CN103773495A - Hydrotreatment-catalytic cracking combination process method - Google Patents
Hydrotreatment-catalytic cracking combination process method Download PDFInfo
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- CN103773495A CN103773495A CN201210410162.3A CN201210410162A CN103773495A CN 103773495 A CN103773495 A CN 103773495A CN 201210410162 A CN201210410162 A CN 201210410162A CN 103773495 A CN103773495 A CN 103773495A
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- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 49
- 239000003502 gasoline Substances 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 17
- 238000005336 cracking Methods 0.000 claims abstract description 13
- 239000002283 diesel fuel Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 133
- 230000003197 catalytic effect Effects 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000006477 desulfuration reaction Methods 0.000 claims description 11
- 230000023556 desulfurization Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005194 fractionation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000011814 protection agent Substances 0.000 claims 3
- 239000010724 circulating oil Substances 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 23
- 239000003223 protective agent Substances 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 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
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
一种加氢处理—催化裂化组合工艺方法，蜡油和催化裂化循环油一起进入加氢处理反应区，在氢气和加氢催化剂存在下进行加氢脱金属、加氢脱硫、加氢脱氮及芳烃加氢饱和等反应，得到的加氢尾油进入催化裂化装置，在催化裂化催化剂存在下进行裂化反应，经分离后得到干气、液化气、催化裂化汽油、催化裂化轻柴油、催化裂化循环油和油浆，其中催化裂化轻柴油在催化裂化装置自循环，而催化裂化循环油循环至加氢处理反应区。采用本发明提供的方法，能大幅提高汽油产品的收率和质量。
A hydroprocessing-catalytic cracking combined process method, wax oil and catalytic cracking cycle oil enter the hydroprocessing reaction zone together, and perform hydrodemetallization, hydrodesulfurization, hydrodenitrogenation and hydrodenitrogenation in the presence of hydrogen and a hydrogenation catalyst Aromatic hydrocarbon hydrogenation saturation and other reactions, the obtained hydrogenated tail oil enters the catalytic cracking unit, and undergoes cracking reaction in the presence of catalytic cracking catalyst, and after separation, dry gas, liquefied gas, catalytic cracking gasoline, catalytic cracking light diesel oil, catalytic cracking cycle Oil and oil slurry, in which the catalytic cracking light oil is recycled in the catalytic cracking unit, and the catalytic cracking cycle oil is recycled to the hydrotreating reaction zone. By adopting the method provided by the invention, the yield and quality of gasoline products can be greatly improved.
Description
Technical field
The invention belongs to the method for processing hydrocarbon ils with other step of converting 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 scarcity day by day of crude resources and crude oil heaviness, in poor quality process, how effectively utilizing limited resources maximum to produce light-end products becomes the target that each oil Refining Technologies developer pursues, and the oil Refining Technologies that can improve object product yield and quality becomes the selection of numerous refinerys.
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 hydrogenation preconditioning technique can significantly reduce its sulphur nitrogen content, increases hydrogen richness, thereby reduces the sulphur nitrogen content of cracked product, improves product and distributes.Prior art is mainly that single fcc raw material adds hydrogen pretreatment or raw material adds hydrogen pretreatment-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 producing (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.Conventionally need newly-built catalytic cracking diesel oil hydro-upgrading unit or the oil fuel using catalytic cracking diesel oil as low value to dispatch from the factory.On the other hand, catalytic cracking unit is for increasing catalytic cracking transformation efficiency and yield of light oil, conventionally heavy cycle oil (HCO) self is circulated 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, has increased revivifier load, has reduced 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 need to, by independent heavy cycle oil hydrotreatment, increase plant investment a lot, and only solve 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, separate and obtain gas, petroleum naphtha and heavier product (comprising diesel oil and heavy cycle oil); After hydrotreater of heavier product introduction, separate and obtain petroleum naphtha, diesel oil and hydrogenation tail oil; Catalytic cracking unit is returned in hydrogenation tail oil recirculation.This combination process has solved the problem that coke yield is high, diesel quality is poor preferably, but need to set up separately hydrogenation unit, and does not solve the problem that catalytic gasoline sulphur content is high.
CN10434496C discloses the combined technical method of a kind of VGO and catalytic cracking unit.Catalytic cracking diesel oil (LCO) and heavy cycle oil that the method is produced catalytic cracking unit all loop back VGO, are conducive to improve the quality of product yield and catalytic cracking diesel oil.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of wax oil hydrogenation to process and catalytic cracking two-way combined process, is a kind of wax oil hydrogenation processing-catalytic cracking combination process that improves 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, under hydrogen and hydrogenation catalyst existence, carry out hydrodemetallation (HDM), hydrogenating desulfurization, the reactions such as hydrodenitrification and aromatic hydrogenation are saturated, the reaction obtaining generates oil at high pressure hot separator, thermal low-pressure separators, cold high pressure separator, after cold low separator and fractionation facility separate, obtain gas, hydrotreated naphtha, hydrogenation tail oil, wherein hydrogenation tail oil enters catalytic cracking unit, under existing, catalytic cracking catalyst carries out cracking reaction, after separating, obtain dry gas, 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 that is 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, entering 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 ℃.
Wax oil raw material has significantly reduced raw material sulphur and nitrogen content by hydrotreating unit, as catalytically cracked material, can reduce significantly the content of SOx in catalytic cracking flue gas, the inactivation of catalytic cracking catalyst also can be because the minimizing of nitrogen content in raw material reduces.Catalytic cracking turning oil carries out aromatic hydrogenation saturated reaction at hydrotreating unit, is mononuclear aromatics by above dicyclo aromatic saturation, for catalytic cracking unit provides the high quality raw material of producing stop bracket gasoline.
The operational condition of described hydrotreatment reaction zone is: hydrogen dividing potential drop 3.0 ~ 12.0MPa, 300 ~ 450 ℃ of temperature of reaction, 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, 330 ~ 430 ℃ of temperature of reaction, volume space velocity 0.5 ~ 3.0h
-1, hydrogen to oil volume ratio 300 ~ 1500Nm
3/ m
3.
In described hydrotreatment reaction zone, load successively hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent, hydrotreating catalyst.Take whole catalyzer as 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: take hydrogenation protecting agent as benchmark, and the heavy % of nickel oxide 0.5 ~ 5.0, the heavy % of molybdenum oxide 2.0 ~ 10.0 and surplus alumina supporter.Described hydrogenation protecting agent is the combination of the hydrogenation protecting agent of two kinds of different activities, Different Pore Structures, and adopting two kinds of protectant objects is to rise in order to slow down beds pressure drop, improves running period.
Consisting of of described hydrodemetallation (HDM) agent: take hydrodemetallation (HDM) agent as benchmark, the heavy % of nickel oxide 0.5 ~ 5.0, the heavy % of molybdenum oxide 2.0 ~ 15.0 and surplus alumina supporter.
Consisting of of described hydrogen desulfurization agent: take hydrogen desulfurization agent as benchmark, the heavy % of cobalt oxide 1.0 ~ 10.0, the heavy % of molybdenum oxide 5.0 ~ 30.0 and surplus alumina supporter.
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, 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, enter catalytic cracking unit 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 to hydrotreating unit, reducing foreign matter content in catalytic cycle oil, that the above aromatic hydrocarbons of dicyclo is carried out to appropriateness is saturated, increase hydrogen richness, improve the Catalytic Cracking Performance of catalytic cycle oil as catalytic cracking charging.
Described catalytic cracking solar oil refers to 190 ℃ ~ 270 ℃ cuts in catalytic cracking full distillate product, preferably 205 ℃ ~ 260 ℃.In described catalytic cracking solar oil, aromaticity content is high, especially mononuclear aromatics content is high, and mononuclear aromatics content is higher than 50 quality %, preferably more than 55 quality %, this part mononuclear aromatics returns to catalytic cracking unit entrance and carries out catalytic cracking reaction, can produce stop bracket gasoline.
Described catalytic cracking turning oil refers to 250 ℃ ~ 460 ℃ 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 to hydrotreating unit, and to carry out appropriateness saturated, saturated is mononuclear aromatics, then enter catalytic cracking unit and proceed cracking reaction, provide high-quality charging for producing stop bracket gasoline.
Return to catalytic cracking unit entrance 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 high aromaticity content, cetane value is low is further transformed, realize LCO and entirely transform.
The catalytic cracking unit technique of indication of the present invention comprises all types of fluid catalytic cracking process, and for the catalytic cracking process of specific purpose exploitation, as the MIP technique of the voluminous isomeric olefine of Sinopec exploitation etc.
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 to be referred as agent-oil ratio) 3 ~ 15 of 480 ℃ ~ 620 ℃ of temperature of reaction, 0.5 ~ 7 second reaction times, catalyzer and stock oil, the weight ratio of 600 ~ 800 ℃ of regeneration temperatures, 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, take faulty wax oil, catalytic cracking solar oil, catalytic cracking turning oil as raw material, can produce the high-quality low-sulfur gasoline fraction of high yield, can control catalytic gasoline sulphur content by the reaction depth of controlling hydrotreating unit.
(2) the present invention adopts a hydrotreating unit to realize two kinds of objects, one, and the hydrogenating desulfurization of faulty wax oil raw material, hydrodenitrification, hydrogenation aromatics-removing, produce low-sulphur oil for catalytic cracking unit and supply raw materials; Its two, the hydrogenation removing impurities matter of catalytic cracking turning oil, the appropriate hydrogenation saturated reaction of the above aromatic hydrocarbons of dicyclo, for catalytic cracking unit produce stop bracket gasoline high-quality charging is provided.
(3) in the present invention, further carry out cracking by catalytic cracking light cycle oil being returned to 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, improved 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 after hydrogenation again, has reduced coke yield, the corresponding yield that has improved 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.In figure, omit the equipment of many necessity, as process furnace, pump, interchanger etc.
After mixing with the catalytic cracking turning oil from pipeline 30 from the wax oil raw material of pipeline 10, after mixing with the recycle hydrogen of new hydrogen from pipeline 11 and 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 obtaining enters high pressure hot separator 2 through pipeline 13 and separates.The gaseous stream that high pressure hot separator 2 obtains enters cold high pressure separator 3 through pipeline 15 and further separates, the gaseous stream that cold high pressure separator 3 obtains after desulphurization of recycle hydrogen tank 6 through circulating hydrogen compressor 7, return to hydrotreatment reaction zone entrance through pipeline 23.Cold high pressure separator 3 separates the sour water obtaining and extracts out through pipeline 19, and the liquid phase stream obtaining enters cold low separator 5 through pipeline 17 and further separates.The liquid phase stream that thermal low-pressure separators 2 obtains enters thermal low-pressure separators 4 through pipeline 14 and separates.Thermal low-pressure separators 4 obtains gaseous stream and enters cold low separator 5 through pipeline 18 and separate, and the liquid phase stream obtaining enters separation column 8 through pipeline 16 and carries out component separation.The sour water that cold low separator 5 obtains is extracted out through pipeline 20, and the gas obtaining 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 separation.The isolated hydrotreated naphtha of separation column 8 is extracted out through pipeline 25, the hydrogenation tail oil obtaining 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, being separated into dry gas through fractionation facility extracts out through pipeline 26, liquefied gas is extracted out through pipeline 27, catalytic gasoline is extracted out through pipeline 28, catalysis solar oil returns to catalytic cracking unit through pipeline 29, and catalytic cycle oil returns to 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 and wax oil raw material H used in embodiment take from the hydrotreater charging of different refineries, and character is listed in table 1.
Embodiment 1
Wax oil raw material G and catalytic cycle oil enter hydrotreatment reaction zone after mixing, and 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 to be greater than the cut of 165 ℃.The boiling range of gained catalysis solar oil is 190 ℃ ~ 270 ℃, mononuclear aromatics content 51 quality %, and catalytic cracking unit is returned in self-circulation.The boiling range of catalytic cycle oil is 270 ℃ ~ 460 ℃ 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 distribution 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 further carries out cracking conversion at catalytic cracking unit, and catalytic cycle oil returns to catalytic cracking unit after hydrotreatment, and production is content of sulfur in gasoline 30 μ g/g, meets state's IV motor spirit emission standard requirement, and has higher octane value.
Wax oil raw material H and catalytic cycle oil enter hydrotreatment reaction zone after mixing, and 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 to be greater than the cut of 165 ℃.The boiling range of gained catalysis solar oil is 190 ℃ ~ 255 ℃, mononuclear aromatics content 62 quality %, and catalytic cracking unit is returned in self-circulation.The boiling range of catalytic cycle oil is 255 ℃ ~ 460 ℃ 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 distribution 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 further carries out cracking conversion at catalytic cracking unit, and catalytic cycle oil returns to catalytic cracking unit after hydrotreatment, and production is content of sulfur in gasoline 10 μ g/g, meets state's 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 ℃), 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, ℃ | ||
| 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 | |
|
| Hydrotreating unit catalyzer | 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, ℃ | 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, ℃ | 510 | 510 |
| Reaction times, second | 6 | 6 |
| Atomized water, heavy % | 8 | 8 |
| Agent- |
5 | 5 |
Table 3 product distributes
| Embodiment 1 | |
|
| Hydrotreating unit: heavy % | ||
| The side of entering: | ||
| Faulty wax oil | 100 | 100 |
| |
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
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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 |
| CN107286990A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation processing and catalytic cracking combined technique |
| CN109423337A (en) * | 2017-08-22 | 2019-03-05 | 中国石化工程建设有限公司 | A kind of wax oil hydrogenation-catalytic cracking heat integration process system and wax oil processing method |
| CN109666508A (en) * | 2019-02-21 | 2019-04-23 | 上海米素环保科技有限公司 | A kind of remodeling method promoting the hydrogenation plant economical running period |
| CN111378491A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Inferior heavy oil hydrotreating process |
| CN112538385A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Hydrogenation and catalytic cracking combined method |
| CN113136243A (en) * | 2020-01-19 | 2021-07-20 | 中国石油化工股份有限公司 | Hydrocracking-catalytic cracking combined process |
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| CN107286990A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation processing and catalytic cracking combined technique |
| 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 |
| CN109423337A (en) * | 2017-08-22 | 2019-03-05 | 中国石化工程建设有限公司 | A kind of wax oil hydrogenation-catalytic cracking heat integration process system and wax oil processing method |
| CN111378491A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Inferior heavy oil hydrotreating process |
| 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 |
| CN109666508A (en) * | 2019-02-21 | 2019-04-23 | 上海米素环保科技有限公司 | A kind of remodeling method promoting the hydrogenation plant economical running period |
| 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 |
| CN112538385A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Hydrogenation and catalytic cracking combined method |
| 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 |
| CN113136243A (en) * | 2020-01-19 | 2021-07-20 | 中国石油化工股份有限公司 | Hydrocracking-catalytic cracking combined process |
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