CN106950147B - Trace evaluation device and method for catalytic cracking performance of heavy oil - Google Patents
Trace evaluation device and method for catalytic cracking performance of heavy oil Download PDFInfo
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- CN106950147B CN106950147B CN201710317273.2A CN201710317273A CN106950147B CN 106950147 B CN106950147 B CN 106950147B CN 201710317273 A CN201710317273 A CN 201710317273A CN 106950147 B CN106950147 B CN 106950147B
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Abstract
The invention relates to a trace evaluation device and a method for catalytic cracking performance of heavy oil, wherein the device comprises: a microanalysis weighing device for weighing the weight of the heavy oil and the weight of the carbon residue after the heavy oil cracking; a cracking reaction device for controlling the flow rate of the carrier gas and the cracking reaction conditions of the heavy oil; the sample containing device is used for containing heavy oil and a catalyst; carrier gas generating means for supplying a carrier gas; a gas chromatograph for analyzing the percentage of each fraction of the hydrocarbon component of the cracked product; and for analysis of C in cleavage products1‑C4Hydrocarbon component, C5‑C12Hydrocarbon component, C13‑C20A gas chromatography-mass spectrometer of the hydrocarbon composition of the hydrocarbon component; the outlet of the cracking reaction device is connected with the sample inlet of the gas chromatograph, and is divided by the sample inlet, one path is connected with the gas chromatograph, and the other path is connected with the gas chromatograph-mass spectrometer. The method has the advantages of less sample consumption, realization of rapid gasification of heavy oil, catalytic cracking and multichannel online accurate analysis of cracking products, wide raw material application range and simple and convenient operation.
Description
Technical Field
The invention belongs to the technical field of petroleum processing, relates to a heavy oil cracking performance evaluation technology, and particularly relates to a device and a method for micro-evaluation of heavy oil catalytic cracking performance, which are used for micro-evaluation of heavy oil catalytic cracking performance.
Background
About 10 trillion barrels of residual petroleum resources worldwide, more than 70% are heavy oil resources. With the increasing exhaustion of conventional crude oil resources, heavy oil resources are becoming important resources for global future development and utilization, and are the main body of petroleum resource increment. Heavy oil, especially inferior heavy oil, is generally characterized by high density, high viscosity, high content of heteroatoms such as sulfur, nitrogen, oxygen, metal and the like, high carbon residue, high acid value and the like, and the heavy oil resource properties in different regions are greatly different, so that the processing and utilization difficulty of the heavy oil resource is high. Therefore, it is very important to develop an evaluation method and an evaluation device for evaluating the cracking performance of heavy oil to realize the efficient utilization of heavy oil resources.
At present, a micro-evaluation device for researching the catalytic cracking performance of heavy oil in a laboratory mainly comprises a catalytic cracking micro-reaction experimental device, a fixed fluidized bed experimental device and the like. However, because the heavy oil resource has the characteristics of high density, high viscosity, low conversion rate, high carbon residue and the like, the oil inlet amount of trace mercury cannot be accurately determined in a laboratory, the experimental error is large, the repeatability is poor, and the sample injection evaluation even for high-viscosity heavy oil cannot be performed. In addition, because the heavy oil has high boiling point, low gasification rate and poor atomization effect, a large amount of unvaporized heavy oil is left in the reactor, so that the yield of experimental products is low, the loss is large, and the repeatability is poor. Therefore, the existing experimental device is difficult to evaluate the catalytic cracking performance of heavy oil, particularly poor heavy oil.
Disclosure of Invention
Aiming at the problems of large experimental error, heavy oil residue and the like in the prior art, the invention provides a micro-evaluation device and a micro-evaluation method for the catalytic cracking performance of heavy oil, which have the advantages of small experimental error, small heavy oil residue and no limitation of heavy oil quality.
In order to achieve the above object, the present invention provides a micro-evaluation device for catalytic cracking performance of heavy oil, comprising:
the microanalysis weighing device is used for weighing the weight of the heavy oil and the weight of the carbon residue after the heavy oil cracking;
the cracking reaction device is used for controlling the flow rate of the carrier gas and the cracking reaction conditions of the heavy oil;
the sample holding device is used for holding heavy oil and a catalyst and is arranged on the heating part of the cracking reaction device;
the carrier gas generating device is used for providing carrier gas;
the gas chromatograph is used for analyzing the percentage content of each fraction section of the hydrocarbon component of the cracking product;
gas chromatography-mass spectrometer for analyzing C in cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20The hydrocarbon composition of the hydrocarbon component;
the outlet of the cracking reaction device is connected with the sample inlet of the gas chromatograph, and is divided by the sample inlet, one path is connected with the gas chromatograph, and the other path is connected with the gas chromatograph-mass spectrometer.
Preferably, the gas chromatograph comprises a sample inlet, a first column oven, a separation column and a first FID detector, wherein the separation column is placed in the first column oven; the gas chromatography-mass spectrometer comprises a heat transmission pipeline, a second incubator, a capillary chromatographic column, a second FID detector and a mass spectrum detector, wherein the capillary chromatographic column is placed in the second incubator; the sample inlet is divided into two paths, one path is connected with the separation column, the outlet of the separation column is connected with the first FID detector, the other path is connected with the capillary chromatographic column through a heating transmission pipeline, the outlet of the capillary chromatographic column is connected with the three-way element, the three-way element is divided into two paths, the other path is connected with the second FID detector, and the other path is connected with the mass spectrum detector.
Preferably, the number of the separation columns is at least one, and when the number of the separation columns is plural, the plural separation columns are connected in series.
Preferably, the operating temperature of the first column oven is-100 ℃ to 450 ℃.
Preferably, the three-way element is a tee pipe fitting or a three-way valve.
Preferably, the sample holding device is a sample tube.
In order to achieve the above purpose, the invention provides a micro-evaluation method for heavy oil catalytic cracking performance, comprising the following steps:
(1) weighing 0.1-1mg of heavy oil, and filling into a sample tube;
(2) filling catalysts with the mass 1-20 times that of the heavy oil at two sides of the heavy oil respectively, and fixing two ends of the catalysts by adopting quartz cotton;
(3) placing a quartz tube in a heating part of a cracking reaction device;
(4) introducing carrier gas to sweep heavy oil, and carrying out flash evaporation treatment on the heavy oil at the temperature of 150-;
(5) after the flash evaporation treatment, heating the heavy oil at the heating rate of 500-;
(6) the cracked reaction oil gas is divided into two parts, one part enters an on-line gas chromatograph to analyze C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20A hydrocarbon component,>C20The percentage content of each fraction of hydrocarbon components, and the other part of the hydrocarbon components enter an on-line gas chromatography-mass spectrometer for analyzing C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20The hydrocarbon composition of the hydrocarbon component;
(7) and weighing the cracked carbon residue to obtain the coke yield.
Preferably, the heavy oil is one or a mixture of more than two of oil products including atmospheric wax oil, vacuum wax oil, coker wax oil, atmospheric residue oil, vacuum residue oil, oil sand bitumen, super heavy oil, deasphalted oil, shale oil, coal tar or hydrocarbon-rich animal and vegetable oils.
Preferably, the catalyst is an acidic catalyst or a basic catalyst.
Preferably, the heating part of the cracking reaction device adopts resistance heating, induction heating or radiation heating, and the maximum temperature rise rate is more than 1000 ℃/s.
Preferably, the carrier gas is an inert gas.
Compared with the prior art, the invention has the beneficial effects that:
(1) the evaluation device provided by the invention is designed with a cracking reaction device, the heating part of the cracking reaction device can enable the heating rate of heavy oil to reach more than 500 ℃/s and can reach as high as 20000 ℃/s, the heavy oil is instantly gasified and cracked, meanwhile, a heavy oil sample and coke generated by cracking the heavy oil are directly weighed through a microanalysis weighing device, the weighing precision is accurate to +/-0.1 microgram, the outlet of the cracking reaction device is directly connected with the sample inlet of a gas chromatograph, the rapid conveying and the online detection of cracking gas are realized, the residue of the sample is avoided, and the experimental error is reduced.
(2) The evaluation device comprises a gas chromatograph and a gas chromatography-mass spectrometer, wherein when the heavy oil cracking performance is evaluated, the percentage content of each fraction section of hydrocarbon components in reaction oil gas after heavy oil cracking is analyzed on line through the gas chromatograph, the hydrocarbon composition of the hydrocarbon components in the reaction oil gas after heavy oil cracking is analyzed on line through the gas chromatography-mass spectrometer, the fraction distribution of a heavy oil cracking product and the hydrocarbon composition of the hydrocarbon components in the cracking product can be directly obtained through the on-line analysis of the gas chromatograph and the gas chromatography-mass spectrometer, and the experimental error introduced in the collection and sampling process of the cracking product is reduced.
(3) According to the evaluation method provided by the invention, the heavy oil sample amount is microgram level, the sample amount is small, the temperature rise rate of the heavy oil is more than 500 ℃/s, the heavy oil can be instantly gasified and cracked, the generated coke can be directly weighed and analyzed, the problem of heavy oil residue is solved, the raw material application range is wide, and the operation is simple and convenient.
(4) According to the evaluation method provided by the invention, the fraction distribution of the heavy oil cracking product and C in the cracking product can be directly obtained through the on-line analysis of the gas chromatograph and the gas chromatograph-mass spectrometer1-C4Hydrocarbon component (i.e., cracked gas), C5-C12Hydrocarbon component (i.e. gasoline), C13-C20The hydrocarbon composition of the hydrocarbon component (i.e., diesel) reduces experimental error introduced during collection and sampling of the cracked product.
Drawings
Fig. 1 is a schematic diagram showing a configuration of a micro-evaluation apparatus for catalytic cracking performance of heavy oil according to an embodiment of the present invention.
In the figure, 1, a cracking reaction device, 2, a sample inlet, 3, a metal buffer column, 4, a metal separation column, 5, a first FID detector, 6, a heat adding transmission pipeline, 7, a capillary chromatographic column, 8, a second FID detector, 9, a mass spectrum detector, 10, a first column incubator, 11 and a second column incubator.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the 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.
In the description of the present invention, it should be noted that the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Referring to fig. 1, the present invention provides a micro-evaluation apparatus for catalytic cracking performance of heavy oil, comprising:
and the microanalysis weighing device is used for weighing the weight of the heavy oil before heavy oil cracking and the weight of the carbon residue after heavy oil cracking.
The cracking reaction device 1 is used for controlling the flow rate of the carrier gas and the cracking reaction conditions of the heavy oil.
And the sample holding device is used for holding heavy oil and a catalyst and is placed in the heating part of the cracking reaction device.
And the carrier gas generating device is used for providing carrier gas, and the carrier gas provided by the carrier gas generating device carries the reaction oil gas flowing after the heavy oil cracking when the heavy oil cracking reaction is carried out.
The gas chromatograph is used for analyzing the percentage content of each fraction section of the hydrocarbon component of the cracking product;
gas chromatography-mass spectrometer for analyzing C in cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20The hydrocarbon composition of the hydrocarbon component;
the outlet of the cracking reaction device is connected with the sample inlet of the gas chromatograph, and is divided by the sample inlet, one path is connected with the gas chromatograph, and the other path is connected with the gas chromatograph-mass spectrometer.
Referring to fig. 1, further, the gas chromatograph includes a sample inlet 2, a first column oven 10, a separation column and a first FID detector 5, the separation column is placed in the first column oven 10; the gas chromatography-mass spectrometer comprises a heat transfer pipeline 6, a second incubator 11, a capillary chromatographic column 7, a second FID detector 8 and a mass spectrum detector 9, wherein the capillary chromatographic column 7 is placed in the second incubator 11. The outlet of the cracking reaction device is connected with the sample inlet 2, and is divided by the sample inlet 2, one path of the split stream is connected with the separation column, and the outlet of the separation column is connected with the first FID detector 5; the other path is connected with a capillary chromatographic column 7 through a heat adding transmission pipeline 6, the outlet of the capillary chromatographic column 7 is connected with a three-way element, the three-way element is divided into two paths, one path is connected with a second FID detector 8, and the other path is connected with a mass spectrum detector 9.
Referring to fig. 1, as a preferred design of the micro-evaluation device of the present invention, the separation column includes two metal buffer columns 3, one of the metal buffer columns is used for buffering the cracking reaction oil gas and buffering the cracking reaction oil gas, the other is used for separating hydrocarbon components with different carbon numbers, the metal buffer column 3 is connected in series with the metal separation column 4, the metal buffer column 3 is communicated with the cracking reaction device 1 through a sample inlet 2, and an outlet of the metal separation column 4 is connected with a first FID detector 5.
As the preferable design of the micro-evaluation device, the first column oven 10 is a liquid nitrogen cooling column oven, the operation temperature can reach-100 ℃, the separation column can reach lower temperature, and the separation of low carbon number hydrocarbon components in the reaction oil gas after heavy oil cracking is facilitated. In the process of separating hydrocarbon components with different carbon numbers in reaction oil gas after heavy oil cracking by the separation column, the first column temperature box 10 needs to perform temperature programming on the separation column to realize sequential separation of the hydrocarbon components with different carbon numbers in the reaction oil gas after heavy oil cracking, and the temperature after temperature programming can reach 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ and 450 ℃.
As the preferable design of the micro-evaluation device, the second temperature box 11 is a liquid nitrogen cooling column temperature box, the operation temperature can reach-100 ℃, the chromatographic column can reach lower temperature, and the separation of low carbon number hydrocarbon components in reaction oil gas after heavy oil cracking is facilitated. In a preferred embodiment of the invention, the capillary chromatography column has a length of 50-60m for better hydrocarbon separation.
As a preferred design of the above-mentioned micro-evaluation device of the present invention, the collected signals of the first FID detector 5 and the second FID detector 8 are processed by a standard area normalization method, i.e. the peak area of each peak on the spectrogram is expressed as a fraction of the total peak area.
Furthermore, a first channel of the three-way element is connected with an outlet of the capillary chromatographic column, a second channel of the three-way element is connected with the second FID detector, and a third channel of the three-way element is connected with the mass spectrum detector. Preferably, the three-way element is a three-way valve, and the flow areas of two outlets of the three-way valve can be adjusted according to actual operation requirements. The tee joint element can also be a tee joint pipe fitting.
As the preferable design of the micro-evaluation device, the micro-analysis weighing device adopts a micro-analysis balance, and the weighing precision is accurate to +/-0.1 microgram.
In a preferred embodiment of the microanalyzer of the present invention, the cleavage reaction apparatus is a cleavage reactor.
In a preferred embodiment of the micro-evaluation device of the present invention, the sample container is a sample tube, which may be a quartz tube or a metal tube.
When the evaluation device is used for evaluating the catalytic cracking performance of the heavy oil, the micro-analysis weighing balance is adopted to directly weigh the heavy oil and the residual carbon after the heavy oil cracking, the catalytic cracking performance of the heavy oil can be directly evaluated, the detailed hydrocarbon composition of a cracking product and a hydrocarbon component is analyzed on line, the operation is simple, and the reproducibility is good.
The invention also provides a micro-evaluation method of the heavy oil catalytic cracking performance, which is used for evaluating the heavy oil catalytic cracking performance and comprises the following steps:
(1) weighing 0.1-1mg of heavy oil, and filling the heavy oil into a sample containing device; the weighing precision is accurate to +/-0.1 microgram.
(2) Filling catalysts with the mass 1-20 times that of the heavy oil at two sides of the heavy oil respectively, and fixing two ends of the catalysts by adopting quartz cotton;
(3) the sample tube is placed in the heating part of the lysis reaction device.
(4) Introducing carrier gas to sweep heavy oil, and carrying out flash evaporation treatment on the heavy oil at the temperature of 150 ℃ and 300 ℃.
(5) After the flash evaporation treatment, the temperature of the heavy oil is raised at the temperature raising rate of 500-.
(6) The cracked reaction oil gas is divided into two parts, one part enters an on-line gas chromatograph to analyze C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20A hydrocarbon component,>C20The percentage content of each fraction of hydrocarbon components, and the other part of the hydrocarbon components enter an on-line gas chromatography-mass spectrometer for analyzing C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20The hydrocarbon composition of the hydrocarbon component.
(7) And weighing the cracked carbon residue to obtain the coke yield. When the coke yield is calculated, the coke yield can be obtained by dividing the weighed weight of the carbon residue after cracking by the weighed weight of the heavy oil before cracking and multiplying the weight by hundred percent.
As a preferred design of the above-mentioned micro-scale evaluation method of the present invention, the heating unit of the cleavage reaction apparatus is resistance heating, induction heating, or radiation heating, and the maximum temperature rise rate is greater than 1000 ℃/s. The faster the heating rate of the heavy oil is, the better the effect of the instant gasification and cracking of the heavy oil is. It is understood that the heating portion temperature rise rate of the lysis probe can be selected by one skilled in the art according to the experimental needs, for example, the temperature rise rate can be 1500 ℃/s, 3500 ℃/s, 5000 ℃/s, 8000 ℃/s, 10000 ℃/s, 13000 ℃/s, 15000 ℃/s, 18000 ℃/s, etc.
As a preferable design of the above-mentioned micro-evaluation method of the present invention, in the step (1), the heavy oil may be weighed in different amounts, such as 0.25mg, 0.5mg, 0.7mg, and 0.9mg, by those skilled in the art according to actual experimental requirements.
In the preferable embodiment of the method for evaluating a trace amount of the present invention, in the step (4), the heavy oil is subjected to a flash evaporation treatment to rapidly vaporize volatile components such as a solvent in the heavy oil and separate the volatile components from the heavy oil. It is understood that the temperature conditions of the flash evaporation treatment can be properly selected according to the impurities contained in the heavy oil, and the temperature can be varied from 220 ℃, 250 ℃ and 280 ℃.
As a preferable design of the above-mentioned micro-evaluation method of the present invention, in the step (5), the heavy oil is heated at a heating rate of 10000 ℃/s, the reaction temperature is controlled to 700 ℃, and the heating time is kept for 10s to perform the cracking reaction. It is understood that the rate of temperature rise, the reaction temperature, the heating time, and the reaction time can be appropriately adjusted by those skilled in the art according to the experimental needs, and are not limited to the specific values described above. Wherein the reaction temperature can also be 500 ℃, 600 ℃, 800 ℃ and 900 ℃; the heating time may be varied from 20s, 30s, 40s, and 50 s.
In the preferable configuration of the method for evaluating a trace amount of the present invention, in the step (5), the carrier gas is an inert gas, for example: high-purity helium with the purity of more than or equal to 99.999 percent. The reaction oil gas cracked by heavy oil carried by carrier gas enters a gas chromatograph and a gas chromatograph-mass spectrometer together for separation and detection.
According to the method for evaluating the cracking performance of the heavy oil, the sample amount of the heavy oil is microgram, the sample amount is small, the temperature rise rate of the heavy oil is more than 500 ℃/s, the heavy oil can be instantly gasified and cracked, the generated coke can be directly weighed and analyzed, and the cracked product can be subjected to multichannel online analysis, so that the problem of heavy oil residue is solved, the raw material application range is wide, and the operation is simple and convenient.
The device and the method for micro-evaluating the cracking performance of the heavy oil can evaluate the cracking performance of one or a mixture of more than two of heavy oil such as atmospheric wax oil, vacuum wax oil, coking wax oil, atmospheric residue oil, vacuum residue oil, oil sand asphalt, super heavy oil, deasphalted oil, shale oil, coal tar or oil products containing animal and vegetable oils rich in hydrocarbon and biological asphalt.
Example (b): the device and the method for evaluating the catalytic cracking performance of the heavy oil in the embodiment are adopted to carry out micro-evaluation on the catalytic cracking performance of the vacuum residue.
The experimental conditions are as follows: 0.4mg of vacuum residue, the flash evaporation temperature of 250 ℃, the heating rate of 20000 ℃/s, the reaction temperature of 600 ℃, the catalyst of acidic molecular sieve, the mass of catalyst of 10 times of the mass of residue, and the heating time of 30s is kept for cracking reaction.
The percentage contents of coke and oil gas fractions after the catalytic cracking of the vacuum residue are shown in table 1, more than 500 cracking products are detected by a gas chromatography-mass spectrometer, and the typical hydrocarbon composition is shown in table 2.
TABLE 1
| Product Components | Content, wt. -%) |
| C1-C4 | 31.5 |
| C5-C12 | 38.3 |
| C13-C20 | 15.5 |
| >C20 | 6.2 |
| Coke | 8.5 |
TABLE 2
| Serial number | Name (R) | Molecular formula | Molecular weight (g/mol) |
| 1 | Methane | CH4 | 16 |
| 2 | Ethane (III) | C2H6 | 30 |
| 3 | Ethylene | C2H4 | 28 |
| 4 | Propane | C3H8 | 44 |
| 5 | Propylene (PA) | C3H6 | 42 |
| 6 | Butane | C4H10 | 58 |
| 7 | Butene (butylene) | C4H8 | 56 |
| 8 | 1-pentene | C5H10 | 70 |
| 9 | N-pentane | C5H12 | 72 |
| 10 | 1, 3-pentadiene | C5H8 | 68 |
| 11 | 1, 3-cyclopentadiene | C5H6 | 66 |
| 12 | 4-methyl-1-pentene | C6H12 | 84 |
| 13 | 1-hexene | C6H12 | 84 |
| 14 | N-hexane | C6H14 | 84 |
| 15 | 1, 3-cyclohexadienes | C6H8 | 80 |
| 16 | Benzene and its derivatives | C6H6 | 78 |
| 17 | 1-heptene | C7H14 | 98 |
| 18 | N-heptane | C7H16 | 100 |
| 19 | Toluene | C7H8 | 92 |
| 20 | 2-methyl-1-heptene | C8H16 | 112 |
| 21 | 1-octene | C8H16 | 112 |
| 22 | Octane | C8H18 | 114 |
| 23 | 1, 3-dimethyl-1-cyclohexene | C8H14 | 110 |
| 24 | 1,2,4, 4-tetramethylcyclopentene | C9H16 | 124 |
| 25 | Para-xylene | C8H10 | 106 |
| 26 | Styrene (meth) acrylic acid ester | C8H8 | 104 |
| 27 | 1-nonene | C9H18 | 126 |
| 28 | Nonane | C9H20 | 128 |
| 29 | 1, 9-decadiene | C10H18 | 138 |
| 30 | 1-decene | C10H20 | 140 |
| 31 | Decane | C10H22 | 142 |
| 32 | Indene | C9H8 | 116 |
| 33 | 1, 10-undecadiene | C11H20 | 152 |
| 34 | 1-undecene | C11H22 | 154 |
| 35 | Undecane | C11H24 | 156 |
| 36 | 1, 11-dodecadiene | C12H22 | 166 |
| 37 | 1-dodecene | C12H24 | 168 |
| 38 | Dodecane | C12H26 | 170 |
| 39 | 1, 12-tridecadiene | C13H24 | 180 |
| 40 | 1-tridecene | C13H26 | 182 |
| 41 | Tridecane | C13H28 | 184 |
| 42 | 1, 13-tetradecadiene | C14H26 | 194 |
| 43 | 1-tetradecene | C14H28 | 196 |
| 44 | Tetradecane | C14H30 | 198 |
| 45 | 1-pentadecene | C15H30 | 210 |
| 46 | Pentadecane | C15H32 | 212 |
| 47 | 1-hexadecene | C16H32 | 224 |
| 48 | Hexadecane (Hexadecane) | C16H34 | 226 |
| 49 | 1-heptadecene | C17H34 | 238 |
| 50 | Heptadecane | C17H36 | 240 |
| 51 | 1-octadecene | C18H36 | 252 |
| 52 | Octadecane | C18H38 | 254 |
| 53 | 1-nonadecene | C19H38 | 266 |
| 54 | Nonadecane | C19H40 | 268 |
| 55 | 1-eicosene | C20H40 | 280 |
| 56 | Eicosane | C20H42 | 282 |
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are possible within the spirit and scope of the claims.
Claims (6)
1. A device for micro-evaluating the catalytic cracking performance of heavy oil is characterized by comprising:
the microanalysis weighing device is used for weighing the weight of the heavy oil and the weight of the carbon residue after the heavy oil cracking;
the cracking reaction device is used for controlling the flow rate of the carrier gas and the cracking reaction conditions of the heavy oil;
the sample containing device is used for containing heavy oil and a catalyst, and is a sample tube;
the carrier gas generating device is used for providing carrier gas;
gas chromatograph for analyzing cracking product C1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20A hydrocarbon component,>C20The percentage of each fraction of hydrocarbon components;
gas chromatography-mass spectrometer for analyzing C in cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20The hydrocarbon composition of the hydrocarbon component;
the outlet of the cracking reaction device is connected with a sample inlet of a gas chromatograph, and is divided by the sample inlet, one path is connected with the gas chromatograph, and the other path is connected with a gas chromatograph-mass spectrometer;
the gas chromatograph comprises a sample inlet and two separation columns connected in series, the sample inlet is divided into two paths, the first path of sample inlet is connected with the separation columns, and the second path of sample inlet is connected with the gas chromatograph-mass spectrometer; of the two separation columns, the first separation column connected with the sample inlet is a metal buffer column for buffering the oil gas of the cracking reaction, and the other separation column is a metal separation column for separating hydrocarbon components with different carbon numbers; the gas chromatograph also comprises a first column temperature box and a first FID detector, and the separation column is placed in the first column temperature box;
the gas chromatography-mass spectrometer comprises a heat transmission pipeline, a second incubator, a capillary chromatographic column, a second FID detector and a mass spectrum detector, wherein the capillary chromatographic column is placed in the second incubator; the outlet of the separation column is connected with a first FID detector, the second path of sample inlet is connected with a capillary chromatographic column through a heating transmission pipeline, the outlet of the capillary chromatographic column is connected with a tee joint element and is divided into two paths by the tee joint element, one path is connected with a second FID detector, and the other path is connected with a mass spectrum detector;
the micro-evaluation device comprises the following steps of:
(1) weighing 0.1-1mg of heavy oil, and filling the heavy oil into a sample containing device;
(2) filling catalysts with the mass 1-20 times that of the heavy oil at two sides of the heavy oil respectively, and fixing two ends of the catalysts by adopting quartz cotton;
(3) placing the sample containing device in a heating part of the cracking reaction device;
(4) introducing carrier gas to sweep the sample, and carrying out flash evaporation treatment on the heavy oil at the temperature of 150 ℃ and 300 ℃;
(5) after the flash evaporation treatment, heating the heavy oil at the heating rate of 500-;
(6) the cracked reaction oil gas is divided into two parts, one part enters an on-line gas chromatograph to analyze C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20A hydrocarbon component,>C20The percentage content of each fraction of hydrocarbon components, and the other part of the hydrocarbon components enter an on-line gas chromatography-mass spectrometer for analyzing C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20The hydrocarbon composition of the hydrocarbon component; the first column temperature box is a liquid nitrogen cooling column temperature box, the operation temperature reaches-100 ℃, the separation of low-carbon hydrocarbon components in reaction oil gas after heavy oil cracking is facilitated, in the process that the separation column separates different-carbon hydrocarbon components in the reaction oil gas after heavy oil cracking, the first column temperature box performs temperature programming on the separation column, sequential separation of the different-carbon hydrocarbon components in the reaction oil gas after heavy oil cracking is realized, and the temperature after temperature raising reaches 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ and 450 ℃; the second column temperature box is a liquid nitrogen cooling column temperature box, the operation temperature reaches-100 ℃, and the separation of low carbon number hydrocarbon components in reaction oil gas after heavy oil cracking is facilitated;
(7) and weighing the cracked carbon residue to obtain the coke yield.
2. A device for micro-evaluation of catalytic cracking performance of heavy oil according to claim 1, wherein the three-way element is a tee or a three-way valve.
3. A method for micro-evaluating catalytic cracking performance of heavy oil, based on the micro-evaluating device of claim 1 or 2, comprising the steps of:
(1) weighing 0.1-1mg of heavy oil, and filling the heavy oil into a sample containing device;
(2) filling catalysts with the mass 1-20 times that of the heavy oil at two sides of the heavy oil respectively, and fixing two ends of the catalysts by adopting quartz cotton;
(3) placing the sample containing device in a heating part of the cracking reaction device;
(4) introducing carrier gas to sweep the sample, and carrying out flash evaporation treatment on the heavy oil at the temperature of 150 ℃ and 300 ℃;
(5) after the flash evaporation treatment, heating the heavy oil at the heating rate of 500-;
(6) the cracked reaction oil gas is divided into two parts, one part enters an on-line gas chromatograph to analyze C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20A hydrocarbon component,>C20The percentage content of each fraction of hydrocarbon components, and the other part of the hydrocarbon components enter an on-line gas chromatography-mass spectrometer for analyzing C in the cracked product1-C4Hydrocarbon component, C5-C12Hydrocarbon component, C13-C20The hydrocarbon composition of the hydrocarbon component; the first column incubator is a liquid nitrogen cooling column incubator, the operation temperature reaches-100 ℃, the separation of low carbon number hydrocarbon components in reaction oil gas after heavy oil cracking is convenient, and the first column incubator performs programmed temperature rise on the separation column in the process that the separation column separates different carbon number hydrocarbon components in the reaction oil gas after heavy oil cracking, so that the reaction oil gas after heavy oil cracking is realizedSequentially separating hydrocarbon components, wherein the temperature after heating reaches 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ and 450 ℃; the second column temperature box is a liquid nitrogen cooling column temperature box, the operation temperature reaches-100 ℃, and the separation of low carbon number hydrocarbon components in reaction oil gas after heavy oil cracking is facilitated;
(7) and weighing the cracked carbon residue to obtain the coke yield.
4. The method for micro-evaluating the catalytic cracking performance of heavy oil according to claim 3, wherein the heavy oil is one or a mixture of two or more of atmospheric wax oil, vacuum wax oil, coker wax oil, atmospheric residue, vacuum residue, oil sand bitumen, ultra-heavy oil, deasphalted oil, shale oil, coal tar, or oil products such as hydrocarbon-rich animal and vegetable oils and biological asphalt.
5. A method for micro-evaluating the catalytic cracking performance of heavy oil according to claim 3, wherein the catalyst is an acidic catalyst or a basic catalyst.
6. The method of claim 3, wherein the heating unit of the cracking reactor is resistive heating, inductive heating, or radiation heating, and the maximum temperature rise rate is greater than 1000 ℃/s.
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