltd 2 (particle size 32.9-91.9 μm, micropore volume 0.5-0.9 g/ml) at 550 ℃ C. For 4 hours to obtain contact agent B.
Contact agent C: 100mL of 90gAl was taken 2 O 3 Al of/L 2 (SO 4 ) 3 Putting the solution into a beaker, dropwise adding ammonia water under stirring until the pH value of the system is 8 and the neutralization and gel forming temperature is 55 ℃; 50mL of 60g SiO was added with stirring 2 Water glass of/L, heating to 80 ℃ and aging for 4 hours; with NH 4 Cl solution as precipitate (dry basis): ammonium salt: h 2 O=1: 0.8:15, ion exchanging the silicon aluminum precipitate at 60 ℃ to remove sodium ions, repeating the exchange for 0.5 hour each time, washing and filtering each time, drying at 120 ℃ for 15 hours, and roasting at 600 ℃ for 3 hours to obtain the contact agent C.
Heavy oil used in the embodiment of the invention is used for reducing slag in Shijia, the property is shown in table 1, and the property of the common slag in Tahe is shown in table 3.
Test case
The retention times of the C12 n-alkanes, C20 n-alkanes and C40 n-alkanes were determined in this test example in order to obtain in the example a product having a retention time less than the retention time of the C12 n-alkanes, a product having a retention time between the retention times of the C12 and C20 n-alkanes, a product having a retention time between the retention times of the C20 and C40 n-alkanes, and a relative weight content of the product having a retention time greater than the retention time of the C40 n-alkanes and the highest boiling n-alkanes detectable by the gas chromatograph. The specific test method and conditions are as follows:
thermal cracking instrument: 540 ℃ and the nitrogen flow rate is 55mL/min;
gas chromatography: stainless steel superalloy Gao Wenzhu: 5 m.times.530 μm.times.0.15. Mu.m; an EI ion source with an ionization voltage of 70eV; sample inlet temperature: 400 ℃; chromatographic column flow rate: 5mL/min; split ratio (feed-out: feed-in): 10:1; column box temperature: heating to 420 ℃ at a speed of 15 ℃/min at 35 ℃ and keeping for 5min; detector temperature: 430 ℃; hydrogen flow rate: 30mL/min; air flow rate: 360mL/min; tail blow flow: 20mL/min; the sample injection amount is 0.3 mu L, the sample injection position is at the sample cup of the thermal cracking instrument, and the normal paraffin mixed sample standard sample of C5-C100 is obtained by mixing the amounts of substances such as normal paraffin of C5-C100 and the like. The analytical chromatogram of the normal alkane mixed standard is shown in FIG. 2, and the system can determine the highest boiling point of the product to be 688 ℃ (C88).
Example 1
The Shijia caustic sludge is completely dissolved by methylene dichloride and then is immersed on a contact agent A, and the weight ratio of the methylene dichloride, the contact agent and heavy oil is 15:8:1, then placing the immersed 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, thus obtaining the contact agent A loaded with heavy oil. 0.5mg of the heavy oil-loaded contact agent A is weighed in a sample cup, and is placed in a thermal cracking instrument for reaction, and the obtained gas phase product is sent into the gas chromatograph for gas chromatography analysis. The specific operating conditions are as follows:
thermal cracking instrument: 540 ℃ and the nitrogen flow rate is 55mL/min;
gas chromatography: stainless steel superalloy Gao Wenzhu: 5 m.times.530 μm.times.0.15. Mu.m; an EI ion source with an ionization voltage of 70eV; sample inlet temperature: 400 ℃, chromatographic column flow rate: 5mL/min; split ratio (feed-out: feed-in): 10:1; column box temperature: heating to 420 ℃ at a speed of 15 ℃/min at 35 ℃ and keeping for 5min; detector temperature: hydrogen flow at 430 ℃): 30mL/min; air flow rate: 360mL/min; tail blow flow: 20mL/min. The analytical chromatogram of the gas phase product of the heavy oil-loaded contact A is shown in FIG. 3, and the distribution of the product is shown in Table 2.
Example 2
Completely dissolving the amaranth alkali residues by using methylene dichloride, then immersing the amaranth alkali residues on a contact agent B, wherein the weight ratio of the methylene dichloride to the contact agent to heavy oil is 15:8:1, then placing the immersed 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, thus obtaining the contact agent B loaded with heavy oil. 0.5mg of the heavy oil-loaded contact agent B is weighed in a sample cup, and is placed in a thermal cracking instrument for reaction, and the obtained gas phase product is sent into the gas chromatograph for gas chromatography analysis. The specific operating conditions were the same as in example 1. The analytical chromatogram of the gas phase product of the heavy oil loaded contact agent B is shown in FIG. 4, and the distribution of the product is shown in Table 2.
Example 3
The Shijia caustic sludge is completely dissolved by methylene dichloride and then is immersed on a contact agent C, and the weight ratio of the methylene dichloride, the contact agent and heavy oil is 15:8:1, then placing the impregnated contact agent C in a fume hood for 4 hours, and then drying the contact agent C in a drying oven at 115 ℃ for 10 hours to completely evaporate the methylene chloride, thus obtaining a sample C. 0.5mg of the heavy oil-loaded contact agent C is weighed in a sample cup, and is placed in a thermal cracking instrument for reaction, and the obtained gas phase product is sent into the gas chromatograph for gas chromatography analysis. The specific operating conditions were the same as in example 1. The analytical chromatogram of the gas phase product of the heavy oil loaded contact C is shown in FIG. 5, and the distribution of the product is shown in Table 2.
Example 4
The contact agent A and the contact agent C are respectively subjected to contact cracking reaction with the constant slag of the Tahe 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 catalyst to oil weight ratio was 7, the water to oil weight ratio was 0.2, and the product distribution was as shown in Table 4.
As can be seen from Table 2, under the same operating conditions, the distribution of the products of the contact cracking of the Shimadzu slag reduction and the contact agent C is the best, the relative weight content of the products below C40 is the highest, the distribution of the products of the contact cracking of the Shimadzu slag reduction and the contact agent B is the second lowest, and the contact agent C has the best contact cracking performance, and the contact agent B is the worst. As can be seen from Table 4, the light oil yield of contact C was higher than that of contact A on the pilot plant, indicating that the process of the present invention is capable of characterizing good product distribution of contact on the pilot plant.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the present invention can be made, as long as it does not depart from the gist of the present invention, which is also regarded as the content of the present invention.
TABLE 1 slag reduction Properties for Shijia
| Project | Slag reduction for stone house |
| Density/(g/cm) 3 ) | 1.011 |
| Kinematic viscosity at 80 ℃/(mm) 2 /s) | 3463 |
| Carbon residue value/wt% | 18.62 |
| Relative molecular mass | 992 |
| w (element)/weight% | |
| C | 86.10 |
| H | 10.60 |
| S | 2.5 |
| N | 0.47 |
| n(H)/n(C) | 1.48 |
| w (Metal)/(μg/g) | |
| Ni | 54.1 |
| V | 68.8 |
| Fe | 57.8 |
| w (four component)/weight% | |
| Saturation fraction | 16.0 |
| Aromatic components | 44.6 |
| Colloid | 31.9 |
| Asphaltenes | 7.5 |
| Gas chromatography distillation range/°c | |
| Initial point of distillation | 350 |
| 5% by volume | 427 |
| 10% by volume | 471 |
| 30% by volume | 585 |
| 50% by volume | 623 |
TABLE 2 reaction product distribution for different contactors
TABLE 3 Table 3
TABLE 4 Table 4
| Contact agent | A | C |
| Product yield/wt% | ||
| H 2 S | 0.10 | 0.81 |
| Dry gas | 1.73 | 3.31 |
| Liquefied gas | 1.10 | 10.29 |
| C5-205℃ | 6.28 | 23.22 |
| 205℃-350℃ | 17.61 | 24.41 |
| >350℃ | 54.31 | 15.83 |
| Coke | 18.87 | 22.14 |
| Light oil yield | 23.89 | 47.63 |
| Liquid yield × | 79.30 | 73.75 |
* Light oil yield = C5-205 ℃ yield +205 ℃ -350 ℃;
* Liquid yield = liquefied gas yield + C5-205 ℃, yield +205 ℃ -350 ℃, yield + >350 ℃.
Claims (8)
1. A method of evaluating a contact agent for heavy oil contact cracking, the method comprising:
placing the contact agent loaded with heavy oil into a sample cup of a thermal cracking instrument, enabling the heavy oil and the contact agent to carry out contact cracking reaction in the thermal cracking instrument, and sending the obtained gas phase product into a chromatographic column of the gas phase chromatograph through a sample injection needle of the thermal cracking instrument for gas phase chromatographic analysis;
wherein the preparation steps of the heavy oil-loaded contact agent comprise:
dispersing heavy oil by adopting an organic solvent to obtain heavy oil dispersion liquid; wherein the organic solvent is methylene dichloride and/or toluene, and the weight ratio of the organic solvent to heavy oil is (10-100): 1, a step of;
mixing the contact agent with the heavy oil dispersion liquid and then evaporating the organic solvent; wherein the weight ratio of the contact agent to the heavy oil is (1-20): 1, evaporating at 40-150deg.C for 10-20 hr;
the conditions of the contact cracking reaction include: the method is carried out under inert gas, the flow rate of the inert gas is 3-150mL/min, the temperature is 200-800 ℃, and the sample loading amount in a sample cup is 0.1-5mg.
2. The evaluation method according to claim 1, wherein the carbon residue of the heavy oil is more than 15 wt%, and the total content of nickel and vanadium is more than 100ppm.
3. The evaluation method according to claim 1, wherein the heavy oil is one or more selected from the group consisting of vacuum residuum, atmospheric residuum, deoiled asphalt, oil sand heavy oil, and natural asphalt.
4. The method of evaluating according to claim 1, wherein the contact agent comprises a molecular sieve and/or a silicon-aluminum material;
the molecular sieve is one or more selected from an X-type molecular sieve, a Y-type molecular sieve, mordenite, a ZSM-5 type molecular sieve, a layer column clay molecular sieve and an SAPO type molecular sieve;
the silicon aluminum material is one or more selected from amorphous silicon aluminum, clay, kaolin, montmorillonite, rectorite, illite, chlorite, silicon dioxide, alumina sol and pseudo-boehmite.
5. The evaluation method according to claim 1, wherein the sample injection needle is provided with a thermal insulation sleeve on the outer periphery, and the temperature of the sample injection needle is kept between 350 and 400 ℃.
6. The evaluation method according to claim 1, the evaluation method further comprising: delivering part of the gas phase product into a chromatographic column, separating the rest part of the gas phase product from the chromatographic column, and delivering the gas phase product into the chromatographic column with a volume ratio of 1: (1-50).
7. The evaluation method according to claim 1, wherein the conditions of the gas chromatography include:
the temperature of the sample inlet is 200-400 ℃, and the flow rate of the chromatographic column is 3-10mL/min;
the control temperature of the column box is as follows: the initial temperature is 30-40 ℃, the heating rate is 5-20 ℃/min, the final temperature is 300-420 ℃, and the final temperature holding time is 3-15min;
the temperature of the detector is 400-430 ℃, the hydrogen flow is 20-40mL/min, the air flow is 300-400mL/min, the tail blowing flow is 10-30mL/min, the EI ion source and the ionization voltage is 70eV.
8. The evaluation method according to claim 1, the evaluation method further comprising:
C5-C100 normal paraffin mixed sample is sequentially subjected to thermal cracking and gas chromatograph to determine retention time of C12, C20 and C40 normal paraffins and normal paraffins with the highest boiling point which can be detected;
the relative weight content of the gas phase product having a retention time less than the retention time of the C12 normal paraffins, a product having a retention time between the retention times of the C12 and C20 normal paraffins, a product having a retention time between the retention times of the C20 and C40 normal paraffins, and a product having a retention time greater than the retention time of the C40 normal paraffins is obtained bounded by the retention times of the C12, C20, and C40 normal paraffins.
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