CN111100709A - Method for producing high-value chemical products by adopting inferior LCO - Google Patents
Method for producing high-value chemical products by adopting inferior LCO Download PDFInfo
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- CN111100709A CN111100709A CN201811246834.5A CN201811246834A CN111100709A CN 111100709 A CN111100709 A CN 111100709A CN 201811246834 A CN201811246834 A CN 201811246834A CN 111100709 A CN111100709 A CN 111100709A
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- 239000000126 substance Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 44
- 239000003502 gasoline Substances 0.000 claims abstract description 42
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000002283 diesel fuel Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 20
- 238000005336 cracking Methods 0.000 claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- -1 bicyclic aromatic hydrocarbon Chemical class 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 239000011593 sulfur Substances 0.000 abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 57
- 239000000306 component Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012533 medium component Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
-
- 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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- 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 producing high-value chemical products by adopting inferior LCO. The method combines the hydrocracking and catalytic cracking processes of LCO, performs hydrocracking reaction on light and medium fractions LCO of a catalytic cracked product, and performs residual oil hydrogenation reaction on heavy fractions LCO of the catalytic cracked product. The method of the invention can be used for producing chemical products such as high-value gasoline blending components and the like: the RON of the produced light gasoline reaches more than 87, the sulfur content is less than 5 mug/g, and the produced light gasoline can be used as a high-octane gasoline blending component; the RON of the heavy gasoline reaches 95, the sulfur content is less than 3 mug/g, and simultaneously, the low-sulfur clean diesel oil blending component with the sulfur content less than 10 mug/g and the cetane number improved by more than 14 units compared with the raw material can be produced.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for producing a high-value chemical product by adopting inferior LCO.
Background
In China, the catalytic cracking process is widely applied due to good operation flexibility, high gasoline yield and low one-time investment. But at the same time, the yield of catalytic cracking diesel oil in China, namely LCO, accounts for about one third of that of a diesel oil pool. With the increasing strictness of environmental legislation, poor-quality LCO makes upgrading of refinery diesel oil very difficult. How to effectively process LCO, reduce the yield of poor LCO, produce high-value products and improve economic benefits becomes the goal pursued by various oil refining technology developers.
For LCO in the low-value products, a common refinery adopts a conventional hydrofining process to process the LCO, remove impurities such as sulfur, nitrogen and the like in diesel oil and saturate part of aromatic hydrocarbon, and produce low-sulfur diesel oil for blending and leaving the factory. But the cetane number increase range in the process is limited, and the density of the diesel oil is not greatly changed.
The LCO processing and utilization technology develops related technologies in various oil refining enterprises at home and abroad, and the economy of the LCO processing and utilization process is improved. CN101724454A discloses a hydrocracking method for producing high-octane gasoline. The method adopts a hydrofining catalyst for treating diesel oil fraction or heavy oil fraction and a light oil type hydrocracking catalyst, and the nitrogen content of hydrocracking feed needs to be controlled to be 30-100 mu g/g. The method adopts a partial circulation operation mode under a once-through flow, the conversion rate of a hydrocracking single pass is controlled to be 30-60%, and the total conversion rate is controlled to be 50-95%. And the RON of the gasoline fraction produced by the method is 90.8-93.8. CN103865577A discloses a method for producing light aromatic hydrocarbon and clean fuel oil by catalytic cracking diesel oil. The method comprises the following steps: (1) mixing the catalytic cracking diesel oil with hydrogen, mixing with the cracking product, and simultaneously performing hydrofining reaction to remove sulfur and nitrogen impurities, and performing olefin saturation and aromatic hydrocarbon hydrogenation saturation; (2) cutting the refined catalytic cracking diesel, wherein distillate oil with the temperature of more than 355 ℃ is mixed with hydrogen and then returns to be subjected to hydrocracking; (3) extracting cut distillate oil to obtain extract oil rich in polycyclic aromatic hydrocarbon and raffinate oil rich in alkane; (4) the raffinate oil rich in alkane is used as a blending component of clean diesel oil; (5) hydrocracking reaction of the extract oil rich in aromatic hydrocarbon to produce light aromatic hydrocarbon and clean gasoline blending component; (6) the extract oil hydrocracking component is cut and separated, the fraction at the temperature of more than 195 ℃ is used as a clean diesel oil blending component, and the distillate at the temperature of less than 195 ℃ is used for obtaining a light aromatic product and a clean gasoline blending component.
Disclosure of Invention
The invention aims to provide a combined process method for LCO hydrocracking and catalytic cracking on the basis of the prior art, which is a combined process method for improving the gasoline yield and the product quality and prolonging the running period, and can realize the effect of producing high-value chemical products by adopting poor-quality LCO.
The technical idea of the invention is as follows: (1) the catalytic cracking reaction zone separates light and medium fraction LCO from the distillation part, the light and medium fraction LCO enters a hydrocracking reaction zone and is subjected to hydrodesulfurization, hydrodenitrogenation, selective hydrogenation saturation reaction, selective ring opening, alkyl side chain cracking reaction and the like in the presence of hydrogen and a hydrofining-hydrocracking catalyst, and the obtained reaction product oil is separated by a high-pressure separator, a low-pressure separator and a fractionation facility to obtain dry gas, liquefied gas, light gasoline fraction, heavy gasoline fraction, cycle oil fraction and diesel oil fraction. Wherein, part of the cycle oil fraction is returned to the hydrocracking reaction zone for further cycle conversion.
(2) The heavy fraction LCO separated from the distillation part of the catalytic cracking reaction zone and the residual oil enter a residual oil hydrogenation device together to carry out reactions such as hydrodemetallization, hydrodesulfurization, hydrodenitrogenation and the like, reaction products and the hydrogenated residual oil enter a catalytic cracking reaction zone to further carry out catalytic cracking reaction, the cracking reaction is carried out in the presence of a catalytic cracking catalyst, and dry gas, liquefied gas, catalytic cracking gasoline, light and medium fraction LCO, heavy fraction LCO, slurry oil, coke and the like are obtained after separation.
Specifically, the method for producing high-value chemical products by adopting inferior LCO comprises the following steps:
s11: separating reaction products obtained by catalytic cracking reaction in a catalytic cracking reaction zone in a fractionation system to obtain dry gas, liquefied gas, catalytic cracking gasoline, light middle distillate LCO, heavy distillate LCO, oil slurry and coke;
s21: mixing the light middle distillate LCO separated in the step S11 with hydrogen, entering a hydrocracking reaction zone filled with hydrofining and hydrocracking catalysts for hydrocracking reaction, sequentially carrying out hydrodesulfurization, hydrodenitrogenation, aromatic selective hydrogenation saturation, selective ring opening and alkyl side chain cracking reaction, and separating reaction products by a high-pressure separator, a low-pressure separator and a fractionation system to obtain dry gas, liquefied gas, a light gasoline fraction, a heavy gasoline fraction, a cycle oil fraction and a diesel oil fraction for producing a high-octane number gasoline blending component;
s22: the cycle oil fraction generated in the step S21 is re-introduced into a hydrocracking reaction zone to continue to perform the step S21 for cycle conversion;
s31: and (3) allowing the heavy fraction LCO separated in the step (S11) and the residual oil to enter a residual oil hydrogenation reaction zone filled with a residual oil hydrogenation catalyst for residual oil hydrogenation reaction, and returning reaction products and hydrogenated residual oil to a catalytic cracking reaction zone to continuously perform the step (S11) for cyclic conversion after hydrogenation demetalization, hydrodesulfurization, hydrodenitrogenation and polycyclic aromatic hydrocarbon hydrogenation saturation reaction.
The distillation range of the light and medium distillate LCO in the step S11 is 150-340 ℃, the total aromatic hydrocarbon content is higher than 70%, wherein the bicyclic aromatic hydrocarbon content is higher than 45%, and the tricyclic aromatic hydrocarbon content is less than 5%. The light and medium component LCO is from middle base or naphthenic base crude oil or mixed oil of paraffin base crude oil and middle base or naphthenic base crude oil.
The distillation range of the heavy fraction LCO in the step S11 is 330-400 ℃, the total aromatic hydrocarbon content is higher than 70%, wherein the content of monocyclic aromatic hydrocarbon is less than 5%, the content of bicyclic aromatic hydrocarbon is less than 12%, and the content of tricyclic aromatic hydrocarbon and above aromatic hydrocarbon is higher than 50%.
The hydrofining catalyst in the step S21 is an RN-411 refining catalyst, and the hydrocracking catalyst is an RHC-100 cracking catalyst.
In the hydrocracking reaction described in step S21, the reaction conditions are: the hydrogen partial pressure is 2.5MPa to 8.0 MPa; the average reaction temperature of refining and cracking is 300-450 ℃; the volume ratio of hydrogen to oil is 400-2500 Nm3/m3(ii) a The liquid hourly space velocity is 0.2h-1～20.0h-1。
Preferably, the hydrocracking described in step S21In the chemical reaction, the reaction conditions are as follows: the hydrogen partial pressure is 3.5MPa to 6.0 MPa; the average reaction temperature of refining and cracking is 350-430 ℃; the volume ratio of hydrogen to oil is 900-1600 Nm3/m3(ii) a The liquid hourly space velocity is 0.5h-1～3.0h-1。
In the residual oil hydrogenation reaction in the step S31, the weight ratio of the blended heavy fraction LCO (7) is no more than 40% based on the feeding of the residual oil hydrogenation reaction zone (18), and the reaction conditions of conventional residual oil hydrotreating are adopted in the reaction process, such as operating pressure, reaction temperature, volume space velocity, hydrogen-oil ratio, and the like. When the reaction zone is blended with part of the hydrogenation heavy LCO, the residual oil hydrogenation operation condition is the same as that of the blending-free hydrogenation heavy LCO, and the residual oil hydrogenation operation condition can be not adjusted or can be properly adjusted according to the requirement.
Preferably, in the residual oil hydrogenation reaction in the step S31, the weight proportion of the blended heavy fraction LCO (7) is less than or equal to 15 percent based on the feed of the residual oil hydrogenation reaction zone (18).
The residual oil hydrogenation catalyst in the step S31 is any one or any combination of RG-30 series, RDM-32, RDM-33C, RMS-3 and RCS-31 catalysts, or any one or any combination of HDM, HDS, HDCCR and HDN in RHT series catalysts.
In a hydrocracking reaction zone, the light and medium fraction LCO rich in the bicyclic aromatic hydrocarbon and the monocyclic aromatic hydrocarbon is processed by adopting a technology of producing high-octane gasoline RLG by adopting LCO hydrocracking of a Shikojie to produce high-octane gasoline blending components and simultaneously produce part of low-sulfur diesel blending components. In the reaction zone, the light middle distillate LCO with high aromatic hydrocarbon content contacts and reacts with a hydrofining RN-411 catalyst to carry out hydrodesulfurization, hydrodenitrogenation and selective hydrogenation saturation of aromatic hydrocarbon, effectively remove sulfide and nitride, and carry out selective hydrogenation saturation reaction on bicyclic aromatic hydrocarbon to generate the single-ring aromatic hydrocarbon of tetralin. The hydrofined product oil enters a hydrocracking reaction zone to contact and react with an RHC-100 hydrocracking catalyst, so that the selective ring-opening cracking and alkyl side chain cracking reactions of the tetrahydronaphthalene monocyclic aromatic hydrocarbon are completed, the high-octane gasoline blending component is produced, and simultaneously, part of low-sulfur diesel blending component is produced.
The heavy fraction LCO containing a small part of bicyclic aromatic hydrocarbon and rich in aromatic hydrocarbon above three rings enters a residual oil hydrogenation reaction zone to carry out hydrodesulfurization, hydrodenitrogenation, polycyclic aromatic hydrocarbon hydrogenation saturation reaction and the like, and reaction products and hydrogenated residual oil enter a catalytic cracking reaction zone together to be cracked and converted to produce dry gas, liquefied gas, gasoline, light and medium fraction LCO, heavy fraction LCO, HCO, slurry oil, coke and the like. And the heavy fraction LCO is circulated to a residual oil hydrotreatment device for continuous hydrogenation saturation, and then enters a catalytic cracking unit for further cracking and conversion into the gasoline blending component.
The invention is specially designed based on the type characteristics of the existing device and the properties of the raw oil, and has the following advantages:
(1) by adopting the method, low-value and poor-quality LCO can be fully processed, and the poor-quality LCO is reduced by more than 50%;
(2) the method of the invention can be used for producing chemical products such as high-value gasoline blending components and the like: the hydrocracking reaction zone can produce light gasoline with RON more than 87 and sulfur content less than 5 microgram/g, and the light gasoline can be used as a high-octane gasoline blending component; the RON of the heavy gasoline reaches 95, and the sulfur content is less than 3 mu g/g; meanwhile, the method can produce low-sulfur clean diesel oil blending components with the sulfur content of less than 10 mu g/g and the cetane number improved by more than 14 units compared with the raw materials;
(3) by adopting the method, the running period of the RLG device can be prolonged by at least more than 3 months, and better economic benefit is obtained;
(4) by adopting the method of the invention, the catalytic cracking reaction zone can improve the gasoline yield by about 10 percent.
Drawings
FIG. 1 is a schematic view of a process flow for processing an LCO of poor quality to produce a high value product according to the present invention. In the figure: 1, a reaction product of a residual oil hydrogenation reaction zone and hydrogenated residual oil, 2, a catalytic cracking reaction zone, 3, dry gas, 4, liquefied gas, 5, 6, light and medium fraction LCO, 7, heavy fraction LCO, 8 slurry oil, 9 coke, 10, a hydrocracking reaction zone, 11, dry gas, 12, liquefied gas, 13, light gasoline fraction, 14, heavy gasoline fraction, 15, cycle oil fraction, 16 diesel oil fraction and 18 residual oil hydrogenation reaction zones.
Detailed Description
The method provided by the invention is further explained in the following with reference to the attached drawings. The figure is a schematic flow diagram of the process of the present invention, and many devices such as pumps, heat exchangers, compressors, etc. have been omitted, but are well known to those skilled in the art. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
As shown in fig. 1, the method flow provided by the present invention is described in detail as follows: one of the reaction products of the catalytic cracking reaction zone 2, namely light middle distillate LCO (6), is mixed with hydrogen and then enters a hydrocracking reaction zone 10 to be sequentially contacted and reacted with a hydrofining RN-411 catalyst special for RLG technology and a hydrocracking RHC-100 catalyst special for RLG technology, so that hydrodesulfurization, hydrodenitrogenation, aromatic hydrocarbon hydrogenation saturation, selective cracking, alkyl side chain cracking reaction and the like are completed. The reaction product in the hydrocracking reaction zone 10 is separated by a high-low pressure separator and a fractionation system to obtain dry gas 11, liquefied gas 12, light gasoline fraction 13, heavy gasoline fraction 14, cycle oil fraction 15 and diesel oil fraction 16. Wherein, the circulating oil fraction 15 returns to the inlet of the hydrocracking reaction zone 10 to continue the circulating conversion.
One of the reaction products of the catalytic cracking reaction zone 2, namely heavy fraction LCO (7), returns to the residual oil hydrogenation reaction zone 18 to complete the reactions of hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, aromatic hydrocarbon hydrogenation saturation and the like, the reaction products and the hydrogenated residual oil mixed oil enter the catalytic cracking reaction zone 2 through a pipeline, and after the reaction products and the hydrogenated residual oil mixed oil are in contact reaction with a catalytic cracking catalyst, dry gas 3, liquefied gas 4, gasoline 5, light and medium components LCO 6, heavy components LCO 7, oil slurry 8, coke 9 and the like are generated through cracking.
The hydrocracking reaction zone 10 adopts special catalysts of RN-411 refining agent and RHC-100 cracking agent. The catalyst grading is a special catalyst grading scheme for RLG patents (ZL2009810162161.X and ZL 201240411335.3).
The catalyst adopted in the residual oil hydrogenation reaction zone 18 is any one or any combination of RG-30 series, RDM-32, RDM-33C, RMS-3 and RCS-31 catalysts, or any one or any combination of HDM, HDS, HDCCR and HDN in RHT series catalysts, and is autonomously developed by the Shikou institute. (ZL201310432344.5, ZL201310432227.9, ZL201310332676.6, ZL201310308434.3 and ZL 201310308841.4). The catalytic cracking reaction zone 2 adopts the technology of MIP technology developed by Shikou institute and matched catalyst. (ZL200610113673.3, ZL200610169512.6, ZL99105903.4, ZL99109193.0, etc.)
The following examples further illustrate the invention but are not intended to limit the invention thereto. In the examples, the raw material E is a light fraction LCO, the raw material F is a heavy fraction LCO, and the physical and chemical properties of the raw material are shown in Table 1.
Example 1
The raw material E is mixed with hydrogen and hydrogen-rich gas and then enters a hydrocracking reaction zone to react under the condition of RLG. As can be seen from table 2, it is,<the RON of 65 ℃ light gasoline fraction reaches 88, the RON of 65 ℃ to 205 ℃ fraction reaches 95.8, the MON reaches 83.0, and the sulfur content is 1.5 mu g/g;>205 ℃ diesel fraction with a density of 0.892g/cm at 20 DEG C3The sulfur content was 3. mu.g/g, and the cetane number increase value was 16.0.
The 20t/h raw material F enters a residual oil hydrogenation device, is subjected to hydrodesulfurization, hydrodenitrogenation and aromatic hydrogenation saturation, and then returns to a catalytic cracking unit to continue cracking reaction, so that about 8t/h gasoline blending component can be produced.
By adopting the method, the applicant of the invention can reduce the poor LCO by about 40 ten thousand tons/year and prolong the running period of the RLG device by more than three months.
TABLE 1 physicochemical Properties of the raw materials
TABLE 2 physicochemical Properties of the reaction products
| Product Properties | Light gasoline | Heavy gasoline | Diesel oil |
| Fraction range, C | <65 | 65～205 | >205 |
| Density (20 ℃ C.), g/cm3 | 0.635 | 0.825 | 0.892 |
| Sulfur,. mu.g/g | <1 | 1.5 | 3 |
| Nitrogen,. mu.g/g | <1 | <1 | <1 |
| RON/MON | 88/82 | 95.8/83 | - |
| Cetane number increase value | - | 16.0 |
Claims (9)
1. A method for producing high-value chemical products by adopting inferior LCO is characterized by comprising the following steps:
s11: after reaction products obtained by catalytic cracking reaction in the catalytic cracking reaction zone (2) enter a fractionation system for separation, dry gas (3), liquefied gas (4), catalytic cracking gasoline (5), light middle distillate LCO (6), heavy distillate LCO (7), slurry oil (8) and coke (9) are obtained;
s21: mixing the light and medium fraction LCO (6) obtained by separation in the step S11 with hydrogen, entering a hydrocracking reaction zone (10) filled with hydrofining and hydrocracking catalysts for hydrocracking reaction, sequentially carrying out hydrodesulfurization, hydrodenitrogenation, aromatic hydrocarbon selective hydrogenation saturation, selective ring opening and alkyl side chain cracking reaction, and separating reaction products by a high-pressure separator, a low-pressure separator and a fractionation system to obtain dry gas (11), liquefied gas (12), a light gasoline fraction (13), a heavy gasoline fraction (14), a cycle oil fraction (15) and a diesel oil fraction (16) for producing a high-octane gasoline blending component;
s22: the recycle oil fraction (15) generated in the step S21 is re-introduced into the hydrocracking reaction zone (10) to continue to perform the step S21 for cyclic conversion;
s31: and (3) enabling the heavy fraction LCO (7) obtained by separation in the step (S11) and the residual oil to enter a residual oil hydrogenation reaction zone (18) filled with a residual oil hydrogenation catalyst for residual oil hydrogenation reaction, returning reaction products and hydrogenation residual oil to the catalytic cracking reaction zone (2) for continuously performing step (S11) for cyclic conversion after hydrodemetallization, hydrodesulfurization, hydrodenitrogenation and polycyclic aromatic hydrocarbon hydrogenation saturation reaction.
2. The method of producing high value chemical products using low quality LCO of claim 1, wherein: the distillation range of the light and medium distillate LCO (6) in the step S11 is 150-340 ℃, the total aromatic hydrocarbon content is higher than 70%, wherein the bicyclic aromatic hydrocarbon content is higher than 45%, and the tricyclic aromatic hydrocarbon content is less than 5%.
3. The method of producing high value chemical products using low quality LCO of claim 1, wherein: the distillation range of the heavy fraction LCO (7) in the step S11 is 330-400 ℃, the total aromatic hydrocarbon content is higher than 70%, wherein the content of monocyclic aromatic hydrocarbon is less than 5%, the content of bicyclic aromatic hydrocarbon is less than 12%, and the content of tricyclic aromatic hydrocarbon and above aromatic hydrocarbon is higher than 50%.
4. The method of producing high value chemical products using low quality LCO of claim 1, wherein: the hydrofining catalyst in the step S21 is an RN-411 refining catalyst, and the hydrocracking catalyst is an RHC-100 cracking catalyst.
5. The method of claim 1, wherein the hydrocracking reaction of step S21 is performed under the following conditions: the hydrogen partial pressure is 2.5MPa to 8.0 MPa; the average reaction temperature of refining and cracking is 300-450 ℃; the volume ratio of hydrogen to oil is 400-2500 Nm3/m3(ii) a The liquid hourly space velocity is 0.2h-1～20.0h-1。
6. The method of claim 7, wherein the hydrocracking reaction of step S21 is performed under the following conditions: the hydrogen partial pressure is 3.5MPa to 6.0 MPa; the average reaction temperature of refining and cracking is 350-430 ℃; the volume ratio of hydrogen to oil is 900-1600 Nm3/m3(ii) a The liquid hourly space velocity is 0.5h-1～3.0h-1。
7. The method for producing high-value chemical products from low-quality LCO according to claim 1, wherein in the residual hydrogenation reaction in step S31, the weight ratio of the heavy fraction LCO (7) is no more than 40% based on the feeding of the residual hydrogenation reaction zone (18), and the operating pressure, reaction temperature, volume space velocity, hydrogen-oil ratio and the like in the reaction process adopt the reaction conditions of conventional residual hydrogenation treatment.
8. The method for producing high-value chemical products from low-quality LCO according to claim 1, wherein the blending weight ratio of the heavy fraction LCO (7) in the residual oil hydrogenation reaction in the step S31 is less than or equal to 15% based on the feeding material of the residual oil hydrogenation reaction zone (18).
9. The method for producing high-value chemical products from poor-quality LCO according to claim 1, wherein the residual oil hydrogenation catalyst in step S31 is any one of RG-30 series, RDM-32, RDM-33C, RMS-3, RCS-31 catalyst or any combination thereof, or any one of HDM, HDS, HDCCR, HDN in RHT series catalyst or any combination thereof.
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| CN115960627A (en) * | 2021-10-13 | 2023-04-14 | 中国石油化工股份有限公司 | Low energy conversion method and device for producing light aromatic hydrocarbon from catalytic diesel oil |
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| CN115960627A (en) * | 2021-10-13 | 2023-04-14 | 中国石油化工股份有限公司 | Low energy conversion method and device for producing light aromatic hydrocarbon from catalytic diesel oil |
| CN115960627B (en) * | 2021-10-13 | 2024-05-28 | 中国石油化工股份有限公司 | Low energy conversion method and device for producing light aromatic hydrocarbon from catalytic diesel |
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