CN1243083C - Inferior heavy oil and residual oil modifying method - Google Patents
Inferior heavy oil and residual oil modifying method Download PDFInfo
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- CN1243083C CN1243083C CN 200310104918 CN200310104918A CN1243083C CN 1243083 C CN1243083 C CN 1243083C CN 200310104918 CN200310104918 CN 200310104918 CN 200310104918 A CN200310104918 A CN 200310104918A CN 1243083 C CN1243083 C CN 1243083C
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000003921 oil Substances 0.000 title abstract description 56
- 239000000295 fuel oil Substances 0.000 title abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 88
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 238000007667 floating Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000002594 sorbent Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000002745 absorbent Effects 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 7
- 239000000725 suspension Substances 0.000 abstract description 5
- 238000004523 catalytic cracking Methods 0.000 abstract 2
- 239000001828 Gelatine Substances 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 229920000159 gelatin Polymers 0.000 abstract 1
- 235000019322 gelatine Nutrition 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 37
- 230000008569 process Effects 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000002893 slag Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004576 sand Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002010 green coke Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011814 protection agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000003974 emollient agent Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- -1 naphthenate compound Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a method for modifying inferior heavy oil and residual oil, particularly a technological method which produces the catalytic cracking raw material for high-quality heavy oil by combining the hydrocracking of a suspension bed with the hydrotreatment of a fixed bed. Heavy oil and residual oil are moderately hydrocracked by the suspension bed so that the most part or all metallic impurities are dissociated from gelatine and asphaltene; a filler metallic adsorption reactor is replaced by the hydrogenation product by switching operation or on line, and the metallic impurities dissociated from the hydrocracking oil of the suspension bed is adsorbed and eliminated; the product of which the metal is adsorbed and eliminated is sent in a hydrotreating unit of the residual oil fixed bed to be deeply hydrogenized to eliminate other impurities, and the catalytic cracking raw material for high-quality heavy oil is produced.
Description
Technical field
The present invention discloses a kind of inferior heavy, process for upgrading residua, particularly uses floating bed hydrogenation cracking and fixed bed hydrogenation to handle the processing method of combined production high-quality heavy oil fluid catalytic cracking raw material.
Background technology
Hydrogenation is the method that present inferior heavy, residua upgrading extensively adopt.In existing residual hydrogenation method for modifying, the fixed bed residuum hydrodesulfurization is a proven technique method comparatively.The fixed bed residuum hydrodesulfurization has characteristics such as good product quality, technical maturity, occupies very high share in the suitability for industrialized production ability.But traditional residue fixed-bed hydrogen addition technology because the catalyzer duct is easy to be stopped up by metal impurities, causes catalyst deactivation and is difficult to be applied to process the poor residuum raw material with higher metal and carbon residue content.
Floating bed hydrogenation is another important technology route heavy, residua upgrading, particularly obtains broad research because of its hydro-upgrading that is suitable for the inferior raw material of high metal and high carbon residue.Because adopted disperse type catalyzer and empty cartridge reactor, this technology can effectively avoid disadvantageous effects such as obstruction of catalyzer duct and coking deactivation, higher metal removal rate and bottoms conversion can be operated and obtain to process under high-speed simultaneously.But the high conversion down floating bed hydrocracking technology of operation not only faces the disadvantageous effect that high green coke brings, and accounting for of producing the above cracking tail oil of the about 10wt% of combined feed total feed is very difficult further to be used, cause this technology to be difficult to obtain industrial application.
For addressing these problems; United States Patent (USP) 5,879,642 have proposed a kind of fixed bed residual hydrogenation technology of using the catalyst protection bed; the catalyst protection bed that this technology is used can remove the organo-metallic impurity of the overwhelming majority, thereby prolongs the work-ing life of integer catalyzer.Because the protection bed is limited to the carrying capacity of metal; (this technology can reach the effect in the work-ing life that prolongs integer catalyzer during the residual oil raw material of total metal content＜120ppm) than low-metal content in processing; and for the inferior raw material of processing high metal and carbon residue content, the protection bed still can lose the effect of protection downstream bed because metal stops up duct and coking deactivation rapidly.
U.S. Pat P 5,382, and 349 propose a kind of residue fixed-bed hydrogenation method of using solid Hydrodemetalation catalyst, solid Hydrobon catalyst and the solid hydrodenitrogenation catalyst of grating.This method faces the predicament of the raw material that is difficult to adapt to high metal content and high carbon residue content equally.
Chinese patent CN1219569A proposes to use the decentralized metal catalyst with higher hydrogenation activity can effectively suppress green coke reaction heavy, residuum (cracking) process.And because only several hectogammas of catalyzer usage quantity can be avoided the too much and unserviceable difficult problem of solids in the tail oil.However, be subjected to dissolving and the restriction of diffusion and the influence of other factors of hydrogen in heavy oil, hydrogenation reaction can not be carried out thoroughly, and the process transformation efficiency surpasses after the 80wt%, and the green coke amount also will be above 1wt%.Under this green coke amount, continuous apparatus often can not smooth running.Still there is the problem of further processing and utilization in the tail oil of about 20wt% of process generation in addition.
Chinese patent CN1335371A proposes the method for floating bed hydrogenation and fixed bed hydrogenation combination process processing residual oil.When not using or using disperse type catalyzer, the floating bed hydrogenation product all directly enters the fixed bed hydrogenation device in this technological process; This mode can improve overall conversion greatly when the residual oil of the low metals content impurity of processing, help increasing the benefit, but the poor residuum that surpasses 120ppm for containing metal, the metal that the floating bed hydrogenation process removes will adsorb deposition on the fixed bed catalyst bed, cause the beds pressure drop to be increased, inactivation is stopped up in the catalyzer duct.
Summary of the invention
In order to address the above problem, the invention provides a kind of heavy, process for upgrading residua, this method can adapt to the processing inferior raw material, particularly metal content surpasses 120 μ g/g, the carbon residue raw material greater than 10wt% in the raw material, also can production high-quality heavy oil catalytically cracking equipment raw material, avoid generating and contain the solid tail oil.
Inferior heavy of the present invention, process for upgrading residua, comprise the processing of floating bed hydrogenation cracking and fixed bed hydrogenation, wherein inferior heavy, residual oil are carried out fixed bed hydrogenation through the material after the floating bed hydrogenation cracking again and are handled after metal adsorption reactor adsorbing and removing dissociates the metal that and compound thereof, wherein the operational condition of adsorptive reactor is as follows: temperature is 200～350 ℃, be preferably 300～350 ℃, air speed is 0.2～1.5, is preferably 0.5～1.0h
-1, pressure and floating bed hydrogenation reactor keep same equipressure, also can be normal pressures, and sorbent material and stock oil volume ratio are 1: 500～1: 5000, are preferably 1: 500～1: 3500.
The concrete steps of inferior heavy of the present invention, process for upgrading residua are as follows:
A, paucidisperse shaped metal catalyzer (comprising water soluble metal catalyst and oil soluble metal catalyzer) and heavy, residual oil raw material are sent into the floating bed hydrogenation reactor after mixing, introduce hydrogen sulfide and high pressure hydrogen (8～20MPa), the moderate hydrocracking under than demulcent floating bed hydrogenation condition of heavy, residual oil, make most of or whole metals dissociate out from the residual oil macromole, and part residual oil macromolecular cleavage generate low boiler cut through reduction and sulfuration;
B, the material that comes out from suspended-bed reactor are through changeable operation or can online displacement add metal and the compound thereof that the metal adsorption reactor adsorbing and removing of material dissociates and, and the operational condition of adsorptive reactor is as follows: temperature is 200～350 ℃, air speed 0.2～1.5h
-1, pressure and floating bed hydrogenation reactor keep same equipressure, also can be normal pressures; Sorbent material and stock oil volume ratio are 1: 500～1: 5000.
C, will send into residue fixed-bed hydrogenator, under the operational condition that fixed bed hydrogenation is handled, carry out deep hydrofinishing, with production high-quality RFCC raw material through the material that removes metal.
The weight that the present invention relates to, residual oil can be the residual oils that crude distillation obtains, heavy-gravity heavy crude oil, the also organism that obtains of oil sands bitumen, shale oil and the dry distillation of coal.
Wherein, the water-soluble disperse type catalyzer that uses in heavy, the hydrogenation of residual oil suspended bed process can be the heteropolyacid salt aqueous solution of periodic table of elements VIB, VIIB and two or more metallic compounds of group VIII, as phospho-molybdic acid nickel, phospho-wolframic acid nickel etc.; Described oil-soluble catalyst can be the oil soluble organic compound of periodic table of elements VIB, VIIB and two or more metals of group VIII, as many carbonyl compound, naphthenate compound and the porphyrin class inner complex of molybdenum, nickel, cobalt.In weight metal, the content of above-mentioned disperse type catalyzer in raw material is 50～300 μ g/g, is preferably 50～200 μ g/g.
Handle at above-mentioned heavy, hydrogenation of residual oil suspended bed that (be in the step a), the operational condition of hydrogenation of residual oil suspended bed reactor is: pressure 8～20MPa, 400～440 ℃ of temperature of reaction, liquid hourly space velocity 0.2～1.5h
-1, hydrogen to oil volume ratio (under the standard pressure) 200～1200.Be preferably pressure 8～14Mpa, 410～430 ℃ of temperature of reaction, liquid hourly space velocity 0.5～1.2h
-1Hydrogen to oil volume ratio (under the standard pressure) 400～1000.
In above-mentioned step b, the metal absorbent of selecting for use is wherein one or more of wide-aperture gac, molecular sieve (as Y zeolite), aluminum oxide or useless fixed bed residual oil hydrocatalyst.The pore volume of this metal absorbent is that 0.2～1.2ml/g, aperture are 1～100nm, and specific surface area is 100～600m
2/ g; Be preferably pore volume 0.8～1.2ml/g, aperture 40～100nm, specific surface area 100～200m
2/ g.
Described heavy, residue fixed-bed hydrotreatment technology can be any technology of the present invention that is applicable to, its operational condition is generally: 360～410 ℃ of temperature of reaction, preferably 360～390 ℃; Reaction pressure is 8.0～16MPa, and that best is 10.0～15.0MPa; Hydrogen to oil volume ratio is 500～2000, and best is 700～1500; Volume space velocity is 0.1～2.0h during liquid
-1, that best is 0.2～1.5h
-1The heavy residual oil hydrocatalyst that is adopted be meant have weight, the single catalyst or the series catalyst of residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking function.These catalyzer generally all are to be carrier with porous refractory inorganic oxide such as aluminum oxide, the oxide compound of group vib (as W, Mo) and/or VIII family metal (as Co, Ni) is an active ingredient, optionally adds the catalyzer of other various auxiliary agents such as P, Si, elements such as F, B.For example heavy, the residuum hydrogenating and metal-eliminating catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base of CEN, FZC series just belongs to this class catalyzer by serial hydrogenating desulfurization of ZTS, the ZTN of the production of first fertilizer plant of Qilu Petrochemical company and hydrodenitrogenation catalyst.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst are wherein arranged, and the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking catalyst successively.Technology with these several catalyst mix fillings is also arranged certainly.When concrete enforcement is of the present invention, can suitably adjust processing condition and the loading amount of catalyzer and the proportioning of different catalysts of fixed bed residual hydrogenation according to the result of raw materials used character and floating bed hydrogenation processing and metal adsorption.
Advantage of the present invention is:
1, floating bed hydrogenation and fixed bed hydrogenation is combined, can utilize suspension bed hydrogenation process the adaptability of the poor residuum of high metal, high carbon residue to be enlarged the raw material sources of fixed bed hydrogenation technology on the one hand, can utilize fixed bed hydrogenation on the other hand good take off percentage of admixture and take off carbon yield obtain high-quality hydrogenated products, avoid generation to contain solid waste, reach the purpose of protection environment and resource rational utilization;
2, in the floating bed hydrogenation process, adopt disperse type catalyzer, suppress on the one hand the green coke of floating bed hydrogenation process effectively, make not contain solid particulate in the product; Make the organometallic compound in the residual oil obtain the hydrogenation decomposition on the other hand, metal dissociates from the residual oil molecule and obtains fractionation by adsorption, reaches the purpose that purifies residual oil;
3, adopt floating bed hydrogenation and fixed bed hydrogenation combination process to handle residual oil, can obtain the much higher process transformation efficiency of more single conventional fixed bed residual hydrogenation process.
4, the present invention increases the metal adsorption reactor between floating bed hydrogenation and fixed bed hydrogenation processing, but active adsorption removes residual oil decomposes the metal that dissociates and through floating bed hydrogenation, the metal that other adds comprising the floating bed hydrogenation process, avoid these metals to introduce the fixed bed hydrogenation device and the blocking catalyst duct, prolong the fixed bed device on-stream time.
5, the metal absorbent of process use can be the conventional hydrogenation catalyst of depleted, makes this part waste material be reused, and helps reducing the technology cost.
Description of drawings
Fig. 1 is that the present invention is heavy, the process flow diagram of residua upgrading.
Embodiment
Below in conjunction with Fig. 1 process of the present invention is described in detail.
Residual oil raw material and decentralized metal catalyst are pre-mixed evenly, and mixture 2 mixes with sulfur-bearing high pressure hydrogen 1 sends into floating bed hydrogenation reactor 3.The operational condition of floating bed hydrogenation reactor is hydrogen pressure 8～20MPa, feeding liquid hourly space velocity 0.2～1.5h
-1, 400～440 ℃ of temperature of reaction, hydrogen-oil ratio 200～1200 (volume ratio).Reaction product 4 is sent into the metal adsorption reactor 5 that material is added in changeable operation or online displacement.The operational condition of metal adsorption reactor is: temperature is 200～350 ℃, air speed 0.2～1.5h
-1, pressure and floating bed hydrogenation reactor keep same equipressure, also can be normal pressures.Send into through the material 6 that removes metal and to extract part lighting end 8 in the flashing tower 7, fixed bed residual hydrogenation reactor 9 is sent in last running.Fixed bed residual hydrogenation reactor adopts the routine operation condition: 360～410 ℃ of temperature of reaction, reaction pressure are 8.0～16.0MPa, hydrogen to oil volume ratio 500～2000, and volume space velocity is 0.1～2.0h during liquid
-1Residual oil removes heteroatoms and carbon residue through deep hydrogenation, obtains high-quality RFCC raw material 10.
For further specifying all main points of the present invention, enumerate following examples.
Embodiment 1～9
Two kinds of typical inferior heavy, residual oil are used in test, and its feedstock property sees Table 1.Two kinds of residual oil have metal content height, carbon residue height and the high characteristics of sulphur content as shown in Table 1, wherein subtract in the sand slag only the content of nickel, vanadium and iron promptly reach 190 μ g/g, and the normal slag of Tahe is more up to more than the 320 μ g/g; Both asphalt contents surpass 8wt%, and carbon residue content surpasses 18wt%, are that conventional fixed bed Residue Hydrotreating Technology is difficult to the directly poor residuum of processing.
The test-results of two kinds of residual oil raw materials under different floating bed hydrogenations and absorption metal operational condition investigated in this test.By table 2 testing data as can be seen, the residual oil that contains a large amount of metallic impurity and higher carbon residue can be met the product of residue fixed-bed hydrogenation charging requirement behind floating bed hydrogenation and absorption metal.Process demetalization percentage of admixture and take off carbon yield and the process hydrocracking degree of depth is in direct ratio wherein.The floating bed hydrogenation process is carried out under the mitigation condition, helps hydrogenation reaction, and the process that makes does not produce solidss such as coke when obtaining the part light-end products, guaranteed the smooth operation of device.The disperse type catalyzer that floating bed hydrogenation adopts equally by the metal absorbent adsorbing and removing, has avoided introducing the shortcoming of more metallic impurity in fixed bed residual hydrogenation material after the floating bed hydrogenation reaction finishes.
The composition and the character thereof of the used metal absorbent in the embodiment of the invention see Table 3, and wherein useless hydrogenation catalyst is to be carrier with siliceous aluminum oxide, and its sial atomic ratio is 11; The metal protection agent is to be carrier with the aluminum oxide, and the sial atomic ratio of Y zeolite is 2.8.
Table 1 test is with subtracting the slag feedstock property in normal slag of Tahe and the sand
| Project | The normal slag of Tahe | Subtract slag in the sand |
| Density (20 ℃) kg.m -3 | 1001.0 | 1024.8 |
| Carbon residue wt% | 18.3 | 20.7 |
| Ultimate analysis wt% | ||
| C | 86.31 | 83.52 |
| H | 10.74 | 10.43 |
| S | 2.53 | 4.95 |
| N | 0.42 | 0.35 |
| Metallic element μ g.g -1 | ||
| Fe | 2.9 | 8.2 |
| Ni | 38.6 | 43.4 |
| V | 287.4 | 143.6 |
| Four proximate analysis wt% | ||
| Stable hydrocarbon | 29.0 | 9.9 |
| Aromatic hydrocarbon | 33.1 | 52.2 |
| Colloid | 24.5 | 29.5 |
| Bituminous matter | 13.4 | 8.4 |
| Boiling range | ||
| 350℃～500℃ | 32.1 | 0 |
| ＞500℃ | 67.9 | 100.0 |
Experimental data under different floating bed hydrogenations of table 2 and the adsorption operations condition
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | |
| Raw material | Tahe | Tahe | Tahe | Tahe | Tahe | Tahe | Tahe | In the sand | In the sand | |
| The suspension bed reaction conditions | ||||||||||
| Temperature, ℃ | 410 | 415 | 420 | 420 | 425 | 430 | 420 | 420 | 420 | |
| Pressure, MPa | 8 | 10 | 10 | 10 | 10 | 10 | 10 | 14 | 14 | |
| The content of reactive metal in the catalyzer, wt% | Mo | 6 | 6 | 6 | 6 | 6 | 6 | 3.3 | 6 | 3.3 |
| Ni | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.14 | 0.8 | 0.14 | |
| Co | - | - | - | - | - | - | 0.55 | - | 0.55 | |
| W | - | - | - | - | - | - | 2.9 | - | 2.9 | |
| The catalyzer add-on, μ g.g -1 | 150 | 150 | 200 | 200 | 200 | 300 | 200 | 200 | 50 | |
| Hydrogen to oil volume ratio | 400 | 400 | 600 | 600 | 600 | 800 | 1000 | 800 | 1200 | |
| Air speed, h -1 | 0.5 | 0.5 | 0.8 | 0.8 | 1.0 | 1.2 | 0.5 | 0.8 | 0.5 | |
| ＞500 ℃ of transformation efficiencys, wt% | 41.0 | 50.2 | 57.5 | 57.5 | 61.9 | 69.7 | 66.3 | 54.4 | 55.1 | |
| Toluene insolubles, wt% | 0.10 | 0.27 | 0.43 | 0.43 | 0.44 | 0.70 | 0.34 | 0.33 | 0.41 | |
| Metal absorbent | Gac | Gac | Gac | Gac | Gac | Gac | Gac | Useless hydrogenation catalyst | Useless hydrogenation catalyst | |
| The volume ratio of sorbent material and stock oil | 1/500 | 1/500 | 1/500 | 1/500 | 1/500 | 1/500 | 1/500 | 1/500 | 1/500 | |
| The adsorption operations condition | ||||||||||
| Temperature, ℃ | 300 | 300 | 200 | 300 | 300 | 300 | 300 | 350 | 350 | |
| Pressure, MPa | 8 | 10 | 0.1 | 10 | 10 | 10 | 10 | 14 | 14 | |
| Air speed, h -1 | 0.5 | 0.5 | 0.8 | 0.8 | 1.0 | 1.5 | 0.8 | 0.8 | 0.5 | |
| Metal removal rate, wt% (in Fe+Ni+V) | 39.0 | 47.7 | 30.1 | 56.1 | 60.9 | 66.3 | 70.2 | 48.9 | 53.0 | |
| Generate the full cut character of oil | ||||||||||
| Metal Fe+Ni+V μ g.g -1 | 201 | 172 | 235 | 148 | 128 | 111 | 98 | 100 | 92 | |
| Carbon residue, wt% | 14.7 | 14.0 | 12.9 | 12.8 | 11.4 | 11.7 | 10.8 | 11.9 | 11.1 | |
The character of the used metal absorbent in table 3 embodiment of the invention
| The sorbent material kind | Gac | Useless hydrogenation catalyst | The inertia alumina balls | Y zeolite | The metal protection agent |
| Sorbent material character | |||||
| Pore volume, ml/g | 0.8 | 0.21 | 1.1 | 0.45 | 0.9 |
| Can several apertures, nm | 2.1 | 3.5 | 75 | 10 | 75 |
| Specific surface area, m 2/g | 613 | 610 | 130 | 150 | 130 |
| Active ingredient is formed wt% | |||||
| NiO | - | 7.7 | - | - | 2.1 |
| MoO 3 | - | 16.7 | - | - | 8.0 |
| P | - | 1.81 | - | - | - |
Embodiment 10～15
This The effects different metal sorbent material is to the influence of demetallization per.Demetalization raw material and operational condition are the normal slag floating bed hydrogenation of the Tahe described in the embodiment 5 product, and the adsorption operations condition and the test-results that are adopted see Table 4.Data show: the multiple sorbent material of investigation is metallic impurity in the adsorbing and removing raw material to some extent all, but preferable with the sorbing material adsorption effect that is rich in macropore.
The test-results of table 4 floating bed hydrogenation product under different sorbent materials
| Embodiment | 10 | 11 | 12 | 13 | 14 | 15 |
| The sorbent material kind | The inertia alumina balls | The inertia alumina balls | Y zeolite | Useless hydrogenation catalyst | The metal protection agent | The metal protection agent |
| The adsorption operations condition | ||||||
| Temperature, ℃ | 300 | 300 | 300 | 300 | 300 | 300 |
| Pressure, MPa | 10 | 10 | 10 | 10 | 10 | 10 |
| Air speed, h -1 | 1.5 | 1.5 | 1.0 | 0.5 | 0.8 | 0.8 |
| Sorbent material and stock oil volume ratio | 1/500 | 1/3500 | 1/500 | 1/500 | 1/500 | 1/5000 |
| Metal removal rate, wt% | 67 | 44 | 43 | 46 | 69 | 31 |
Embodiment 16～17
Subtract the product of slag after floating bed hydrogenation cracking and sorbent material remove metal in normal slag of this The effects Tahe and the sand, the upgrading performance under conventional fixed bed Residue Hydrotreating Technology condition.Fixed bed residual hydrogenation operational condition is that temperature of reaction is 360 ℃, and air speed is 0.30h
-1, hydrogen pressure is 15.0MPa, and hydrogen to oil volume ratio is 800, and device turned round 1400 hours.
The residue fixed-bed hydrogenation catalyst that uses in the test is heavy, the residuum hydrogenating and metal-eliminating catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base of CEN, FZC series, by ZTN, ZTS series weight, residual hydrogenation denitrogenation, the desulfurization catalyst of first fertilizer plant of Qilu Petrochemical company production.The order of catalyst loading is hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst.The Hydrodemetalation catalyst that uses in this test is CEN-5, CEN-6; Protective material is CEN-2, CEN-4, FZC-16 (over current protection agent); Hydrobon catalyst ZTS-01, ZTS-02, ZTS-03; Hydrodenitrogenation catalyst ZTN-01.Admission space ratio between each catalyzer is: CEN-2: FZC-16: CEN-4: CEN-5: CEN-6: ZTS-01: ZTS-02: ZTS-03: ZTN-01=1: 1.25: 1.5: 2.62: 7.8: 6.63: 0.69: 0.87: 11.
The fixed bed hydrogenation test shows, subtract in normal slag of Tahe and the sand that inferior raw material that this class of slag has a high carbon residue of high metal is handled through floating bed hydrogenation and after metal adsorption removes, can be as the high-quality charging of fixed bed residual hydrogenation equipment, satisfy the requirement of device long-term operation, and produce superior in quality RFCC raw material.
Fixed bed hydrogenation used among table 5 embodiment is handled catalyzer
| Catalyzer | Pore volume, ml/g | Specific surface, m 2/g | Tap density, g/ml | Active ingredient is formed, wt% | |||
| NiO | MoO 3 | P | |||||
| Protective material | CEN-2 | 1.18 | 150 | 0.41 | 2.5 | - | - |
| CEN-4 | 1.22 | 133 | 0.42 | 2.0 | - | - | |
| FZC-16 | 0.49 | 156 | 0.76 | 2.5 | - | - | |
| The hydrodemetallation (HDM) agent | CEN-5 | 0.66 | 136 | 0.55 | 3.1 | - | - |
| CEN-6 | 0.62 | 150 | 0.60 | 3.1 | 8.9 | - | |
| The hydrogenating desulfurization agent | ZTS-01 | 0.38 | 145 | 0.85 | 4.0 | 18.7 | 2.0 |
| ZTS-02 | 0.39 | 145 | 0.85 | 4.4 | 19.2 | 1.8 | |
| ZTS-03 | 0.38 | 147 | 0.84 | 4.4 | 18.8 | 2.0 | |
| Hydrodenitrogenation catalyst | ZTN-01 | 0.40 | 220 | 0.85 | 9.1 | 22.5 | - |
Table 6 embodiment 6 and embodiment 9 generate oil nature
| Raw material | Embodiment 6 | Embodiment 9 |
| Density (20 ℃), kg.m -3 | 943.4 | 940.0 |
| Sulphur, wt% | 1.11 | 1.0 |
| Nitrogen, wt% | 0.25 | 0.21 |
| Carbon residue, wt% | 11.7 | 11.1 |
| (Fe+Ni+V)，μg/g | 111 | 92 |
| Group composition, wt% | ||
| Stable hydrocarbon | 41.0 | 27.1 |
| Aromatic hydrocarbon | 36.2 | 52.1 |
| Colloid | 16.6 | 17.0 |
| Bituminous matter | 6.2 | 3.8 |
Table 7 embodiment 6 and embodiment 9 give birth to olefiant fixed bed hydrogenation testing data
| Embodiment and comparative example | Embodiment 16 | Embodiment 17 | ||
| Raw material | Embodiment 6 generates oil | Embodiment 9 generates oil | ||
| Runtime, hour | 100 | 1400 | 100 | 1400 |
| Generate oil nature | ||||
| Density (20 ℃) kg.m -3 | 937.2 | 942.6 | 933.1 | 935.4 |
| Sulphur, wt% | 0.05 | 0.07 | 0.05 | 0.05 |
| Nitrogen, wt% | 0.12 | 0.17 | 0.15 | 0.15 |
| Carbon residue, wt% | 6.91 | 7.51 | 6.80 | 6.82 |
| (Fe+Ni+V)，μg/g | 34.0 | 37.1 | 32.7 | 33.0 |
| Group composition, wt% | ||||
| Stable hydrocarbon | 50.5 | 49.1 | 39.6 | 38.9 |
| Aromatic hydrocarbon | 30.6 | 31.7 | 32.5 | 32.7 |
| Colloid | 14.9 | 15.0 | 14.6 | 15.3 |
| Bituminous matter | 4.0 | 4.2 | 2.1 | 2.3 |
Claims (11)
1, the method for modifying of a kind of inferior heavy, residual oil, comprise the processing of floating bed hydrogenation cracking and fixed bed hydrogenation, it is characterized in that inferior heavy, residual oil carry out fixed bed hydrogenation through the material after the floating bed hydrogenation cracking again and handle after metal adsorption reactor adsorbing and removing dissociates the metal that and compound thereof, wherein the operational condition of adsorptive reactor is as follows: temperature is 200～350 ℃, air speed 0.2～1.5h
-1, pressure and floating bed hydrogenation reactor keep with equipressure or normal pressure, and sorbent material and stock oil volume ratio are 1: 500～1: 5000, and the pore volume of described sorbent material is 0.2～1.2ml/g, and the aperture is 1～100nm, specific surface area is 100～600m
2/ g.
2, method for modifying according to claim 1 is characterized in that the operational condition of adsorptive reactor is as follows: temperature is 300～350 ℃, air speed 0.5～1.0h
-1, sorbent material and stock oil volume ratio are 1: 500～1: 3500.
3, method for modifying according to claim 1 is characterized in that the water-soluble or oil soluble disperse type catalyzer of described floating bed hydrogenation cracking employing, and in weight metal, the content of disperse type catalyzer in raw material is 50～300 μ g/g.
4, method for modifying according to claim 3 is characterized in that described disperse type catalyzer, and in weight metal, the content in raw material is 50～200 μ g/g.
5, method for modifying according to claim 1 is characterized in that described floating bed hydrogenation cracked operational condition is: pressure 8～20MPa, 400～440 ℃ of temperature of reaction, liquid hourly space velocity 0.2～1.5h
-1, hydrogen to oil volume ratio 200～1200.
6, method for modifying according to claim 1 is characterized in that described floating bed hydrogenation cracked operational condition is: pressure 8～14Mpa, 410～430 ℃ of temperature of reaction, liquid hourly space velocity 0.5～1.2h
-1Hydrogen to oil volume ratio 400～1000.
7, method for modifying according to claim 1 is characterized in that described metal adsorption reactor is changeable operation or the reactor that can online displacement adds material.
8, method for modifying according to claim 1 is characterized in that used metal absorbent in the described metal adsorption reactor is one or more in wide-aperture gac, molecular sieve, aluminum oxide or the useless fixed bed residual oil hydrocatalyst.
9, method for modifying according to claim 1, the pore volume that it is characterized in that described sorbent material are that 0.8～1.2ml/g, aperture are that 40～100nm, specific surface area are 100～200m
2/ g.
10, method for modifying according to claim 1, it is characterized in that the operational condition that described fixed bed hydrogenation is handled is: 360～410 ℃ of temperature of reaction, reaction pressure is 8.0～16.0MPa, hydrogen to oil volume ratio 500～2000, and volume space velocity is 0.1～2.0h during liquid
-1
11, method for modifying according to claim 1, it is characterized in that the operational condition that described fixed bed hydrogenation is handled is: 360～390 ℃ of temperature of reaction, reaction pressure is 10.0～15.0MPa, hydrogen to oil volume ratio 700～1500, and volume space velocity is 0.2～1.5h during liquid
-1
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| US11078434B2 (en) | 2017-09-11 | 2021-08-03 | China Petroleum & Chemical Corporation | Process and system for upgrading low-quality oils |
| US11692146B1 (en) | 2022-01-03 | 2023-07-04 | Saudi Arabian Oil Company | Systems and processes for upgrading crude oil through hydrocracking and solvent assisted on-line solid adsorption of asphaltenes |
| US12006482B2 (en) | 2023-05-08 | 2024-06-11 | Saudi Arabian Oil Company | Systems and processes for upgrading crude oil through hydrocracking and solvent assisted on-line solid adsorption of asphaltenes |
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| CN101724463B (en) * | 2008-10-29 | 2012-11-21 | 中国石油化工股份有限公司 | Combined process method for performing hydro-cracking and catalytic cracking on suspension bed residual oil |
| CN107670699B (en) * | 2016-08-01 | 2021-04-13 | 北京华石联合能源科技发展有限公司 | Heavy oil suspension bed hydrogenation catalyst adopting composite carrier |
| CN107641525B (en) * | 2016-07-29 | 2020-07-14 | 北京三聚环保新材料股份有限公司 | Suspension bed hydrogenation combined process and system |
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| US11078434B2 (en) | 2017-09-11 | 2021-08-03 | China Petroleum & Chemical Corporation | Process and system for upgrading low-quality oils |
| US11692146B1 (en) | 2022-01-03 | 2023-07-04 | Saudi Arabian Oil Company | Systems and processes for upgrading crude oil through hydrocracking and solvent assisted on-line solid adsorption of asphaltenes |
| US12006482B2 (en) | 2023-05-08 | 2024-06-11 | Saudi Arabian Oil Company | Systems and processes for upgrading crude oil through hydrocracking and solvent assisted on-line solid adsorption of asphaltenes |
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