CN103773495B - A kind of hydrotreatment-catalytic cracking combination process - Google Patents
A kind of hydrotreatment-catalytic cracking combination process Download PDFInfo
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Abstract
A kind of hydrotreatment-catalytic cracking combination process, wax oil enters hydrotreatment reaction zone together with catalytic cracking turning oil, hydrodemetallation (HDM) is carried out under hydrogen and hydrogenation catalyst exist, hydrogenating desulfurization, hydrodenitrification and the reaction such as aromatic hydrogenation is saturated, the hydrogenation tail oil obtained enters catalytic cracking unit, cracking reaction is carried out under catalytic cracking catalyst exists, dry gas is obtained after being separated, liquefied gas, catalytically cracked gasoline, catalytic cracking solar oil, catalytic cracking turning oil and slurry oil, wherein catalytic cracking solar oil is in catalytic cracking unit self-circulation, and catalytic cracking turning oil is circulated to hydrotreatment reaction zone.Adopt method provided by the invention, significantly can improve yield and the quality of gasoline products.
Description
Technical field
The invention belongs to by other the method for step of converting process hydrocarbon ils of a hydroprocessing technique process and, in particular, is the method for a kind of hydrotreatment-catalytic cracking combined technique fecund high value gasoline.
Background technology
Along with the aggravation of the day by day deficient of crude resources and crude oil heaviness, in poor quality process, how effectively to utilize limited resources maximum production light-end products to become the target of each oil Refining Technologies developer pursuit, the oil Refining Technologies that can improve object product yield and quality becomes the selection of numerous refinery.
In China, catalytic cracking is because flexibility of operation is good, gasoline yield is high, and one-time investment is low and be widely used.Single catalytic cracking process has certain requirement to fcc raw material, and the raw material of high sulfur content not only makes SOx discharge in catalytic cracking flue gas not meet environmental requirement, and the sulphur content of gasoline products can not meet product specification requirement.High nitrogen-containing in catalytically cracked material can increase the agent consumption of cracking catalyst, increases process cost.Catalytically cracked material weighted BMO spaces technology significantly can reduce its sulphur nitrogen content, increases hydrogen richness, thus reduces the sulphur nitrogen content of cracked product, improves product slates.The fcc raw material weighted BMO spaces that prior art is mainly single or raw material weighted BMO spaces-catalytic cracking combined technique technology.
Concerning catalytic cracking unit, using the wax oil raw material through hydrotreatment as catalytic cracking (comprising multiple catalytic cracking process) charging, can the lower catalytically cracked gasoline of production sulphur content, but the catalytic cracking diesel oil produced (LCO) sulphur content is higher, and aromaticity content is high, generally more than 50%, even reach more than 80%, and cetane value is low, stability is poor, can not directly dispatch from the factory, need further processing treatment.The newly-built catalytic cracking diesel oil hydro-upgrading unit of usual need or the oil fuel of catalytic cracking diesel oil as low value is dispatched from the factory.On the other hand, catalytic cracking unit is for increasing catalytic cracking conversion and yield of light oil, usually by heavy cycle oil (HCO) repeats itself in catalytic cracking unit, but because HCO aromaticity content is high, its cracking effect is unsatisfactory, a big chunk of HCO is converted into coke, then add revivifier load, reduces treatment capacity and the economic benefit of catalytic cracking unit.
US20010052482A1 discloses the combination process of a kind of two-stage catalytic cracking and hydrotreatment.The method be the heavy cycle oil of first paragraph catalytic cracking after hydrotreatment, enter second segment catalytic cracking unit and carry out cracking, two-stage catalytic cracking adopts dissimilar catalyzer for different material.But the method needs independent for heavy cycle oil hydrotreatment, increase plant investment a lot, and solve only the high problem of catalytic cracking unit coke yield.
US5770044 discloses the combination process of a kind of catalytic cracking and hydrotreatment.The method be fresh feed after catalytic cracking, be separated obtain gas, petroleum naphtha and heavier product (comprising diesel oil and heavy cycle oil); After heavier product introduction hydrotreater, be separated and obtain petroleum naphtha, diesel oil and hydrogenation tail oil; Catalytic cracking unit is returned in hydrogenation tail oil recirculation.This combination process solves the problem that coke yield is high, diesel quality is poor preferably, but needs to set up hydrogenation unit separately, and does not solve the high problem of catalytic gasoline sulphur content.
CN10434496C discloses the combined technical method of a kind of VGO and catalytic cracking unit.The catalytic cracking diesel oil (LCO) that catalytic cracking unit is produced by the method and heavy cycle oil all loop back VGO, are conducive to the quality improving product yield and catalytic cracking diesel oil.
Summary of the invention
The object of the invention is to provide a kind of wax oil hydrogenation process and catalytic cracking two-way combined process on the basis of existing technology, is a kind of wax oil hydrogenation process-catalytic cracking combination process improving yield of gasoline and quality product.
Method provided by the invention comprises: wax oil raw material enters hydrotreatment reaction zone together with catalytic cracking turning oil, hydrodemetallation (HDM) is carried out under hydrogen and hydrogenation catalyst exist, hydrogenating desulfurization, hydrodenitrification and the reaction such as aromatic hydrogenation is saturated, the reaction obtained generates oil at high pressure hot separator, thermal low-pressure separators, cold high pressure separator, after cold low separator and fractionation facility are separated, obtain gas, hydrotreated naphtha, hydrogenation tail oil, wherein hydrogenation tail oil enters catalytic cracking unit, cracking reaction is carried out under catalytic cracking catalyst exists, dry gas is obtained after being separated, liquefied gas, catalytically cracked gasoline, catalytic cracking solar oil, catalytic cracking turning oil and slurry oil, wherein catalytic cracking solar oil is in catalytic cracking unit self-circulation, and catalytic cracking turning oil is circulated to hydrotreatment reaction zone.
Described wax oil raw material is one or more in straight run decompressed wax oil, wax tailings and deasphalted oil.At hydrotreating unit, after faulty wax oil raw material mixes with hydrogen with catalytic cracking turning oil, enter the hydrotreatment reaction zone being filled with at least two kinds of hydrogenation catalyst combinations, under middle pressure, carry out the reactions such as hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), aromatic saturation, reaction generates oil through separation removal H
2s and NH
3after, enter separation column and be separated into hydrotreated naphtha and hydrogenation tail oil, hydrogenation tail oil is as the charging of catalytic cracking unit.The initial boiling point of described hydrogenation tail oil is 165 DEG C.
Wax oil raw material considerably reduces raw material sulphur and nitrogen content by hydrotreating unit, as catalytically cracked material, can reduce the content of SOx in catalytic cracking flue gas significantly, the inactivation of catalytic cracking catalyst also can reduce due to the minimizing of nitrogen content in raw material.Catalytic cracking turning oil carries out aromatic hydrogenation saturated reaction at hydrotreating unit, is mononuclear aromatics by above for dicyclo aromatic saturation, for catalytic cracking unit provides the high quality raw material producing stop bracket gasoline.
The operational condition of described hydrotreatment reaction zone is: hydrogen dividing potential drop 3.0 ~ 12.0MPa, temperature of reaction 300 ~ 450 DEG C, volume space velocity 0.1 ~ 3.0h
-1, hydrogen to oil volume ratio 300 ~ 2000Nm
3/ m
3; Preferred operational condition is: hydrogen dividing potential drop 4.0 ~ 12.0MPa, temperature of reaction 330 ~ 430 DEG C, volume space velocity 0.5 ~ 3.0h
-1, hydrogen to oil volume ratio 300 ~ 1500Nm
3/ m
3.
Hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent, hydrotreating catalyst is loaded successively in described hydrotreatment reaction zone.With whole catalyzer for benchmark, hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrotreating catalyst admission space percentage ratio are respectively 2 ~ 10 volume %, 0 ~ 30 volume %, 0 ~ 40 volume %, 60 ~ 98 volume %.
Described hydrogenation protecting agent consists of: with hydrogenation protecting agent for benchmark, the heavy % of the heavy % of nickel oxide 0.5 ~ 5.0, molybdenum oxide 2.0 ~ 10.0 and remainder alumina carrier.Described hydrogenation protecting agent is the combination of hydrogenation protecting agent of two kinds of different activities, Different Pore Structures, adopts two kinds of protectant objects to be to slow down beds pressure drop rise, improves running period.
Consisting of of described hydrodemetallation (HDM) agent: with hydrodemetallation (HDM) agent for benchmark, the heavy % of the heavy % of nickel oxide 0.5 ~ 5.0, molybdenum oxide 2.0 ~ 15.0 and remainder alumina carrier.
Consisting of of described hydrogen desulfurization agent: take hydrogen desulfurization agent as benchmark, the heavy % of the heavy % of cobalt oxide 1.0 ~ 10.0, molybdenum oxide 5.0 ~ 30.0 and remainder alumina carrier.
Consisting of of described hydrotreating catalyst: take hydrotreating catalyst as benchmark, nickel oxide 1 ~ 10%, molybdenum oxide and Tungsten oxide 99.999 sum are 10 ~ 50 heavy %, the heavy % of fluorine 1 ~ 10, and the heavy % of phosphorus oxide 0.5 ~ 8, surplus is silica-alumina.
At catalytic cracking unit, from the hydrogenation tail oil of hydrotreating unit as catalytically cracked stock, catalytic cracking unit is entered together with catalytic cracking solar oil, part heavy distillate, under the existence of catalytic cracking catalyst, carry out cracking reaction, reaction generates gas, catalytic gasoline, catalytic cracking solar oil, catalytic cracking turning oil and the coke that oil obtains after fractionation.Wherein, catalytic cracking solar oil carries out self-circulation at catalytic cracking unit, catalytic cracking turning oil returns hydrotreating unit, in reduction catalytic cycle oil foreign matter content, the above aromatic hydrocarbons of dicyclo to be carried out to appropriateness saturated, increase hydrogen richness, improve the Catalytic Cracking Performance of catalytic cycle oil as catalytic cracking feeds.
Described catalytic cracking solar oil refers to 190 DEG C ~ 270 DEG C cuts in catalytic cracking full distillate product, preferably 205 DEG C ~ 260 DEG C.In described catalytic cracking solar oil, aromaticity content is high, especially mononuclear aromatics content is high, mononuclear aromatics content higher than 50 quality %, preferably more than 55 quality %, this part mononuclear aromatics returns catalytic cracking unit entrance and carries out catalytic cracking reaction, can produce stop bracket gasoline.
Described catalytic cracking turning oil refers to 250 DEG C ~ 460 DEG C cuts in catalytic cracking full distillate product.In described catalytic cracking turning oil, the above aromaticity content of dicyclo is high, the above aromaticity content of dicyclo is more than 55 quality %, preferably more than 60 quality %, this part cut returns hydrotreating unit, and to carry out appropriateness saturated, saturated is mononuclear aromatics, then entering catalytic cracking unit and proceed cracking reaction, providing high-quality charging for producing stop bracket gasoline.
Catalytic cracking unit entrance is returned by catalytic cracking solar oil, and catalytic cracking turning oil enters catalytic cracking unit and carries out cracking reaction after hydrotreatment, can greatly improve catalytic gasoline quality and yield, and this device can improve the octane value of catalytic gasoline, the LCO that aromaticity content is high, cetane value is low transforms further, realizes LCO and entirely transforms.
The catalytic cracking unit technique of indication of the present invention comprises all types of fluid catalytic cracking process, and in order to the catalytic cracking process of specific purpose exploitation, as the MIP technique etc. of voluminous isomeric olefine of Sinopec exploitation.
The catalyzer that catalytic cracking unit adopts is made up of zeolite, inorganic oxide and/or clay etc., and described zeolite is selected from one or more in REY, REHY, ZSM-5.
Catalytic cracking unit adopts the reaction process condition of riser reactor to be: the weight ratio (hereinafter referred to as agent-oil ratio) 3 ~ 15 of temperature of reaction 480 DEG C ~ 620 DEG C, 0.5 ~ 7 second reaction times, catalyzer and stock oil, the weight ratio of regeneration temperature 600 ~ 800 DEG C, absolute pressure 0.1 ~ 0.5MPa, water vapour and stock oil is 0.1 ~ 0.6.
Tool of the present invention has the following advantages:
(1) by hydrotreatment-catalytic cracking combined technique provided by the invention, with faulty wax oil, catalytic cracking solar oil, catalytic cracking turning oil for raw material, the high-quality low-sulfur gasoline fraction of high yield can be produced, control catalytic gasoline sulphur content by the reaction depth controlling hydrotreating unit.
(2) the present invention adopts a hydrotreating unit to realize two kinds of objects, one, the hydrogenating desulfurization of faulty wax oil raw material, hydrodenitrification, hydrogenation aromatics-removing, produces low-sulphur oil supply raw materials for catalytic cracking unit; Its two, the appropriate hydrotreated lube base oil reaction of the hydrogenation removing impurities matter of catalytic cracking turning oil, the above aromatic hydrocarbons of dicyclo, produces stop bracket gasoline for catalytic cracking unit and provides high-quality charging.
(3) in the present invention, cracking is carried out further by catalytic cracking light cycle oil is returned catalytic cracking unit, do not produce the output of the low-value products such as the LCO that aromaticity content is high, cetane value is low at catalytic cracking unit, improve quality and the yield of stop bracket gasoline.
(4) good quality of product, the gasoline fraction that catalytic cracking is produced has low sulphur content and olefin(e) centent; Product yield is high, and the turning oil that catalytic cracking unit is produced enters catalytic cracking unit again after hydrogenation, reduces coke yield, the corresponding yield that improve gasoline and liquefied gas.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of the hydrotreatment-catalytic cracking combination process of voluminous high value gasoline provided by the invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed.
Accompanying drawing is the schematic flow sheet of the hydrotreatment-catalytic cracking combination process of voluminous gasoline provided by the invention.The equipment of much necessity is eliminated, as process furnace, pump, interchanger etc. in figure.
After wax oil raw material from pipeline 10 mixes with the catalytic cracking turning oil from pipeline 30, after mixing from the new hydrogen of pipeline 11 and the recycle hydrogen of pipeline 23, enter hydrotreatment reaction zone 1 through pipeline 12 and carry out hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, aromatic hydrogenation saturated reaction etc., the reaction generation oil obtained enters high pressure hot separator 2 through pipeline 13 and is separated.The gaseous stream that high pressure hot separator 2 obtains enters cold high pressure separator 3 through pipeline 15 and is separated further, the gaseous stream that cold high pressure separator 3 obtains after desulphurization of recycle hydrogen tank 6 through circulating hydrogen compressor 7, return hydrotreatment reaction zone entrance through pipeline 23.Cold high pressure separator 3 is separated the sour water obtained and extracts out through pipeline 19, and the liquid phase stream obtained enters cold low separator 5 through pipeline 17 and is separated further.The liquid phase stream that thermal low-pressure separators 2 obtains enters thermal low-pressure separators 4 through pipeline 14 and is separated.Thermal low-pressure separators 4 obtains gaseous stream and enters cold low separator 5 through pipeline 18 and be separated, and the liquid phase stream obtained enters separation column 8 through pipeline 16 and carries out Component seperation.The sour water that cold low separator 5 obtains is extracted out through pipeline 20, and the gas obtained is extracted out through pipeline 22, and the liquid phase stream that cold low separator obtains enters separation column 8 through pipeline 21 and carries out Component seperation.The isolated hydrotreated naphtha of separation column 8 is extracted out through pipeline 25, the hydrogenation tail oil obtained enters catalytic cracking unit 9 and carries out cracking reaction after pipeline 24 mixes with catalytic cracking solar oil 29, then in catalytic cracking unit, be separated into dry gas through fractionation facility to extract out through pipeline 26, liquefied gas is extracted out through pipeline 27, catalytic gasoline is extracted out through pipeline 28, catalysis solar oil returns catalytic cracking unit through pipeline 29, and catalytic cycle oil returns hydrotreating unit through pipeline 30, and catalytic slurry is extracted out through pipeline 31.
The following examples will be further described method provided by the invention, but therefore not limit the present invention.
In embodiment; the trade names of hydrogenation protecting agent A are RG-30A, and the trade names of hydrogenation protecting agent B are RG-30B, and the trade names of hydrogen desulfurization agent C are RVS-420; the trade names of hydrodemetallation (HDM) agent D are RDM-2, and the trade names of hydrotreating catalyst E are RN-32V.The trade names of catalytic cracking catalyst F are CGP-2, and above catalyzer is produced by Sinopec catalyzer Chang Ling branch office.
Wax oil raw material G used in embodiment and wax oil raw material H takes from the hydrotreater charging of different refineries, and character lists in table 1.
Embodiment 1
Enter hydrotreatment reaction zone after wax oil raw material G and catalytic cycle oil mixing, successively with hydrogenation protecting agent A, hydrogenation protecting agent B, hydrogen desulfurization agent C and hydrotreating catalyst E contact reacts, the admission space of above-mentioned catalyzer is than being 4:4:20:72.Adopt technical process shown in the drawings, the hydrogenation tail oil of gained is be greater than the cut of 165 DEG C.The boiling range of gained catalysis solar oil is 190 DEG C ~ 270 DEG C, and mononuclear aromatics content 51 quality %, catalytic cracking unit is returned in self-circulation.The boiling range of catalytic cycle oil is 270 DEG C ~ 460 DEG C cuts, and the above aromaticity content of dicyclo is 69 quality %, and catalytic cycle oil returns to hydrotreatment reaction zone.
Table 2, table 3 and table 4 are respectively each reaction zone processing parameter, product slates and product property etc.Visible, adopt combination process of the present invention, the catalysis solar oil of catalytic cracking unit, catalytic cycle oil are all utilized, and can improve gasoline products yield.Catalysis solar oil carries out cracking conversion further at catalytic cracking unit, and catalytic cycle oil returns catalytic cracking unit after hydrotreatment, and production is content of sulfur in gasoline 30 μ g/g, meets state IV motor spirit emission standard requirement, and has higher octane value.
Embodiment 2
Enter hydrotreatment reaction zone after wax oil raw material H and catalytic cycle oil mixing, successively with hydrogenation protecting agent A, hydrogenation protecting agent B, hydrodemetallation (HDM) agent D and hydrotreating catalyst E contact reacts, the admission space of above-mentioned catalyzer is than being 5:5:15:75.Adopt technical process shown in the drawings, the hydrogenation tail oil of gained is be greater than the cut of 165 DEG C.The boiling range of gained catalysis solar oil is 190 DEG C ~ 255 DEG C, and mononuclear aromatics content 62 quality %, catalytic cracking unit is returned in self-circulation.The boiling range of catalytic cycle oil is 255 DEG C ~ 460 DEG C cuts, and the above aromaticity content of dicyclo is 65 quality %, and catalytic cycle oil returns to hydrotreatment reaction zone.
Table 2, table 3 and table 5 are respectively each reaction zone processing parameter, product slates and product property etc.Visible, adopt combination process of the present invention, the catalysis solar oil of catalytic cracking unit, catalytic cycle oil are all utilized, and can improve gasoline products yield.Catalysis solar oil carries out cracking conversion further at catalytic cracking unit, and catalytic cycle oil returns catalytic cracking unit after hydrotreatment, and production is content of sulfur in gasoline 10 μ g/g, meets state V motor spirit emission standard requirement, and has higher octane value.
Table 1 hydrotreatment reaction zone wax oil feedstock property
| Material name | Wax oil raw material G | Wax oil raw material H |
| Density (20 DEG C), g/cm 3 | 0.9377 | 0.9282 |
| Refractive index n D 70 | 1.5072 | |
| C, heavy % | 85.23 | 87.18 |
| H, heavy % | 11.60 | 12.05 |
| S，μg/g | 31000 | 9700 |
| N，μg/g | 1600 | 2500 |
| Boiling range ASTM D-1160, DEG C | ||
| Initial boiling point/10% | 249/406 | 256/347 |
| 30%/50% | 438/508 | 394/426 |
| 70%/90% | 525/557 | 457/498 |
| 95% | 563 | 516 |
Table 2 hydrotreating unit and catalytic cracking unit processing condition
| Embodiment 1 | Embodiment 2 | |
| Hydroprocessing unit catalyst agent | A/B/C/E | A/B/D/E |
| Hydrotreating unit processing condition: | ||
| Stock oil | Wax oil raw material G+ catalytic cycle oil | Wax oil raw material H+ catalytic cycle oil |
| Hydrogen dividing potential drop, MPa | 9.8 | 8.0 |
| Temperature of reaction, DEG C | 375 | 380 |
| Cumulative volume air speed, h -1 | 1.5 | 1.65 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 600 | 500 |
| Catalytic cracking unit processing condition: | ||
| Stock oil | Hydrogenation tail oil+catalysis solar oil | Hydrogenation tail oil+catalysis solar oil |
| Temperature of reaction, DEG C | 510 | 510 |
| Reaction times, second | 6 | 6 |
| Atomized water, heavy % | 8 | 8 |
| Agent-oil ratio | 5 | 5 |
Table 3 product slates
| Embodiment 1 | Embodiment 2 | |
| Hydrotreating unit: heavy % | ||
| The side of entering: | ||
| Faulty wax oil | 100 | 100 |
| Catalytic cycle oil | 20 | 18.6 |
| Chemical hydrogen consumption | 1.38 | 1.10 |
| The side of going out: | ||
| H 2S+NH 3 | 3.90 | 1.15 |
| Hydrotreated naphtha | 1.26 | 1.62 |
| Hydrogenation tail oil (directly removing catalytic cracking unit) | 116.22 | 116.93 |
| Catalytic cracking unit: heavy % | ||
| The side of entering: | ||
| Hydrogenation tail oil | 116.22 | 116.93 |
| Catalysis solar oil | 11.55 | 10.20 |
| The side of going out: | ||
| Dry gas | 2.80 | 2.75 |
| Liquefied gas | 28.90 | 27.50 |
| Gasoline | 59.70 | 62.48 |
| Catalysis solar oil (going to catalytic cracking reaction zone) | 11.55 | 10.20 |
| Catalytic cycle oil (going to hydrotreatment reaction zone) | 20.00 | 18.6 |
| Coke | 4.82 | 5.60 |
Table 4 product property
Table 5 product property
Claims (11)
1. hydrotreatment-catalytic cracking combination process, it is characterized in that, wax oil raw material enters hydrotreatment reaction zone together with catalytic cracking turning oil, hydrodemetallation (HDM) is carried out under hydrogen and hydrogenation catalyst exist, hydrogenating desulfurization, hydrodenitrification and aromatic hydrogenation saturated reaction, the reaction obtained generates oil at high pressure hot separator, thermal low-pressure separators, cold high pressure separator, after cold low separator and fractionation facility are separated, obtain gas, hydrotreated naphtha, hydrogenation tail oil, wherein hydrogenation tail oil enters catalytic cracking unit, cracking reaction is carried out under catalytic cracking catalyst exists, dry gas is obtained after being separated, liquefied gas, catalytically cracked gasoline, catalytic cracking solar oil, catalytic cracking turning oil and slurry oil, wherein catalytic cracking solar oil is in catalytic cracking unit self-circulation, and catalytic cracking turning oil is circulated to hydrotreatment reaction zone, described catalytic cracking solar oil refers to 190 DEG C ~ 270 DEG C cuts in catalytic cracking full distillate product, mononuclear aromatics content is higher than 50 quality %, described catalytic cracking turning oil refers to 250 DEG C ~ 460 DEG C cuts in catalytic cracking full distillate product, in described catalytic cracking turning oil, the above aromaticity content of dicyclo is more than 55 quality %.
2. in accordance with the method for claim 1, it is characterized in that, described wax oil raw material is one or more in straight run decompressed wax oil, wax tailings and deasphalted oil.
3. in accordance with the method for claim 1, it is characterized in that, the operational condition of described hydrotreatment reaction zone is: hydrogen dividing potential drop 3.0 ~ 12.0MPa, temperature of reaction 300 ~ 450 DEG C, volume space velocity 0.1 ~ 3.0h
-1, hydrogen to oil volume ratio 300 ~ 2000Nm
3/ m
3.
4. in accordance with the method for claim 1, it is characterized in that, the operational condition of described hydrotreatment reaction zone is: hydrogen dividing potential drop 4.0 ~ 12.0MPa, temperature of reaction 330 ~ 430 DEG C, volume space velocity 0.5 ~ 3.0h
-1, hydrogen to oil volume ratio 300 ~ 1500Nm
3/ m
3.
5. in accordance with the method for claim 1; it is characterized in that; hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent, hydrotreating catalyst is loaded successively in described hydrotreatment reaction zone; with whole catalyzer for benchmark; hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrotreating catalyst admission space percentage ratio are respectively 2 ~ 10 volume %; 0 ~ 30 volume %, 0 ~ 40 volume %, 60 ~ 98 volume %.
6. in accordance with the method for claim 5, it is characterized in that, consisting of of described hydrogenation protecting agent: with hydrogenation protecting agent for benchmark, the alumina supporter of 0.5 ~ 5.0 heavy % nickel oxide, 2.0 ~ 10.0 heavy % molybdenum oxides and surplus.
7. in accordance with the method for claim 5, it is characterized in that, consisting of of described hydrodemetallation (HDM) agent: with hydrodemetallation (HDM) agent for benchmark, the heavy % of the heavy % of nickel oxide 0.5 ~ 5.0, molybdenum oxide 2.0 ~ 15.0 and remainder alumina carrier.
8. in accordance with the method for claim 5, it is characterized in that, consisting of of described hydrogen desulfurization agent: take Hydrobon catalyst as benchmark, the heavy % of the heavy % of cobalt oxide 1.0 ~ 10.0, molybdenum oxide 5.0 ~ 30.0 and remainder alumina carrier.
9. in accordance with the method for claim 5, it is characterized in that, what described hydrotreating catalyst was consists of: take hydrotreating catalyst as benchmark, nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 % by weight to being less than or equal to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is silica-alumina.
10. in accordance with the method for claim 1, it is characterized in that, the initial boiling point of described hydrogenation tail oil is 165 DEG C.
11. in accordance with the method for claim 1, it is characterized in that, catalytic cracking unit adopts riser reactor, its reaction process condition is: the weight ratio 3 ~ 15 of temperature of reaction 480 ~ 620 DEG C, 0.5 ~ 7 second reaction times, catalyzer and stock oil, the weight ratio 0.1 ~ 0.6 of regeneration temperature 600 ~ 800 DEG C, absolute pressure 0.10 ~ 0.5MPa, water vapor and stock oil.
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| CN104312625A (en) * | 2014-09-30 | 2015-01-28 | 中国石油化工股份有限公司 | Energy-saving type wax oil hydrogenation equipment in petrochemical industry |
| CN107286990B (en) * | 2016-04-12 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of processing of heavy-oil hydrogenation and catalytic cracking combined technique |
| CN109423337B (en) * | 2017-08-22 | 2020-08-04 | 中国石化工程建设有限公司 | Wax oil hydrogenation-catalytic cracking heat combined process system and wax oil treatment method |
| CN111378491B (en) * | 2018-12-28 | 2021-08-31 | 中国石油化工股份有限公司 | Inferior heavy oil hydrotreating process |
| CN109666508B (en) * | 2019-02-21 | 2023-11-14 | 上海米素环保科技有限公司 | Transformation method for improving economic operation period of hydrogenation device |
| CN112538385B (en) * | 2019-09-20 | 2022-04-12 | 中国石油化工股份有限公司 | Hydrogenation and catalytic cracking combined method |
| CN113136243B (en) * | 2020-01-19 | 2022-11-11 | 中国石油化工股份有限公司 | Hydrocracking-catalytic cracking combined process |
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