CN116286077A - Method for directly preparing chemicals from raw oil - Google Patents
Method for directly preparing chemicals from raw oil Download PDFInfo
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- CN116286077A CN116286077A CN202111521554.2A CN202111521554A CN116286077A CN 116286077 A CN116286077 A CN 116286077A CN 202111521554 A CN202111521554 A CN 202111521554A CN 116286077 A CN116286077 A CN 116286077A
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- 239000000126 substance Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000003921 oil Substances 0.000 claims abstract description 168
- 239000003054 catalyst Substances 0.000 claims abstract description 159
- 238000006243 chemical reaction Methods 0.000 claims abstract description 136
- 239000010779 crude oil Substances 0.000 claims abstract description 75
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 60
- 239000003502 gasoline Substances 0.000 claims abstract description 25
- 239000002283 diesel fuel Substances 0.000 claims abstract description 16
- 239000000295 fuel oil Substances 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 239000000571 coke Substances 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims description 50
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 238000003795 desorption Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- -1 diesel Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000003027 oil sand Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000007670 refining Methods 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000001993 wax Substances 0.000 description 40
- 238000005516 engineering process Methods 0.000 description 23
- 239000002585 base Substances 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000004523 catalytic cracking Methods 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005194 fractionation Methods 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 6
- 238000012824 chemical production Methods 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of oil refining and chemical catalysis, and discloses a method for directly preparing chemicals from raw oil, which comprises the following steps: (1) The raw oil is contacted with DPC-1 catalyst to generate a first reaction, so as to obtain a first reaction product containing the to-be-generated DPC-1 catalyst; (2) Contacting the first reaction product containing the spent DPC-1 catalyst, recycle oil and the DPC-2 catalyst to generate a second reaction to obtain a second reaction product; (3) Fractionating the second reaction product to obtain a chemical; (4) Recycling at least one of gasoline, diesel oil and wax oil to step (2) as the recycle oil; wherein the DPC-1 catalyst has stronger alkalinity than the DPC-2 catalyst, and the DPC-1 catalyst and the DPC-2 catalyst are not separated in the second reaction link. The method provided by the invention has strong adaptability to raw materials, can be used for treating high-quality crude oil, can also be used for treating poor-quality crude oil and various heavy oils, can improve the distribution of chemicals, can improve the yield and quality of the chemicals, and can reduce the yield of coke.
Description
Technical Field
The invention relates to the technical field of oil refining and chemical catalysis, in particular to a method for directly preparing chemicals from raw oil.
Background
Crude oil chemical production techniques can be divided into two major categories, crude oil maximization chemical production techniques and crude oil direct chemical production techniques. The technology for preparing chemicals by maximizing crude oil is to integrate mature process technologies in the current oil refining and chemical industry, such as residual oil hydrogenation, delayed coking, diesel oil hydrocracking, catalytic cracking (deep catalytic cracking such as DCC technology), continuous reforming process technology and the like, and supply an ethylene cracking device to produce light olefins in a mode of maximizing ethylene cracking raw materials such as light naphtha, hydrocracking tail oil and the like; or maximizing and optimizing (typically feedstock deep hydrogenation techniques) the production of catalytic cracking feedstock, which is then converted to lower olefins and aromatics by DCC technology; or maximizing the production of heavy naphtha to produce mixed aromatic hydrocarbon by a continuous reforming process, and then maximizing the production of para-xylene (PX) by aromatic hydrocarbon extraction, adsorption separation, disproportionation, isomerization and other technologies.
The technology of directly preparing chemicals from crude oil can be divided into two main categories, namely a catalytic technical route and a non-catalytic technical route. The non-catalytic technology route of crude oil direct chemical preparation refers to technology of directly converting crude oil into light olefins without adopting catalytic (catalyst) technology, and at present, only ExxonMobil (ExxonMobil) company in the world puts into production one set of such devices in Singapore, so that industrialization is realized, and the principle is that: the method comprises the steps of heating the specially selected crude oil (usually paraffin-based light and high-quality crude oil) through heat exchange, separating the crude oil by a flash evaporation unit, and directly feeding about 70-75% of gas phase fraction (light component) into a traditional ethylene cracking furnace, namely cracking and converting the gas phase fraction into light olefin by a high-temperature steam cracking mode, wherein 25-30% by weight of heavy component in the crude oil leaves the flash evaporation unit, and further processing the heavy component into fuel oil or lubricating oil raw material by means of a traditional oil refining technology.
There are two types of crude oil direct cracking chemical manufacturing technologies declared by Saudi amo (Saudi amamco) corporation, TC2C, which is a hot crude oil manufacturing chemical TM Technology and catalytic crude oil to make chemicals CC2C TM However, both of these techniques have not been industrially used. The core technology comprises the steps of directly processing crude oil by utilizing hydrotreating, steam cracking and coking processes, producing olefin and aromatic hydrocarbon petrochemicals in a mode of maximizing the production of steam cracking raw materials, and converting the heavy part of the crude oil into petroleum coke and ethylene raw materials by the traditional oil refining technology (coking technology).
The catalytic technology route for directly preparing chemicals from crude oil refers to a method for directly converting crude oil into light olefins and aromatic hydrocarbons under the action of a catalyst so as to realize the maximized production of the olefins and aromatic hydrocarbons. Indian trust corporation developed a multi-zone catalytic cracking (MCC) process for directly cracking crude oil without the use of atmospheric and vacuum units, and could also be used in combination with cracking of condensate, shale oil, and dense oil, among others. Two methods for directly preparing chemicals from crude oil are proposed by China petrochemical science institute, wherein one method is used for treating paraffin-based high-quality light crude oil: firstly, paraffin-based high-quality light crude oil is cut into light fraction and heavy fraction, and then the light fraction and the heavy fraction are respectively subjected to catalytic cracking in a double-riser reactor so as to maximize the production of low-carbon olefin; a process for treating a naphthenic intermediate crude oil: the intermediate crude oil of naphthene is first hydrofined and then catalytically cracked. Other research units, such as China university of Petroleum (China east) and China academy of sciences of process research, have also conducted research on direct preparation of chemicals from crude oil, but all use high-quality light paraffin-based crude oil as raw materials, and consider a method of dividing the raw materials into light and heavy fractions to enter two risers respectively for catalytic cracking, and the technology of each of the above-mentioned units also stresses that severe conditions such as very high reaction temperature (e.g. 670-730 ℃) and very high catalyst-to-oil ratio (e.g. more than 25) are required. The university of Qinghua emphasizes the technology of a downstream bed reactor, and has the advantage of increasing the yield of propylene compared with the traditional catalytic cracking technology.
Compared with the technology of preparing chemicals by maximizing crude oil, the technology of preparing chemicals by directly using crude oil can maximally convert crude oil resources into basic organic chemical raw materials, and is an effective way for fully utilizing primary fossil resources of crude oil; the method can skip the processes of atmospheric and vacuum distillation, raw material refining and the like of the traditional oil refining, and can reduce the investment of devices, the waste of resources, the processing energy consumption and the emission of greenhouse gases.
However, molecular sieve catalysts are generally adopted in the existing crude oil direct chemical production technical route, so that the existing crude oil direct chemical production technical route is generally poor in substantial adaptability to raw materials, generally can only be used for treating high-quality raw oil, such as paraffin-based light crude oil, and cannot be directly used for processing non-paraffin-based inferior raw oil. Even if the poor quality raw oil is diluted or hydrotreated with the high quality raw oil, it is difficult to obtain a high yield and high quality chemical.
Therefore, it is needed to provide a method for directly preparing chemicals from raw oil, which has strong raw material adaptability and can improve chemical distribution and increase chemical yield.
Disclosure of Invention
The invention aims to solve the problems of poor raw material adaptability, poor chemical distribution, low yield and high coke yield in the crude oil direct chemical preparation technology in the prior art, and provides a method for directly preparing chemicals from raw oil.
In order to achieve the above object, the present invention provides a method for directly preparing chemicals from raw oil, the method comprising the steps of:
(1) The raw oil is contacted with DPC-1 catalyst to generate a first reaction, so as to obtain a first reaction product containing the to-be-generated DPC-1 catalyst;
(2) Contacting the first reaction product containing the spent DPC-1 catalyst, recycle oil and the DPC-2 catalyst to generate a second reaction to obtain a second reaction product;
(3) Fractionating the second reaction product to obtain a chemical;
(4) Recycling at least one of gasoline, diesel and wax oil in the chemical to step (2) as the recycle oil;
wherein the DPC-1 catalyst is more basic than the DPC-2 catalyst.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
1) The method for directly preparing chemicals from raw oil provided by the invention has the advantages that the DPC-1 catalyst is firstly utilized to perform a first reaction with the raw oil, and then the first reaction product containing the to-be-generated DPC-1 catalyst is contacted with recycle oil and the DPC-2 catalyst to perform a second reaction, so that the adaptability of the method for directly preparing chemicals from the raw oil to raw materials is improved, and the method can be used for treating high-quality crude oil, poor-quality crude oil and various heavy oils;
2) The method for directly preparing chemicals from the raw oil improves the distribution of the chemicals, improves the yield and quality of the chemicals, and reduces the yield of coke;
3) The method for directly preparing chemicals from the raw oil provided by the invention does not need to separate the catalyst from the reaction product of the first reaction product, has simple process flow and low investment, and is suitable for industrial popularization.
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 basicity of the catalyst can be determined by a temperature-programmed carbon dioxide adsorption method (CO 2 TPD) was tested on a Quantachrome ChemBet 3000 chemisorber. Taking 150mg of catalyst sample, pretreating at 600 ℃ for 1h under He gas atmosphere, and then cooling to 100 ℃ for CO 2 And (5) adsorption. The volume ratio of the use is 1: CO of 9 2 The mixture of He and the catalyst is used as adsorption gas, adsorbed for 30min at 100 ℃, and then purged for 30min by He gas to remove physically adsorbed CO 2 . Finally, under the He atmosphere, the temperature is 16 ℃ for min -1 Is desorbed at a rate of from 100 ℃ to 600 ℃ to obtain CO 2 -TPD profile. From CO 2 Reading CO in TPD profile 2 The desorption peak temperature, calculate CO 2 Number of base centers at the desorption peak position. Wherein CO 2 The higher the desorption peak temperature, the higher the CO 2 The more the number of base centers at the desorption peak position, the more basic the catalyst.
The invention provides a method for directly preparing chemicals from raw oil, which comprises the following steps:
(1) The raw oil is contacted with DPC-1 catalyst to generate a first reaction, so as to obtain a first reaction product containing the to-be-generated DPC-1 catalyst;
(2) Contacting the first reaction product containing the spent DPC-1 catalyst, recycle oil and the DPC-2 catalyst to generate a second reaction to obtain a second reaction product;
(3) Fractionating the second reaction product to obtain a chemical;
(4) Recycling at least one of gasoline, diesel and wax oil in the chemical to step (2) as the recycle oil;
wherein the DPC-1 catalyst is more basic than the DPC-2 catalyst.
In the present invention, the method provided by the present invention does not separate the DPC-1 catalyst and the DPC-2 catalyst in the second reaction stage (step (2)).
In step (1):
in the invention, the first reaction of the raw oil contacted with the DPC-1 catalyst comprises a cracking shearing reaction and a refining reaction, and is used for removing substances such as sulfur, nitrogen, metal, carbon residue and the like in the raw oil so as to improve the catalytic cracking effect of the subsequent raw oil, improve the distribution of chemicals and improve the yield and quality of the chemicals.
In a preferred embodiment, the feedstock is selected from crude oil and/or heavy oil; the crude oil refers to petroleum which is not extracted, the heavy oil refers to residues left after the crude oil is processed and light components are extracted, and the residues can be selected from various types of intermediate, intermediate-cycloalkyl and cycloalkyl heavy distillate oil such as straight-run wax oil, coker wax oil, hydrogenated wax oil, atmospheric residue, vacuum residue and the like.
In the method for directly preparing chemicals from the raw oil, provided by the invention, the raw oil has strong adaptability, and crude oil is not required to be specially limited. Specifically, when the base property of crude oil is classified, the crude oil may be classified into paraffinic crude oil, intermediate base crude oil, intermediate-naphthenic crude oil and naphthenic crude oil, and the method for directly preparing chemicals from raw oil provided by the present invention may be used for treating both paraffinic crude oil and intermediate base crude oil, intermediate-naphthenic crude oil and naphthenic crude oil. When the density of crude oil is divided, the crude oil can be divided into light crude oil, medium crude oil, heavy crude oil and extra thick crude oil. The raw oil in the invention can be single crude oil or single heavy oil, or multiple crude oils, multiple heavy oils or mixed oil of crude oil and heavy oil. That is, the raw oil is one or more selected from oil sand asphalt, venezuela extra heavy oil, straight run wax oil, coker wax oil, hydrogenated wax oil, atmospheric residue and vacuum residue.
In a preferred embodiment, the DPC-1 catalyst comprises 85-99 parts by weight of carrier I and 1-15 parts by weight of active metal oxide I; wherein the carrier I is at least one selected from alumina, silica, titania and zirconia; the active metal oxide I is selected from alkali metal oxide and/or alkaline earth metal oxide.
In a preferred embodiment, the DPC-1 catalyst comprises 90-98 parts by weight, preferably 94-97 parts by weight, of carrier I and 2-10 parts by weight, preferably 3-6 parts by weight, of active metal oxide I.
In a preferred embodiment, the support I is selected from alumina and/or silica, preferably silica.
In a preferred embodiment, the active metal oxide I is selected from at least one of calcium oxide, magnesium oxide, barium oxide, strontium oxide, preferably magnesium oxide and/or barium oxide.
In a preferred embodiment, the DPC-1 catalyst is CO 2 The desorption peak temperature is 185-195 ℃, preferably 187-192 ℃; CO 2 The number of base centers at the desorption peak position is 16 to 22mmol/g, preferably 18 to 21mmol/g.
In a preferred embodiment, the DPC-1 catalyst has a bulk ratio of 0.5 to 0.65g/mL, preferably 0.55 to 0.6g/mL; the particle size is 40-120. Mu.m, preferably 70-90. Mu.m.
In a preferred embodiment, the reaction conditions of the first reaction include: the mass ratio of the DPC-1 catalyst to the raw oil is 5-20:1, preferably 8-15:1.
in a preferred embodiment, the reaction conditions of the first reaction further comprise: the feed temperature of the feed oil is 180-340 ℃, preferably 200-330 ℃, more preferably 210-300 ℃; the DPC-1 catalyst is fed at a temperature of 580-750deg.C, preferably 600-670 deg.C.
In a preferred embodiment, the reaction conditions of the first reaction further comprise: the angle between the injection direction of the feed oil and the flow direction of the DPC-1 catalyst flow is 0-180 °, preferably 90-180 °.
In the invention, when the raw oil contacts with the DPC-1 catalyst, when the included angle between the flowing direction of the raw oil and the flowing direction of the DPC-1 catalyst is 180 degrees, the flowing directions of the raw oil and the DPC-1 catalyst are opposite, and countercurrent contact is carried out between the raw oil and the DPC-1 catalyst; when the included angle between the flowing direction of the raw oil and the flowing direction of the DPC-1 catalyst is 0 DEG, the flowing direction of the raw oil is the same as that of the DPC-1 catalyst, and the raw oil and the DPC-1 catalyst are in concurrent contact.
In a preferred embodiment, the reaction conditions of the first reaction further comprise: the temperature of the first reaction is 380-550 ℃, preferably 410-535 ℃, more preferably 430-530 ℃; the pressure of the first reaction is 0.1-1MPa, preferably 0.1-0.4MPa; the time of the first reaction is 0.1 to 4s, preferably 0.5 to 3s.
In step (2):
in a preferred embodiment, the cycle oil is selected from at least one of gasoline, diesel, wax oil in the chemicals.
In a preferred embodiment, the cycle oil is gasoline. The gasoline is selected as recycle oil, so that the content of low-carbon olefin in the second reaction product can be increased, and the yield of liquefied gas is improved.
In a preferred embodiment, the cycle oil is diesel and/or wax oil. Wherein diesel oil and/or wax oil is selected as recycle oil, and C in the second reaction product can be increased 2 -C 5 The content of olefin and 1-5 ring aromatic hydrocarbon reduces the wax oil yield, and increases the yields of liquefied gas, gasoline and diesel oil; furthermore, diesel oil and/or wax oil is selected as recycle oil, and C in liquefied gas can be also obtained 3 -C 4 The content of olefin is increased, C in gasoline 5 The content of olefin and mono-cyclic aromatic hydrocarbon is increased, and the content of 2-5 cyclic aromatic hydrocarbon in diesel oil and wax oil is increased.
In a preferred embodiment, the DPC-2 catalyst comprises 59-68 parts by weight of carrier II,0-3 parts by weight of active metal oxide II and 30-40 parts by weight of molecular sieve; wherein the carrier II is at least one of alumina, silica, titania and zirconia; the active metal oxide II is selected from alkali metal oxide and/or alkaline earth metal oxide; the molecular sieves include mesoporous molecular sieves and optionally macroporous molecular sieves.
In a preferred embodiment, the DPC-2 catalyst preferably comprises 60 to 67.4 parts by weight of carrier II,0.5 to 1.5 parts by weight of active metal oxide II and 31 to 35 parts by weight of molecular sieve.
In a preferred embodiment, the support II is selected from alumina and/or silica, preferably silica.
In a preferred embodiment, the active metal oxide II is selected from at least one of calcium oxide, magnesium oxide, barium oxide, strontium oxide, preferably calcium oxide and/or magnesium oxide.
In a preferred embodiment, support I and metal active component I in the DPC-1 catalyst are the same as support II and metal active component II in the DPC-2 catalyst.
In a preferred embodiment, the molecular sieve comprises a medium pore molecular sieve and a large pore molecular sieve, wherein the mass ratio of medium pore molecular sieve to large pore molecular sieve is 100:1-20, preferably 100:10-15.
In a preferred embodiment, the medium pore molecular sieve is selected from ZSM-5 molecular sieve and/or ZSM-48 molecular sieve and the large pore molecular sieve is selected from Y-type molecular sieves.
The silica-alumina ratio of the ZSM-5 molecular sieve, the ZSM-48 molecular sieve and the Y-type molecular sieve is not particularly limited, and the silica-alumina ratio commonly used in the molecular sieves in the field can be used in the invention. The sources of the ZSM-5 molecular sieve, the ZSM-48 molecular sieve and the Y-type molecular sieve are not particularly limited, and the molecular sieve can be a commercial product or can be prepared according to a conventional method in the field. The preparation method of the molecular sieve is not repeated in the invention. Preferably, the mole ratio of silica/alumina in the ZSM-5 molecular sieve is from 10 to 100:1, preferably 25-50:1, a step of; the mole ratio of silica/alumina in the ZSM-48 molecular sieve is 50:200, preferably 100-150:1, a step of; the molar ratio of silicon oxide to aluminum oxide in the Y-type molecular sieve is 3-30:1, preferably 4-15:1.
in a preferred embodiment, the mesoporous molecular sieve is selected from the group consisting of ZSM-5 molecular sieves and ZSM-48 molecular sieves; wherein the mass ratio of the ZSM-5 molecular sieve to the ZSM-48 molecular sieve is 5-20:1, preferably 10-15:1.
in a preferred embodiment, the DPC-2 catalyst is CO 2 The desorption peak temperature is 165-184 ℃, preferably 169-182 ℃; CO 2 The number of base centers at the desorption peak position is 3 to 14mmol/g, preferably 4 to 12mmol/g.
In a preferred embodiment, the DPC-2 catalyst has a bulk ratio of 0.65-0.8g/mL, preferably 0.7-0.75g/mL; the particle size is 20-120. Mu.m, preferably 30-80. Mu.m.
In a preferred embodiment, the DPC-1 catalyst is CO 2 The number of the alkali centers at the desorption peak position is at least 2mmol/g higher than that of the DPC-2 catalyst; the DPC-2 catalyst has a greater bulk ratio than the DPC-1 catalyst.
In a preferred embodiment, the recycle oil is fed at a temperature of 180 to 260 ℃, preferably 200 to 230 ℃; the DPC-2 catalyst is fed at a temperature of 580-750 ℃, preferably 610-680 ℃.
In a preferred embodiment, the DPC-2 catalyst is contacted with the recycle oil under the first reaction product support; the included angle between the flow direction of the DPC-2 catalyst and the injection direction of the cycle oil is 0-180 °, preferably 90-180 °.
When the DPC-2 catalyst is in contact with the recycle oil, when the included angle between the flowing direction of the DPC-2 catalyst and the moving direction of the recycle oil is 180 degrees, the DPC-2 catalyst and the recycle oil are in countercurrent contact; when the included angle between the flowing direction of the DPC-2 catalyst and the flowing direction of the recycle oil is 0 DEG, the first reaction product is in concurrent contact with the recycle oil.
In a preferred embodiment, the reaction conditions of the second reaction comprise a recycling ratio of 0.1 to 0.5, preferably 0.2 to 0.4. Wherein, the recycle ratio refers to the ratio of recycle oil to fresh feed oil.
In a preferred embodiment, the reaction conditions of the second reaction further comprise: the DPC-2 catalyst and recycle oil are used in amounts such that the reaction temperature of the second reaction is 5-120 ℃, preferably 8-90 ℃, more preferably 10-50 ℃ higher than the reaction temperature of the first reaction; the pressure of the second reaction is 0.1-1MPa, preferably 0.1-0.4MPa; the time for the second reaction is 0.5 to 5s, preferably 0.5 to 3s.
In a preferred embodiment, the first and second reactions are carried out in a riser reactor; the riser reactor comprises a first reaction zone, a second reaction zone and a settler, wherein raw oil and DPC-1 catalyst are contacted in the first reaction zone under the action of a pre-lifting medium to generate the first reaction, so as to obtain a first reaction product containing the to-be-generated DPC-1 catalyst; the first reaction product containing the spent DPC-1 catalyst, recycle oil and DPC-2 catalyst enter the second reaction zone, and contact and generate the second reaction in the second reaction zone to obtain a mixture containing the spent DPC-1 catalyst, the spent DPC-2 catalyst and the second reaction product; the mixture is contacted with stripping steam in a settler to strip, and the second reaction product is separated from the spent DPC-1 catalyst and the spent DPC-2 catalyst to obtain the second reaction product.
In a preferred embodiment, the pre-lifting medium is selected from at least one of steam, dry gas, natural gas and liquefied gas, preferably steam.
In a preferred embodiment, the mass ratio of the feedstock oil to the pre-lifting medium is 100:1-15, preferably 100:1-8.
In a preferred embodiment, the stripping steam is selected from at least one of steam, dry gas, natural gas and liquefied gas, preferably steam.
In a preferred embodiment, the mass ratio of the feed oil to the stripping steam is 100:1-15, preferably 100:10-15.
In a preferred embodiment, the yield of the catalytic coke in the second reaction is 30% to 130%, preferably 50% to 100% of the carbon residue value of the feedstock oil. Wherein, in the present invention, catalytic coke refers to coke formed during the reaction.
In step (3):
in a preferred embodiment, the chemicals include dry gas, liquefied gas, gasoline, diesel and wax oil. Wherein the distillation range of gasoline is 30-205 ℃, the distillation range of diesel oil is 120-380 ℃, and the wax oil is distillate oil above 380 ℃.
Wherein, the dry gas obtained in the invention is rich in ethylene, the liquefied gas is rich in propylene and butylene, the gasoline is rich in olefins with more than C5, and the diesel oil and wax oil are rich in 2-5 cyclic aromatic hydrocarbons. The fractionation of the second reaction product is not particularly limited in the present invention, and the fractionation may be performed according to conventional fractionation operations in the art according to the specific distribution of chemicals in the second reaction product, and will not be described in detail.
In a preferred embodiment, the yield of dry gas is 0.3-8%, preferably 0.6-4.5%; the yield of the liquefied gas is 10-45%, preferably 20-35%; the yield of the gasoline is 24-45%, preferably 27-38%; the yield of the diesel oil is 15-37%, preferably 20-30%; the yield of the wax oil is 5-25%, preferably 4-15%.
In a preferred embodiment, the ethylene content in the dry gas is 40-55wt%, preferably 42-53wt%. The method for directly preparing chemicals from the raw oil provided by the invention has the advantages that the yield of the dry gas is lower in the prepared chemicals, but the ethylene content in the dry gas is high, and the product value is high.
In a preferred embodiment, the total amount of carbon tri-and carbon tetra-olefins in the liquefied gas is 60 to 98wt%, preferably 70 to 95wt%; in the gasoline, C 5 The above olefins are present in an amount of 30 to 60wt%, preferably 40 to 55wt%.
In a preferred embodiment, the aromatic hydrocarbon content of the diesel fuel is 70-95wt%, preferably 75-90wt%.
The method for directly preparing chemicals from the raw oil provided by the invention has strong raw material adaptability, can be used for treating light crude oil, heavy crude oil and heavy oil, can improve chemical distribution, increase chemical yield, obtain high-quality chemicals, and is suitable for industrial popularization.
The present invention will be described in detail by examples. Wherein the DPC-1 catalyst used in the examples contains 95wt% of silica and 5wt% of magnesia, CO of the DPC-1 catalyst 2 The desorption peak temperature is 189 ℃, CO 2 The number of alkali centers at the desorption peak position is 20.27mmol/g, the heap ratio is 0.55g/mL, and the particle size is 80 mu m;
the DPC-2 catalyst contains 67wt% of silicon oxide, 0.5wt% of calcium oxide, 1.0wt% of magnesium oxide, 26.0wt% of ZSM-5 molecular sieve (the mol ratio of silicon oxide to aluminum oxide is 30:1), 2.0wt% of ZSM-48 molecular sieve (the mol ratio of silicon oxide to aluminum oxide is 100:1) and 3.5wt% of Y-type molecular sieve (the mol ratio of silicon oxide to aluminum oxide is 5:1); CO of DPC-2 catalyst 2 The desorption peak temperature is 172 ℃, CO 2 The number of base centers at the desorption peak position was 8.85mmol/g, the mass ratio was 0.75g/mL, and the particle diameter was 50. Mu.m.
The mid-cycloalkyl marine heavy crude oil PL19-3, mid-cycloalkyl wax oil, mid-cycloalkyl vacuum residuum, mid-base atmospheric residuum in the examples were all from Huiz petrochemical Co.
Example 1
(1) Under the action of pre-lifting steam (water vapor), the DPC-1 catalyst and the intermediate-cycloalkyl marine heavy crude oil PL19-3 are in countercurrent contact in a first reaction zone of a riser reactor to generate a first reaction, wherein the temperature of the first reaction is 480 ℃, the pressure of the first reaction is 0.23MPa, and the time of the first reaction is 2s, so that a first reaction product containing the spent DPC-1 catalyst is obtained; wherein the entering temperature of the DPC-1 catalyst is 630 ℃, the feeding temperature of the intermediate-cycloalkyl marine heavy crude oil PL19-3 is 230 ℃, the mass ratio of the DPC-1 catalyst to the intermediate-cycloalkyl marine heavy crude oil PL19-3 is 8:1, and the mass ratio of the intermediate-cycloalkyl marine heavy crude oil PL19-3 to the pre-lifting medium is 100:3.3;
(2) The first reaction product carrying DPC-2 catalyst enters a second reaction zone of a riser reactor and is in countercurrent contact with recycle oil in the second reaction zone to generate a second reaction, wherein the temperature of the second reaction is 525 ℃, the pressure of the second reaction is 0.23MPa, and the time of the second reaction is 3s, so that a mixture containing the to-be-generated DPC-1 catalyst, the to-be-generated DPC-2 catalyst and the second reaction product is obtained; wherein the recycle oil is wax oil, the feeding temperature is 200 ℃, the entering temperature of the DPC-2 catalyst is 650 ℃, the recycle ratio is 0.3, and the use amount of the DPC-2 catalyst and the recycle oil ensures that the reaction temperature of the second reaction is higher than the reaction temperature of the first reaction by 45 ℃;
the mixture is contacted with stripping steam (water vapor) in a settler to strip, and the second reaction product is separated from the spent DPC-1 catalyst and the spent DPC-2 catalyst to obtain a second reaction product; wherein the mass ratio of the intermediate-cycloalkyl marine heavy crude oil PL19-3 to the stripping steam is 100:14;
analyzing the separated spent DPC-1 catalyst and spent DPC-2 catalyst to obtain a catalyst Jiao Shoulv which is 70wt% of the carbon residue value of the raw oil;
(3) Fractionating the second reaction product to obtain dry gas with ethylene content of 46.2wt%, and liquefied gas with total content of carbon tri-olefin and carbon tetra-olefin of 94.6wt%, C 5 Gasoline with 49.2wt% of the olefin, diesel with 80wt% of aromatic hydrocarbon, and wax oil; wherein, the yield of the dry gas is 2.2%, the yield of the liquefied gas is 27.0%, the yield of the gasoline is 32.5%, the yield of the diesel oil is 24.5%, and the yield of the wax oil is 8.9%;
(4) And (3) recycling the wax oil obtained by fractionation to the step (2) as recycle oil.
Example 2
(1) Under the action of pre-lifting steam (water vapor), the DPC-1 catalyst and the intermediate-cycloalkyl wax oil are in countercurrent contact in a first reaction zone of a riser reactor to generate a first reaction, wherein the temperature of the first reaction is 420 ℃, the pressure of the first reaction is 0.35MPa, and the time of the first reaction is 3s, so that a first reaction product containing the to-be-generated DPC-1 catalyst is obtained; wherein the entering temperature of the DPC-1 catalyst is 600 ℃, the feeding temperature of the intermediate-cycloalkyl wax oil is 300 ℃, the mass ratio of the DPC-1 catalyst to the intermediate-cycloalkyl wax oil is 9:1, and the mass ratio of the intermediate-cycloalkyl wax oil to the pre-lifting medium is 100:4, a step of;
(2) The first reaction product carrying DPC-2 catalyst enters a second reaction zone of a riser reactor and is in countercurrent contact with recycle oil in the second reaction zone to generate a second reaction, wherein the temperature of the second reaction is 490 ℃, the pressure of the second reaction is 0.25MPa, and the time of the second reaction is 2s, so that a mixture containing the to-be-generated DPC-1 catalyst, the to-be-generated DPC-2 catalyst and the second reaction product is obtained; wherein the recycle oil is wax oil, the feeding temperature is 200 ℃, the entering temperature of the DPC-2 catalyst is 660 ℃, the recycle ratio is 0.15, and the use amount of the DPC-2 catalyst and the recycle oil ensures that the reaction temperature of the second reaction is 70 ℃ higher than that of the first reaction;
the mixture is contacted with stripping steam (water vapor) in a settler to strip, and the second reaction product is separated from the spent DPC-1 catalyst and the spent DPC-2 catalyst to obtain a second reaction product; wherein, the mass ratio of the intermediate-cycloalkyl wax oil to the stripping steam is 100:15;
analyzing the separated spent DPC-1 catalyst and spent DPC-2 catalyst to obtain the yield of the catalytic coke which is 68wt% of the carbon residue value of the raw oil;
(3) Fractionating the second reaction product to obtain dry gas with ethylene content of 42.6wt%, and liquefied gas with total content of carbon tri-olefin and carbon tetra-olefin of 89.6wt%, C 5 Gasoline with 46.6wt% of the olefin, diesel with 83wt% of aromatic hydrocarbon, and wax oil; wherein, the yield of the dry gas is 2.50 percent, the yield of the liquefied gas is 30.50 percent, the yield of the gasoline is 36.15 percent, the yield of the diesel oil is 21.95 percent, and the yield of the wax oil is 4.5 percent;
(4) And (3) recycling the wax oil obtained by fractionation to the step (2) as recycle oil.
Example 3
(1) Under the action of pre-lifting steam (water vapor), the DPC-1 catalyst and the intermediate-cycloalkyl vacuum residue are in countercurrent contact in a first reaction zone of a riser reactor to generate a first reaction, wherein the temperature of the first reaction is 510 ℃, the pressure of the first reaction is 0.26MPa, and the time of the first reaction is 2.0s, so that a first reaction product containing the to-be-generated DPC-1 catalyst is obtained; wherein the entering temperature of the DPC-1 catalyst is 660 ℃, the feeding temperature of the intermediate-cycloalkyl vacuum residue is 250 ℃, the mass ratio of the DPC-1 catalyst to the intermediate-cycloalkyl vacuum residue is 12:1, and the mass ratio of the intermediate-cycloalkyl vacuum residue to the pre-lifting medium is 100:5.5;
(2) The first reaction product carrying DPC-2 catalyst enters a second reaction zone of a riser reactor and is in countercurrent contact with recycle oil in the second reaction zone to generate a second reaction, wherein the temperature of the second reaction is 560 ℃, the pressure of the second reaction is 0.26MPa, and the time of the second reaction is 3s, so that a mixture containing the to-be-generated DPC-1 catalyst, the to-be-generated DPC-2 catalyst and the second reaction product is obtained; wherein the recycle oil is wax oil, the feeding temperature is 200 ℃, the entering temperature of the DPC-2 catalyst is 680 ℃, the recycle ratio is 0.45, and the use amount of the DPC-2 catalyst and the recycle oil ensures that the reaction temperature of the second reaction is 50 ℃ higher than that of the first reaction;
the mixture is contacted with stripping steam (water vapor) in a settler to strip, and the second reaction product is separated from the spent DPC-1 catalyst and the spent DPC-2 catalyst to obtain a second reaction product; wherein the mass ratio of the intermediate-cycloalkyl vacuum residuum to the stripping steam is 100:14;
analyzing the separated spent DPC-1 catalyst and spent DPC-2 catalyst to obtain a catalyst Jiao Shoulv which is 67wt% of the carbon residue value of the raw oil;
(3) Fractionating the second reaction product to obtain dry gas with 49.2wt% of ethylene content and liquefied gas with 93.5wt% of total content of carbon tri-olefin and carbon tetra-olefin, C 5 Gasoline with the content of the olefin of 51.2 weight percent, diesel with the content of the aromatic hydrocarbon of 81 weight percent, and wax oil; wherein, the yield of the dry gas is 3.4wt%, the yield of the liquefied gas is 26.0wt%, the yield of the gasoline is 33.5wt%, the yield of the diesel oil is 21.5wt%, and the yield of the wax oil is 7.2wt%;
(4) And (3) recycling the wax oil obtained by fractionation to the step (2) as recycle oil.
Example 4
(1) Under the action of pre-lifting steam (water vapor), the DPC-1 catalyst and the intermediate base atmospheric residuum are in countercurrent contact in a first reaction zone of a riser reactor to generate a first reaction, wherein the temperature of the first reaction is 520 ℃, the pressure of the first reaction is 0.27MPa, and the time of the first reaction is 2.5s, so that a first reaction product containing the to-be-generated DPC-1 catalyst is obtained; wherein the entering temperature of the DPC-1 catalyst is 670 ℃, the feeding temperature of the intermediate base atmospheric residuum is 215 ℃, the mass ratio of the DPC-1 catalyst to the intermediate base atmospheric residuum is 15:1, and the mass ratio of the intermediate base atmospheric residuum to the pre-lifting medium is 100:4.5;
(2) The first reaction product carries DPC-2 catalyst and enters a second reaction zone of a riser reactor to be in countercurrent contact with recycle oil in the second reaction zone to generate a second reaction, wherein the temperature of the second reaction is 530 ℃, the pressure of the second reaction is 0.27MPa, and the time of the second reaction is 2.5s, so that a mixture containing the spent DPC-1 catalyst, the spent DPC-2 catalyst and the second reaction product is obtained; wherein the recycle oil is wax oil, the feeding temperature is 210 ℃, the entering temperature of the DPC-2 catalyst is 670 ℃, the recycle ratio is 0.35, and the use amount of the DPC-2 catalyst and the recycle oil ensures that the reaction temperature of the second reaction is 10 ℃ higher than that of the first reaction;
the mixture is contacted with stripping steam (water vapor) in a settler to strip, and the second reaction product is separated from the spent DPC-1 catalyst and the spent DPC-2 catalyst to obtain a second reaction product; wherein the mass ratio of the medium-based atmospheric residuum to the stripping steam is 100:10;
analyzing the separated spent DPC-1 catalyst and spent DPC-2 catalyst to obtain the yield of the catalytic coke which is 65wt% of the carbon residue value of the raw oil;
(3) Fractionating the second reaction product to obtain dry gas with ethylene content of 48.9wt%, and liquefied gas with total content of carbon tri-olefin and carbon tetra-olefin of 94.5wt%, C 5 Gasoline with the olefin content of 52.2 weight percent, diesel with the aromatic hydrocarbon content of 79 weight percent, and wax oil; wherein, the yield of the dry gas is 2.7wt%, the yield of the liquefied gas is 22.0wt%, the yield of the gasoline is 35.5wt%, the yield of the diesel oil is 27.8wt%, and the yield of the wax oil is 5.1wt%;
(4) And (3) recycling the wax oil obtained by fractionation to the step (2) as recycle oil.
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 (10)
1. A method for directly preparing chemicals from raw oil, the method comprising the steps of:
(1) The raw oil is contacted with DPC-1 catalyst to generate a first reaction, so as to obtain a first reaction product containing the to-be-generated DPC-1 catalyst;
(2) Contacting the first reaction product containing the spent DPC-1 catalyst, recycle oil and the DPC-2 catalyst to generate a second reaction to obtain a second reaction product;
(3) Fractionating the second reaction product to obtain a chemical;
(4) Recycling at least one of gasoline, diesel and wax oil in the chemical to step (2) as the recycle oil;
wherein the DPC-1 catalyst is more basic than the DPC-2 catalyst.
2. The method of claim 1, wherein the feedstock is selected from crude oil and/or heavy oil; preferably, the crude oil includes light crude oil, medium crude oil, heavy crude oil and extra thick crude oil; the heavy oil is selected from straight-run wax oil, coker wax oil, hydrogenated wax oil, atmospheric residue and vacuum residue;
preferably, the raw oil is one or more selected from oil sand asphalt, venezuela extra heavy oil, straight run wax oil, coker wax oil, hydrogenated wax oil, atmospheric residue and vacuum residue.
3. The process according to claim 1 or 2, wherein the DPC-1 catalyst comprises 85-99 parts by weight of carrier I and 1-15 parts by weight of active metal oxide I; wherein the carrier I is at least one selected from alumina, silica, titania and zirconia; the active metal oxide I is selected from alkali metal oxide and/or alkaline earth metal oxide;
preferably, the support I is selected from alumina and/or silica, further preferably silica;
preferably, the active metal oxide I is at least one selected from calcium oxide, magnesium oxide, barium oxide and strontium oxide, and more preferably magnesium oxide and/or barium oxide;
preferably, the DPC-1 catalyst is CO 2 The desorption peak temperature is 185-195 ℃, preferably 187-192 ℃; CO 2 The number of the alkali centers at the desorption peak positions is 16-22mmol/g, preferably 18-21mmol/g;
preferably, the DPC-1 catalyst has a bulk ratio of 0.5-0.65g/mL, preferably 0.55-0.6g/mL; the particle size is 40-120. Mu.m, preferably 70-90. Mu.m.
4. A method according to any one of claims 1-3, wherein the reaction conditions of the first reaction comprise: the mass ratio of the DPC-1 catalyst to the raw oil is 5-20:1, preferably 8-15:1, a step of;
preferably, the reaction conditions of the first reaction further include: the feed temperature of the feed oil is 180-340 ℃, preferably 200-330 ℃, more preferably 210-300 ℃; the feed temperature of the DPC-1 catalyst is 580-750 ℃, preferably 600-670 ℃;
preferably, the reaction conditions of the first reaction further include: the included angle between the spraying direction of the raw oil and the flowing direction of the DPC-1 catalyst flow is 0-180 degrees, preferably 90-180 degrees;
preferably, the reaction conditions of the first reaction further include: the temperature of the first reaction is 380-550 ℃, preferably 410-535 ℃, more preferably 430-530 ℃; the pressure of the first reaction is 0.1-1MPa, preferably 0.1-0.4MPa; the time of the first reaction is 0.1 to 4s, preferably 0.5 to 3s.
5. The process of any of claims 1-4, wherein the DPC-2 catalyst comprises 59-68 parts by weight of carrier II,0-3 parts by weight of active metal oxide II, and 30-40 parts by weight of molecular sieve; wherein the carrier II is at least one of alumina, silica, titania and zirconia; the active metal oxide II is selected from alkali metal oxide and/or alkaline earth metal oxide; the molecular sieves include a medium pore molecular sieve and optionally a large pore molecular sieve;
preferably, the support II is selected from alumina and/or silica, preferably silica;
preferably, the active metal oxide II is at least one selected from calcium oxide, magnesium oxide, barium oxide and strontium oxide, preferably calcium oxide and/or magnesium oxide;
preferably, the molecular sieve comprises a medium pore molecular sieve and a large pore molecular sieve, wherein the mass ratio of the medium pore molecular sieve to the large pore molecular sieve is 100:1-20, preferably 100:10-15 parts;
preferably, the medium pore molecular sieve is selected from ZSM-5 molecular sieve and/or ZSM-48 molecular sieve, and the large pore molecular sieve is selected from Y-type molecular sieve;
preferably, the DPC-2 catalyst is CO 2 The desorption peak temperature is 165-184 ℃, preferably 169-182 ℃; CO 2 The number of the alkali centers at the desorption peak position is 3-14mmol/g, preferably 4-12mmol/g;
preferably, the DPC-2 catalyst has a bulk ratio of 0.65-0.8g/mL, preferably 0.7-0.75g/mL; the particle size is 20-120. Mu.m, preferably 30-80. Mu.m.
6. The method of any one of claims 1-5, wherein the reaction conditions of the second reaction comprise: the feeding temperature of the recycle oil is 180-260 ℃, preferably 200-230 ℃; the feed temperature of the DPC-2 catalyst is 580-750 ℃, preferably 610-680 ℃;
preferably, the reaction conditions of the second reaction further include: contacting said DPC-2 catalyst with said cycle oil under said first reaction product support; the included angle between the flowing direction of the DPC-2 catalyst and the spraying direction of the recycle oil is 0-180 degrees, preferably 90-180 degrees;
preferably, the reaction conditions of the second reaction further include: the recycling ratio is 0.1-0.5, preferably 0.2-0.4; the DPC-2 catalyst and recycle oil are used in amounts such that the reaction temperature of the second reaction is 5-120 ℃, preferably 8-90 ℃, more preferably 10-50 ℃ higher than the reaction temperature of the first reaction; the pressure of the second reaction is 0.1-1MPa, preferably 0.1-0.4MPa; the time for the second reaction is 0.5 to 5s, preferably 0.5 to 3s.
7. The method of any of claims 1-6, wherein the first and second reactions are performed in a riser reactor; the riser reactor comprises a first reaction zone, a second reaction zone and a settler, wherein raw oil and DPC-1 catalyst are contacted in the first reaction zone under the action of a pre-lifting medium to generate the first reaction, so as to obtain a first reaction product containing the to-be-generated DPC-1 catalyst; the first reaction product containing the spent DPC-1 catalyst, recycle oil and DPC-2 catalyst enter the second reaction zone, and contact and generate the second reaction in the second reaction zone to obtain a mixture containing the spent DPC-1 catalyst, the spent DPC-2 catalyst and the second reaction product; the mixture is contacted with stripping steam in a settler to strip, and the second reaction product is separated from the spent DPC-1 catalyst and the spent DPC-2 catalyst to obtain the second reaction product.
8. The method according to claim 7, wherein the pre-lifting medium is selected from at least one of steam, dry gas, natural gas, liquefied gas, preferably steam;
preferably, the mass ratio of the raw oil to the pre-lifting medium is 100:1-15, preferably 100:1-8;
preferably, the stripping steam is selected from at least one of steam, dry gas, natural gas, liquefied gas, preferably steam;
preferably, the mass ratio of the raw oil to the stripping steam is 100:1-15, preferably 100:10-15 parts;
preferably, in the second reaction, the yield of the catalytic coke is 30% -130%, preferably 50% -100% of the carbon residue value of the raw oil.
9. The method of any one of claims 1-8, wherein the chemical comprises dry gas, liquefied gas, gasoline, diesel, and wax oil;
preferably; the yield of the dry gas is 0.3-8%, preferably 0.6-4.5%; the yield of the liquefied gas is 10-45%, preferably 20-35%; the yield of the gasoline is 24-45%, preferably 27-38%; the yield of the diesel oil is 15-37%, preferably 20-30%; the yield of the wax oil is 5-25%, preferably 4-15%.
10. The process according to claim 9, wherein the ethylene content in the dry gas is 40-55wt%, preferably 42-53wt%;
preferably, the total content of carbon tri-olefins and carbon tetra-olefins in the liquefied gas is 60-98wt%, preferably 70-95wt%;
preferably, in the gasoline, C 5 The content of the above olefins is 30 to 60wt%, preferably 40 to 55wt%;
preferably, the aromatic hydrocarbon content of the diesel oil is 70-95wt%, preferably 75-90wt%.
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| CN109694722B (en) * | 2017-10-24 | 2021-08-06 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing clean gasoline from inferior raw oil |
| CN109705904B (en) * | 2017-10-25 | 2020-12-04 | 中国石油化工股份有限公司 | Processing method and processing system for hydrocarbon oil capable of producing ethylene and propylene in high yield |
| CN108485704B (en) * | 2018-04-17 | 2020-04-28 | 中国石油大学(华东) | Process for preparing chemical raw materials in maximized mode by combining millisecond-graded gas-phase catalytic cracking and hydrogenation of crude oil |
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2021
- 2021-12-13 CN CN202111521554.2A patent/CN116286077A/en active Pending
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2022
- 2022-12-13 WO PCT/CN2022/138729 patent/WO2023109823A1/en unknown
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| Publication number | Publication date |
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| WO2023109823A1 (en) | 2023-06-22 |
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