CN109988632B - Method for producing gasoline and diesel oil by catalyst grading technology - Google Patents
Method for producing gasoline and diesel oil by catalyst grading technology Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 239000003502 gasoline Substances 0.000 title claims abstract description 72
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- 238000000034 method Methods 0.000 claims abstract description 80
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 238000006011 modification reaction Methods 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 56
- 238000005984 hydrogenation reaction Methods 0.000 claims description 46
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 30
- 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 30
- 239000002808 molecular sieve Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 23
- 239000000295 fuel oil Substances 0.000 claims description 20
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005194 fractionation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 37
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 13
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007670 refining Methods 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001833 catalytic reforming Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 229910052976 metal sulfide Inorganic materials 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
- C10G2400/02—Gasoline
-
- 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
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for producing gasoline and productive diesel oil by using a catalyst grading technology. The conventional heavy raw material is subjected to restrictive hydrofining, then subjected to hydro-conversion and modification reaction, and subjected to limited process conditions and a graded catalyst system to produce high-quality gasoline or blending components, and diesel components can be produced to the maximum. The invention converts heavy distillate oil into high-quality gasoline and diesel oil to the utmost extent according to the composition characteristics, and provides an economic and feasible route for processing inferior raw materials and producing gasoline.
Description
Technical Field
The invention relates to a method for treating wax oil components, in particular to a method for producing high-quality gasoline, high-quality diesel oil with maximum quantity and other liquid phase products by processing wax oil raw materials through a catalyst grading technology.
Background
Gasoline is one of the most used light petroleum products, is an important fuel of an engine, can be obtained by different units for petroleum refining, and in the process of crude oil processing, units such as distillation, catalytic cracking, thermal cracking, hydrocracking, catalytic reforming and the like all produce gasoline components, but have different octane numbers, such as the octane number of straight-run gasoline is low, and the gasoline cannot be independently used as engine fuel; in addition, the sulfur content of impurities is different, so that the gasoline component with high sulfur content also needs to be desulfurized and refined, and finally, the gasoline component is blended, and if necessary, a high-octane component needs to be added, so that the gasoline product meeting the national standard is finally obtained.
At present, the main ways for producing gasoline in China are catalytic cracking and catalytic reforming. The catalytic cracking is the most important secondary processing process in the petroleum refining industry at present, and is also the core process for the heavy oil lightening, along with the increasing heavy oil of the world, the processing capacity of an FCC device is continuously improved, various heavy oils are used as raw materials, the main product, namely the high-octane gasoline, is obtained through catalytic cracking reaction, but because the emission standard of the gasoline at present is improved, the production of the catalytic cracking gasoline requires the pre-refining of the raw materials and the post-refining of the product; the catalytic reforming is a process for rearranging the molecular structure of hydrocarbons in gasoline fractions into a new molecular structure, is an important means for improving the quality of gasoline and producing petrochemical raw materials, is an essential process for producing gasoline at present, and has high requirements on the source and cleanliness of the raw materials due to the reaction process and the characteristic requirements of catalysts.
The hydrocracking technology has the advantages of strong raw material adaptability, flexible product scheme, high liquid product yield, good product quality and the like, and is favored by oil refining enterprises of various countries in the world for many years. Hydrocracking, which is one of the main processes for deep processing of heavy oil, can also indirectly produce gasoline components, and due to the characteristics of the processes, the produced heavy naphtha has extremely low impurity content and low octane number, which is exactly opposite to that of catalytic gasoline, and the heavy naphtha is used as a feed of a catalytic reforming unit to produce high-octane gasoline after molecular structure rearrangement.
CN104611029A discloses a catalytic cracking diesel oil hydro-conversion method, wherein catalytic diesel oil and hydrogen gas are mixed and then enter a hydrofining reactor for hydrofining reaction, and then enter a hydrocracking reactor for hydrocracking reaction. Although gasoline with high octane number is produced through a hydro-conversion process, catalytic cracking diesel oil is still used as a raw material essentially, and the range of the raw material for producing high-quality gasoline is not expanded, so that the method has certain limitation.
CN101724454A introduces a hydrocracking method for producing high-octane gasoline, raw oil and hydrogen are mixed and then enter a reactor to be sequentially subjected to hydrofining and hydrocracking reactions, although the method has the characteristics of capability of processing more inferior raw materials, long operation period of a catalyst, good quality of a hydrocracking product and the like. But the used raw material is still the diesel oil component, and heavy oil is not used for directly producing high-octane gasoline.
CN103184073A introduces a hydrocracking method for producing high-octane gasoline blending components, wherein raw oil is subjected to controlled hydrofining and hydro-conversion reaction, although the target product can be high-octane gasoline or blending components through process control, the selection range of the raw material is single, the production cannot be carried out by utilizing heavy oil products, and meanwhile, the catalyst is not effectively improved aiming at the process.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a hydrocracking process method for processing heavy raw materials to produce high-octane gasoline. The method carries out restrictive hydrogenation saturation on a conventional heavy raw material, then carries out hydro-conversion and modification reaction, produces a certain amount of high-quality gasoline or blending component under the conditions of certain process condition limitation and special catalyst gradation, and simultaneously carries out modification and cracking reaction on a by-product liquid phase component, and also can produce other high-quality fuel oil products, such as high-quality gasoline, ethylene cracking raw materials and the like, wherein the diesel oil component can realize maximum production.
The invention provides a method for producing gasoline and diesel oil by using a catalyst grading technology, which comprises the following steps:
a) under the condition of hydrofining, the heavy oil raw material and hydrogen are mixed and then pass through a reaction zone containing a hydrofining catalyst bed layer to carry out limited hydrofining reaction;
b) passing the hydrofining effluent obtained in the step a) through a graded hydrogenation catalyst bed layer, and firstly carrying out a restrictive hydrogenation conversion reaction in a reaction zone containing a wax oil hydrogenation conversion catalyst bed layer under the condition of a hydrogenation conversion process; the obtained reaction effluent is subjected to a limited hydro-upgrading reaction through a reaction zone containing a hydro-upgrading catalyst bed under the hydro-upgrading process condition; the effluent of the hydro-upgrading reaction enters a reaction zone containing a hydro-conversion catalyst for continuous reaction.
c) Carrying out gas-liquid separation and fractionation on the reaction effluent obtained in the step b) to obtain converted gasoline, modified diesel oil and unconverted oil; the unconverted oil can be discharged as oil product and can also be subjected to two-stage conventional hydrocracking reaction, thereby obtaining high-quality liquid-phase target product.
The final boiling point of the heavy oil raw material in the step a) is generally 450-580 ℃, preferably 480-570 ℃, and the density is generally 0.90g/cm3Above, preferably 0.93g/cm3Above, the total aromatic hydrocarbon in the raw material is above 40wt%, preferably above 45wt%, and the nitrogen content is 800mg g-1Above, preferably 1000mg g-1The above. Generally, the oil is one or more of vacuum wax oil, deasphalted oil or coker wax oil, and can be selected from the above-mentioned components obtained by processing middle east crude oil or Liaohe crude oil, and the other impurity properties of the raw material must be the common knowledge in the field, and must meet the requirements of that it can be used as feed of hydrocracking equipment.
The hydrofining process conditions in the step a) are as follows: the reaction pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 200: 1-3000: 1, and the volume airspeed is 0.1-5.0 h-1The reaction temperature is 260-435 ℃; the preferable operation conditions are that the reaction pressure is 7.0-12.0 MPa, the volume ratio of hydrogen to oil is 300: 1-900: 1, and the volume airspeed is 1.0-3.0 h-1The reaction temperature is 300-430 ℃.
The limiting hydrofining reaction in step a) is to control a certain depth of hydrogenation saturation to avoid the over saturation of the aromatic hydrocarbon component in the heavy oil feedstock from affecting the octane number of the gasoline fraction product, and generally the refined oil (i.e., the refined oil obtained in step a) needs to be controlled according to the difference of the aromatic hydrocarbon and nitrogen content in the feedstockReaction effluent of (b) has a nitrogen content of 50 to 250mg g-1Preferably 100 to 200 mg/g-1Thus, the nitrogen content of the refined oil can be reduced while the aromatic hydrocarbon component in the raw material can be retained to the maximum extent. It should be noted that, in the course of the hydrorefining reaction, by controlling the nitrogen content of the refined oil, the aromatic hydrocarbon component in the reaction effluent has a low content of tricyclic and higher aromatic hydrocarbon components, and the total content is generally 1 to 20wt%, preferably 2 to 15 wt%.
The hydroconversion process conditions in the step b) are as follows: the reaction pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 300: 1-2000: 1, and the volume airspeed is 0.1-8.0 h-1The reaction temperature is 280-455 ℃; the preferable operation conditions are that the reaction pressure is 7.0-12.0 MPa, the volume ratio of hydrogen to oil is 400: 1-1000: 1, and the volume airspeed is 2.0-5.0 h-1The reaction temperature is 310-440 ℃.
The limiting hydroconversion reaction in the step b) is to control a certain hydroconversion depth, so that the octane number of a gasoline fraction product is prevented from being influenced by excessive cracking of non-aromatic hydrocarbon components in the reaction effluent in the step a), and the yield of high-quality gasoline fractions in the total product is generally controlled to be 1-15 wt% according to the difference of the raw materials and the aromatic hydrocarbon in the reaction effluent in the step a), so that the aromatic hydrocarbon components in the raw materials can be retained to the maximum extent and converted into the gasoline fractions while the heavy oil raw materials are processed, and the octane number of the gasoline product is improved.
The hydro-upgrading process conditions in the step b) are as follows: the reaction pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 300: 1-2000: 1, and the volume airspeed is 0.1-8.0 h-1The reaction temperature is 280-455 ℃; the preferable operation conditions are that the reaction pressure is 7.0-12.0 MPa, the volume ratio of hydrogen to oil is 400: 1-1000: 1, and the volume airspeed is 1.0-4.0 h-1The reaction temperature is 310-440 ℃.
The limiting hydro-upgrading reaction in the step b) is to control certain hydro-upgrading depth to avoid the influence on the octane number of a gasoline fraction product caused by excessive cracking of non-aromatic components in the effluent in the front-stage reaction process, and the process aims to carry out targeted reaction on the ring-opening but continuous chain-breaking of the bicyclic aromatic hydrocarbon in the raw material. According to the difference of aromatic hydrocarbons in the raw materials and the effluent of the former stage reaction, the total temperature rise of the diesel oil reaction in the process unit is generally controlled to be not more than 20 ℃, and the yield of the diesel oil is maintained at 95-98 wt%, so that the targeted modification reaction can be carried out on the bicyclic aromatic hydrocarbon component in the raw materials to the maximum extent while the heavy oil raw materials are processed, the yield and the cetane number of the diesel oil product are improved while the octane number of the gasoline product is ensured, and the yield of the diesel oil can be maximized.
The hydrofining catalyst of step a) comprises a carrier and a hydrogenation metal loaded. Based on the weight of the catalyst, the catalyst generally comprises 10-35% of metal components in VIB group of the periodic table of elements, such as tungsten and/or molybdenum, calculated by oxide, and preferably 15-30%; group VIII metals such as nickel and/or cobalt are present in amounts of 1% to 7%, preferably 1.5% to 6%, calculated as oxides. The carrier is inorganic refractory oxide, and is generally selected from alumina, amorphous silica-alumina, silica, titanium oxide and the like. The conventional hydrocracking pretreatment catalyst can be selected from various conventional commercial catalysts, such as hydrogenation refining catalysts developed by the Fushu petrochemical research institute (FRIPP), such as 3936, 3996, FF-16, FF-26, FF-36, UDS-6 and the like; it can also be prepared according to the common knowledge in the field, if necessary. The purification catalyst should be loaded upstream of the conversion catalyst.
In the invention, the grading hydrogenation catalyst in the step b) at least comprises three hydrocracking catalysts containing molecular sieves according to the difference of the types of aromatic hydrocarbons in the raw oil. And sequentially filling a heavy aromatic hydrocarbon hydro-conversion catalyst, a hydro-upgrading catalyst and a monocyclic aromatic hydrocarbon retention catalyst from top to bottom according to the reactant flow direction.
The corresponding heavy aromatics hydroconversion catalyst is a hydroconversion catalyst containing a molecular sieve, and is a catalyst specially prepared according to the method. The hydrogenation conversion catalyst comprises hydrogenation active metal, a molecular sieve component and an alumina carrier. The general hydro-conversion catalyst is composed of hydrogenation active metal components such as Wo, Mo, Co, Ni and the like, a molecular sieve component, an alumina carrier and the like. Which comprises WO by weight3(or MoO)3) 9-29 wt%, NiO (or CoO) 5-10 wt%, Y-type molecular sieve 15-45 wt% and20-50 wt% of alumina. In the heavy aromatics hydroconversion catalyst, the Y-type molecular sieve is a small-grain Y-type molecular sieve. The grain size of the small-grain Y-type molecular sieve is 400-600 nm, the infrared total acid is 0.3-0.7 mmol/g, and the proportion of the medium-strong acid is 50% (mmol/g)-1/mmol·g-1) The unit cell parameter is 2.435-2.440 nm; the pore volume is 0.5-0.7 cm3The proportion of the 2-8nm secondary pore volume in the total pore volume is more than 60 percent. The Y-type molecular sieve has more accessible and exposed acid centers, is beneficial to the diffusion of hydrocarbon molecules, can improve the preferential conversion capability of cyclic hydrocarbons, particularly tricyclic and higher aromatic hydrocarbons, directionally saturates and breaks aromatic rings in the tricyclic aromatic hydrocarbons, and produces gasoline components with high octane number to the maximum extent. The hydroconversion catalyst containing the small-grain Y-shaped molecular sieve has the main function of performing selective reaction on tricyclic aromatic hydrocarbon in raw materials, and has poor selectivity on non-tricyclic two-ring and monocyclic aromatic hydrocarbon. The Y-type molecular sieve has a certain difference with the conventional Y-type molecular sieve, the grain size of the conventional modified molecular sieve is generally 800-1200 nm, and the pore volume is 0.35-0.50 cm3The proportion of secondary pore volume to total pore volume is generally 30-50%, and the proportion of medium-strong acid is 50-70% (mmol. g)-1/mmol·g-1). The hydroconversion catalyst may be used to prepare a satisfactory catalyst in accordance with common general knowledge in the art, as described above.
The corresponding hydrogenation modification catalyst is a hydrogenation catalyst containing a molecular sieve, which is a hydrogenation catalyst used for modifying oil products and is a conventional hydrogenation conversion catalyst in the field. The hydrogenation modification catalyst is a bifunctional hydrogenation conversion catalyst, which takes alumina and a Y-type molecular sieve as carriers, contains at least one VIB group metal and at least one VIII group metal, and the catalyst carrier contains 40-80 w% of alumina, 0-20 w% of amorphous silica-alumina and 5-30 w% of molecular sieve by weight; wherein the pore volume of the Y molecular sieve is 0.40-0.52 mL/g, and the specific surface is 750-900 m2(ii)/g, unit cell constant of 2.420 to 2.500nm, SiO2/Al2O3The molecular ratio is 7-15, the content of VIB group metal oxide in the catalyst is 10-30 w%, and the content of VIII group metal oxide is 2-15 w%. The alumina is a crystalThe phase is pseudo-boehmite alumina, and the content is 40-80 w%. The carrier contains amorphous silicon-aluminum oxide with the weight ratio of 1: 2-2: 1, and the content is 0-20 w%, preferably 10-20 w%. The hydrogenation metal can be the combination of at least one VIB group metal oxide or sulfide and at least one VIII group metal oxide or sulfide, the VIB group metal can be Mo or W, preferably W, with the content of 10W% -30W%, the VIII group metal can be Ni or Co, preferably Ni, with the content of 2W% -15W%. The conventional hydrogenation reforming catalyst can be selected from various commercial catalysts, such as 3963, FC-18 and other catalysts developed by FRIPP. A specific hydroupgrading catalyst may be prepared as required according to the common knowledge in the art, and for example, a satisfactory hydroupgrading (conversion) catalyst may be prepared by referring to the disclosure of CN1184843A and CN 1178238A.
The corresponding single-ring aromatic hydrocarbon retention catalyst is a hydroconversion catalyst containing a molecular sieve, and the hydroconversion catalyst comprises hydrogenation active metal, a molecular sieve component and an alumina carrier. The general hydro-conversion catalyst is composed of hydrogenation active metal components such as Wo, Mo, Co, Ni and the like, a molecular sieve component, an alumina carrier and the like. The hydroconversion catalyst metal composition specific for the present invention is preferably Mo-Co, which includes MoO by weight35-25 wt%, CoO 3-8 wt%, Y-type molecular sieve 20-40 wt% and alumina 30-50 wt%. Further, the preferred Y-type molecular sieve has the following properties: the particle size is 500-700 nm, the unit cell parameter is 2.438-2.440 nm, the infrared total acid is 0.6-0.7 mmol/g, and the proportion of the medium-strong acid is 70% (mmol/g)-1/mmol·g-1) The proportion of the secondary pore volume of 2-8nm to the total pore volume is5155 percent. The catalyst is characterized in that the preparation process of the molecular sieve adopts a modified Y-type molecular sieve which has moderate acid strength and more non-framework aluminum and is beneficial to retaining monocyclic aromatic hydrocarbon. The main function of the catalyst is to retain monocyclic aromatic hydrocarbons in the upper transfer stream and to selectively react other components than monocyclic aromatic hydrocarbons. The present hydroconversion catalysts may be prepared in accordance with common general knowledge in the art, as described above.
In the present invention, the technical term "strong acid" is conventional knowledge well known to those skilled in the art. Catalyst and process for preparing sameIn the preparation field, NH is adopted for medium and strong acid3TPD was analyzed, with 150 ℃ desorption defined as weak acid, 250 ℃ desorption defined as medium strong acid, and 400 ℃ desorption defined as strong acid.
The three catalysts need to consider the excessive cracking performance in the grading process, namely, the heavy aromatic hydrocarbon hydroconversion catalyst at the top contacts the refined oil containing nitrogen and mainly reacts on the polycyclic aromatic hydrocarbon, so the cracking performance does not need to be excessively high; the hydrogenation modification catalyst filled at the lower part of the catalyst has the task of producing high-yield and high-quality diesel oil, bicyclic aromatic hydrocarbon needs to be reacted, and the cracking activity of the catalyst is higher than that of a heavy aromatic hydrocarbon hydrogenation conversion catalyst; the function of the single-ring aromatic hydrocarbon retaining catalyst at the lowest part is to retain the single-ring aromatic hydrocarbon and simultaneously prevent low-octane components from entering the gasoline fraction, so that the cracking activity of the catalyst is not too high and is close to or slightly lower than that of a heavy aromatic hydrocarbon hydro-conversion catalyst.
The gas-liquid separation and fractionation process described in step c) are well known to those skilled in the art. The gas-liquid separation is a separation process of products in the hydrogenation process, and generally mainly comprises a high-pressure separator, a low-pressure separator, a circulating hydrogen system and the like; the fractionation process is a process for further refining a liquid-phase product of gas-liquid separation, and generally mainly comprises a stripping tower, a fractionating tower, a side-line tower and the like.
The converted gasoline in the step c) is a gasoline component obtained in the hydro-conversion process, generally the sulfur content is less than 10 mug/g, and the research octane number is more than 85.
The second-stage conventional hydrocracking reaction in step c) refers to the residual liquid phase component after the high-quality gasoline component is produced by the method, and because the aromatic hydrocarbon content is very low, the method can be directly used for producing high-quality hydrocracking products or used as a raw material for preparing ethylene by steam cracking, and the process is well known by persons skilled in the art and will not be described again.
Compared with the prior art, the method for producing the high-quality gasoline has the following advantages:
1. proper heavy oil raw materials are selected, and after selective saturation and ring-opening chain scission through the hydrogenation conversion of a special catalyst, polycyclic aromatic hydrocarbon in the raw materials is converted into high-quality gasoline components, the obtained gasoline components have the characteristics of low sulfur content and high octane number, the quality of the properties of the gasoline components is closely related to the content of aromatic hydrocarbon in the raw materials and the conversion depth controlled by a technological process, and products can be produced in a blending mode. Under the condition of the method, the obtained diesel oil component is subjected to a special modification process, key properties such as cetane number and the like are improved to the maximum extent, the yield can be ensured to the maximum extent, and the method has the characteristics of dual-function and double-quality products. Other components also have certain advantages, and can be produced according to special oil products, or further converted into high-quality aviation kerosene, diesel oil or tail oil fractions after conventional hydrocracking reaction. The heavy distillate oil can be converted into high-quality gasoline as a target product to the maximum extent according to the characteristics of the components, and a large amount of diesel oil is produced at the same time, so that an economical and feasible line is found for processing inferior raw materials and producing gasoline, and the method has great practical advantages.
2. The method of the invention carries out grading sectional processing on the heavy oil hydro-conversion and modification in the process flow, and obtains ideal comprehensive processing effect on the basis of improving the quality of gasoline and diesel oil products. In the process flow, the method does not need to modify the device, realizes the purpose of high-quality production only by the combination of the catalyst and the adjustment of physical properties, has the advantages of equipment saving, low operating cost and the like, reduces the investment, and has wide application prospect.
3. The method of the invention has certain limitation on the process condition, has rigid requirements on the reaction depth of a refining section and a conversion section, and aims to convert polycyclic aromatic hydrocarbon in heavy raw oil into monocyclic aromatic hydrocarbon as much as possible and retain the monocyclic aromatic hydrocarbon in gasoline fraction, convert bicyclic aromatic hydrocarbon into monocyclic aromatic hydrocarbon and retain the monocyclic aromatic hydrocarbon in diesel oil components to the maximum extent, and simultaneously produce high-quality gasoline and diesel oil products.
3. According to the method of the invention, a new hydrogenation conversion catalyst is developed, which is a great reflection of technical progress, the production way of high-quality gasoline can be widened, in addition, the newly developed hydrogenation conversion catalyst and the modified catalyst are purposefully graded, researched and filled according to the content of aromatic hydrocarbon in the raw material, the degree of main reaction proceeding of the method under the conversion working condition can be realized, and the production of high-quality target products is considered, in the production process, for the hydrogenation process of the wax oil raw material, if light fractions are produced, only heavy naphtha raw material with high aromatic hydrocarbon potential can be provided for a catalytic reforming device, but high-quality gasoline can not be directly produced, and by adopting the method, the wax oil raw material can be directly converted into gasoline products with market demands, the technology has great competitive advantages, more production flexibility and high-quality gasoline and diesel oil products can be provided for enterprises, can bring intuitive economic benefits.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The combined process of the present invention will be described in detail with reference to the accompanying drawings. Only the main description of the process flow is given in fig. 1, and some necessary equipment and vessels are also omitted from the schematic.
As shown in FIG. 1, the process flow for producing gasoline of the present invention is as follows: mixing a heavy raw material 1 and hydrogen 2, and then entering a hydrofining reaction zone to contact and react with a hydrofining catalyst 3; the reaction effluent 4 enters a hydro-conversion reaction zone to be in contact reaction with a graded hydro-conversion catalyst 5, a hydro-upgrading catalyst 6 and a hydro-conversion catalyst 7; the product 10 obtained after the reaction effluent 8 enters the separation system 9 continuously enters a fractionation system 11, the upper part discharges the converted gasoline 12, the middle part discharges the modified diesel oil 13, and the rest components 14 can be used as special oil products to be discharged out of the system or enter a second-stage hydrocracking reaction zone 15 for subsequent reaction. The catalyst 3 is a hydrofining catalyst, and the catalysts 5, 6 and 7 are respectively a heavy aromatic hydrocarbon hydrogenation conversion catalyst, a hydrogenation modification catalyst and a monocyclic aromatic hydrocarbon retention hydrogenation conversion catalyst.
The combined process of the present invention is further illustrated by the following specific examples.
Example 1
The combined process flow shown in figure 1 is adopted, straight-run wax oil is selected as a raw material to carry out hydrogenation to produce gasoline and diesel, certain refining (nitrogen content 100 ppm) and conversion depth (gasoline yield is about 10%) are controlled, and the diesel yield in the hydrogenation modification process is 96 wt%. The catalysts used in the examples were a commercial catalyst FF-36 hydrotreating catalyst, a specialty hydroconversion catalyst A, a commercial catalyst FC-18 hydro-upgrading catalyst, and a C single ring aromatics retention hydroconversion catalyst.
The properties of catalysts A and C are shown in Table 1, the properties of the feed oil are shown in Table 2, and the operating conditions are shown in Table 3.
Example 2
The combined process flow shown in figure 1 is adopted, straight-run wax oil is selected as a raw material to carry out hydrogenation to produce gasoline and diesel, certain refining (nitrogen content of 200 ppm) and conversion depth (gasoline yield is about 10%) are controlled, and the diesel yield in the hydrogenation modification process is 96 wt%. The catalysts used in the examples were a commercial catalyst FF-36 hydrotreating catalyst, a specialty hydroconversion catalyst A, a commercial catalyst FC-18 (hydro-upgrading catalyst), and a single ring aromatics retention hydroconversion catalyst C.
The properties of catalysts A and C are shown in Table 1, the properties of the feed oil are shown in Table 2, and the operating conditions are shown in Table 3.
Example 3
The combined process flow shown in figure 1 is adopted, straight-run wax oil is selected as a conversion raw material to carry out hydrogenation to produce gasoline, certain refining (nitrogen content of 200 ppm) and conversion depth (gasoline yield is about 5%) are controlled, and the diesel oil yield in the hydrogenation modification process is 96 wt%. The catalysts used in the examples were a commercial catalyst FF-36 hydrotreating catalyst, a specialty hydroconversion catalyst A, a commercial catalyst FC-18 hydro-upgrading catalyst, and a C single ring aromatics retention hydroconversion catalyst.
The properties of catalysts A and C are shown in Table 1, the properties of the feed oil are shown in Table 2, and the operating conditions are shown in Table 3.
Comparative example 1
Comparative example 1 is a hydrocracking process for processing straight-run wax oil, the naphtha yield was controlled to 10% according to the conventional hydrofining depth, the comparative product was heavy naphtha, and the catalysts used in the comparative example were a commercial catalyst FF-36 hydrotreating catalyst and an FC-50 hydrocracking catalyst.
The properties of the feed oil are shown in Table 2, and the operating conditions are shown in Table 3.
Comparative example 2
Comparative example 1 is a hydrocracking process for processing straight-run wax oil, the naphtha yield was controlled to 5% according to the conventional hydrofining depth, the comparative product was heavy naphtha, and the catalysts used in the comparative example were commercial catalysts FF-36 hydrotreating catalyst and FC-50 hydrocracking catalyst.
The properties of the feed oil are shown in Table 2, and the operating conditions are shown in Table 3.
TABLE 1 tailoring the principal physicochemical properties of the conversion catalyst
TABLE 2 raw oil Properties Table
TABLE 3 reaction conditions
TABLE 4 Main Properties
As can be seen from the above examples, the treatment of heavy oil feedstock by the present invention can omit the catalytic reforming process, directly produce high octane, low sulfur gasoline product, and by-product high cetane diesel fraction, compared with the comparative examples.
Claims (14)
1. A method for producing gasoline and diesel oil by using a catalyst grading technology comprises the following steps:
a) under the condition of hydrofining, the heavy oil raw material and hydrogen are mixed and then pass through a reaction zone containing a hydrofining catalyst bed layer to carry out limited hydrofining reaction; the limiting hydrofining means controlling the nitrogen content of hydrofined oil to be 50-250 mu g.g-1；
b) Passing the hydrofining effluent obtained in the step a) through a graded hydrogenation catalyst bed layer, and firstly carrying out a restrictive hydrogenation conversion reaction in a reaction zone containing a heavy aromatic hydrocarbon hydrogenation conversion catalyst bed layer under the condition of a hydrogenation conversion process; the limiting hydroconversion reaction is to control the yield of gasoline fraction in the total product to be 1-15 wt%; the reaction effluent obtained by the hydroconversion is subjected to a limited hydroupgrading reaction through a reaction zone containing a hydroupgrading catalyst bed under the condition of a hydroupgrading process; the effluent of the hydrogenation modification reaction enters a reaction zone containing a monocyclic aromatic hydrocarbon retention catalyst bed layer for continuous reaction; the limiting hydrogenation modification reaction means that the yield of the diesel oil in the process is controlled to be 95-98 wt%;
c) carrying out gas-liquid separation and fractionation on the reaction effluent obtained in the step b) to obtain converted gasoline, modified diesel oil and unconverted oil;
the total aromatic hydrocarbon content in the heavy oil raw material is more than 40wt%, and the nitrogen content is 800 mu g.g-1The above;
the heavy aromatics hydroconversion catalyst comprises hydrogenation active metal, a Y-type molecular sieve and an alumina carrier; the particle size of the Y-type molecular sieve is 400-600 nm, the infrared total acid is 0.3-0.7 mmol/g, the proportion of the medium-strong acid is more than 50%, and the unit cell parameter is 2.435-2.440 nm; the pore volume is 0.5-0.7 cm3The proportion of the 2-8nm secondary pore volume in the total pore volume is more than 60%;
the monocyclic aromatic hydrocarbon retaining catalyst comprises hydrogenation active metal, a Y-type molecular sieve and alumina; the particle size of the Y-type molecular sieve is 500-700 nm, the unit cell parameter is 2.438-2.440 nm, the infrared total acid is 0.6-0.7 mmol/g, the proportion of the medium strong acid is more than 70%, and the proportion of the secondary pore volume of 2-8nm in the total pore volume is 51-55%.
2. The process according to claim 1, wherein the unconverted oil obtained is discharged as an oil product or subjected to a two-stage conventional hydrocracking reaction.
3. The process of claim 1 wherein said heavy oil feedstock has a total aromatics content of greater than 45 wt.% and a nitrogen content of 1000 μ g-g-1The above.
4. The process according to claim 3, wherein the heavy oil feedstock has an end point of 450 to 580 ℃ and a density of 0.90g/cm3The above.
5. The process of claim 1, 3 or 4, wherein the heavy feedstock oil is selected from one or more of vacuum wax oil, deasphalted oil or coker wax oil.
6. The process of claim 1, wherein the hydrofinishing conditions of step a) are: the reaction pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 200: 1-3000: 1, and the volume airspeed is 0.1-5.0 h-1The reaction temperature is 260-435 ℃.
7. The method according to claim 1, wherein the limited hydrofinishing of step a) is to control the nitrogen content of the refined oil obtained in step a) to be 100-200 μ g-g-1。
8. The method according to claim 1 or 7, wherein the content of tricyclic and higher aromatic components in the aromatic hydrocarbon component in the reaction effluent obtained in step a) is 1 to 20 wt%.
9. The process of claim 1, wherein the hydroconversion process conditions in step b) are: the reaction pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 300: 1-2000: 1, and the volume airspeed is 0.1-5.0 h-1The reaction temperature is 280-455 ℃.
10. The process of claim 1 wherein said heavy aromatics hydroconversion catalyst comprises WO, by weight3Or MoO39-29 wt%, NiO or CoO 5-10 wt%, Y-type molecular sieve 15-45 wt% and alumina 20-50 wt%.
11. The method of claim 1, wherein the single ring aromatics retention catalyst comprises MoO by weight35-25 wt%, CoO 3-8 wt%, Y-type molecular sieve 20-40 wt% and alumina 30-50 wt%.
12. The process of claim 1, wherein said hydro-upgrading process conditions are: the reaction pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 300: 1-2000: 1, and the volume airspeed is 0.1-8.0 h-1The reaction temperature is 280-455 ℃.
13. The process according to claim 4, wherein the heavy oil feedstock has an end point of 480 to 570 ℃ and a density of 0.93g/cm3The above.
14. The method according to claim 8, wherein the content of tricyclic and higher aromatic components in the aromatic hydrocarbon component in the reaction effluent obtained in step a) is 2 to 15 wt%.
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