CN113897220A - High aromatic hydrocarbon oil and preparation method and application thereof - Google Patents
High aromatic hydrocarbon oil and preparation method and application thereof Download PDFInfo
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- CN113897220A CN113897220A CN202111122400.6A CN202111122400A CN113897220A CN 113897220 A CN113897220 A CN 113897220A CN 202111122400 A CN202111122400 A CN 202111122400A CN 113897220 A CN113897220 A CN 113897220A
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention relates to a high aromatic hydrocarbon oil material, a preparation method and application thereof. The method comprises the following steps: (1) carrying out catalytic cracking/cracking reaction on FCC raw oil with the weight percent of less than or equal to 99 percent to generate oil gas; (2) introducing the oil gas below a washing and de-superheating section of a fractionating tower, and carrying out countercurrent contact on the oil gas and residual FCC raw oil with the weight percent of more than or equal to 1% so as to elute catalyst powder; (3) the eluted oil gas rises along the fractionating tower, enters a rectifying tower plate section and is in countercurrent contact with reflux; (4) withdrawing from the side stream a high aromatic oil comprising an ash content of <20 μ g/g; and (5) carrying out catalytic cracking/cracking reaction on the washing raw oil containing catalyst powder and the FCC raw oil in the step (1) to generate oil gas; (6) and (5) repeating the steps (2) to (5) to form a cycle. Wherein the catalytic cracking/cracking catalyst comprises a macroporous in-situ crystallization catalytic cracking catalyst, and more than or equal to 97 wt% of the oil gas enters the high aromatic oil material extraction plate. The method has simple process, less equipment investment and greatly reduced operation cost.
Description
Technical Field
The invention relates to the field of petroleum refining, in particular to a high aromatic hydrocarbon oil prepared by catalytic cracking/cracking, and a preparation method and application thereof.
Technical Field
Catalytic cracking/cracking is one of the most important upgrading processes and a major source of profit for the oil refining industry. The main products are divided into gasoline, diesel oil, liquefied gas, dry gas and oil slurry through a fractionating tower and an absorption stabilizing system. The early catalytic cracking of wax oil has light raw material and low oil slurry yield, and the oil slurry is basically used for recycling without producing oil slurry products. The current catalytic cracking/cracking unit basically adopts heavy raw materials, wherein the yield of slurry oil is high, the coke yield of the system is high due to full recycle or most of the recycle, the activity of the catalyst is reduced, the product distribution is poor, and a regeneration system is difficult to bear and only can be thrown outwards. The thrown-out slurry oil contains a large amount of solids (2-6g/L) such as catalyst powder. If the solid matters such as catalyst powder and the like are removed, the high aromatic oil material can be used as a raw material for producing carbonaceous materials such as needle coke, carbon fiber and carbon black, fine chemical products such as rubber softeners and fillers, petroleum aromatic plasticizers, heat transfer oil, petroleum sulfonate surfactants and the like, and fuel oil blending components. The solid content is shown in Table 1 (Chenjun Wu et al, eds. "catalytic cracking Process and engineering (third edition), 2015: 679, Beijing: China petrochemical Press). Can only be treated or sold as low value coking feedstock and low grade fuel oil without solidifying. If a catalytic slurry oil de-solidification purification unit is additionally built, such as sedimentation, filtration, extraction, distillation, centrifugation, electrostatic separation and the like, the investment and operation cost is high, the effect is not ideal, and new dangerous waste, namely oil stains or oil with waste catalytic cracking/cracking catalyst powder is generated. Chenjunwu et al concluded that: for the purification of catalytic cracking slurry oil, the settling separation method can remove solid impurities of the slurry oil, but the efficiency is about 80 percent at most, and the settling time is longer; the electrostatic separation method has higher separation efficiency, but the property of the oil slurry and the operation condition have great influence on the separation effect; the distillation method can completely remove impurities, but the yield of clear liquid is low, the operation period of the device is influenced by the fact that oil slurry coking is accelerated due to overhigh distillation temperature, and meanwhile, a residue utilization approach is still to be developed; the filtering separation method can remove more than 95% of solid impurities in the oil slurry, and the yield reaches more than 82%, but the investment is high, and the operation is complex. "(" catalytic cracking process and engineering (third edition), 2015: 680-
TABLE 1 solid content requirement for oil slurries for different petrochemical products
| Product(s) | Solid content/. mu.g/g |
| Carbon black or rubber filler | <500 |
| Needle coke | <100 |
| Carbon fiber | <20 |
| Hydrotreating (cracking) feedstock | <20 |
| Fuel oil blending component | <200 |
CN100549141C discloses a raw material pretreatment method for producing needle coke: raw oil is subjected to reduced pressure distillation to remove non-ideal components, ideal components are contacted with hydrogen and a hydrogenation catalyst, and hydrogenation material flow is separated to obtain a raw material for producing needle coke. When the feedstock oil is a catalytically cracked slurry oil or a clarified oil, it is necessary to filter the slurry oil to remove catalyst fines and thereby reduce ash content. In the examples, the catalytically clarified oil was distilled under reduced pressure at 400 ℃ under 20mmHg to yield 82.5% by weight.
Ding Yi Wen reported the application of "slurry pressure-reducing topping device to the production of needle coke raw material". The vacuum column overhead was 61.5% by weight at 2.5 to 3.5kPa at 390 ℃ and 420 ℃. Only the vacuum tower middle distillate is used as a precursor raw material for producing the needle coke. Not only is a vacuum tower added, but also the bottom slurry is still difficult to process. ("China petrochemical 2016. catalytic cracking technology and meeting talking book of China" pages 50-54)
Linmin reports the application of oil slurry vacuum topping technology in catalytic cracking unit, and oil slurry at 320 deg.c is fed directly into vacuum tower with two-stage steam jet pump to distill off only 30 wt%. (chemical engineering management 2014(11) 229-
CN112725031A discloses an "oil material suitable for producing needle coke and its preparation method and system", fractionating catalytic cracking slurry oil or catalytic cracking clarified oil or other raw materials in a distillation tower to obtain crude wax oil and bottom oil, then performing steam stripping, hydrogenation, polycondensation and other processes for four times to obtain needle coke raw material, and the equipment investment and operation cost are very high.
The effective technical improvement of the early wax oil catalytic cracking is reported by Zhoushijun, wherein raw materials are directly fed into the bottom of a fractionating tower, mixed with oil slurry for heat exchange and then directly fed into a riser reactor. ("Beijing Economy", 1990(3), 14-15).
CN106924984B discloses a method for controlling the liquid level at the bottom of a fractionating tower and the reaction severity. The catalytic cracking raw oil medium is introduced into the side wall of the fractionating tower near the vertical height of the herringbone plate at the bottom of the fractionating tower, so that the problem of liquid level fluctuation at the bottom of the fractionating tower after the severity of catalytic cracking reaction changes is solved, and the coking at the bottom of the fractionating tower is controlled. But still a large amount of catalytic slurry with a large amount of catalyst fines is produced. In fact, as described in the technical questions of catalytic cracking units published as early as 1993 (Ma Bernoulli eds., pp. 161-162), "when the liquid level (at the bottom of the fractionation column) has fallen too low to be adjusted, … … can temporarily supplement the feed oil (or reactor feed) directly to the bottom of the column to maintain the liquid level". Because the liquid level at the bottom of the fractionating tower is reduced due to the increase of the reaction severity, the control of the liquid level at the bottom of the fractionating tower and the reaction severity are the same thing. Therefore, the technique disclosed in CN106924984B has been known in practice.
CN112574777A discloses a process technology and a method for stopping oil slurry products from a catalytic cracking and cracking device. Wherein, the reaction conditions of catalytic cracking and cracking are changed to improve the depth of the cracking reaction and realize the one-way deep conversion of the reaction, so that the adjusted reaction product has no components of oil slurry, and the raw oil, residual oil or heavy oil components in the raw oil are connected in series to the bottom of the fractionating tower through a fractionating accident bypass line or an oil slurry lower return line to replace the components of the oil slurry, so as to keep the normal circulation of the oil slurry, and then the raw material connected in series to the bottom of the tower and the washed catalyst dust are returned to the reaction regeneration system to be mixed with the raw oil for recycling. However, CN112574777A does not mention how to increase the reaction depth, and further does not mention specific implementation details and implementation methods. Even if the scheme is feasible, the method is only suitable for deep single-pass cracking which does not generate large molecular components of slurry oil, and no method for improving the reaction depth for achieving the purpose is disclosed at present.
With current heavy feed catalytic cracking/splitting units and processes, slurry components with large amounts of catalyst fines are produced without exception. Therefore, there is a need for a novel, simple and efficient method for converting catalytic slurry oils into high value added high aromatic oil stocks in high yield. In addition, increasing the yield of high value liquid products such as liquefied gas, gasoline, and diesel oil from catalytic cracking/cracking units and decreasing the yield of low value products such as coke and dry gas are the growing points for demand and benefits of oil refineries.
Disclosure of Invention
The present invention is directed to addressing the above-mentioned and other deficiencies of the prior art, and more particularly, to a highly aromatic hydrocarbon oil, a method for making the same and applications thereof with low investment and low operating cost, and to provide more high value products of liquefied gas, gasoline and diesel.
In order to achieve the above objects, one aspect of the present invention provides a method for preparing a highly aromatic oil, the method comprising:
(1) based on 100 wt% of catalytic cracking/cracking raw oil, sending the catalytic cracking/cracking raw oil with the weight not more than 99 wt% into a catalytic cracking/cracking reactor containing a catalyst to perform catalytic cracking/cracking reaction to generate oil gas;
(2) introducing the oil gas below a washing de-superheating section of a catalytic cracking/cracking fractionating tower, and carrying out countercurrent contact on the oil gas and residual catalytic cracking/cracking raw oil with the weight being more than or equal to 1% in the washing de-superheating section so as to elute catalyst powder in the oil gas;
(3) the oil gas after the eluted catalyst powder leaving the washing and de-superheating section rises along the catalytic cracking/cracking fractionating tower, enters a rectifying tower plate section of the fractionating tower and is in countercurrent contact with a reflux liquid from the upper part of the fractionating tower;
(4) extracting liquid oil from a side line of a rectifying tower plate section adjacent to the washing and de-superheating section to prepare the high aromatic hydrocarbon oil, wherein the high aromatic hydrocarbon oil contains ash content of less than 20 mug/g; and
(5) feeding the washing raw oil containing catalyst powder extracted from the bottom of the fractionating tower and the catalytic cracking/cracking raw oil in the step (1) into a catalytic cracking/cracking reactor together for catalytic cracking/cracking reaction to generate oil gas;
(6) and (5) repeating the steps (2) to (5) to form a cycle.
Wherein the catalytic cracking/cracking catalyst comprises a macroporous in-situ crystallization catalytic cracking catalyst, and more than or equal to 97 wt% of the oil gas enters the extraction plate of the high aromatic hydrocarbon oil; preferably, the proportion of the macroporous in-situ crystallization catalytic cracking catalyst in the total amount of the catalyst is 1-100 wt%, and more than or equal to 99 wt% of the oil gas enters the high aromatic oil material extraction plate.
In one embodiment of the present invention, after the catalytic cracking/cracking reaction in step (1) and step (5), the catalyst enters a regenerator for regeneration and then returns to the catalytic cracking/cracking reactor.
In one embodiment of the present invention, the more than or equal to 1 wt% of the remaining catalytically cracked/cracked feedstock oil is preferably selected from the group consisting of one or more of straight-run atmospheric residue, straight-run vacuum residue, hydrogenated atmospheric residue, hydrogenated vacuum residue, deasphalted oil, and heavy crude oil.
In one embodiment of the invention, the residual catalytically cracked/cracked feedstock oil with weight percent of more than or equal to 1 percent is introduced into the catalytic cracking/cracking fractionating tower above, below or both the washing de-superheating section.
In one embodiment of the invention, a part of the washed raw oil containing the eluted catalyst powder in the step (2) is cooled by heat exchange and then circulated back to the upper part or the upper part and the lower part of the washing de-superheating section, wherein the washed raw oil circulated back to the upper part of the washing de-superheating section is in countercurrent contact with the oil gas to elute the catalyst powder in the oil gas; the washing raw oil which is circulated back to the lower part of the washing de-superheating section cools the washing raw oil positioned at the bottom of the tower; feeding the other part of the washing raw oil and the catalytic cracking/cracking raw oil in the step (1) into a catalytic cracking/cracking reactor containing a catalyst together to perform catalytic cracking/cracking reaction;
in one embodiment of the invention, in the catalytic cracking/cracking separation tower, the washing desuperheating section comprises 6-20 layers of herringbone baffles or regular grid packing; the rectification tray section comprises 26-50 trays and has 1-4 pumparounds in the rectification tray section.
In one embodiment of the present invention, in the catalytic cracking/cracking fractionating tower, high aromatic hydrocarbon oil and diesel oil are sequentially extracted from bottom to top, and are separated by a subsequent gas-liquid separator and an absorption stabilization system to obtain gasoline, liquefied gas and dry gas.
In one embodiment of the present invention, the diesel oil is divided into light diesel oil and heavy diesel oil, and the heavy diesel oil and the light diesel oil are sequentially extracted from bottom to top in the catalytic cracking/cracking fractionating tower, wherein the heavy diesel oil is recycled to the catalytic cracking/cracking reactor containing the catalyst to perform the catalytic cracking/cracking reaction, or is output as a product.
In one embodiment of the present invention, the catalytic cracking/cracking raw oil is selected from one or more of straight-run wax oil, straight-run atmospheric residue, straight-run vacuum residue, hydrogenated wax oil, hydrogenated atmospheric residue, hydrogenated vacuum residue, coker wax oil, coker hydrogenated wax oil, deasphalted oil, shale oil, tar sand oil, heavy crude oil, low grade diesel oil, animal oil, vegetable oil, and synthetic oil.
In one embodiment of the present invention, the catalytic cracking/cracking reactor is any of the current catalytic cracking/cracking reactor types, including coaxial or high-low parallel riser reactors, MIP, MIP-CGP, MIP-LTG, MIP-DCR, FDFCC, DCC, CPP, HCC, MGG, MGD, TSRFCC, HSCC, IHCC, and the like.
In one embodiment of the invention, the catalyst is selected from one or more of macroporous in-situ crystallization catalytic cracking catalyst, bonding Y, ZSM-5, beta molecular sieve and composite catalyst thereof, in-situ crystallization Y-type catalyst, propylene auxiliary agent, octane auxiliary agent, sulfur reduction catalyst, nitrogen reduction catalyst and heavy metal resistant catalyst.
In one embodiment of the invention, the reaction temperature of the catalytic cracking/cracking reaction is 480-650 ℃, the pressure is 0.1-0.5 Mpa, the regeneration temperature of the catalyst is 650-780 ℃, and the mass ratio of the catalyst to the catalytic cracking/cracking raw oil is 4-15.
In one embodiment of the invention, the high aromatic oil comprises at least 45 wt% total aromatics, asphaltenes<1% by weight, sulfur content<0.5 wt% and a density (20 ℃) of not less than 1.03g/cm3And ash content<20μg/g。
In another aspect, the invention provides a high aromatic oil comprising an ash of <20 μ g/g.
In one embodiment of the invention, the invention provides a high aromatic oil comprising at least 45 wt% total aromatics, asphaltenes<1% by weight, sulfur content<0.5 wt% and a density (20 ℃) of not less than 1.03g/cm3And ash content<20μg/g。
In still another aspect, the present invention provides the use of the highly aromatic oil for the preparation of needle coke, carbon fiber, carbon black, rubber softeners and fillers, petroleum aromatic plasticizers, heat transfer oil, petroleum sulfonate surfactants, blend fuel oils, and hydrotreated (cracked) feedstocks.
Compared with the prior art, the invention has the obvious advantages that:
1. in the invention, the catalytic cracking/cracking reaction oil gas and the circulating washing raw oil extracted from the bottom of the fractionating tower and/or part of the catalytic cracking/cracking raw oil are in countercurrent contact at the washing superheating-removing section at the bottom of the tower, the catalyst powder in the reaction oil gas is eluted, and the extracted high-aromatic-hydrocarbon oil with extremely low ash content can be directly used for producing carbon materials with high added value, fine chemical products and blend fuel oil, so that the steps of filtering, vacuum distillation or solvent extraction and other catalyst powder removal steps required by the catalytic oil slurry for producing the carbon materials with high added value, the fine chemical products and the blend fuel oil are omitted, and the equipment investment and the operation cost are greatly saved.
2. The invention omits the recycle oil and the oil slurry recycle aiming at low hydrogen/carbon ratio in the prior art, greatly reduces the raw coke, improves the processing capacity of the catalytic cracking/cracking device, obviously improves the product distribution, not only improves the yield of high-benefit products of the catalytic cracking/cracking device, such as gasoline, diesel oil and liquefied gas, but also provides a large amount of short high-aromatic-hydrocarbon oil with high added value.
3. The invention selects the macroporous in-situ crystallization catalytic cracking catalyst, greatly reduces the yield of heavy distillate oil and coke, improves the product distribution and improves the aromatic hydrocarbon content of high aromatic hydrocarbon oil.
4. According to the data calculation of the embodiment of the invention, the economic benefit of the existing 100-kiloton/year catalytic cracking/cracking device can be increased by at least 2 million yuan each year when the invention is implemented.
Drawings
The invention may be better understood by describing exemplary embodiments thereof in conjunction with the accompanying drawings. In the drawings, there is shown in the drawings,
FIG. 1 is a process schematic for a process for producing a high aromatic oil feed in one embodiment of the present invention.
The numbering is as follows:
1. a catalytic cracking/cracking settler; 2. a catalytic cracking/cracking fractionator; 3. a gas-liquid separator; 4a raw wax oil; 4b, raw heavy oil; 5. a mixed raw material feed line; 6. a reaction atomizing nozzle; 7. a riser reactor; 8. lifting gas; 9. a catalyst stripping section; 10. stripping steam; 11. a reaction oil gas outlet line; 12(12a and 12b) heavy feed to a fractionation column line; 13. washing and de-superheating; 14. washing a raw oil extraction line at the bottom of the tower; 15. a fractionating tower bottom heat exchanger; 16(16a and 16b) washing the stock oil circulation line; 17. washing raw oil to enter a reactor line; 18. a fractionating tower rectifying tower plate section; 19. a high aromatic oil draw-out line; 20. a heavy diesel oil extraction line; 21. heavy diesel oil recycling line; and 22. light diesel oil extraction line.
Detailed Description
The present invention will be described more fully hereinafter with reference to exemplary embodiments thereof. These exemplary embodiments are described so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Indeed, this invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.
Furthermore, the technical features presented in the detailed description of the present application may be combined with each other to form a complete technical solution without conflict, and are within the scope of the present disclosure.
In the present invention, the manner of connection between the various systems/devices should be understood broadly, unless explicitly stated or limited otherwise. For example, the connection may be a direct pipe connection, or a pipe connection connected with a pumping device, a metering device, a valve pipe fitting, or other conventional conveying, metering, and control devices, or may be a fixed connection or a detachable connection. The specific meaning of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, the term "catalytically cracked/cracked feedstock (FCC feedstock)" means an oil refinery conventional catalytically cracked/cracked feedstock, including feedstock wax oils such as: straight-run wax oil, hydrogenated wax oil, coked hydrogenated wax oil and hydrocracking tail oil; feedstock heavy oils, such as: straight-run atmospheric residue (normal residue), straight-run vacuum residue (reduced residue), hydrogenated atmospheric residue (hydrogenated normal residue), hydrogenated vacuum residue (hydrogenated reduced residue), deasphalted oil (DAO) and heavy crude oil; also included are unconventional raw oils such as: shale oil, tar sand oil, poor diesel oil, animal oil, vegetable oil, synthetic oil, waste lubricating oil, low-value oil in oil refining and petrochemical processes, and the like.
In the present invention, the term "in-situ crystallization catalytic cracking catalyst" refers to a catalyst having catalytic cracking activity, which is prepared by spray granulating a silica-alumina material such as kaolin into microspheres, calcining at a high temperature to adjust the proportion of active silica-alumina, crystallizing the microspheres in situ inside and outside at a suitable temperature and in a suitable liquid composition to obtain a Y-type molecular sieve, and performing chemical and/or hydrothermal modification. The macroporous in-situ crystallization catalytic cracking catalyst refers to the in-situ crystallization catalytic cracking catalyst with abundant pore size distribution of 10-60 nm. More specifically, the BJH desorption specific surface area is 100m2The total pore volume of the BJH is more than 50% of the pores with the pore diameter of more than 10 nm.
In the invention, the term "high aromatic hydrocarbon oil" refers to liquid oil which is extracted by a side extraction plate when more than or equal to 97 wt% of catalytic cracking/cracking reaction oil gas enters the catalytic cracking/cracking fractionating tower and is close to a washing de-superheating section, and ash content of the liquid oil is less than 20 mug/g.
In the present invention, the term "catalyst-to-oil ratio" refers to the mass ratio of the catalyst used in the catalytic cracking reaction to the catalytic cracking/cracked stock oil.
In the present invention, the term "wash feed oil" refers to oil containing catalyst powder extracted from the bottom of a fractionation tower after oil gas from a catalytic cracking/cracking reactor is in countercurrent contact with more than or equal to 1 wt% of catalytic cracking/cracking feed oil and/or oil containing catalyst powder extracted from the bottom of the fractionation tower on the premise that more than or equal to 1 wt% of catalytic cracking/cracking feed oil is connected above and/or below a washing and superheating section of the fractionation tower in series.
In the present invention, the recycle oil withdrawal of the current catalytic cracking/cracking fractionator may be used as the withdrawal of the high aromatic hydrocarbon oil of the present invention. In a preferred embodiment, the high aromatic oil may be provided with 2-5 extraction ports on different levels of trays, and the extraction position may be adjusted according to the nature of the oil component being extracted.
The present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the drawings described herein are not to be construed as limiting the scope of the invention.
As shown in fig. 1, a mixed feedstock (FCC feed oil) including a raw wax oil and a raw heavy oil enters a riser reactor 7 through lines 4a, 4b and 5 from a reaction atomizing nozzle 6, contacts a regenerated catalytic cracking/cracking catalyst (not shown) lifted by a lift gas 8, and performs a catalytic cracking/cracking reaction to form a reaction oil gas. If the MIP reactor format is used, the riser has a corresponding expanded diameter section (not shown). The reaction oil gas is separated from the catalyst in the settler 1, and the reaction oil gas is extracted from the top of the settler 1 through a reaction oil gas outlet line 11 and introduced below a washing and de-superheating section 13 of a subsequent fractionating tower 2. Under the action of gravity, the catalytic cracking/cracking catalyst is stripped out of occluded oil gas by stripping steam 10 in a stripping section 9, and the oil gas is used as spent catalyst (not shown) and enters a regenerator for regeneration.
The heavy feedstock from heavy feedstock to fractionation tower lines 12, 12a, 12b is passed above and below the scrubbing de-superheating section 13, respectively. The washing raw oil extracted from the bottom of the fractionating tower is circulated to the upper part and the lower part of the washing de-superheating section 13 after heat exchange by a pipeline 14 and a heat exchanger 15. The raw material heavy oil and the circulating washing raw oil which enter the upper part of the washing de-superheating section 13 are in sufficient countercurrent contact with the reaction oil gas in the washing de-superheating section so as to elute the catalyst powder contained in the reaction oil gas. The raw material heavy oil and the circularly washed raw material oil which enter the lower part of the washing and de-superheating section 13 regulate the temperature of the bottom of the fractionating tower. The total amount and proportion of the raw heavy oil introduced from the heavy feedstock into the fractionation tower lines 12a, 12b, respectively, and the total amount and proportion of the recycled washed raw oil introduced through 16a, 16b may be determined according to the amount of the catalyst powder to be eluted in the reaction oil gas from the catalytic cracking reactor. If the amount of the catalyst fines to be eluted is large, the ratio of the raw heavy oil introduced from the heavy feedstock into the fractionating column line 12b to the recycled washed feedstock oil introduced into the washed feedstock oil recycling line 16b is high. This can be adjusted in real time as needed in actual operation.
After elution and desuperheating, the reaction oil gas rises into the fractionating tower rectifying tower plate section 18. While the washed feed oil containing catalyst fines is withdrawn from the bottom via a bottom washed feed oil withdrawal line 14. One part of the washing raw oil is used as circulating washing raw oil, and the other part of the washing raw oil is sent into the riser reactor 7 together with the mixed raw oil from the mixed raw oil feeding line 5 through the washing raw oil feeding line 17 to carry out catalytic cracking/cracking reaction.
In fig. 1, the reaction oil gas after the elution process rises into the fractionation tower plate section 18 and after fractionation through, for example, 1-8 rectification plates, the high aromatic oil is withdrawn from the high aromatic oil draw line 19 of the fractionation tower 2. Heavy diesel oil is withdrawn from the heavy diesel oil withdrawal line 20 of the fractionation column 2 after fractionation, for example, over 4 to 25 rectification trays. After fractionation, e.g. 4-20 trays, light diesel oil is withdrawn from the light diesel oil draw-off line 22 of the fractionation column 2. At the top of the fractionating tower 2, after the reaction oil gas is subjected to heat exchange, a gas-liquid separator 3 and cooling, gasoline, liquefied gas and dry gas (not shown) are formed. In a specific embodiment, the heavy diesel oil extracted from the heavy diesel oil extraction line 20 may be fed into the riser reactor 7 through the heavy diesel oil recycle line 21 together with the wash stock oil from the wash stock oil inlet line 17 and the mixed stock oil from the mixed stock feed line 5 to undergo the catalytic cracking/cracking reaction again. Heavy diesel oil can be extracted as a product without recycling.
In a specific embodiment of the present invention, the catalytically cracked/cracked feedstock oil entering the bottom of the fractionation tower is preferably deasphalted oil (DAO), normal residue, hydrogenated normal residue, reduced residue or hydrogenated reduced residue, more preferably reduced residue or hydrogenated reduced residue or DAO.
In a specific embodiment of the present invention, a person skilled in the art can adjust the process conditions according to conventional means and knowledge, such that more than or equal to 97 wt% of the reaction oil gas enters the high aromatic hydrocarbon oil extraction plate, and preferably more than or equal to 99 wt% of the oil gas enters the high aromatic hydrocarbon oil extraction plate. For example, by adjusting the mass and temperature of the system below the high aromatic hydrocarbon extraction plate introduced into the catalytic reaction unit and the fractionating tower, adjusting the heat extraction amount of the heat exchanger 15, adjusting the heat extraction amount of the middle-stage reflux (not shown), and the like, more than or equal to 97 wt% of the reaction oil gas enters the high aromatic hydrocarbon oil extraction plate, and preferably more than or equal to 99 wt% of the oil gas enters the high aromatic hydrocarbon oil extraction plate. Height ofThe aromatic hydrocarbon oil contains ash<20. mu.g/g. Preferably, the high aromatic oil contains at least 45 wt% total aromatics, asphaltenes<1% by weight, sulfur content<0.5 wt% and a density (20 ℃) of not less than 1.03g/cm3And ash content<20μg/g。
In the invention, the high aromatic hydrocarbon oil prepared by the method is applied to preparing needle coke, carbon fiber, carbon black, rubber softener and filler, petroleum aromatic hydrocarbon plasticizer, heat conducting oil, petroleum sulfonate surfactant, blending fuel oil and raw materials for hydrotreating (cracking).
Examples
The present invention will be described in further detail with reference to specific examples, so that the advantages of the present invention will be more apparent. It should be understood that the description is intended for purposes of illustration only and is not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
In an embodiment, the FCC feed oil:
paraffin base wax oil (VGO), vacuum residue oil (reduced slag), and atmospheric residue oil (normal slag), which are obtained from Ullin oil refinery of the extended petrochemical company;
intermediate group: VGO, slag reduction and slag removal, wherein the slag is obtained from oil refineries of Qilu petrochemical company;
import in the middle east: VGO, slag reduction, normal slag, hydrogenated atmospheric residue (hydrogenated normal slag), and hydrogenated vacuum residue (hydrogenated slag reduction) were obtained from the oil refining department of Shanghai petrochemical company.
Catalytic cracking/cracking catalysts used in the examples:
semi-synthesis catalyst: CDC, CGP-C (from Changling catalyst works), COKC (from Zhoucun catalyst works);
in-situ crystallization catalyst: FCA-100M (macroporous in situ crystallization catalytic cracking catalyst) and FCA-100S (sulfur reduction catalyst) are all obtained from Shanghai Nake auxiliary agent Co., Ltd.
Catalytic cracking catalyst: DMMC-1, available from Anqing petrochemical company.
A propylene auxiliary agent: CP-01B, obtained from Shanghai Nake auxiliary agent Co., Ltd.
Example 1
As shown in fig. 1, FCC feed oil and a catalytic cracking/cracking catalyst undergo catalytic cracking/cracking reaction in a riser reactor 7 to form reaction oil gas. The operating conditions for the catalytic cracking/splitting reaction are shown in table 2 below.
As shown in fig. 1, the reaction oil gas from the reaction unit is fed to the lower part of the washing and de-superheating section of the catalytic cracking/cracking fractionating tower 2, and the reaction oil gas is fully contacted with the FCC raw oil in the washing and de-superheating section 13 so as to elute the catalyst powder contained in the reaction oil gas. The operating conditions of the fractionation column are shown in table 2 below.
In the fractionating tower, high aromatic hydrocarbon oil, heavy diesel oil (as required) and light diesel oil are sequentially extracted from bottom to top, and are separated by a subsequent gas-liquid separator and an absorption stabilizing system to obtain gasoline, liquefied gas and dry gas. The product distribution of example 1 can be seen in table 2 below. Also, the properties of the high aromatic oil produced in example 1 are shown in table 2 below.
Examples 2 to 4
The preparation of the high aromatic oil was carried out in analogy to the procedure described in example 1, following the conditions described in table 2. The product distribution for examples 2-4 can be seen in Table 2 below. Also, the properties of the high aromatic oil stocks produced in examples 2-4 are shown in table 2 below.
TABLE 2
Comparative examples 1 to 3
The catalytic cracking/cracking reaction and subsequent fractionation were carried out in a similar manner to example 1, following the conditions described in table 3 below. The difference lies in that: comparative examples 1-2 recycle oil refining and external throwing slurry; comparative example 3 high aromatic oil is extracted and heavy diesel oil is recycled, but a macroporous in-situ crystallization catalyst is not selected.
The product distribution of comparative examples 1-3 can be seen in table 3 below. Also, the properties of the slurry prepared in comparative examples 1-2 and the properties of the high aromatic oil prepared in comparative example 3 are shown in table 3 below.
Comparative example 4
The catalytic cracking/cracking reaction and the subsequent fractionation were carried out in a similar manner to example 1, according to the technical scheme of CN112574777A and the conditions described in table 3 below. The difference lies in that: comparative example 4a recycle oil and slurry oil recycle were carried out.
The product distribution of comparative example 4 can be seen in table 3 below.
TABLE 3
Example 5
The preparation of the high aromatic oil was carried out in analogy to the procedure described in example 1, following the conditions described in table 4. The product distribution of example 5 can be seen in table 4 below. Also, the properties of the high aromatic oil produced in example 5 are shown in table 4 below.
Comparative example 5
The catalytic cracking/cracking reaction and subsequent fractionation were carried out in a similar manner to example 1, following the conditions described in table 4 below. The difference lies in that: comparative example 5 recycle oil and external throwing slurry, no feed oil was fed in series to the bottom of the fractionation column.
The product distribution of comparative example 5 can be seen in table 4 below. Also, the properties of the slurry prepared in comparative example 5 are shown in table 4 below.
Comparative example 6
According to the method of CN100549141C example, the paraffin-based catalytic slurry oil is distilled under reduced pressure at 400 ℃ and 20mmHg on a continuous distillation device, and the distillate accounts for 75 wt%.
TABLE 4
Application example 1
Comparing table 2, table 4 and table 5 above, it can be seen that the high aromatic oil of the present invention meets the requirements for feedstock for needle coke production.
TABLE 5 needle coke requirements for feedstock Properties
| Properties of | Index (I) |
| Density (20 ℃ C.)/g/cm3 | ≥1.03 |
| Sulfur content/weight% | ≤0.5 |
| Asphaltenes/weight% | <1.0 |
| Aromatic fraction (aromatic content)/weight% | ≥45 |
| Ash content/microgram/g | <100 |
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A method of producing a highly aromatic oil, the method comprising:
(1) based on 100 wt% of catalytic cracking/cracking raw oil, sending the catalytic cracking/cracking raw oil with the weight not more than 99 wt% into a catalytic cracking/cracking reactor containing a catalyst to perform catalytic cracking/cracking reaction to generate oil gas;
(2) introducing the oil gas below a washing de-superheating section of a catalytic cracking/cracking fractionating tower, and carrying out countercurrent contact on the oil gas and residual catalytic cracking/cracking raw oil with the weight being more than or equal to 1% in the washing de-superheating section so as to elute catalyst powder in the oil gas;
(3) the oil gas after the eluted catalyst powder leaving the washing and de-superheating section rises along the catalytic cracking/cracking fractionating tower, enters a rectifying tower plate section of the fractionating tower and is in countercurrent contact with a reflux liquid from the upper part of the fractionating tower;
(4) extracting liquid oil from a side line of a rectifying tower plate section adjacent to the washing and de-superheating section to prepare the high aromatic hydrocarbon oil, wherein the high aromatic hydrocarbon oil contains ash content of less than 20 mug/g;
(5) feeding the washing raw oil containing catalyst powder extracted from the bottom of the fractionating tower and the catalytic cracking/cracking raw oil in the step (1) into a catalytic cracking/cracking reactor together for catalytic cracking/cracking reaction to generate oil gas; and
(6) repeating the steps (2) to (5) to form a cycle;
wherein the catalytic cracking/cracking catalyst comprises a macroporous in-situ crystallization catalytic cracking catalyst, and more than or equal to 97 wt% of the oil gas enters the extraction plate of the high aromatic hydrocarbon oil.
2. The method of claim 1, wherein the proportion of the macroporous in-situ crystallization catalytic cracking catalyst to the total catalyst amount is 1-100 wt%, and more than or equal to 99 wt% of the oil gas enters the high aromatic oil extraction plate.
3. The process of any of claims 1 and 2, wherein the ≥ 1 wt% of the remaining catalytically cracked/cracked feedstock oil is selected from the group consisting of straight-run atmospheric residuum, straight-run vacuum residuum, hydrogenated atmospheric residuum, hydrogenated vacuum residuum, deasphalted oil, heavy crude oil, and is introduced into the catalytic cracking/cracking fractionator above, below, or both of the washed desuperheating section.
4. The method according to claim 1, characterized in that, in the step (2), a part of the washing raw oil containing the eluted catalyst powder is cooled by heat exchange and then circulated back to the upper part or the upper part and the lower part of the washing desuperheating section; and (2) feeding the other part of the washing raw oil and the catalytic cracking/cracking raw oil in the step (1) into a catalytic cracking/cracking reactor containing a catalyst together to perform catalytic cracking/cracking reaction.
5. The method of claim 1, wherein in the catalytic cracking/cracking fractionating tower, the washing desuperheating section comprises 6-20 layers of herringbone baffles or regular grid packing; the rectifying tower plate section comprises 26-50 layers of tower plates and 1-4 circulating refluxes in the rectifying tower plate section; in the catalytic cracking/cracking fractionating tower, high aromatic hydrocarbon oil and diesel oil are sequentially pumped out from bottom to top, and are separated by a subsequent gas-liquid separator and an absorption stabilizing system to obtain gasoline, liquefied gas and dry gas.
6. The method of claim 5, wherein the diesel is separated into light diesel and heavy diesel, and the heavy diesel and the light diesel are sequentially extracted from the bottom to the top in the catalytic cracking/cracking fractionating tower, wherein the heavy diesel is recycled to the catalytic cracking/cracking reactor containing the catalyst to perform the catalytic cracking/cracking reaction, or is output as a product.
7. The process of claim 1, wherein the catalytically cracked/cracked feedstock oil is selected from the group consisting of straight run wax oil, straight run atmospheric resid, straight run vacuum resid, hydrogenated wax oil, hydrogenated atmospheric resid, hydrogenated vacuum resid, coker wax oil, coker hydrogenated wax oil, deasphalted oil, shale oil, tar sand oil, heavy crude oil, low grade diesel oil, animal oil, vegetable oil, synthetic oil; the catalytic cracking/cracking reactor comprises a coaxial type or a high-low parallel type; or
The catalyst is selected from one or more of a macroporous in-situ crystallization catalytic cracking catalyst, a bonding Y, ZSM-5, a beta molecular sieve and a composite catalyst thereof, an in-situ crystallization Y-type catalyst, a propylene auxiliary agent, an octane number auxiliary agent, a sulfur reduction catalyst, a nitrogen reduction catalyst and a heavy metal resistant catalyst; or
The reaction temperature of the catalytic cracking/cracking reaction is 480-650 ℃, the pressure is 0.1-0.5 Mpa, the regeneration temperature of the catalyst is 650-780 ℃, and the mass ratio of the catalyst to the catalytic cracking/cracking raw oil is 4-15.
8. The method of claim 1, wherein the high aromatic oil comprises at least 45 wt% total aromatics, asphaltenes <1 wt%, sulfur <0.5 wt%, density
(20℃)≥1.03g/cm3And ash content<20μg/g。
9. A high aromatic hydrocarbon oil produced by the process of any one of claims 1 to 8, comprising ash<20 mu g/g; or the high aromatic oil contains at least 45 wt% total aromatics, asphaltenes<1% by weight, sulfur content<0.5 wt% and a density (20 ℃) of not less than 1.03g/cm3And ash content<20μg/g。
10. Use of the highly aromatic hydrocarbon oil of claim 9 for the preparation of needle coke, carbon fiber, carbon black, rubber softeners and fillers, petroleum aromatics plasticizers, thermal oils, petroleum sulfonate surfactants, blend fuel oils, hydrotreated (cracked) feedstocks.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023046081A1 (en) * | 2021-09-24 | 2023-03-30 | 上海纳科助剂有限公司 | High aromatic oil, and preparation method therefor and use thereof |
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