CN109423330B - Method for treating catalytic cracking slurry oil - Google Patents
Method for treating catalytic cracking slurry oil Download PDFInfo
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- CN109423330B CN109423330B CN201710766275.XA CN201710766275A CN109423330B CN 109423330 B CN109423330 B CN 109423330B CN 201710766275 A CN201710766275 A CN 201710766275A CN 109423330 B CN109423330 B CN 109423330B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for treating catalytic cracking slurry oil, which comprises the following steps: a. mixing the catalytic cracking oil slurry with catalytic cracking diesel oil to obtain mixed distillate oil; wherein the mixing weight ratio of the catalytic cracking slurry oil to the catalytic cracking diesel oil is 1: (0.2-10); the viscosity of the mixed distillate oil at 80 ℃ is not higher than 60 mm2A/second; b. and separating the obtained mixed distillate oil by adopting catalyst fine powder separation equipment to obtain clarified and separated oil and oil sludge. The treatment method provided by the invention can reduce the viscosity of the catalytic cracking slurry oil, improve the separation efficiency of solid particles in the slurry oil and ensure the long-period operation of separation equipment.
Description
Technical Field
The invention relates to a method for treating catalytic cracking slurry oil.
Background
The heavy fraction extracted from the bottom of the catalytic cracking fractionating tower is called oil slurry, the oil slurry contains a certain amount of catalyst fine powder, generally speaking, the oil slurry is a fraction with the distillation range of more than 350 ℃ (initial boiling point), has the characteristics of high aromatic hydrocarbon content, relatively high colloid content, relatively high sulfur content and nitrogen content, and is a component which is difficult to convert in a catalytic cracking device, and the hydrogen content can still reach 7-9.5 percent although the hydrogen content is relatively low. The catalytic cracking slurry oil contains catalyst fine powder, so the catalytic cracking slurry oil is difficult to directly utilize, and the catalytic cracking slurry oil can be further utilized only by removing the catalyst fine powder.
Chinese patent CN01113134.9 discloses a method for separating catalyst powder from catalytic cracking slurry oil by washing, settling and adding 5-10% of water and 100-1000 PPM of surfactant compound as a settling aid into the catalytic cracking slurry oil, fully and uniformly mixing, keeping the temperature of the slurry oil in a settling tank at 60-90 ℃, naturally settling for 12-60 hours, and then periodically discharging the mixture of the catalyst powder and the water settled at the bottom of the tank.
Chinese patent CN201210123869.6 discloses a method for removing catalyst from catalytic cracking slurry oil, which comprises settling the catalytic cracking slurry oil in a settling tank, allowing the catalyst in the slurry oil to enter an outward delivery pipeline from a bottom hole of the tank after settling in the settling tank, pushing the mixture to a receiving tank by a screw propeller in the outward delivery pipeline, pumping the slurry mixture of the catalyst and oil in the receiving tank into a high-level tank by a pump, discharging the catalyst in the high-level tank into a squeezer for squeezing, pressing the oil in the catalyst out, and discharging the catalyst in the squeezer, thus continuously separating the catalyst from the slurry oil in the catalytic cracking slurry oil and reducing the oil content in the catalyst.
Chinese patent CN201310456765.1 discloses a purifying device and a purifying method for purifying catalytic cracking slurry oil, the method comprises the steps of leading the catalytic cracking slurry oil to enter a settling tank through a pipeline, leading overflow to a primary electrostatic separator through a pipeline, leading underflow to a centrifugal machine through a pipeline, discharging solid phase at the bottom of the settling tank through a drain pipe at the bottom of the tank, leading the solid phase to a lifting pipe through a pipeline after centrifugation, leading the liquid phase to the primary electrostatic separator through a pipeline after centrifugation, leading the oil slurry product after electrostatic purification to a product tank through a pipeline, leading in the catalytic cracking slurry oil to be purified through a pipeline to carry out back washing on the catalytic cracking slurry oil from the bottom of the primary electrostatic separator after the filler of the primary electrostatic separator is adsorbed and saturated, returning back washing liquid to the settling tank through a pipeline from the top of the separator, and discharging the purified oil slurry product to the product tank through a pipeline.
Chinese patent CN201310334457.1 discloses an automatic back-purging filter device for coking and catalytic dry gas. The device is provided with an automatic back-blowing filtering device for coking and catalytic dry gas, and comprises a filtering unit and an automatic back-blowing unit, wherein the filtering unit comprises a filter shell, a filtering element and a tube plate, the tube plate is arranged at the upper part of the filter shell, the filtering element is fixed at the lower side of the tube plate, and an air inlet is arranged on the side wall of the tube plate; the automatic back-blowing unit comprises an automatic back-blowing control device and a buffer tank, wherein the air inlet end of the automatic back-blowing control device is connected with the buffer tank, and the air outlet end of the automatic back-blowing control device is connected with the air inlet on the side wall of the tube plate.
Chinese patent CN201110032024.1 discloses a two-stage filtration oil slurry filtering device for a catalytic cracking unit, which comprises a first stage filtration and a second stage filtration connected in series, wherein the first stage filtration is one or two filters, and the second stage filtration is at least two filters; the filter element adopted by the filter of the first stage of filtration is a wedge-shaped metal wire winding filter element which is formed by winding metal wires with wedge-shaped sections, and a gap between each circle of metal wires and the adjacent metal wires is fixed and is in a continuous funnel shape; the filter for the second stage of filtration adopts a metal powder sintered filter element.
Chinese patent CN201210274634.7 discloses a catalytic filter system comprising: a filtration vessel having a fluid inlet and a fluid outlet; a partition wall disposed in an interior of the filtration vessel; and a plurality of filter candles; the partition wall divides the interior into a raw gas chamber and a purge gas chamber; the dividing wall includes a plurality of openings designed to sealingly receive the plurality of filter candles; the fluid inlet is arranged in fluid communication with the raw gas chamber upstream of the plurality of filter candles; the fluid outlet is arranged in fluid communication with the purge gas chamber downstream of the plurality of filter candles; and the filter system comprises a first catalytic medium accommodated in the purge gas chamber downstream of the filter candles and upstream of the fluid outlet.
Chinese patent CN200510122904.2 discloses a filter for reaction system of petroleum catalytic cracking experimental apparatus, comprising: the filter comprises a filter support body, a filter body and a connecting piece, wherein the filter body is a ceramic membrane with the pore size of 50 nanometers to 0.2 micrometer, the filter body is a streamline cylinder with the wall thickness of 4-5 millimeters, the support body is arranged below the filter body, and the connecting piece is arranged above the filter body. In order to enable the bottom of the filter and oil gas at the periphery to pass through, 4 rectangular holes are formed in the side face of the support body, round holes are formed in the bottom of the support body, and the support body is connected with an outlet pipe of the reactor through a steel connecting piece. After the device is used, the entrainment phenomenon of the catalyst is greatly reduced, and basically no solid particles are seen in the outlet pipe of the reactor and the product receiving bottle, so that the smooth operation of the catalytic cracking experiment is ensured.
Chinese patent CN201110329376.3 discloses a method for filtering solid-liquid slurry, which comprises: injecting the solid-liquid slurry into a ceramic membrane filter for filtering to obtain a purified material and a concentrated material, wherein the solid content of the concentrated material is higher than that of the solid-liquid slurry, and the solid content of the purified material is lower than that of the solid-liquid slurry; before the solid-liquid slurry is injected into the ceramic membrane filter, the temperature of a filter element of the ceramic membrane filter is increased at a temperature increasing speed of 5-150 ℃/h, so that the difference between the temperature of the filter element and the temperature of the solid-liquid slurry is not more than 50 ℃.
In the prior art, the sedimentation method has the characteristics of simple equipment, low running cost, simple operation and the like, but the catalyst fine powder with the particle size of less than 20 mu m is difficult to remove because the catalyst fine powder in the oil slurry is smaller and is hindered by colloid and asphaltene in the oil slurry. The filtering and separating method can well remove catalyst fine powder in the oil slurry, and the key technology is to select a proper filtering material and an effective backwashing method. At present, in order to better eat dry squeezed raw materials, the density of oil slurry of a catalytic cracking device is generally controlled to be 1000kg/m3Above, the viscosity is higher, and the existing separation equipment is difficult to ensure long-period operation.
Disclosure of Invention
The invention aims to provide a processing method of catalytic cracking slurry oil, which can reduce the viscosity of the catalytic cracking slurry oil, improve the separation efficiency of solid particles in the slurry oil and ensure the long-period operation of separation equipment.
In order to achieve the above object, the present invention provides a method for treating catalytic cracking slurry oil, comprising: a. mixing the catalytic cracking oil slurry with catalytic cracking diesel oil to obtain mixed distillate oil; wherein the mixing weight ratio of the catalytic cracking slurry oil to the catalytic cracking diesel oil is 1: (0.2-10); the viscosity of the mixed distillate oil at 80 ℃ is not higher than 60 mm2A/second; b. separating the obtained mixed distillate oil by adopting catalyst fine powder separation equipmentAnd (4) obtaining clarified and separated oil and oil sludge.
Optionally, the method further includes: b, sending the oil sludge obtained in the step b into a catalytic cracking reactor, mixing the oil sludge with a regenerated catalytic cracking catalyst, and carrying out catalytic cracking reaction on the oil sludge and the catalytic cracking raw oil; and/or sending the obtained oil sludge to a catalytic cracking regenerator for regeneration.
Optionally, the method further includes: and c, washing the oil sludge obtained in the step b by adopting catalytic cracking diesel oil to obtain clarified washing oil and catalyst fine powder, wherein the washing weight ratio of the oil sludge to the catalytic cracking diesel oil is 1: (0.1-6).
Optionally, the method further includes: and drying the catalyst fine powder.
Optionally, the method further includes: subjecting the resulting at least partially clarified wash oil to said wash treatment as catalytically cracked diesel and/or mixing with said catalytically cracked slurry oil in step a.
Optionally, the clarified and separated oil obtained in the step b is subjected to hydrofining treatment to obtain a hydrofined product.
Optionally, the obtained hydrorefined product is mixed with catalytic cracking raw oil, and then the mixture is contacted with a catalytic cracking catalyst in a catalytic cracking reactor to carry out catalytic cracking reaction.
Optionally, the obtained hydrofined product is used as a catalytic cracking raw material to be contacted with a catalytic cracking catalyst in a catalytic cracking reactor for carrying out catalytic cracking reaction independently.
Optionally, the hydrorefining conditions include: the temperature is 250 ℃ and 500 ℃, the hydrogen partial pressure is 2-30 MPa, and the volume space velocity is 0.1-30 hours-1。
Optionally, the catalytic cracking raw oil is at least one selected from atmospheric residue, vacuum residue, coker gas oil, deasphalted oil and hydrotreated residue; the catalytic cracking catalyst comprises a molecular sieve, a carrier and a binder; the catalytic cracking reaction conditions comprise the temperature of 400-750 ℃, the reaction pressure of 0.10-1.0 MPa, the weight ratio of the catalyst to the raw material of 1-100 and the weight ratio of the steam to the raw material of 0.02-1.0; the catalytic cracking reactor is a riser reactor and/or a fluidized bed reactor.
Optionally, the catalyst fine powder separation device in step b is at least one selected from a settling separation device, a filtering separation device, an electrostatic separation device and a centrifugal separation device.
Optionally, the natural settling conditions include: the temperature is 10-360 ℃, and the time is 0.5-240 hours.
Optionally, the filtering treatment is preferably a filter, the filter is a metal sintered porous material and/or a ceramic porous material, and the filtering precision of the filter for 1.2 micron particles is 99.9%. The optional catalyst fine powder separation process is to carry out natural sedimentation and then filter.
Optionally, the method further includes: cutting the clarified and separated oil obtained in the step b in a fractionating tower to obtain a diesel fraction and an oil slurry fraction; wherein the cutting point of the cutting is 340-380 ℃.
Optionally, the distillation range initial boiling point of the catalytic cracking slurry oil is greater than 290 ℃.
Optionally, the distillation range of the catalytic cracking diesel oil is 180-380 ℃.
Optionally, the mixed distillate has a viscosity of not higher than 50 mm at 80 ℃2In seconds.
Compared with the prior art, the method of the invention has the following main advantages:
1. the catalytic cracking diesel oil is used for dissolving the heavy colloid coated on the outer side of the catalyst fine powder in the oil slurry, so that the viscosity of the filtered oil slurry is reduced, the catalyst fine powder in the oil slurry can be effectively separated, and the long-period operation of separation equipment is ensured;
2. the low-viscosity clarified and separated oil after filtration can be subjected to catalytic cracking after being subjected to hydrofining treatment, so that the high-efficiency utilization of oil products is realized.
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 schematic flow diagram of one embodiment of the process of the present invention.
FIG. 2 is a schematic flow diagram of another embodiment of the process of the present invention.
FIG. 3 is a graph showing the change of the filtration time and the flow rate of the slurry oil according to example 1 and comparative example 1 of the present invention.
FIG. 4 is a graph showing the 200 ℃ viscosity (abscissa, unit: mm) of the feed oil summarized in the present invention2Per second) and nozzle atomized droplet diameter (ordinate, unit: microns).
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. 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.
It should be noted that, unless otherwise specified, diesel oil and light cycle oil are a type of distillate in the present invention.
As shown in FIG. 1, the present invention provides a method for treating catalytic cracking slurry oil, which comprises the following steps: a. mixing the catalytic cracking oil slurry with catalytic cracking diesel oil to obtain mixed distillate oil; wherein the mixing weight ratio of the catalytic cracking slurry oil to the catalytic cracking diesel oil is 1: (0.2-10); the viscosity of the mixed distillate oil at 80 ℃ is not higher than 60 mm2A/second; b. and separating the obtained mixed distillate oil by adopting catalyst fine powder separation equipment to obtain clarified and separated oil and oil sludge.
In the normal operation condition of the catalytic cracking device, the catalytic cracking slurry oil contains 1 g/L-15 g/L of catalyst fine powder, and the inventor of the invention unexpectedly finds that the catalyst fine powder in the slurry oil is wrapped by heavy colloid with the thickness of 0.1 micron-8 microns, and the catalyst fine powder wrapped by the heavy colloid has strong viscosity, so that the catalyst fine powder in the slurry oil is difficult to separate and the long-term operation of separation equipment is difficult to ensure.
The oil slurry treatment method adopts the catalytic cracking diesel oil and the catalytic cracking oil slurry to be mixed so as to dissolve the heavy colloid on the surface of the catalyst fine powder in the catalytic cracking oil slurry, so that the mixed distillate oil is easier to filter, the blockage of the separation equipment is effectively prevented, and the filtering speed and the running period of the separation equipment are improved.
According to the invention, the oil sludge obtained by the separation in the step b contains catalyst fine powder and part of heavy colloid, the composition of the oil sludge is similar to that of a carbon deposit catalyst with high hydrogen content, and in order to effectively utilize the part of the oil sludge, the method can further comprise the following steps: b, sending the oil sludge obtained in the step b into a catalytic cracking reactor, mixing the oil sludge with a regenerated catalytic cracking catalyst, and carrying out catalytic cracking reaction on the oil sludge and the catalytic cracking raw oil; and/or sending the obtained oil sludge to a catalytic cracking regenerator for regeneration. The separated oil sludge is sent into a catalytic cracking reactor, so that the activity of the catalyst can be reduced, heavy oil is prevented from being over-cracked, and coke formation is reduced. The separated oil sludge is sent to a catalytic cracking regenerator, so that the regeneration temperature can be increased, and other fuels are saved.
According to the present invention, since the heavy gum in the sludge is also valuable, in order to utilize the part of the heavy gum, the method may further include: and c, washing the oil sludge obtained in the step b by adopting catalytic cracking diesel oil to obtain clarified washing oil and catalyst fine powder, wherein the washing weight ratio of the oil sludge to the catalytic cracking diesel oil is 1: (0.1-6). The step can wash most of hydrocarbons in the oil sludge to improve the utilization rate, so that the catalyst fine powder basically only contains catalytic cracking diesel oil as a solvent, and in order to recover the part of diesel oil, the method can further comprise the following steps: and drying the catalyst fine powder, wherein the temperature of the drying treatment can be above the distillation range of the diesel oil, and can also be gradually increased from the initial distillation point of the diesel oil to the final distillation point of the diesel oil, so that the coking of the diesel oil is effectively prevented.
Because the oil sludge contains less heavy colloid, the used clarified wash oil can be recycled, for example, the method can further comprise: subjecting the resulting at least partially clarified wash oil to said wash treatment as catalytically cracked diesel and/or mixing with said catalytically cracked slurry oil in step a. The clarified washing oil is continuously recycled, so that the utilization efficiency of the catalytic cracking diesel oil can be improved.
The inventor of the invention finds that the raw oil viscosity has a good linear relation with the diameter of the atomized fog drops of the nozzle through diligent research. As shown in fig. 4, Y (droplet diameter) ═ AX (raw oil viscosity) + B, where the slope a and constant B are determined by the nozzle type and pressure drop, and after high viscosity catalytic cracking raw oil is mixed with low viscosity fraction oil, the viscosity of catalytic cracking raw oil can be significantly reduced, the nozzle atomization effect is improved, and the coke and dry gas yield are reduced, so as to change the traditional method of reducing viscosity mainly by raising the raw oil temperature, and overcome the disadvantage of precipitation and coking of colloid and asphaltene in raw oil caused by excessively high raw oil preheating temperature. Based on the above findings, the method of the present invention may further comprise: b, performing hydrofining treatment on the clarified and separated oil obtained in the step b (at least part of aromatic hydrocarbons in the clarified and separated oil can be saturated) to obtain a hydrofined product; mixing the obtained hydrofined product with catalytic cracking raw oil, and then contacting the mixture with a catalytic cracking catalyst in a catalytic cracking reactor to perform catalytic cracking reaction, or contacting the obtained hydrofined product serving as a catalytic cracking raw material with the catalytic cracking catalyst in the catalytic cracking reactor to perform catalytic cracking reaction independently. The hydrofining product is rich in naphthene and/or monocyclic aromatic hydrocarbon, not only can reduce the viscosity of catalytic cracking raw oil, but also can avoid the problem of increasing the yield of dry gas and coke caused by the generation of non-classical carbonium ions when the hydrofining product reacts alone because negative hydrogen ions generated by the catalytic cracking raw oil can be effectively transferred to the hydrofining product, thereby realizing better effect than the single reaction in the aspect of reducing the yield of the dry gas and the coke.
Hydrofinishing is used to saturate some of the aromatics in the clarified separated oil, and its reaction conditions and reactors are well known to those skilled in the art, for example, the conditions of the hydrofinishing process include: the temperature is 250-500 ℃, the hydrogen partial pressure is 2-30 MPa, and the volume space velocity is 1-30h-1The reactor is a fixed bed reactor, a fluidized bed reactor or a slurry bed reactor. Catalytic cracking is well known to those skilled in the art, and is described inThe catalytic cracking raw oil can be at least one selected from atmospheric residue, vacuum residue, coker gas oil, deasphalted oil and hydrotreated residue; the conditions of the catalytic cracking reaction may include: the temperature is 400-750 ℃, the reaction pressure is 0.10-1.0 MPa, the weight ratio of the catalyst to the raw material is 1-100, and the weight ratio of the steam to the raw material is 0.02-1.0; the catalytic cracking reactor may be a riser reactor and/or a fluidized bed reactor. Other reaction conditions and reactors may be employed as desired by those skilled in the art and are not described in detail herein.
The catalyst fine powder separation apparatus according to the present invention is well known to those skilled in the art, and may be, for example, at least one selected from the group consisting of a settling separation apparatus, a filtering separation apparatus, an electrostatic separation apparatus and a centrifugal separation apparatus, preferably a filtering separation apparatus.
According to the present invention, the clarified and separated oil is low in solid particles and can be further processed, for example, as shown in fig. 2, the method further comprises: cutting the clarified and separated oil obtained in the step b in a fractionating tower to obtain a diesel fraction and an oil slurry fraction; wherein the cutting point of the cutting is 340-380 ℃. The diesel oil fraction and the oil slurry fraction obtained by cutting can be further subjected to subsequent treatment so as to improve the fraction utilization rate.
According to the present invention, the catalytically cracked slurry oil is the product with the highest carbon content and highest distillation range in the catalytically cracked product, for example, the initial distillation point of the catalytic cracking slurry oil may be greater than 290 ℃, preferably greater than 300 ℃, and more preferably greater than 330 ℃. The catalytic cracking diesel oil is a product with a distillation range between gasoline and slurry oil, for example, the distillation range of the catalytic cracking diesel oil can be 180-380 ℃, preferably 190-380 ℃, and further preferably 250-370 ℃. In the invention, the gasoline distillation range is distilled by adopting an ASTM D86 standard, and high boiling point fractions such as diesel oil, slurry oil and the like are distilled by adopting an ASTM D1160 standard.
According to the invention, after the catalytic cracking diesel oil is mixed with the catalytic cracking oil slurry, the viscosity of the oil slurry can be reduced, so that the oil slurry is suitable for catalytic cracking, for example, the viscosity of the mixed distillate oil at 80 ℃ can be not higher than 60 mm2Second, excelPreferably not higher than 50 mm2Second, further preferably not higher than 40 mm2Second, and more preferably not higher than 30 mm2In seconds.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto.
The trade designations of the hydrogenation protective agent, the hydrogenation demetallizing agent, the hydrogenation refining agent and the hydrogenation modifying agent adopted in the examples and the comparative examples are RG-10B, RDM-2, RN-32V and RIC-1 respectively, which are all produced by Changling catalyst factories of China petrochemical catalyst division.
The commercial designations of the catalytic cracking catalysts used in the examples and comparative examples, CGP-1 and ASC-4, were produced by Changling catalyst works, China petrochemical catalyst division.
In the embodiment and the comparative example of the invention, the cutting point of the gasoline and the light cycle oil is 201 ℃, and the cutting point of the light cycle oil and the slurry oil is 365 ℃.
Example 1
As shown in figure 1, catalytic cracking slurry A and catalytic cracking diesel B are mixed according to the weight ratio of 1: 1 are mixed in a mixing tank to obtain mixed distillate C. And (3) separating the catalyst fine powder in the mixed distillate oil C by adopting a suction filtration method, wherein the aperture of the filter membrane is 0.22 micron, and the vacuum degree is 0.085 MPa. The properties of the catalytic cracking slurry A, the catalytic cracking diesel oil B and the mixed distillate C are shown in Table 1, the catalytic cracking slurry A and the catalytic cracking diesel oil B are obtained from Yanshan, a petrochemical company in China, and the flow change trend of a filter membrane in the separation process is shown in figure 3.
Comparative example 1
The process is essentially the same as in example 1, except that: the oil slurry is separated separately, and the flow change trend of the filter membrane in the separation process is shown in figure 3.
It can be seen from fig. 3 that the method of example 1 according to the invention still maintains a very high flow rate with increasing filtration time, whereas the method of comparative example 1 starts to experience a flow rate drop over 3 minutes, especially more rapidly after a filtration time of more than 10 minutes, indicating that the method according to the invention can increase the operating cycle of the filtration plant.
Example 2
As shown in fig. 1, according to the process of the present invention, a medium sized catalytic cracking unit having the properties shown in table 4 was prepared by mixing a diesel oil J and a slurry oil K produced by itself in a weight ratio of 1: 1.29 and then carrying out sedimentation separation to obtain a sedimentation mixed distillate oil M, wherein the properties of the sedimentation mixed distillate oil M are shown in a table 4, and the sedimentation separation conditions and results are shown in a table 5.
Comparative example 2
The same separation method as in example 2 was used, except that: the slurry oil is separated separately.
As can be seen from Table 5, in example 1, the slurry solids content after settling separation was reduced by 23. mu.g/g from 71. mu.g/g to 67.6 wt.% compared to comparative example 2 when the slurry was treated by the method of the present invention.
Example 3
Sending the settled mixed distillate oil M in the example 2 into a hydrogenation device to contact with a hydrofining catalyst, performing hydrofining treatment, and returning to a medium-sized catalytic cracking device to be mixed with catalytic cracking raw oil B shown in the table 2 according to the weight ratio of 1: 2.28 mix as catalytic cracking feed, catalytic cracking catalyst with a brand of ASC-4, specific properties and composition are shown in Table 3, and specific operating conditions and product distribution are shown in Table 6.
Comparative example 3
Basically the same as the comparative example 3, except that the catalytic cracking raw oil B was subjected to catalytic cracking reaction alone, the specific operating conditions and product distribution are shown in Table 6.
As can be seen from Table 6, although the catalytically cracked feedstock B has high density and high carbon residue, compared with the feedstock alone, the gasoline yield in the product by the method of the present invention is 62.90%, and the total liquid yield (liquefied gas yield + gasoline yield + diesel oil yield, referred to as total liquid yield for short) is 86.95%.
TABLE 1
| Distillate numbering | Oil slurry A | Diesel oil B | Mixed distillate C |
| Density (20 ℃ C.)/(kg. m)-3) | 1059.8 | 957.2 | 1008.5 |
| Particulate matter content/(g.l)-1) | 5.3 | 0.0 | 2.5 |
| Viscosity (80 ℃ C.)/(mm)2Second of-1) | 77.96 | 1.23 | 39.6 |
| Distillation range/. degree.C | |||
| IBP | 304.9 | 185.9 | / |
| 5% by weight | 316.8 | 232.6 | / |
| 10% by weight | 386.8 | 240.3 | / |
| 30% by weight | 432.9 | 262.4 | / |
| 95% by weight | / | 366.9 | / |
| FBP | / | 377.2 | / |
TABLE 2
| Catalytic cracking raw oil numbering | B |
| Density (20 ℃ C.)/(kg. m)-3) | 952.8 |
| Carbon residue value/weight% | 13.2 |
| Freezing point/. degree.C | 42 |
| Viscosity (80 ℃ C.)/(mm)2·s-1) | 784 |
| Metal content/(microgram. g)-1) | |
| |
30 |
| Ni | 44 |
| V | 0.6 |
| The mass composition of the elements per weight% | |
| H | 11.86 |
| S | 0.51 |
| N | 0.62 |
| Mass composition of hydrocarbons/weight% | |
| Saturated hydrocarbons | 24.3 |
| Aromatic hydrocarbons | 35.2 |
| Glue | 40.1 |
| Asphaltenes | 0.4 |
| Distillation range/. degree.C | |
| IBP | >440 |
| 5% by weight | / |
| 10% by weight | / |
| 30% by weight | / |
| FBP | / |
TABLE 3
| Catalyst brand | ASC-4 |
| Chemical composition/weight% | |
| Al2O3 | 53.0 |
| Na2O | 0.21 |
| SiO2 | 37.1 |
| P2O5 | 0.352 |
| SO3 | 0.173 |
| K2O | 0.367 |
| TiO2 | 0.164 |
| Physical Properties | |
| Total specific surface area/(meter)2G-1) | 92 |
| Specific surface area of matrix/(meter)2G-1) | 44 |
| Specific surface area of micropores/(meter)2G-1) | 48 |
| Total pore volume/(ml. g)-1) | 0.148 |
| Micropore volume/(ml. g)-1) | 0.029 |
| Sieving mass composition/% | |
| 0 to 20 |
0 |
| 0 to 40 μm | 10.2 |
| 0 to 80 μm | 69.7 |
| 0 to 105 μm | 86.3 |
| 0 to 149 μm | 98.5 |
TABLE 4
| Distillate numbering | Diesel oil J | Oil slurry K | Settling mixed distillate oil M |
| Density/(kg. meter)-3) | 928.3 | 980.2 | 957.6 |
| Solid content/(g.l)-1) | 0 | 6.1 | 4.0 |
| Viscosity (80 ℃ C.)/(mm)2Second) | 1.21 | 25.4 | 16.1 |
| Hydrogen content/weight% | 11.01 | 10.42 | 10.68 |
| Distillation range/. degree.C | |||
| IBP | 223 | 345 | 222 |
| 5% by weight | 234 | 379 | / |
| 10% by weight | 239 | 382 | 244 |
| 30% by weight | 253 | 399 | 300 |
| 50% by weight | 274 | 421 | 358 |
| 70% by weight | 299 | 441 | 414 |
| 90% by weight | 325 | 482 | 469 |
| FBP | 339 | / | / |
TABLE 5
| Examples | Example 2 | Comparative example 2 |
| Settling time/hour | 24 | 24 |
| Sedimentation temperature/. degree.C | 85 | 85 |
| The content of solid particles in the settled oil slurry is/(microgram-gram)-1) | 23 | 71 |
TABLE 6
Based on fresh feed oil.
Claims (12)
1. A process for treating a catalytically cracked slurry oil, the process comprising:
a. mixing the catalytic cracking oil slurry with catalytic cracking diesel oil to obtain mixed distillate oil; wherein the mixing weight ratio of the catalytic cracking slurry oil to the catalytic cracking diesel oil is 1: (0.2-10); the viscosity of the mixed distillate oil at 80 ℃ is not higher than 60 mm2A/second;
b. separating the obtained mixed distillate oil by adopting catalyst fine powder separation equipment to obtain clarified and separated oil and oil sludge;
carrying out hydrofining treatment on the clarified separated oil obtained in the step b to obtain a hydrofined product;
mixing the obtained hydrofined product with catalytic cracking raw oil, contacting with a catalytic cracking catalyst in a catalytic cracking reactor, and carrying out catalytic cracking reaction.
2. The method of claim 1, further comprising: b, sending the oil sludge obtained in the step b into a catalytic cracking reactor, mixing the oil sludge with a regenerated catalytic cracking catalyst, and carrying out catalytic cracking reaction on the oil sludge and the catalytic cracking raw oil; and/or
And (4) sending the obtained oil sludge into a catalytic cracking regenerator for regeneration.
3. The method of claim 1, further comprising: and c, washing the oil sludge obtained in the step b by adopting catalytic cracking diesel oil to obtain clarified washing oil and catalyst fine powder, wherein the washing weight ratio of the oil sludge to the catalytic cracking diesel oil is 1: (0.1-6).
4. The method of claim 3, further comprising: and drying the catalyst fine powder.
5. The method of claim 3, further comprising: subjecting the resulting at least partially clarified wash oil to said wash treatment as catalytically cracked diesel and/or mixing with said catalytically cracked slurry oil in step a.
6. The method of claim 5, wherein,the conditions of the hydrofining treatment comprise: the temperature is 250 ℃ and 500 ℃, the hydrogen partial pressure is 2-30 MPa, and the volume space velocity is 0.1-30 hours-1。
7. The method according to claim 1 or 2, wherein the catalytically cracked feedstock oil is at least one selected from the group consisting of atmospheric residue, vacuum residue, coker gas oil, deasphalted oil and hydrotreated residue;
the catalytic cracking catalyst comprises a molecular sieve, a carrier and a binder;
the conditions of the catalytic cracking reaction include: the temperature is 400-750 ℃, the reaction pressure is 0.10-1.0 MPa, the weight ratio of the catalyst to the raw material is 1-100, and the weight ratio of the steam to the raw material is 0.02-1.0;
the catalytic cracking reactor is a riser reactor and/or a fluidized bed reactor.
8. The process according to claim 1, wherein the catalyst fine powder separation device in step b is at least one selected from the group consisting of a settling separation device, a filtering separation device, an electrostatic separation device and a centrifugal separation device.
9. The method of claim 1, further comprising: cutting the clarified and separated oil obtained in the step b in a fractionating tower to obtain a diesel fraction and an oil slurry fraction; wherein the cutting point of the cutting is 340-380 ℃.
10. The process of claim 1 wherein the initial boiling point of the catalytic cracking slurry oil is greater than 290 ℃.
11. The process as claimed in claim 1, wherein the catalytic cracking diesel distillation range is 180-380 ℃.
12. The process of claim 1, wherein the mixed distillate has a viscosity of not greater than 50 mm at 80 ℃2In seconds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1262306A (en) * | 1999-01-28 | 2000-08-09 | 中国石油化工集团公司 | Hydrogenation and catalystic cracking combined process for residual oil |
| CN102732312A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
| CN102732313A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1262306A (en) * | 1999-01-28 | 2000-08-09 | 中国石油化工集团公司 | Hydrogenation and catalystic cracking combined process for residual oil |
| CN102732312A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
| CN102732313A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
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