CN1202219C - Single section medium pressure hydrocracking and catalytic cracking integrated process - Google Patents
Single section medium pressure hydrocracking and catalytic cracking integrated process Download PDFInfo
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- CN1202219C CN1202219C CN 02144545 CN02144545A CN1202219C CN 1202219 C CN1202219 C CN 1202219C CN 02144545 CN02144545 CN 02144545 CN 02144545 A CN02144545 A CN 02144545A CN 1202219 C CN1202219 C CN 1202219C
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims description 42
- 230000008569 process Effects 0.000 title claims description 40
- 238000004523 catalytic cracking Methods 0.000 title claims description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000005336 cracking Methods 0.000 claims abstract description 9
- 238000007670 refining Methods 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 38
- 229910021536 Zeolite Inorganic materials 0.000 claims description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 33
- 239000010457 zeolite Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 23
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000003209 petroleum derivative Substances 0.000 claims description 5
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 4
- 230000001131 transforming effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000002283 diesel fuel Substances 0.000 abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 18
- 239000005864 Sulphur Substances 0.000 abstract description 14
- 239000003921 oil Substances 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000003075 superhydrophobic effect Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012084 conversion product Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 101100004286 Caenorhabditis elegans best-5 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a reversed order once-through medium pressure hydrocracking technology of a combined FCC apparatus, which is used for obtaining middle distillate oil by treating a heavy hydrocarbon material and for providing a hydrogenation modified material for the FCC apparatus. The technology is characterized in that clean diesel oil and a hydrogenation raw material for the material feeding of the downstream FCC apparatus are produced in a once-through operation mode by adopting the reversed order hydrocracking flow that a raw material firstly passes through a cracking section and secondly passes through a refining section, and simultaneously, the technology provides a flow that LCO is circulated back to a hydrorefining reactor and re-refined to convert the inferior LCO into a low-sulphur diesel oil component through hydrodesulphurization. In the technology of the present invention, the LCO is maximally maintained within the boiling range of diesel oil to improve the selectivity of middle distillate oil, and simultaneously, the operating conditions of the hydrocracking section, of which the limitations are reduced, are flexibly adjusted.
Description
Technical field
The present invention relates to a kind of single hop middle pressure hydrocracking and catalytic cracking (FCC) process integration, specifically unite FCC apparatus once by middle pressure hydrocracking technology, this technology is in production part hydrocracking light-end products, for FCC apparatus provides charging of hydrogenation pre-refining and the further light cycle oil inferior of handling the FCC apparatus output.
Background technology
Environmental regulation makes the oil fuel quality index harsh day by day.With clean diesel production specification standard is example: sulphur, nitrogen content, cetane value, density, indexs such as aromaticity content are strict day by day.Catalytic cracking (FCC) device is the important source of gasoline, and it also is the main source of sulphur in gasoline and the diesel oil simultaneously.Reduce sulphur content in the FCC oil fuel and mean or handle the FCC raw material, or handle the FCC product.Handling the FCC product need handle various products, must adopt multiple processing mode, for example the processing of the processing of the processing of petroleum naphtha, light cycle oil, stack gas etc.Handle the FCC raw material as it is carried out the hydrogenation pre-treatment, these multiple last handling processes are all carried out in a device, and handle the FCC raw material and can improve and adorn FCC and put transformation efficiency, increase purpose product yield, reduce the sulphur content in gasoline and the diesel oil, also can reduce the discharging of SOx, help the lifting of device benefit, refinery's profit to increase.
Though FCC apparatus is based on the oil that steams, some refinery wishes with requiring season and the market requirement changes the ratio of product.Here mainly be meant for example production of diesel oil of distillate product.But, obtain the middle distillate oil that more comprises diesel oil and guarantee that its quality can deal with more and more harsher environmental requirement, simply the FCC raw material is carried out the hydrogenation pre-treatment, perhaps the FCC product is carried out hydro-upgrading, on production control and cost, all be faced with serious challenge.
The catalytic cracking by product LCO of FCC process, its sulphur nitrogen content is its aromaticity content height especially.LCO usually and diesel oil in same boiling range, only after hydrotreatment, can be used as the blend component of diesel oil.Except the index of sulphur, if require diesel oil to reach higher cetane value specification requirement, only the quality that improves LCO by hydrotreatment can not achieve the goal.General scheme is to become the blend component of diesel oil or the hydrocracking by full transform mode that its upgrading is become the super low sulfur petroleum naphtha LCO upgrading by hydrotreatment.
American UOP company provides the method for LCO upgrading and conversion: Unionfining is handled and Unionfining part conversion process.It is a kind of middle single hop and low pressure two-section joint technology of pressing that this Unionfining is handled, and uses non-noble metal hydrogenation catalyst and precious metal dearomatization catalyst respectively; Unionfining part conversion process flow process has adopted two parallel reactors, with hydrotreatment and hydrocracking assigned to two with conversion zone, to avoid all fresh feeds hydrocracking reactor of all flowing through.These technology main purposes are the outlets that account for a fraction of LCO of FCC product for solution, and not only charging limits to some extent, and transformation efficiency is all lower, do not lose the raw material that enters FCC apparatus as far as possible.
How to remain on LCO in the diesel boiling range and satisfy new finished diesel fuel standard, promptly reduce its sulphur content again suitably the open loop cracking to reduce aromatic hydrocarbons be the important consideration that following refinery solves quality product and improves product bavin gas ratio.Hydrocracking is converted into one of main oil refining process of raw material production high grade light-end products as heavy distillate inferior, in the handiness of producing, to the characteristics in the handiness of raw material adaptive flexibility and production control, more and more paid close attention to and deep research.Simultaneously, hydrocracking process not only can satisfy harsh day by day environmental requirement, and the rocket engine fuel and the clean diesel product of energy maximum production market in urgent need, by selection to hydrocracking catalyst, it can handle worse, more difficult cracked heavier feeds, this also meets the refinery, and to be faced with the density that is processed raw material more and more heavier, quality reality worse and worse.In this case, the diesel oil that obtained of FCC technology can not satisfy existing specification of quality and product fully and is in harmonious proportion needs.Therefore, hydrocracking be attached to the pretreated notion of FCC hydrofining in, not only can utilize the hydrogenating function of hydrocracking process to solve the raw material hydro-upgrading of FCC apparatus, and can make full use of that the selective splitting of hydrocracking catalyst and open loop are active to come voluminous intermediate oil and LCO circulation repeated hydrogenation, selective splitting, the open loop of poor quality is converted into fine distillate product.
US6387245 discloses a kind of hydrocracking process, and this process characteristic is that hydrocarbon material and the hot unconverted material of circulation cracked enter a high pressure hot separator after by the hydrocracking reaction section and carry in the reaction pressure therapeutic method to keep the adverse qi flowing downward with hydrogen-rich gas and obtain comprising hydrogen, hydrogen sulfide, ammonia and conversion product first vapor phase stream and defluent hot unconverted material liquid phase stream.The hydrogenation zone that this invention utilization is positioned at the high pressure hot separator bottom contacts the hydrogen of dirty material with Hydrobon catalyst and upper reaches, thereby it is made with extra care, and the hydrogen at upper reaches is carried the material gas that enters high pressure hot separator simultaneously.The per pass conversion of this technology is lower, generally at 15-45wt%.US5954944 discloses a kind of middle pressure hydrocracking technology of heavy hydrocarbon oil, this process using single hop tandem process, pressure comprises hydrocracking section and hydrofining section at 6.0-10MPa, and wherein hydrocracking catalyst and Hydrobon catalyst all contain the F modified component of 0.5-5wt%.
Summary of the invention
At the deficiencies in the prior art, the invention provides middle pressure hydrocracking technology a kind of and the FCC apparatus associating, be used for the material that treatment of heavy hydrocarbon material obtains intermediate oil and hydro-upgrading is provided for FCC apparatus.The present invention also provides a kind of LCO to loop back the hydrofining reactor mode of re-refining, and being used for LCO hydrogenating desulfurization inferior becomes the low-sulfur diesel-oil component.
Process of the present invention is once passed through middle pressure hydrocracking technology for associating FCC apparatus, and its process comprises:
(1) in the presence of hydrogen, petroleum hydrocarbon raw material contacted with hydrocracking catalyst at hydrocracking reactor and obtain material I;
(2) cracking material I enters hydrofining reactor and contacts with Hydrobon catalyst and obtain material II;
(3) material II enters cut product and the oil III of the unconverted end that fractionating system obtains transforming behind gas-liquid separator;
(4) unconverted end oil III enters FCC apparatus and carries out light-end products and the light cycle IV (LCO) that catalytic cracking obtains transforming;
(5) light cycle IV is re-circulated to hydrofining reactor and cracking mixing of materials to enter hydrofining reactor more refining.
The raw material of above-mentioned middle pressure hydrocracking technology is because through refining, and sulphur, nitrogen equal size are higher, therefore needs the hydrocracking catalyst of anti-sulphur, nitrogen.The present invention selects zeolite type hydrocracking catalyst and/or amorphous type hydrocracking catalyst:
The zeolite type hydrocracking catalyst, its composition comprises: (a) Y zeolite 1-30wt% is preferably 1～20wt%; (b) macropore refractory oxide 10-70wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%.Wherein Y zeolite has following feature: SiO
2/ Al
2O
3Mol ratio is 5-20, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume, specific surface 500-750m
2/ g, infrared acidity 0.25-0.50mmol/g, Na
2O content＜0.2wt%.Above-mentioned macropore refractory oxide mainly comprises macroporous aluminium oxide (pore volume 0.8～1.5ml/g, specific surface 300～500m
2/ g), macropore sial (pore volume 0.8～1.5ml/g, specific surface 350～600m
2/ g, silica weight content 20%～60%) etc., the pore volume 0.4～0.8ml/g of little porous aluminum oxide, specific surface 150～300m
2/ g.
The amorphous type hydrocracking catalyst, its composition comprises: (a) acid amorphous aluminum silicide 10-75wt%; (b) aperture aluminum oxide 15-35wt%; (c) group vib metal oxide 10-40wt%; (d) VIII metal oxide 1-10wt%.Wherein acid invisible sial has following feature: SiO
2Content is 20～60%, specific surface 350-600m
2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g.Pore volume 0.4～the 0.8ml/g of above-mentioned little porous aluminum oxide, specific surface 150～300m
2/ g.
Technology of the present invention combines middle pressure hydrocracking and FCC technology, not only can utilize the raw material hydro-upgrading of the hydrogenating function solution FCC apparatus of hydrocracking process, and can make full use of that the selective splitting of hydrocracking catalyst and open loop are active to come voluminous intermediate oil, the more important thing is by LCO circulation repeated hydrogenation to be converted into the low-sulfur quality products with poor quality.The present invention adopts first hydrocracking back end hydrogenation to make with extra care this backward, and (flow sequence is the cracking of first hydrofining back end hydrogenation usually, flow process of the present invention is that first hydrocracking back end hydrogenation is refining, therefore claim backward) once by the hydrocracking flow process, utilized on the one hand the hydrogenation performance of dual-function catalyst more, obtained to splitting that hydrogenation to a certain degree is saturated, desulfurization nitrogen and be cracked into carrying out hydrofining and will obtaining better hydrofining effect of light-end products through the hydrocracking section; In addition LCO is looped back hydrofining reactor and re-refine and be converted into cleaning low-sulfur diesel-oil component, and under the too high situation of hydrocracking section depth of conversion, avoid making diesel component transform the petroleum naphtha component too much through the hydrocracking section once more and the middle distillates oil selectivity that reduces the hydrocracking part with what realize LCO hydrogenating desulfurization inferior.Technology of the present invention remains on LCO in the diesel boiling range to greatest extent, improves the intermediate oil selectivity, and the restricted minimizing of operational condition of the section of hydrocracking simultaneously can be adjusted more neatly.Technical process of the present invention is simple, can adjust products scheme flexibly according to the turn of the market situation, has improved the adaptability of production equipment.
Embodiment
Principal feature of the present invention is the combination and the reasonable assembly of scheme, and the operational condition of each technique unit is same as the prior art, and the formant process is as follows.
The backward that the present invention unites FCC apparatus is a kind of one-stage serial hydrocracking technical process that comprises hydrocracking reactor and a hydrofining reactor series connection use and a shared cover recycle hydrogen system by middle pressure hydrocracking technology once.The main petroleum hydrocarbon raw material of handling the heavy hydrocarbon material of 200-650 ℃ of boiling range is the vacuum gas oil that general frequent processing boiling range is 320-580 ℃.This middle pressure hydrocracking technology is the hydrocracking process that exists stock oil to contact with catalyzer at hydrogen, the reaction pressure 3～12MPa of system, best 5～10MPa; Hydrogen-oil ratio 100～5000,500～2000.The backward that the present invention the unites FCC apparatus once per pass conversion by the middle pressure hydrocracking technological process is preferably in 20-50wt% at 15-60wt%.The control of per pass conversion is based on the material balance of whole machinery, and Various Seasonal and and turn of the market product requirement is adjusted the output of gasoline and diesel oil.In addition, adapt to the different material cracking by control and reach the needed depth of conversion requirement of certain product quality indicator per pass conversion.Concrete reaction conditions can be determined by ordinary skill according to the requirement of feedstock property and products scheme.
The backward of the associating FCC apparatus that the present invention relates to is conventional non-noble metal hydrogenation catalyst for refining by the employed Hydrobon catalyst of middle pressure hydrocracking technological process once, 3936 catalyzer of producing as the Fushun Petrochemical Company catalyst plant, 3996 catalyzer etc.
The backward of the associating FCC apparatus that the present invention relates to once can be used a kind of single amorphous type hydrocracking catalyst or a kind of single zeolite type hydrocracking catalyst by the middle pressure hydrocracking technological process; Also can be that two kinds of hydrocracking catalysts mix or grating is used, comprise the mechanically mixing filling.Because what relate to is a kind of backward hydrocracking flow process, therefore no matter use the sort of catalyzer or use which kind of catalyst combination loading mode, the hydrocracking catalyst of selection must have high anti-nitrogen/anti-nitrogen ability.Amorphous type hydrocracking catalyst itself just is to use under single hop list agent technology; The zeolite type hydrocracking catalyst then is that certain range of choice is arranged.Usually, the employed zeolite component content of the so high anti-nitrogen/zeolite type of anti-nitrogen hydrocracking catalyst is lower, and acidity is also lower, and Y zeolite is used more generally.Simultaneously, this backward once by the hydrocracking flow process because the characteristics of the catalyzer that uses will help the improvement of middle distillates oil selectivity to a certain extent.
The modification treating processes of the Y zeolite of high anti-nitrogen/anti-nitrogen ability: with Na
2O content is raw material less than the Y zeolite of 3.0wt%, places the high-temperature roasting stove, at self water vapour or feed water vapour, and 450-600 ℃, under the 0.01-0.2MPa pressure water steam roasting 0.5-3.0 hour.Carry out ion-exchange techniques then and make Na
2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, and at self water vapour or feeding water vapour, 550-700 ℃, 0.01-1.0MPa pressure water steam was handled 0.5-10 hour down, promptly got SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0.The above-mentioned super-hydrophobic Y zeolite that obtains with chemical process dealuminzation optionally, can be got SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5-20.The Y zeolite that aforesaid method is handled has lower acidity, and select suitable content to cooperate with other carrier component, make it on catalyzer, have moderate acid site density, the catalyzer coking inactivation of avoiding the multidigit condensation reaction of intensive strong acid center to cause, with suitable hydrogenation active centre synergy, therefore has stronger anti-nitrogen performance simultaneously.
The FCC process adopts common catalyzer and processing condition.
Embodiment 1
Different is with the FCC raw material pretreatment process, the present invention program's characteristics be through backward once by middle pressure hydrocracking technology, isocrackate to enter earlier that a fractionating system obtains comprising the conversion product of petroleum naphtha and wide cut diesel fuel and through hydrogenation heavy unconverted oil.The heavy unconverted oil of hydrogenation is as the charging of FCC apparatus, and the LCO light cycle of FCC apparatus loops back the back segment hydrofining reactor of hydrocracking part simultaneously.This programme has two reactors, comprises hydrofining reactor and hydrocracking reactor, two reactors in series uses and a shared cover recycle hydrogen system, belong to the one-stage serial technical process.
The catalyst loading scheme: hydrofining reactor loads 3936 Hydrobon catalysts.Hydrocracking reactor loads a kind of Y zeolite type hydrocracking reactor, and catalyzer consists of: Y zeolite 20wt%, sial (specific surface 520m
2/ g, SiO
235wt%, pore volume 1.2ml/g) 25wt%, little porous aluminum oxide (specific surface 240m
2/ g, pore volume 0.4ml/g) 25wt%, nickel oxide 8wt%, Tungsten oxide 99.999 22wt%.
Y zeolite modifying process wherein is as follows: with Na
2O content is less than the SiO of 3.0wt%
2/ Al
2O
3Be that 5 Y zeolite is a raw material, place the high-temperature roasting stove, feed water vapour, 580 ℃, roasting is 2.0 hours under the 0.12MPa pressure water steam.Carry out ion-exchange techniques then and make Na
2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, is feeding water vapour, and 600 ℃, 0.4MPa pressure water steam was handled 3.0 hours down, got super-hydrophobic Y zeolite.With the above-mentioned super-hydrophobic Y zeolite concentration that obtains is the nitric acid treatment of 1.0mol/L, obtains SiO
2/ Al
2O
3Mol ratio is 18 super-hydrophobic Y zeolite.The secondary pore pore volume that obtains Y zeolite 2～10nm accounts for 45% of total pore volume, specific surface 705m
2/ g, infrared acidity 0.28mmol/g.
This process program is handled a kind of heavy vacuum gas oil VGO, and this petroleum hydrocarbon material main character is: proportion 0.8985cm
3/ g, 340 ℃-545 ℃ of boiling ranges, carbon residue 0.20wt%, sulphur 1.78wt%, nitrogen 1420 μ g/g.The sulphur content 1.6wt% of circulation hydrotreatment LCO.
This process program operating parameters: reaction pressure 9.5MPa, hydrogen-oil ratio 1500.Hydrofining section air speed 1.2h
-1, hydrocracking section air speed 1.0h
-1
385 ℃ of hydrocracking average reaction temperature, per pass conversion 50wt%; 380 ℃ of hydrofining section average reaction temperature.Middle distillates oil selectivity 79.5% to raw material.Product diesel oil sulphur content is 280 μ g/g.
Embodiment 2
Flow process is identical with embodiment 1, changes part to be:
Hydrocracking catalyst is selected a kind of amorphous silicon catalyzer for use, consists of: (a) acid amorphous aluminum silicide 50wt%; (b) aperture aluminum oxide 20wt%; (c) Tungsten oxide 99.999 21wt%; (d) nickel oxide 9wt%.Wherein acid invisible sial has following feature: SiO
2Content is 45%, specific surface 480m
2/ g, pore volume 1.0ml/g, infrared acidity 0.5mmol/g.The pore volume 0.4ml/g of above-mentioned little porous aluminum oxide, specific surface 240m
2/ g.
410 ℃ of cracking zone temperature of reaction, reaction pressure 9.5MPa, hydrogen-oil ratio 1500, hydrocracking section air speed 0.8h
-1Per pass conversion 45% is to the middle distillates oil selectivity 83.5% of raw material.The sulphur content 260 μ g/g of diesel product.
Embodiment 3
Flow process is identical with embodiment 1, changes part to be:
Catalyzer consists of: Y zeolite 10wt%, sial (specific surface 520m
2/ g, SiO
235wt%, pore volume 1.2ml/g) 35wt%, little porous aluminum oxide (specific surface 240m
2/ g, pore volume 0.4ml/g) 25wt%, nickel oxide 8wt%, Tungsten oxide 99.999 22wt%.The SiO of Y zeolite wherein
2/ Al
2O
3Mol ratio is that the secondary pore pore volume of 14,2～10nm accounts for 38% of total pore volume, specific surface 670m
2/ g, infrared acidity 0.3mmol/g.
This process program operating parameters: reaction pressure 9.5MPa, hydrogen-oil ratio 1500.Hydrofining section air speed 1.2h
-1, hydrocracking section air speed 1.0h
-1
390 ℃ of hydrocracking average reaction temperature, per pass conversion 40wt%; 380 ℃ of hydrofining section average reaction temperature.Middle distillates oil selectivity 82.0% to raw material.Product diesel oil sulphur content is 270 μ g/g.
Annotate: oil refers to rocket engine fuel and diesel oil generally speaking, the cut coverage 132-282 of rocket engine fuel ℃, and the cut coverage 282-350 of diesel oil ℃.The general down wide cut diesel fuel of producing 132-350 ℃ of middle press strip spare.It is to obtain divided by the liquid yield that has transformed by the intermediate oil yield that middle distillates oil selectivity calculates.
Claims (8)
1, a kind of single hop middle pressure hydrocracking and catalytic cracking combined technology is characterized in that technological process comprises:
(1) in the presence of hydrogen, petroleum hydrocarbon raw material contacted with hydrocracking catalyst at hydrocracking reactor and obtain material I; Described hydrocracking catalyst comprises zeolite type hydrocracking catalyst and/or amorphous type hydrocracking catalyst;
(2) cracking material I enters hydrofining reactor and contacts with Hydrobon catalyst and obtain material II;
(3) material II enters cut product and the oil III of the unconverted end that fractionating system obtains transforming behind gas-liquid separator;
(4) unconverted end oil III enters FCC apparatus and carries out light-end products and the light cycle IV that catalytic cracking obtains transforming;
(5) light cycle IV is re-circulated to hydrofining reactor and cracking mixing of materials to enter hydrofining reactor more refining;
The composition of wherein said zeolite type hydrocracking catalyst comprises: (a) Y zeolite 1-30wt%; (b) macropore refractory oxide 10-70wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%; Wherein Y zeolite has following feature: SiO
2/ Al
2O
3Mol ratio is 5-20, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume, specific surface 500-750m
2/ g, infrared acidity 0.25-0.50mmol/g, Na
2O content＜0.2wt%;
The composition of wherein said amorphous type hydrocracking catalyst comprises: (a) acid amorphous aluminum silicide 10-75wt%; (b) macropore refractory oxide 10-75wt%; (c) aperture aluminum oxide 15-35wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%; Wherein acid amorphous aluminum silicide has following feature: SiO
2Content is 20～60%, specific surface 350-600m
2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g.
2,, it is characterized in that the pore volume 0.4～0.8ml/g of little porous aluminum oxide used in the described amorphous type hydrocracking catalyst, specific surface 150～300m according to the described technology of claim 1
2/ g.
3,, it is characterized in that described petroleum hydrocarbon raw material is boiling range 200-650 ℃ a heavy hydrocarbon material according to the described technology of claim 1.
4,, it is characterized in that described heavy hydrocarbon material is a vacuum gas oil according to the described technology of claim 3.
5,, it is characterized in that described middle pressure hydrocracking technology is the hydrocracking process that exists stock oil to contact with catalyzer at hydrogen, the reaction pressure 3～12MPa of system according to the described technology of claim 1.
6,, it is characterized in that described reaction pressure is 5～10MPa according to the described technology of claim 5.
7, according to the described technology of claim 1, the per pass conversion that it is characterized in that described middle pressure hydrocracking technology is 15-60wt%.
8,, it is characterized in that described per pass conversion is 20-50wt% according to the described technology of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144545 CN1202219C (en) | 2002-11-02 | 2002-11-02 | Single section medium pressure hydrocracking and catalytic cracking integrated process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144545 CN1202219C (en) | 2002-11-02 | 2002-11-02 | Single section medium pressure hydrocracking and catalytic cracking integrated process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1493666A CN1493666A (en) | 2004-05-05 |
| CN1202219C true CN1202219C (en) | 2005-05-18 |
Family
ID=34232011
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02144545 Expired - Lifetime CN1202219C (en) | 2002-11-02 | 2002-11-02 | Single section medium pressure hydrocracking and catalytic cracking integrated process |
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| Country | Link |
|---|---|
| CN (1) | CN1202219C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8529753B2 (en) | 2006-12-27 | 2013-09-10 | Research Institute Of Petroleum Processing, Sinopec | Combined process for hydrotreating and catalytic cracking of residue |
| US9260667B2 (en) | 2007-12-20 | 2016-02-16 | China Petroleum & Chemical Corporation | Combined process of hydrotreating and catalytic cracking of hydrocarbon oils |
-
2002
- 2002-11-02 CN CN 02144545 patent/CN1202219C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8529753B2 (en) | 2006-12-27 | 2013-09-10 | Research Institute Of Petroleum Processing, Sinopec | Combined process for hydrotreating and catalytic cracking of residue |
| US9260667B2 (en) | 2007-12-20 | 2016-02-16 | China Petroleum & Chemical Corporation | Combined process of hydrotreating and catalytic cracking of hydrocarbon oils |
| US9309467B2 (en) | 2007-12-20 | 2016-04-12 | China Petroleum And Chemical Corp. | Integrated process for hydrogenation and catalytic cracking of hydrocarbon oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1493666A (en) | 2004-05-05 |
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