CN115197747B - Method and system for producing high-yield low-carbon olefin - Google Patents
Method and system for producing high-yield low-carbon olefin Download PDFInfo
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- CN115197747B CN115197747B CN202110396618.4A CN202110396618A CN115197747B CN 115197747 B CN115197747 B CN 115197747B CN 202110396618 A CN202110396618 A CN 202110396618A CN 115197747 B CN115197747 B CN 115197747B
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- 238000000034 method Methods 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003921 oil Substances 0.000 claims abstract description 283
- 238000006243 chemical reaction Methods 0.000 claims abstract description 271
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 206
- 239000002904 solvent Substances 0.000 claims abstract description 67
- 239000000295 fuel oil Substances 0.000 claims abstract description 52
- 239000002893 slag Substances 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims description 108
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 238000000926 separation method Methods 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010426 asphalt Substances 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 39
- 238000009826 distribution Methods 0.000 description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 18
- 238000007233 catalytic pyrolysis Methods 0.000 description 17
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011017 operating method Methods 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- YBYGVLNOTPYQQM-UHFFFAOYSA-N pentane Chemical compound CCCCC.CCCCC.CCCCC.CCCCC.CCCCC.CCCCC YBYGVLNOTPYQQM-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Landscapes
- 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 the field of petroleum processing, and discloses a method and a system for producing high-yield low-carbon olefins. The method comprises the following steps: introducing the residual oil raw material into a fixed bed residual oil hydrotreating reaction zone for hydrotreating reaction I, separating residual oil hydrotreating reaction effluent, introducing catalytic cracking slurry oil and partial hydrogenation slag reduction into a solvent deasphalting zone for solvent deasphalting and separating, introducing first hydrogenated heavy oil and deasphalted oil into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, separating wax oil hydrotreating reaction effluent, introducing second hydrogenated heavy oil and residual hydrogenation slag reduction into the catalytic cracking reaction zone for catalytic cracking reaction, and separating catalytic cracking reaction effluent to obtain light olefins. The invention can obviously improve the hydrogenation depth of the residual oil raw material and finally realize obviously improving the yield of the low-carbon olefin high-value product in the combined process.
Description
Technical Field
The invention relates to the field of hydrocarbon oil processing, in particular to a method and a system for producing a large amount of low-carbon olefin.
Background
The low-carbon olefin represented by ethylene and propylene is a basic raw material in the chemical industry, can be used for producing various organic chemical products, and plays an important role in national economy. In the traditional petrochemical industry, naphtha is mainly used as a raw material to prepare ethylene through steam cracking. However, in recent years, the price of petroleum is increasing and the shale gas extraction technology is maturing, and steam cracking devices using shale gas as raw material are widely used in north america, and the economy of ethylene cracking process using naphtha as raw material is being squeezed.
Compared with the ethylene product market, the impact of propylene by shale gas revolution is smaller, and the gap of the market on propylene is still larger. Therefore, in the period of relatively low price of crude oil, the process technology for producing more propylene is developed, and the method has wide application prospect in the future.
At present, about 60% -65% of propylene in the world is prepared by a steam cracking process, about 30% of propylene is prepared by a catalytic cracking process (including a catalytic cracking process), and the rest of propylene is prepared by processes such as propane dehydrogenation. The main raw materials of the catalytic cracking device comprise wax oil and residual oil, and the catalytic cracking device has certain advantages in raw material cost.
However, the propylene yield of the catalytic cracking device is not high, for example, the yield of propylene in the catalytic cracking unit can reach 20% or even more than 30% by taking intermediate hydrogenated wax oil as a raw material, for example, the yield of propylene in the catalytic cracking unit is generally not more than 20% by taking intermediate hydrogenated residual oil as a raw material. In addition, if a residuum hydrogenation apparatus using only hydrogenated residuum as a catalytic cracking feedstock needs to be operated at a higher reaction severity, the operating cycle or economy of the residuum hydrogenation apparatus may be affected.
It can be seen that it is necessary to increase the propylene yield of the catalytic cracking of the residuum feedstock and to reduce the operating severity of the catalytic cracking feedstock pretreatment unit by selecting an appropriate process route.
CN101045884a discloses a process for producing clean diesel oil and low-carbon olefin from residuum and heavy distillate oil, in which process residuum and optional catalytic cracking slurry oil enter a solvent deasphalting unit, the obtained deasphalted oil and optional heavy distillate oil enter a hydrogenation unit, hydrocracking reaction is carried out in the presence of hydrogen, and the reaction products are separated to obtain light and heavy naphtha fractions, diesel oil fractions and hydrogenated tail oil; the hydrogenated tail oil enters a catalytic cracking unit for catalytic cracking reaction, products are separated to obtain low-carbon olefin, gasoline fraction, diesel fraction and slurry oil, all the catalytic cracking diesel fraction is recycled to the catalytic cracking reactor, and all or part of the catalytic cracking slurry oil is returned to the solvent deasphalting unit. The method organically combines the deasphalting, hydrocracking and catalytic cracking of the residual oil solvent, improves the utilization rate of heavy oil, and produces partial low-carbon olefin in a more productive manner, but the residual oil raw material in the method is not completely used as the raw material of catalytic cracking, and the yield of the low-carbon olefin is not maximized.
CN101063047a discloses a method for hydrotreating-catalytic cracking of heavy raw materials to increase propylene yield, wherein heavy distillate oil and optionally light cycle oil from a catalytic cracking unit can be reacted together in one reaction zone, or can be reacted in two hydrogenation reaction zones filled with different hydrogenation catalysts respectively, and after cooling, separating and fractionating the reaction effluent, the obtained heavy liquid phase fraction is sent to the catalytic cracking unit, and the catalytic cracking reaction product is separated to obtain the final product. The method provided by the invention is suitable for treating wax oil raw materials, and has the defects of short operation period, low impurity removal rate and the like when treating heavy residual oil raw materials.
CN101747935a provides a method for producing low-carbon olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons, wherein a wax oil raw material and light and heavy cycle oil of a catalytic cracking device are subjected to hydrogenation reaction in a first reaction zone, a reaction effluent is mixed with residual oil and then enters a second reaction zone to be subjected to hydrogenation reaction, and separated heavy fraction obtained by hydrogenation enters the catalytic cracking reaction zone to react to obtain the required products such as low-carbon olefins and monocyclic aromatic hydrocarbons. The method widens the source of the catalytic cracking raw material by introducing residual oil before the second reaction zone, increases the processing amount of low-value residual oil, and solves the problem of heat balance of the catalytic cracking unit.
Disclosure of Invention
The invention aims to overcome the defect of low yield of low-carbon olefin products such as ethylene, propylene and the like in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a method for producing a high yield of light olefins, comprising:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction I, and separating residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction;
(2) Introducing the catalytic cracking slurry oil and a part of the hydrogenation slag reduction into a solvent deasphalting zone in the presence of a solvent to carry out solvent deasphalting and separation to obtain deasphalted oil and deasphalted asphalt;
(3) Introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
(4) Introducing the second hydrogenated heavy oil and the rest of the hydrogenated slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating a catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(5) And (3) independently carrying out at least one operation of leading-out devices, recycling the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil to the fixed bed wax oil hydrotreating reaction zone and recycling the catalytic cracking slurry oil to the fixed bed residual oil hydrotreating reaction zone, and recycling the catalytic cracking slurry oil to the solvent deasphalting zone.
In a second aspect the present invention provides a system for the production of high yields of light olefins, the system comprising:
the fixed bed residuum hydrotreatment reaction unit is used for carrying out hydrotreatment reaction I on a residuum raw material to obtain residuum hydrotreatment reaction effluent;
the first separation unit is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction;
the solvent deasphalting unit is used for solvent deasphalting and separating the catalytic cracking slurry oil and a part of the hydrogenation slag reduction to obtain deasphalted asphalt and deasphalted oil;
the fixed bed wax oil hydrotreating reaction unit is used for carrying out hydrotreating reaction II on the first hydrogenated heavy oil and the deasphalted oil to obtain a wax oil hydrotreating reaction effluent;
the second separation unit is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
The catalytic cracking reaction unit is used for carrying out catalytic cracking reaction on the second hydrogenated heavy oil and the rest of the hydrogenated slag reduction to obtain a catalytic cracking reaction effluent;
the third separation unit is used for separating the catalytic cracking reaction effluent to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil, wherein the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are respectively and independently led out of the device, recycled to the fixed bed wax oil hydrotreating reaction zone and recycled to at least one operation in the fixed bed residual oil hydrotreating reaction zone, and the catalytic cracking slurry oil is recycled to the solvent deasphalting unit through a pipeline.
The inventor discovers that the hydrogenation depth of the residual oil raw material can be obviously improved by organically combining the fixed bed residual oil hydrotreating process, the fixed bed wax oil hydrotreating process, the catalytic cracking process and the solvent deasphalting process, thereby obviously improving the yield of low-carbon olefin products such as propylene, ethylene and the like in the combined process.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of the method of the present invention.
Description of the reference numerals
1. Residuum raw material 2, fixed bed residuum hydrotreatment reaction unit
3. Residuum hydrotreatment reaction effluent 4, first separation unit
5. First gas effluent 6, first hydrogenated naphtha
7. First hydrogenated heavy oil 8, hydrogenation slag reduction
9. Solvent deasphalting unit 10, deasphalted oil
11. Deoiling asphalt 12, fixed bed wax oil hydrotreatment reaction unit
13. Wax oil hydrotreating reaction effluent 14, second separation unit
15. Second gas effluent 16, second hydrogenated naphtha
17. Second hydrogenated heavy oil 18, catalytic cracking reaction unit
19. Catalytic cracking reaction effluent 20, third separation unit
21. Low carbon olefins 22 and catalytically cracked naphtha
23. Catalytic cracking light cycle oil 24 and catalytic cracking heavy cycle oil
25. Catalytic cracking slurry oil
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the pressures are gauge pressures unless otherwise specified.
In the present invention, the particle size of the residuum hydrotreating catalyst refers to the maximum linear distance between two different points on the particle cross section, unless otherwise specified. The particle size of the wax oil hydrotreating catalyst is of similar definition.
In the present invention, the low-carbon olefin includes, but is not limited to, ethylene, propylene, unless otherwise specified.
In the invention, the liquid hourly space velocity is the residual oil volumetric space velocity, i.e. the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are not calculated when the volumetric space velocity is calculated without corresponding description.
As previously described, a first aspect of the present invention provides a process for the production of high yields of lower olefins, the process comprising:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction I, and separating residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction;
(2) Introducing the catalytic cracking slurry oil and a part of the hydrogenation slag reduction into a solvent deasphalting zone in the presence of a solvent to carry out solvent deasphalting and separation to obtain deasphalted oil and deasphalted asphalt;
(3) Introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
(4) Introducing the second hydrogenated heavy oil and the rest of the hydrogenated slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating a catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(5) The catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are respectively and independently subjected to at least one operation of a leading-out device, recycling to the fixed bed wax oil hydrotreating reaction zone and recycling to the fixed bed residual oil hydrotreating reaction zone; recycling the catalytic cracking slurry oil back to the solvent deasphalting zone.
The present invention has no special requirement for the subsequent treatment of the catalytic pyrolysis naphtha, the catalytic pyrolysis light cycle oil, the catalytic pyrolysis heavy cycle oil and the catalytic pyrolysis slurry oil, and the present invention can be performed by those skilled in the art by using operations known in the art, for example, the catalytic pyrolysis naphtha is extracted after being led out of the device, or the catalytic pyrolysis slurry oil is extracted after being subjected to hydrogenation treatment to remove sulfides to obtain monocyclic aromatic hydrocarbon, and the catalytic pyrolysis slurry oil can be directly or after being filtered and then led into the solvent deasphalting zone.
The inventor finds that after the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are recycled to the fixed bed wax oil hydrotreating reaction zone and/or the fixed bed residual oil hydrotreating reaction zone for hydrotreating, the low-carbon olefin and the monocyclic aromatic hydrocarbon can be generated by cracking in the subsequent catalytic cracking reaction zone, so that the yield of the low-carbon olefin product is greatly improved.
It should be noted that, the catalytic cracking slurry oil and at least part of the hydrogenated slag reduction can also be introduced into the delayed coking reaction zone separately or after being mixed according to the process requirements. In the step (3) of the present invention, the first hydrogenated heavy oil and the deasphalted oil can be introduced into the fixed bed wax oil hydrotreating reaction zone separately or after mixing according to process requirements. In the step (4) of the present invention, the second hydrogenated heavy oil and the remaining part of the hydrogenated slag reduction can also be introduced into the catalytic cracking reaction zone separately or after being mixed according to the process requirements.
Preferably, in step (1), the residuum feedstock is selected from at least one of atmospheric residuum, vacuum residuum.
Preferably, in step (1), the reaction conditions of the fixed bed residuum hydroprocessing reaction zone include: the reaction temperature is 300-460 ℃, the hydrogen partial pressure is 6-25MPa, and the liquid hourly space velocity is 0.10-1.0h -1 The volume ratio of hydrogen to oil is 100-1500.
More preferably, in step (1), the reaction conditions of the fixed bed residuum hydroprocessing reaction zone include: the reaction temperature is 350-440 ℃, the hydrogen partial pressure is 12-20MPa, and the liquid hourly space velocity is 0.15-0.4h -1 The volume ratio of hydrogen to oil is 300-1000.
Preferably, in step (1), the fixed bed residuum hydroprocessing reaction zone is charged with a residuum hydroprocessing catalyst having an average particle size of from 0.5 to 50mm and a bulk density of from 0.3 to 1.2g/cm 3 Average pore diameter of 6-30nm and specific surface area of 50-400m 2 /g。
Preferably, in step (1), the residuum hydrotreating catalyst is selected from at least one of guard catalyst I, hydrodemetallization catalyst, hydrodesulfurization catalyst, and hydrodecarbon residue catalyst.
Preferably, the fixed bed residuum hydrotreating reaction zone is sequentially filled with the protection catalyst I, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbon residue catalyst along the stream direction.
More preferably, the packing volume ratio of the protective catalyst I, the hydrodemetallization catalyst, the hydrodesulphurisation catalyst, and the hydrodecarbon residue catalyst is 1:4-8:1-5:2-6.
According to a particularly preferred embodiment, in step (1), the residuum hydroprocessing catalyst contains a support selected from at least one of alumina, silica and titania, and an active metal element selected from group VIB metal elements and/or group VIII metal elements supported on the support.
Preferably, in the residuum hydrotreating catalyst, the active metal element is selected from at least one of a combination of nickel-tungsten, a combination of nickel-tungsten-cobalt, a combination of nickel-molybdenum, and a combination of cobalt-molybdenum.
Preferably, in the residuum hydrotreating catalyst, the carrier further contains at least one element of boron, germanium, zirconium, phosphorus, chlorine, and fluorine.
Preferably, in the residuum hydroprocessing catalyst, the content of the active metal element in terms of oxide is from 1 to 30wt%, preferably from 1 to 25wt%, based on the total weight of the residuum hydroprocessing catalyst.
In the present invention, the resid hydrotreating catalyst may be selected from commercial catalysts conventional in the art or prepared using conventional methods of the prior art, and illustratively, the resid hydrotreating catalyst may employ commercial catalysts of RG series, RDM series, RMS series, RCS series, and RSN series developed by the institute of petrochemical and petrochemical industries, china.
Preferably, in step (1), the separation conditions of the residuum hydrotreating reaction effluent are controlled such that the initial boiling point of the first hydrogenated naphtha is 50 to 70 ℃, the cut points of the first hydrogenated naphtha and the first hydrogenated heavy oil are 160 to 180 ℃, and the final boiling point of the first hydrogenated heavy oil is 500 to 580 ℃.
Preferably, in step (2), the solvent is C 3 -C 7 Alkanes and/or C 3 -C 7 At least one of the olefins.
More preferably, in step (2), the solvent is C 4 -C 6 Alkanes and/or C 4 -C 6 At least one of the olefins.
Preferably, in step (2), the operating conditions of the solvent deasphalting zone comprise: the temperature is 50-260 ℃, the pressure is 1-7MPa, and the volume ratio of the solvent to the hydrogenated slag reduction amount is 2-12:1.
More preferably, in step (2), the operating conditions of the solvent deasphalting zone comprise: the temperature is 60-240 ℃, the pressure is 2-6MPa, and the volume ratio of the solvent to the hydrogenated slag reduction amount is 3-10:1.
Preferably, in step (2), the deasphalted oil comprises from 10 to 80 wt% of the total amount of feedstock introduced into the solvent deasphalting zone.
More preferably, in step (2), the deasphalted oil comprises from 30 to 70% by weight of the total amount of feedstock introduced into the solvent deasphalting zone.
Preferably, in step (3), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone and/or the catalyst fractionation in the fixed bed wax oil hydrotreating reaction zone are controlled such that the hydrogen content of the wax oil hydrotreating reaction effluent is less than 13.2 wt%, preferably less than 13.5 wt%. The inventors have found that with this preferred embodiment, the yield of the low carbon olefin product can be made higher.
Preferably, in step (3), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone include: the hydrogen partial pressure is 6-25MPa, the reaction temperature is 300-460 ℃, and the liquid hourly space velocity is 0.1-5.0h -1 The volume ratio of hydrogen to oil is 200-2000.
More preferably, in step (3), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone include: the hydrogen partial pressure is 10-20MPa, the reaction temperature is 350-440 ℃, and the liquid hourly space velocity is 0.5-2.0h -1 The volume ratio of hydrogen oil is 400-1200.
Preferably, in the step (3), the fixed bed wax oil hydrotreating reaction zone is filled with a wax oil hydrotreating catalyst, and the bulk density of the wax oil hydrotreating catalyst is 0.4-1.3g/cm 3 The average grain diameter is 0.5-50mm, and the specific surface area is 50-400m 2 /g。
According to a particularly preferred embodiment, in step (3), the wax oil hydrotreating catalyst is selected from at least one of a guard catalyst II, a wax oil hydrofinishing catalyst.
Preferably, the fixed bed wax oil hydrotreating reaction zone is filled with the protection catalyst II and the wax oil hydrofining catalyst in sequence along the flow direction.
More preferably, the loading volume ratio of the protection catalyst II to the wax oil hydrofining catalyst is 1:9-99.
Preferably, in the step (3), the wax oil hydrotreating catalyst contains a carrier and an active metal element supported on the carrier, the carrier is selected from at least one of alumina, a combination of alumina and silica, and titania, and the active metal element is selected from at least one of nickel, cobalt, molybdenum, and tungsten.
More preferably, in the wax oil hydrotreating catalyst, the total content of nickel and cobalt in terms of oxide is 0 to 30 wt%, the total content of molybdenum and tungsten in terms of oxide is 0 to 35 wt%, and the sum of the contents of nickel, cobalt, molybdenum, tungsten in terms of oxide is greater than 0, based on the total weight of the wax oil hydrotreating catalyst.
Preferably, in step (3), the separation conditions of the wax oil hydrotreating reaction effluent are controlled such that the initial boiling point of the second hydrogenated naphtha is 50 to 70 ℃, the cutting points of the second hydrogenated naphtha and the second hydrogenated heavy oil is 160 to 180 ℃, and the final boiling point of the second hydrogenated heavy oil is 500 to 580 ℃.
Preferably, in the step (4), the catalytic cracking reaction zone is filled with a catalytic cracking catalyst, the catalytic cracking catalyst contains zeolite, inorganic oxide, optionally, and clay, the inorganic oxide is at least one of silica, alumina, zirconia, titania and amorphous silica-alumina, the content of the zeolite is 10-50 wt%, the content of the inorganic oxide is 5-90 wt%, and the content of the clay is 0-70 wt%, based on the total weight of the catalytic cracking catalyst.
Preferably, in the catalytic cracking catalyst, the zeolite is at least one selected from a Y-type zeolite containing or not containing a rare earth element, an HY-type zeolite containing or not containing a rare earth element, an ultrastable Y-type zeolite containing or not containing a rare earth element, and a zeolite having an MFI structure.
The apparatus of the catalytic cracking reaction zone and the separation zone, which may use a conventional catalytic cracking system, may include, for example, a reactor, a regenerator and fractionation system, and an absorption stabilization system, and may employ a composite reactor type consisting of a riser and a dense-phase fluidized bed, is not particularly limited.
According to a particularly preferred embodiment, in step (4), the reaction conditions of the catalytic cracking reaction zone are: the weight ratio of the atomized steam to the residual oil raw material is 0.05-0.5:1, the weight ratio of the agent to the oil is 6-20:1, the temperature is 500-680 ℃, and the weight hourly space velocity is 1-6h -1 The reaction pressure is 0.05-1MPa.
In the present invention, the catalyst to oil weight ratio is the weight ratio of the sum of the total weight of the catalytic cracking catalyst and the raw material introduced into the catalytic cracking reaction zone, unless otherwise specified. Wherein, the raw materials of the catalytic cracking reaction zone comprise the second hydrogenated wax oil and the rest part of the hydrogenated slag reduction.
Preferably, in the step (4), the separation condition of the catalytic cracking reaction effluent is controlled such that the initial distillation point of the catalytic cracking light cycle oil is 150-180 ℃, the cutting point of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil is 340-360 ℃, and the final distillation point of the catalytic cracking heavy cycle oil is 500-580 ℃.
Preferably, in step (4), the hydrodewaxing introduced into the catalytic cracking reaction zone represents 5 to 95% by weight, preferably 20 to 80% by weight, of the total weight of the hydrodewaxing.
Preferably, the method further comprises: and separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
The present invention is not particularly limited to the subsequent processing of the light naphtha and the heavy naphtha and may be carried out by those skilled in the art using procedures known in the art, for example, the light naphtha of the present invention may be introduced into the catalytic cracking reaction zone for the catalytic cracking reaction and the heavy naphtha may be withdrawn from the apparatus as a feedstock for aromatics extraction.
Preferably, the separation conditions of the first hydrogenated naphtha and/or the second hydrogenated naphtha are controlled such that the initial boiling point of the light naphtha is 50 to 70 ℃, the cutting point of the light naphtha and the heavy naphtha is 120 to 140 ℃, and the final boiling point of the heavy naphtha is 170 to 190 ℃.
As previously described, a second aspect of the present invention provides a system for the production of high yields of low olefins, the system comprising:
the fixed bed residuum hydrotreatment reaction unit is used for carrying out hydrotreatment reaction I on a residuum raw material to obtain residuum hydrotreatment reaction effluent;
the first separation unit is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction;
The solvent deasphalting unit is used for solvent deasphalting and separating the catalytic cracking slurry oil and a part of the hydrogenation slag reduction to obtain deasphalted asphalt and deasphalted oil;
the fixed bed wax oil hydrotreating reaction unit is used for carrying out hydrotreating reaction II on the first hydrogenated heavy oil and the deasphalted oil to obtain a wax oil hydrotreating reaction effluent;
the second separation unit is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
the catalytic cracking reaction unit is used for carrying out catalytic cracking reaction on the second hydrogenated heavy oil and the rest of the hydrogenated slag reduction to obtain a catalytic cracking reaction effluent;
the third separation unit is used for separating the catalytic cracking reaction effluent to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil, and at least one operation of leading out the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil respectively and independently, recycling the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil back to the fixed bed wax oil hydrotreating reaction zone and recycling the catalytic cracking heavy cycle oil back to the fixed bed residual oil hydrotreating reaction zone; and recycling the catalytic cracking slurry oil to the solvent deasphalting unit through a pipeline.
Preferably, the fixed bed residuum hydroprocessing reaction unit includes at least 1 fixed bed reactor.
According to a particularly preferred embodiment, the fixed bed residuum hydroprocessing reaction unit includes 3 to 6 fixed bed reactors.
Preferably, the fixed bed wax oil hydroprocessing reaction unit comprises at least 1 fixed bed reactor.
According to a particularly preferred embodiment, the fixed bed wax oil hydroprocessing reaction unit comprises 1-3 fixed bed reactors.
Preferably, the system further comprises: and the fourth separation unit is used for separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
The following provides a process flow of a preferred embodiment of the method for producing high yields of light olefins according to the present invention in combination with fig. 1:
(1) Introducing a residual oil raw material 1 into a fixed bed residual oil hydrotreating reaction unit 2 in the presence of hydrogen to carry out hydrotreating reaction I, and introducing a residual oil hydrotreating reaction effluent 3 obtained after the hydrotreating reaction I into a first separation unit 4 to carry out separation to obtain a first gas effluent 5, first hydrogenated naphtha 6, first hydrogenated heavy oil 7 and hydrogenated slag reduction 8;
(2) Introducing the catalytic cracking slurry oil 25 and a part of the hydrogenation slag reduction 8 into a solvent deasphalting unit 9 for solvent deasphalting and separation in the presence of a solvent to obtain deasphalted oil 10 and deasphalted asphalt 11;
(3) Introducing the first hydrogenated heavy oil 7 and the deasphalted oil 10 into a fixed bed wax oil hydrotreating reaction unit 12 in the presence of hydrogen to carry out hydrotreating reaction II, and introducing a wax oil hydrotreating reaction effluent 13 obtained after the hydrotreating reaction II into a second separation unit 14 to carry out separation to obtain a second gas effluent 15, second hydrogenated naphtha 16 and second hydrogenated heavy oil 17;
(4) Introducing the second hydrogenated heavy oil 17 and the rest of the hydrogenated slag reduction 8 into a catalytic cracking reaction unit 18 for catalytic cracking reaction, and introducing a catalytic cracking reaction effluent 19 obtained after the catalytic cracking reaction into a third separation unit 20 for separation to obtain low-carbon olefin 21, catalytic cracking naphtha 22, catalytic cracking light cycle oil 23, catalytic cracking heavy cycle oil 24 and catalytic cracking slurry oil 25;
(5) The catalytic cracking light cycle oil 23 and the catalytic cracking heavy cycle oil 24 are respectively and independently led out, circulated back to the fixed bed wax oil hydrotreating reaction unit 12 and circulated back to the fixed bed residual oil hydrotreating reaction unit 2, and the catalytic cracking slurry oil 25 is circulated back to the solvent deasphalting unit 9.
The method of the invention also has the following specific advantages:
1. the invention adopts 100% residual oil raw material (normal slag and/or reduced slag) to produce high-quality catalytic cracking raw material, and can reduce the raw material cost for producing low-carbon olefin to the greatest extent.
2. The invention realizes deep hydrogenation of wax oil fraction contained in residual oil raw material, first hydrogenated heavy oil cracked in residual oil hydrotreating reaction, deasphalted oil, catalytic cracking light cycle oil and catalytic cracking heavy cycle oil, thereby providing better raw material for catalytic cracking.
3. The residuum hydrotreatment reaction zone of the invention can be operated under the process conditions of conventional residuum hydrogenation without operating at high severity for producing catalytic cracking feedstock, which is beneficial to long-period operation of residuum hydrogenation equipment.
The invention will be described in detail below by way of examples. In the following examples, various raw materials used without particular description are commercially available.
In the following examples, without corresponding description:
the hydrotreating reaction I is carried out in a fixed bed residual oil hydrotreating medium-sized device;
the hydrotreating reaction II is carried out in a fixed bed wax oil hydrotreating medium-sized device;
The catalytic cracking reaction is carried out in a catalytic cracking medium-sized device.
The residuum feedstock was middle east residuum with properties as set forth in table 1.
In a fixed bed residuum hydrotreatment reaction zone, a catalyst A, a catalyst B, a catalyst C and a catalyst D are sequentially filled along the flow direction, wherein the filling volume ratio of the catalyst A to the catalyst B to the catalyst C to the catalyst D is 5:40:25:30;
in the solvent deasphalting zone, the solvent is pentane;
in a fixed bed wax oil hydrotreating reaction zone, a catalyst A and a catalyst E are sequentially filled along the flow direction, wherein the filling volume ratio of the catalyst A to the catalyst E is 5:95;
the catalysts A-E are produced by a kaolin catalyst factory of China petrochemical catalyst division company, and the properties of the catalysts A-E are shown in Table 2;
wherein, the catalyst A is a protecting catalyst, the catalyst B is a hydrodemetallization catalyst, the catalyst C is a hydrodesulfurization catalyst, the catalyst D is a hydrodecarbonization catalyst, and the catalyst E is a wax oil hydrotreating catalyst.
The catalytic cracking catalysts are MMC-2, and are produced by Qilu division of China petrochemical Co., ltd, and the MMC-2 properties are shown in Table 3.
The dry gas and the liquefied gas can be rectified to obtain low-carbon olefins such as ethylene, propylene and the like.
In the examples below, the feed and product flow rates for each reaction zone were calculated (without hydrogen) at 100g/h based on fresh residuum feed, unless otherwise indicated.
Table 1: residuum feedstock properties
| Properties of (C) | |
| Density (20 ℃), g/cm 3 | 0.9747 |
| Hydrogen content, wt% | 11.16 |
| Carbon residue content, weight percent | 10.34 |
| Sulfur content, wt% | 3.56 |
| Nitrogen content, wt% | 0.24 |
| Content of (nickel+vanadium), μg/g | 60.6 |
Table 2: composition and physicochemical properties of residuum hydrotreating catalyst and wax oil hydrotreating catalyst
| Project | Catalyst A | Catalyst B | Catalyst C | Catalyst D | Catalyst E |
| MO 3 Weight percent | 3.0 | 8.4 | 13.0 | 16.2 | 2.3 |
| NiO, wt% | 0.8 | 1.5 | 3.5 | 4.5 | 2.4 |
| WO 3 Weight percent | - | - | - | - | 26.0 |
| Pore volume, mL/g | 0.80 | 0.66 | 0.64 | 0.64 | 0.28 |
| Specific surface area, m 2 /g | 100 | 157 | 210 | 186 | 150 |
| Bulk density, g/cm 3 | 0.45 | 0.47 | 0.62 | 0.64 | 0.82 |
| Particle size, mm | 3.5 | 1.1 | 1.1 | 1.1 | 1.1 |
Table 3: catalytic cracking catalyst Properties
Example 1
The embodiment provides a method for producing a plurality of low-carbon olefins, which comprises the following steps:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone filled with a residual oil hydrotreating catalyst in the presence of hydrogen to carry out hydrotreating reaction I, and separating a residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction; wherein the first hydrogenated naphtha and the first hydrogenated heavy oil have a cut point of 175 ℃;
(2) Introducing the catalytic cracking slurry oil and 50 weight percent of the hydrogenation slag reduction into a solvent deasphalting zone containing a solvent for solvent deasphalting and separating to obtain deasphalted oil and deasphalted asphalt;
(3) Introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone filled with a wax oil hydrotreating catalyst in the presence of hydrogen to carry out hydrotreating reaction II, and separating wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil; wherein the cut point of the second hydrogenated naphtha and the second hydrogenated heavy oil is 175 ℃;
(4) Introducing the second hydrogenated heavy oil and 50 weight percent of the hydrogenated slag serving as raw materials for catalytic pyrolysis into a catalytic pyrolysis reaction zone filled with a catalytic pyrolysis catalyst for catalytic pyrolysis reaction, and separating a catalytic pyrolysis reaction effluent obtained after the catalytic pyrolysis reaction to obtain dry gas and liquefied gas, catalytic pyrolysis naphtha, catalytic pyrolysis light cycle oil, catalytic pyrolysis heavy cycle oil and catalytic pyrolysis slurry oil; the cutting point of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil is 350 ℃, the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are led out of the device in a circulating way, and the catalytic cracking slurry oil is circulated back to the solvent deasphalting zone.
The reaction conditions and the product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the process conditions and the product distribution of the solvent deasphalting zone are shown in table 5, the reaction conditions and the product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 6, the properties of the catalytic cracking raw materials are shown in table 7, and the reaction conditions and the product distribution of the catalytic cracking reaction zone are shown in table 8;
as can be seen from the data in tables 4-8, 5.2g ethylene and 18.6g propylene were obtained per 100g residuum feedstock in this example.
Comparative example 1
This comparative example is similar to the process of example 1, except that a fixed bed residuum hydroprocessing-solvent deasphalting-catalytic cracking process is employed to produce lower olefins, i.e., the residuum feedstock is reacted in a fixed bed residuum hydroprocessing reaction zone and separated from a first gaseous effluent, a first hydrogenated naphtha, a first hydrogenated heavy oil, and a hydrodeslag, then a catalytic cracking slurry and 50 wt.% of the hydrodeslag are introduced into a solvent deasphalting zone for solvent deasphalting and separation to obtain deasphalted oil and deasphalted bitumen, and finally the first hydrogenated heavy oil, deasphalted oil, and 50 wt.% of the hydrodeslag are introduced into a catalytic cracking reaction zone for catalytic cracking reaction.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the process conditions and product distribution of the solvent deasphalting zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 4.5g ethylene and 16.6g propylene were obtained per 100g residuum feedstock in this comparative example.
Example 2
This example is similar to the operating method of example 1, except that the hydroprocessed slag reduction introduced into the catalytic cracking reaction zone comprises 30 wt% of the total weight of the hydroprocessed slag reduction, and the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are mixed and introduced into the fixed bed wax oil hydroprocessing reaction zone.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the process conditions and product distribution of the solvent deasphalting zone are shown in table 5, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.8g ethylene and 21.2g propylene were obtained per 100g residuum feedstock in this example.
Example 3
This example is similar to the operating method of example 1, except that the hydroprocessed residue introduced into the catalytic cracking reaction zone comprises 60 wt.% of the total weight of the hydroprocessed residue, and the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are mixed and introduced into the fixed bed residuum hydroprocessing reaction zone.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the process conditions and product distribution of the solvent deasphalting zone are shown in table 5, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.7g ethylene and 20.5g propylene were obtained per 100g residuum feedstock in this example.
Example 4
This example is similar to the method of operation of example 1, except that the first and second hydrogenated naphthas are mixed to separate light naphthas and heavy naphthas, the light naphthas also being introduced into the catalytic cracking reaction zone for catalytic cracking reactions.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the process conditions and product distribution of the solvent deasphalting zone are shown in table 5, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.4g ethylene and 18.8g propylene were obtained per 100g residuum feedstock in this example.
Example 5
This example is similar to the operating method of example 1, except that in step (3) the effluent hydrogen content in the fixed bed wax oil hydrogenation reaction zone is 13.07 wt%.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the process conditions and product distribution of the solvent-extended deasphalting zone are shown in table 5, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 6, the properties of the catalytic cracking feedstock are shown in table 7, and the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 8.
As can be seen from the data in tables 4-8, 4.6g ethylene and 16.7g propylene were obtained per 100g residuum feedstock in this example.
Table 4: reaction conditions and product distribution in fixed bed residuum hydrotreatment reaction zone
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Table 5: process conditions and product distribution in solvent deasphalting zone
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| Feed flow, g/h | ||||||
| Hydrogenation slag reduction | 20.8 | 29.1 | 16.8 | 20.8 | 20.8 | 19.9 |
| Catalytic cracking slurry oil | 2.6 | 2.3 | 2.3 | 2.6 | 2.6 | 3.2 |
| Totalizing | 23.4 | 31.4 | 19.1 | 23.4 | 23.4 | 23.1 |
| Process conditions | ||||||
| Solvent(s) | Pentane | Pentane | Pentane | Pentane | Pentane | Pentane |
| Temperature, DEG C | 150 | 150 | 150 | 150 | 150 | 150 |
| Pressure, MPa | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Volume ratio of solvent to hydrogenated slag reduction | 5:1 | 5:1 | 5:1 | 5:1 | 5:1 | 5:1 |
| Product flow, g/h | ||||||
| Deasphalted oil | 11.8 | 15.9 | 9.6 | 11.8 | 11.8 | 11.5 |
| Deoiling asphalt | 11.6 | 15.5 | 9.5 | 11.6 | 11.6 | 11.6 |
| Totalizing | 23.4 | 31.4 | 19.1 | 23.4 | 23.4 | 23.1 |
Table 6: reaction condition and product distribution of fixed bed wax oil hydrotreatment reaction zone
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Table 7: catalytic cracking reaction zone feedstock properties
| Properties of (C) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Density (20 ℃), g/cm 3 | 0.8924 | 0.8806 | 0.8942 | 0.8914 | 0.9121 | 0.9200 |
| Hydrogen content, wt% | 13.08 | 13.35 | 13.05 | 13.08 | 12.64 | 12.46 |
| Carbon residue, weight percent | 3.13 | 1.81 | 3.42 | 3.11 | 3.11 | 3.02 |
| The sulfur content of the product is determined,weight percent | 0.20 | 0.11 | 0.21 | 0.20 | 0.20 | 0.17 |
| Nitrogen content, wt% | 0.065 | 0.031 | 0.059 | 0.065 | 0.055 | 0.050 |
| Content of (nickel+vanadium), μg/g | 3.8 | 2.1 | 3.5 | 3.8 | 3.9 | 3.3 |
Table 8: reaction conditions and product distribution in catalytic cracking reaction zone
From the results in tables 4 to 8, it can be seen that: the invention organically combines the fixed bed residual oil hydrotreating process, the fixed bed wax oil hydrotreating process, the catalytic cracking process and the solvent deasphalting process, and can obviously improve the hydrogenation depth of residual oil raw materials, thereby obviously improving the yield of low-carbon olefin products such as propylene, ethylene and the like in the combined process.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (40)
1. A method for producing high yields of light olefins, comprising:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction I, and separating residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction;
(2) Introducing the catalytic cracking slurry oil and a part of the hydrogenation slag reduction into a solvent deasphalting zone in the presence of a solvent to carry out solvent deasphalting and separation to obtain deasphalted oil and deasphalted asphalt;
(3) Introducing the first hydrogenated heavy oil and the deasphalted oil into a fixed bed wax oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
(4) Introducing the second hydrogenated heavy oil and the rest of the hydrogenated slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating a catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(5) At least one operation of leading out a device, recycling the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil to the fixed bed wax oil hydrotreating reaction zone and recycling the catalytic cracking heavy cycle oil to the fixed bed residual oil hydrotreating reaction zone is carried out independently, and the catalytic cracking slurry oil is recycled to the solvent deasphalting zone;
wherein in the step (3), the reaction condition of the fixed bed wax oil hydrotreating reaction zone and/or the catalyst grading mode in the fixed bed wax oil hydrotreating reaction zone are controlled so that the hydrogen content of the wax oil hydrotreating reaction effluent is not less than 13.2 wt%.
2. The process according to claim 1, wherein in step (1), the residuum feedstock is selected from at least one of atmospheric residuum, vacuum residuum.
3. The process of claim 1 or 2, wherein in step (1), the reaction conditions of the fixed bed residuum hydroprocessing reaction zone comprise: the reaction temperature is 300-460 ℃, the hydrogen partial pressure is 6-25MPa, and the liquid hourly space velocity is 0.10-1.0h -1 The volume ratio of hydrogen to oil is 100-1500.
4. The process of claim 3 wherein in step (1), the reaction conditions of the fixed bed residuum hydroprocessing reaction zone comprise: the reaction temperature is 350-440 ℃, the hydrogen partial pressure is 12-20MPa, and the liquid hourly space velocity is 0.15-0.4h -1 The volume ratio of hydrogen to oil is 300-1000.
5. The process according to claim 1 or 2, wherein in step (1), the fixed bed residuum hydrotreating reaction zone is charged with a residuum hydrotreating catalyst having an average particle size of 0.5 to 50mm and a bulk density of 0.3 to 1.2g/cm 3 Average pore diameter of 6-30nm and specific surface area of 50-400m 2 /g。
6. The process of claim 5, wherein in step (1), the residuum hydrotreating catalyst is selected from at least one of guard catalyst I, hydrodemetallization catalyst, hydrodesulphurisation catalyst, and hydrodecarbon residue catalyst.
7. The process according to claim 5, wherein in step (1), the residuum hydrotreating catalyst contains a support selected from at least one of alumina, silica, and titania, and an active metal element selected from group vib metal elements and/or group viii metal elements supported on the support.
8. The method of claim 7, wherein in step (1), in the residuum hydroprocessing catalyst, the active metal element is selected from at least one of a combination of nickel-tungsten, a combination of nickel-tungsten-cobalt, a combination of nickel-molybdenum, a combination of cobalt-molybdenum.
9. The process of claim 7 wherein in the residuum hydroprocessing catalyst the support further comprises at least one element from the group consisting of boron, germanium, zirconium, phosphorus, chlorine, and fluorine.
10. The process according to claim 7, wherein the content of the active metal element in oxide is 1 to 30wt% based on the total weight of the resid hydrotreating catalyst in the resid hydrotreating catalyst.
11. The process according to claim 10, wherein the content of the active metal element in oxide is 1 to 25wt% based on the total weight of the resid hydrotreating catalyst in the resid hydrotreating catalyst.
12. The process according to claim 1 or 2, wherein in step (1), the separation conditions of the residuum hydrotreating reaction effluent are controlled such that the primary boiling point of the first hydrogenated naphtha is 50 to 70 ℃, the cut point of the first hydrogenated naphtha and the first hydrogenated heavy oil is 160 to 180 ℃, and the final boiling point of the first hydrogenated heavy oil is 500 to 580 ℃.
13. According toThe process of claim 1 or 2, wherein in step (2), the solvent is C 3 -C 7 Alkanes and/or C 3 -C 7 At least one of the olefins.
14. The method of claim 13, wherein in step (2), the solvent is C 4 -C 6 Alkanes and/or C 4 -C 6 At least one of the olefins.
15. The process of claim 1 or 2, wherein in step (2) the operating conditions of the solvent deasphalting zone comprise: the temperature is 50-260 ℃, the pressure is 1-7MPa, and the volume ratio of the solvent to the hydrogenated slag reduction amount is 2-12:1.
16. The process of claim 15, wherein in step (2), the operating conditions of the solvent deasphalting zone comprise: the temperature is 60-240 ℃, the pressure is 2-6MPa, and the volume ratio of the solvent to the hydrogenated slag reduction amount is 3-10:1.
17. the process of claim 1 or 2, wherein in step (2) the deasphalted oil comprises from 10 to 80 wt% of the total amount of feedstock introduced to the solvent deasphalting zone.
18. The process of claim 17 wherein in step (2) the deasphalted oil comprises from 30 to 70 weight percent of the total amount of feedstock introduced to the solvent deasphalting zone.
19. The process according to claim 1 or 2, wherein in step (3) the reaction conditions of the fixed bed wax oil hydroprocessing reaction zone and/or the catalyst fractionation pattern in the fixed bed wax oil hydroprocessing reaction zone are controlled such that the hydrogen content of the wax oil hydroprocessing reaction effluent is less than 13.5 wt-%.
20. The method according to claim 1 or 2, which comprisesIn step (3), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone include: the hydrogen partial pressure is 6-25MPa, the reaction temperature is 300-460 ℃, and the liquid hourly space velocity is 0.1-5.0h -1 The volume ratio of hydrogen to oil is 200-2000.
21. The process of claim 20, wherein in step (3), the reaction conditions of the fixed bed wax oil hydroprocessing reaction zone comprise: the hydrogen partial pressure is 10-20MPa, the reaction temperature is 350-440 ℃, and the liquid hourly space velocity is 0.5-2.0h -1 The volume ratio of hydrogen oil is 400-1200.
22. The process according to claim 1 or 2, wherein in step (3) the fixed bed wax oil hydroprocessing reaction zone is packed with a wax oil hydroprocessing catalyst having a bulk density of 0.4-1.3g/cm 3 The average grain diameter is 0.5-50mm, and the specific surface area is 50-400m 2 /g。
23. The method of claim 22, wherein in step (3), the wax oil hydrotreating catalyst is selected from at least one of guard catalyst II, wax oil hydrofinishing catalyst.
24. The method according to claim 23, wherein in step (3), the wax oil hydrotreating catalyst contains a support selected from at least one of alumina, a combination of alumina-silica, and titania, and an active metal element selected from at least one of nickel, cobalt, molybdenum, and tungsten, supported on the support.
25. The method of claim 23, wherein in step (3), in the wax oil hydrotreating catalyst, the total content of nickel and cobalt in terms of oxides is 0 to 30 wt%, the total content of molybdenum and tungsten in terms of oxides is 0 to 35 wt%, and the sum of the contents of nickel, cobalt, molybdenum, tungsten in terms of oxides is greater than 0, based on the total weight of the wax oil hydrotreating catalyst.
26. The process according to claim 1 or 2, wherein in step (3), the separation conditions of the wax oil hydrotreating reaction effluent are controlled such that the initial boiling point of the second hydrogenated naphtha is 50-70 ℃, the cutting points of the second hydrogenated naphtha and the second hydrogenated heavy oil is 160-180 ℃, and the final boiling point of the second hydrogenated heavy oil is 500-580 ℃.
27. The process according to claim 1 or 2, wherein in step (4), the catalytic cracking reaction zone is packed with a catalytic cracking catalyst comprising zeolite, an inorganic oxide, optionally together with clay, the inorganic oxide being at least one selected from silica, alumina, zirconia, titania and amorphous silica alumina, the zeolite being present in an amount of 10 to 50 wt%, the inorganic oxide being present in an amount of 5 to 90 wt% and the clay being present in an amount of 0 to 70 wt%, based on the total weight of the catalytic cracking catalyst.
28. The method according to claim 27, wherein in the catalytic cracking catalyst, the zeolite is at least one selected from a Y-type zeolite with or without rare earth elements, an HY-type zeolite with or without rare earth elements, an ultrastable Y-type zeolite with or without rare earth elements, and a zeolite having MFI structure.
29. The process of claim 27, wherein in step (4), the reaction conditions of the catalytic cracking reaction zone are: the weight ratio of the atomized steam to the residual oil raw material is 0.05-0.5:1, the weight ratio of the agent to the oil is 6-20:1, the temperature is 500-680 ℃, and the weight hourly space velocity is 1-6h -1 The reaction pressure is 0.05-1MPa.
30. The method according to claim 1 or 2, wherein in step (4), the separation conditions of the catalytic cracking reaction effluent are controlled such that the initial boiling point of the catalytic cracking light cycle oil is 150-180 ℃, the cutting points of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are 340-360 ℃, and the final boiling point of the catalytic cracking heavy cycle oil is 500-580 ℃.
31. The process of claim 1 or 2, wherein in step (4), the hydroprocessed slag introduced into the catalytic cracking reaction zone comprises 5-95 wt% of the total weight of the hydroprocessed slag.
32. The process of claim 31, wherein in step (4), the hydropulped slag introduced into the catalytic cracking reaction zone comprises 20-80 wt% of the total weight of the hydropulped slag.
33. The method according to claim 1 or 2, wherein the method further comprises: and separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
34. The process of claim 33, wherein the separation conditions of the first and/or second hydrogenated naphtha are controlled such that the light naphtha has an initial boiling point of 50-70 ℃, the light naphtha and the heavy naphtha have a cut point of 120-140 ℃, and the heavy naphtha has a final boiling point of 170-190 ℃.
35. A system for producing more light olefins, the system comprising:
the fixed bed residuum hydrotreatment reaction unit is used for carrying out hydrotreatment reaction I on a residuum raw material to obtain residuum hydrotreatment reaction effluent;
the first separation unit is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated heavy oil and hydrogenated slag reduction;
The solvent deasphalting unit is used for solvent deasphalting and separating the catalytic cracking slurry oil and a part of the hydrogenation slag reduction to obtain deasphalted asphalt and deasphalted oil;
the fixed bed wax oil hydrotreating reaction unit is used for carrying out hydrotreating reaction II on the first hydrogenated heavy oil and the deasphalted oil to obtain a wax oil hydrotreating reaction effluent;
the second separation unit is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha and second hydrogenated heavy oil;
the catalytic cracking reaction unit is used for carrying out catalytic cracking reaction on the second hydrogenated heavy oil and the rest of the hydrogenated slag reduction to obtain a catalytic cracking reaction effluent;
the third separation unit is used for separating the catalytic cracking reaction effluent to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil, wherein the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are respectively and independently led out of the device, recycled to the fixed bed wax oil hydrotreating reaction zone and recycled to at least one operation in the fixed bed residual oil hydrotreating reaction zone, and the catalytic cracking slurry oil is recycled to the solvent deasphalting unit through a pipeline.
36. The system of claim 35, wherein the fixed bed residuum hydroprocessing reaction unit comprises at least 1 fixed bed reactor.
37. The system of claim 35, wherein the fixed bed residuum hydroprocessing reaction unit comprises 3-6 fixed bed reactors.
38. The system of any of claims 35-37, wherein the fixed bed wax oil hydroprocessing reaction unit comprises at least 1 fixed bed reactor.
39. The system of any of claims 38, wherein the fixed bed wax oil hydroprocessing reaction unit comprises 1-3 fixed bed reactors.
40. The system of any one of claims 35-37, wherein the system further comprises:
and the fourth separation unit is used for separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
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| CN106701188A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Heavy oil product treatment processing method |
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| CN101045884A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil |
| CN106701188A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Heavy oil product treatment processing method |
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