CN114381303A - Heavy oil lightening method - Google Patents
Heavy oil lightening method Download PDFInfo
- Publication number
- CN114381303A CN114381303A CN202011118954.4A CN202011118954A CN114381303A CN 114381303 A CN114381303 A CN 114381303A CN 202011118954 A CN202011118954 A CN 202011118954A CN 114381303 A CN114381303 A CN 114381303A
- Authority
- CN
- China
- Prior art keywords
- heavy oil
- hydrogenation
- catalyst
- hydrogen
- infinitesimal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000295 fuel oil Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 110
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 64
- 239000006185 dispersion Substances 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003921 oil Substances 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 claims description 11
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000010426 asphalt Substances 0.000 claims description 5
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000002817 coal dust Substances 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 239000002358 oil sand bitumen Substances 0.000 claims description 2
- 239000004058 oil shale Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000013585 weight reducing agent Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 28
- 239000000725 suspension Substances 0.000 description 25
- 239000012071 phase Substances 0.000 description 22
- 239000007791 liquid phase Substances 0.000 description 19
- 238000004517 catalytic hydrocracking Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- -1 organic acid salt Chemical class 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000571 coke Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 239000011964 heteropoly acid Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 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
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method for lightening heavy oil, which comprises the following steps: hydrogen and heavy oil raw materials mixed with a catalyst enter a hydrogenation reactor, and a lightweight product is obtained through hydrogenation reaction; wherein, the system for realizing the hydrogenation reaction is a dispersion system in which hydrogen is dispersed in the heavy oil raw material by bubbles with the size not more than 500 microns. The method for lightening the silicon carbide can achieve higher conversion rate and has the advantages of simple process flow and the like.
Description
Technical Field
The invention belongs to the field of petroleum processing, and particularly relates to a heavy oil lightening method.
Background
With continuous heavy and inferior petroleum resources, heavy oil becomes an important raw material for refineries, and the efficient conversion processing of inferior heavy oil resources to produce more clean light oil products becomes an important way for dealing with the shortage of petroleum resources. According to the change of the mass ratio of carbon to hydrogen of oil products in the processing process, the heavy oil upgrading process can be divided into two types of hydrogenation and decarburization, wherein the decarburization process mainly comprises the processes of catalytic cracking, delayed coking and the like, is the main processing process for upgrading the heavy oil at the present stage, and accounts for about 83% of the processing amount of the whole heavy oil, however, the coke yield is high, and precious carbon atoms in the heavy oil are difficult to be fully utilized, which is a major problem in the process; the hydrogenation process accounts for about 17% of the total heavy oil processing amount, and compared with the decarburization process, the hydrogenation process can basically realize 100% utilization of carbon atoms in the heavy oil, so the hydrogenation process gradually becomes a main development trend of heavy oil lightening.
At present, a heavy oil hydrogenation process mainly comprises fixed bed hydrogenation, fluidized bed hydrogenation and suspension bed hydrogenation processes, and is taken as general knowledge in the industry, the fixed bed hydrogenation process generally requires that the total metal content in raw oil is not higher than 150ppm (mu g/g), the carbon residue value is not higher than 15%, the asphaltene content is not higher than 5%, and the raw material adaptability is limited; the fluidized bed hydrogenation process needs continuous replacement of partial catalyst in the reactor, and has the problems of complex engineering equipment, poor operation stability and the like; the suspension bed hydrogenation process can process inferior heavy oil with relatively poorer properties, and has the advantages of larger conversion depth, higher yield of light oil, higher carbon residue removal rate, higher metal removal rate and the like compared with other hydrogenation processes.
The suspension bed hydrogenation process is a hydrogenation process in which a catalyst with a certain particle size is driven to move by adjusting the flow velocity of a fluid to form a gas-liquid-solid three-phase bed layer, so that hydrogen, raw oil and the catalyst are contacted to complete a hydrocracking reaction.
U.S. patent document US2011303580a1 discloses a slurry hydrocracking process in which one or more hydrocarbon feedstocks and a slurry hydrocracking catalyst comprising a carrier are combined as a feed to a slurry hydrocracking reaction zone; fractionating the effluent (product) from the slurry hydrogenation reaction zone to obtain a light vacuum gas oil, a heavy vacuum gas oil, a mixture comprising bitumen and a slurry hydrocracking catalyst; separating the pitch from at least a portion of the slurry hydrocracking catalyst, the slurry hydrocracking catalyst obtained after separation being contained in a suspension; the suspension is recycled back to the slurry hydrocracking reaction zone. The process aims to improve the utilization rate of the asphalt, and therefore, the proposal of separating the asphalt from the slurry hydrogenation catalyst after vacuum distillation is provided, although the process can realize the lightening of heavy oil to a certain extent, the process has the defects of low single-pass conversion rate, large tail oil circulation amount, high energy consumption, high operation cost and the like.
Another U.S. patent document US2016122663a1 discloses an integrated slurry hydrocracking process in which a heavy residual hydrocarbon feedstock and a hydrogen stream are introduced into a slurry hydrocracking zone, the heavy residual hydrocarbon feedstock is hydrocracked under slurry hydrocracking conditions over a shiny hydrocracking catalyst to form a slurry hydrocracked effluent (product), at least a portion of said effluent is introduced into a first end of a distillate hydrotreater and hydrogen is supplied to said first end, said at least a portion of the effluent is hydrotreated under hydrotreating conditions, the resulting hydrotreated product exits the distillate hydrotreater from a second end opposite the first end, the hydrotreated product is then separated into a liquid stream and a gaseous stream, and at least a portion of the gaseous stream containing hydrogen is recycled to the slurry hydrocracking zone. The process also has the problems of complex process flow, limited conversion rate and the like.
Chinese patent document CN001239929A discloses a normal pressure heavy oil suspension bed hydrogenation process using a multi-metal liquid catalyst, wherein the slurry after being fully mixed and heated enters a suspension bed hydrocracking reactor from the bottom, the top effluent of the reactor enters a high temperature and high pressure separation system for separation, a vapor phase material flow enters an on-line fixed bed hydrofining reactor, a liquid phase material flow enters a low pressure separation system, the liquid phase material flow of the low pressure separation system also enters a previous fixed bed hydrofining reactor, and the material flow after being hydrofined by the fixed bed finally enters a conventional separation system for separation to obtain various products. The process combines a suspension bed hydrocracking reactor and a fixed bed hydrofining reactor and needs to be matched with at least three stages of separation systems (a high-temperature high-pressure separation system, a low-pressure separation system, a conventional separation system and the like) to realize the lightening of heavy oil, and the whole process system and flow are complex, the energy consumption is high and the cost is high.
Chinese patent document CN107892941B discloses a heavy oil suspension bed hydrocracking method, in the method, an inferior heavy oil suspension bed hydrogenation catalyst and inferior heavy oil are mixed uniformly and then enter a suspension bed hydrogenation reactor, then the reactor is heated to 320-500 ℃ for hydrogenation reaction, the reaction pressure is 5-20 MPa, the time is 0.5-4h, the hydrogen-oil volume ratio is 100-2000, and the space velocity is 0.2-4.0h-1(ii) a Wherein, the hydrogenation catalyst consists of zinc oxide powder (with the content of 10-56 wt%) and fluidized ore component powder, or the hydrogenation catalyst consists of zinc oxide powder (with the content of 10-56 wt%), vulcanized ore component powder and vulcanized micro-mesoporous lanthanum ferrite (with the content of 0.2-8 wt%). The method improves the effect of lightening the heavy oil raw material by improving the hydrogenation catalyst, but the special requirement on the catalyst also increases the cost and complexity of the whole process flow, and the practical industrial application has greater limitation.
The heavy oil is lightened through the hydrogenation process, and no matter which hydrogenation process is adopted, the common mechanism of the system material is that hydrogen is firstly dispersed and dissolved in the heavy oil, and then is activated by the hydrogenation catalyst dissolved or dispersed in the heavy oil, and further reacts with the component to be reacted in the heavy oil, so that the heavy oil is hydrogenated and lightened. In the process, the full contact of the heavy oil raw material, hydrogen and the catalyst is realized, which is very important for ensuring the high efficiency of the heavy oil hydrogenation and is the common essence of the difficult problems in the implementation process of various hydrogenation processes. Taking the suspension bed hydrogenation process as an example, after hydrogen enters a suspension bed hydrogenation reactor in a bubble form, the hydrogen needs to be transferred to liquid-phase heavy oil through a bubble-heavy oil phase interface and then is activated by a catalyst dissolved (oil-soluble or water-soluble homogeneous catalyst) or dispersed (solid granular heterogeneous catalyst) in the heavy oil, under a certain operating pressure (mass transfer driving force), the mass transfer rate of the hydrogen to the heavy oil is determined by the phase interface area between the hydrogen bubbles and the heavy oil, while the size of the hydrogen bubbles dispersed in the heavy oil in the existing suspension bed hydrogenation reactor is generally not less than 5mm, which cannot provide enough phase interface area for the transfer of the hydrogen to the heavy oil, and because the bubbles are large, the buoyancy in the heavy oil is also large, the rising speed is fast, the retention time is short, and the hydrogen has insufficient time to contact and react with the heavy oil, sufficient hydrogen radicals which can quickly capture macromolecular radicals generated by heating heavy oil are difficult to supplement in time, heavy oil macromolecular radicals are easy to collide with each other to cause superposition and even coking, so that the existing suspension bed hydrogenation process is usually implemented under a large operating pressure (most of which is greater than 18MPa) to increase the mass transfer driving force of hydrogen to the heavy oil and relieve the problems of poor contact reaction between the hydrogen and the heavy oil, easy coking and the like, and the large operating pressure has high requirements on equipment, an operating process and the like, so that the industrial application of the suspension bed hydrogenation process is very limited.
In fact, the above-mentioned hydrogenation processes such as the suspension bed generally face the common problem that it is difficult to achieve full contact of the heavy oil, the hydrogen and the catalyst, which is also the essential reason that the processes have the defects of large operation pressure, harsh conditions and the like, although the above-mentioned suspension bed hydrogenation processes such as the above-mentioned reports can achieve effective conversion of the heavy oil or reduce the operation pressure of the suspension bed reactor to a certain extent by jointly adopting a plurality of reactors and/or improving the catalyst and the like, the processes generally face the problems of complicated whole process flow and the like, and the industrial application is limited.
Therefore, the development of a novel heavy oil lightening process can reduce the operation pressure, simplify the process flow and improve the industrial applicability while ensuring or even improving the heavy oil conversion rate, and has become a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a heavy oil lightening method which can realize high-efficiency conversion of heavy oil, and has simple process flow and strong industrial practicability.
The invention provides a method for lightening heavy oil, which comprises the following steps: hydrogen and heavy oil raw materials mixed with a catalyst enter a hydrogenation reactor, and a lightweight product is obtained through hydrogenation reaction; wherein, the system for realizing the hydrogenation reaction is a dispersion system in which hydrogen is dispersed in the heavy oil raw material by bubbles with the size not more than 500 microns.
The invention provides a heavy oil lightening method, which adopts a hydrogenation reactor to lighten a heavy oil raw material, disperses hydrogen in the heavy oil raw material mixed with a catalyst by bubbles with the size not more than 500 microns, forms a dispersion system (also can be called as a dispersion flow form) by taking the heavy oil raw material (liquid phase) as a continuous phase, the catalyst and highly dispersed micron-scale (not more than 500 microns) hydrogen bubbles as a discrete phase under the reaction state in the hydrogenation reactor, and carries out hydrogenation reaction under the dispersion system state, so that the heavy oil raw material, the catalyst and the hydrogen can be fully contacted, the conversion rate of the heavy oil raw material and the yield of a light product can be obviously improved, the condensation and the coking of the heavy oil raw material can be inhibited, and simultaneously, the hydrogenation reaction can be carried out under the conditions of lower operation pressure and the like because all the raw materials are fully contacted, so that the reaction condition is more moderate, and the energy consumption and the cost are saved.
It will be appreciated that the hydrogen bubbles dispersed in the heavy oil feedstock are similar to spheres, and that the above-mentioned dimensions generally refer to the diameter of the hydrogen bubbles, and that the methods of measurement and control are conventional. The present invention can adopt the conventional material micro-dispersion or bubble generation method in the field to disperse hydrogen in the heavy oil raw material in the form of bubbles with the size not more than 500 microns, for example, the present invention can specifically adopt the conventional bubble generation device (or referred to as infinitesimal generation device) in the field to carry out micro-dispersion treatment on the feed, so that the hydrogen entering the hydrogenation reactor and the heavy oil raw material carry out hydrogenation reaction in the dispersion system.
In general, the gas phase and the liquid phase may be passed through the infinitesimal generator together to form an infinitesimal dispersion system in which the gas phase (e.g., hydrogen) is dispersed in the liquid phase (e.g., heavy oil feedstock) in the form of bubbles, or the gas phase may be fed separately through the infinitesimal generator, and when the gas phase (e.g., hydrogen in the separate feeding portion) is fed separately, the infinitesimal generator (e.g., the second infinitesimal generator described below) may be generally buried in the liquid phase, or the gas phase may be inserted into the interior of the hydrogenation reactor through the inlet of the infinitesimal generator and contacted with the liquid phase (e.g., oil in the second infinitesimal dispersion system described below), thereby facilitating the formation of bubbles dispersed in the liquid phase after the gas phase enters the hydrogenation reactor from the infinitesimal generator.
Specifically, in an embodiment of the present invention, a infinitesimal dispersion system (referred to as a first infinitesimal dispersion system) in which hydrogen and hydrogen obtained by dispersing the heavy oil raw material by the infinitesimal generator are dispersed in the heavy oil raw material in bubbles with a size of not greater than 500 micrometers may be introduced into the hydrogenation reactor to form the dispersion system (i.e., the dispersion system in the reactor is formed by introducing the first infinitesimal dispersion system into the hydrogenation reactor). In the process of lightening, the main body flow directions of the gas phase (mainly hydrogen, cracked gas, product oil gas and the like) and the liquid phase (heavy oil raw material mixed with catalyst, generated light oil and the like) in the first infinitesimal dispersion system can be the same (uniform gravity field or uniform inverse gravity field) or opposite (gas phase is in the same direction of the gravity field and the liquid phase is in the opposite direction of the gravity field, or gas phase is in the opposite direction of the gravity field and the liquid phase is in the same direction of the gravity field). As a preferred embodiment, the first infinitesimal dispersion system can generally enter the hydrogenation reactor from the top or the bottom of the hydrogenation reactor, and under the process conditions of the invention, the flow form of the liquid phase in the hydrogenation reactor and solid phase materials such as coke and the like generated by the reaction mixed in the liquid phase is close to an ideal plug flow, which is beneficial to the reaction and the operation stability of the whole system.
Alternatively, in another embodiment, a part of the hydrogen gas and the heavy oil feedstock may be subjected to a first infinitesimal generation device to form a infinitesimal dispersion (denoted as a second infinitesimal dispersion) in which the hydrogen gas is dispersed in the heavy oil feedstock in the form of bubbles having a size of not more than 500 μm; allowing the second infinitesimal dispersion to enter the hydrogenation reactor from the bottom of the hydrogenation reactor; meanwhile, the rest part of hydrogen is processed by the second infinitesimal generator and enters the hydrogenation reactor from the bottom of the hydrogenation reactor to form the dispersion system together with the second infinitesimal dispersion system (namely, the rest part of hydrogen is processed by the second infinitesimal generator and enters the hydrogenation reactor to form bubbles with the size not more than 500 microns and is dispersed in the heavy oil raw material in the second infinitesimal dispersion system to form the dispersion system). Specifically, a part of hydrogen is dispersed in a heavy oil raw material by a first infinitesimal generating device in the form of bubbles with the size not larger than 500 microns to form the second infinitesimal dispersion system, and then the second infinitesimal dispersion system is fed; the second infinitesimal generation means disperses the remaining portion of hydrogen (i.e., the hydrogen of the separate feed portion) into the heavy oil feedstock in the second infinitesimal dispersion into the hydrogenation reactor as bubbles having a size of no greater than 500 microns, thereby forming the dispersion described above. Wherein the portion of hydrogen gas forming the second infinitesimal dispersion with the heavy oil feedstock is generally controlled to be 10% to 90% of the total hydrogen gas feed (mass), and further may be 20% to 50% or 20% to 40%, for example, in one embodiment, 30% of hydrogen gas and the heavy oil feedstock mixed with the catalyst are passed through the first infinitesimal generator to form the second infinitesimal dispersion, and the second infinitesimal dispersion is fed into the hydrogenation reactor, and at the same time, the remaining 70% of hydrogen gas is treated by the second infinitesimal generator into the hydrogenation reactor to form the dispersion together with the second infinitesimal dispersion; the second infinitesimal dispersion system and the rest hydrogen enter the hydrogenation reactor from the bottom of the hydrogenation reactor, and the specific entering positions can be the same or different.
Specifically, the above-mentioned infinitesimal generating device may be selected from at least one of a microporous ceramic membrane infinitesimal generating device, a venturi-type infinitesimal generating device, and an ultrasonic cavitation device, and the size of the formed hydrogen bubbles can be generally controlled by selecting a microporous ceramic membrane infinitesimal generating device with a certain aperture, or adjusting the conditions (or parameters) such as the gas velocity of the venturi-type infinitesimal generating device/ultrasonic cavitation device, for example, when bubbles are generated by using a microporous ceramic membrane infinitesimal generating device with a pore diameter of 100 μm (wherein the pore diameter of the microporous ceramic membrane is 100 μm), the gas phase (such as the above-mentioned hydrogen) enters the liquid phase (such as the above-mentioned heavy oil raw material) through the microporous ceramic membrane to form bubbles, and the size of the formed bubbles is generally considered to be also about 100 μm on average; when the Venturi-type micro-element generating device (or the ultrasonic cavitation device) is used for generating bubbles, the larger the gas velocity of the gas phase is, the larger the size of the formed bubbles is, and vice versa, and the bubbles with specific sizes can be formed by controlling the gas velocity.
Considering the weight reduction effect, the system operation stability, the operation difficulty and other factors, in one embodiment of the present invention, the size of the hydrogen bubbles may be 10-500 μm, further 50-350 μm, such as 100-.
According to the research of the invention, in the lightening process, the infinitesimal generating device and the hydrogenation reactor are jointly adopted, the whole heavy oil lightening system is simple and easy to operate, and the lightening effect on the heavy oil raw material can be obviously improved.
Through further research, the conditions of the hydrogenation reactor (i.e. hydrogenation reaction conditions) may be: the operation pressure is 6-15 MPa, further 8-15 MPa or 8-13 MPa, the reaction temperature is 420-480 ℃, further 450-470 ℃,the weight hourly space velocity is 0.1-1.5 h-1Further, the time can be 0.2 to 0.8h-1The hydrogen-oil ratio is 600-2500 Nm3/m3Further, it may be 800-2000Nm3/m3Further, 1000 to 2000Nm may be used3/m3For example, it may be 1000-1500Nm3/m3The condition is favorable for hydrogenation reaction of heavy oil raw materials, improves the conversion rate and simultaneously is favorable for ensuring the running stability of the whole system.
Further, in the heavy oil feedstock mixed with the catalyst, the mass ratio of the catalyst to the heavy oil feedstock may be 0.5 to 3.0%, further 0.8 to 2.3%, and for example, 0.8 to 1.5% or 1 to 1.3%.
The catalyst may be a hydrogenation catalyst having hydrogenation activity and/or coking-inhibiting property, which is conventional in the art, and may be at least one selected from a homogeneous hydrogenation catalyst and a heterogeneous hydrogenation catalyst, for example, wherein the homogeneous hydrogenation catalyst may be at least one selected from an oil-soluble catalyst and a water-soluble catalyst, a raw material of the heterogeneous hydrogenation catalyst includes a carrier and a metal component (denoted as a first metal component) supported on the carrier, the carrier may be at least one selected from coal dust and activated carbon, and the metal component may be at least one selected from Fe, Co, Mo, Zn, and the like.
In a preferred embodiment of the present invention, the catalyst used may include the above heterogeneous hydrogenation catalyst, and under the process conditions of the present invention, the catalyst can achieve excellent catalytic effect, and has the advantages of cheap and easily available raw materials, simple preparation, low cost, and the like, and has great practical significance in industry.
Furthermore, in the heterogeneous hydrogenation catalyst, the mass content (mass fraction) of the first metal component can be 1-10%, which is beneficial to further improving the lightening effect of the heavy oil raw material.
Of course, homogeneous hydrogenation catalysts, or a mixture of homogeneous and heterogeneous hydrogenation catalysts, may also be employed in the present invention. Specifically, the oil-soluble catalyst may be at least one of an organic acid salt and an organic metal compound, the organic acid salt may be one or more selected from naphthenate, fatty acid salt of C2 or more, citrate, aromatic acid salt, tartrate, fatty group-substituted formate, fatty group-substituted phosphate, and the like, and the organic metal compound may be one or more selected from organic compounds such as acetylacetone compound, carbonyl compound, (sulfonated) phthalocyanine compound, cyclopentadienyl compound, EDTA compound, porphyrin compound, nitrile compound, and the like, and organic metal compounds formed from metals; the water-soluble catalyst may include a complex which is at least one of a heteropoly acid such as one or more of phosphomolybdic acid, homomolybdic acid, phosphotungstic acid, phosphovanadic acid, silicomolybdic acid, silicotungstic acid, silicovanadic acid, thiomolybdic acid, and the like, a complex of a carbonyl compound and a metal component (referred to as a second metal component), a second metal component such as at least one selected from Mo, Fe, Ni, Co, and the like, and/or an inorganic salt such as at least one selected from a heteropoly acid salt (such as a salt formed from the heteropoly acid as described above) which is generally specifically an ammonium salt or an alkali metal salt of the heteropoly acid, and a sulfate, a hydrochloride, a carbonate, a basic carbonate, a nitrate, and the like containing a metal component (referred to as a third metal component) which is generally a heteropoly acid salt or an alkali metal salt, and/or a third metal component which is specifically selected from Mo, a carbonyl compound, a metal component (referred to as a second metal component), Fe. At least one of Ni and Co.
In the process, when the catalyst is a homogeneous hydrogenation catalyst, the dispersion system in the hydrogenation reactor is a gas-liquid two-phase system; when the catalyst used comprises a heterogeneous hydrogenation catalyst (i.e. the catalyst used is a heterogeneous hydrogenation catalyst, or a mixture of a homogeneous hydrogenation catalyst and a heterogeneous hydrogenation catalyst), the above-mentioned dispersion system is a gas-liquid-solid three-phase system (but may also be referred to as a gas-liquid pseudo-two-phase system since the amount of catalyst used is generally small (i.e. the solid phase is small).
The present invention can mix the catalyst in the heavy oil feedstock by a method conventional in the art to form the above-mentioned heavy oil feedstock mixed with the catalyst, and is not particularly limited. In specific implementation, the catalyst is generally dispersed or dissolved in the heavy oil feedstock as uniformly as possible, for example, when a heterogeneous hydrogenation catalyst or other catalyst that is not soluble in the heavy oil feedstock is used, the catalyst can form a micro-element structure of solid particles with micron scale (e.g., the size of the hydrogen bubbles is equivalent to that of the above-mentioned hydrogen bubbles) and is uniformly dispersed in the heavy oil feedstock, so that a uniformly distributed dispersion system with the heavy oil as a continuous phase and the highly dispersed micron scale hydrogen bubbles and catalyst particles as discrete phases is formed in the hydrogenation reactor, which is more favorable for the reaction and the lightening effect.
Generally, the hydrogenation reaction product (i.e. the lightening product) from the hydrogenation reactor is mainly a mixture containing distillate oil including light oil and tail oil, cracked gas, coke, and unreacted hydrogen, and in an embodiment of the present invention, the hydrogenation reaction product may further include: separating the lightweight product, returning the separated tail oil to the hydrogenation reactor for circular processing, and controlling the circulation ratio (the mass ratio of the tail oil to the fresh heavy oil raw material) to be 0.1-0.7, further 0.2-0.5, so as to be beneficial to the high conversion of the heavy oil raw material; in specific implementation, coke in the tail oil can be removed by a device such as a liquid-solid separator and then returned for circulation. Of course, the separated tail oil may be thrown off, for example, as fuel.
Specifically, the light product flowing out (or output) from the hydrogenation reactor is first introduced into a gas-liquid separator or other devices for gas-liquid separation to obtain a gas-phase component (mainly a mixed gas of cracked gas and hydrogen) and a liquid-phase component (distillate oil and a small amount of coke entrained therein); then the liquid phase components enter devices such as a fractionating tower (a distillation tower) and the like for fractionation treatment to obtain products such as gasoline fractions (less than 200 ℃ fraction section), diesel oil fractions (200-350 ℃ fraction section), wax oil fractions (350-500 ℃ fraction section), tail oil (more than 500 ℃ fraction section) and the like; wherein, hydrogen (recycle hydrogen) in the gas phase component can be further separated, and the hydrogen is mixed with fresh hydrogen for recycling; the light product may flow from a location at the top, middle, or bottom of the hydrogenation reactor. Of course, in the present invention, the light product may also flow out from multiple positions of the top, middle, bottom, etc. of the hydrogenation reactor, and the products flowing out from each position may generally have different fraction distributions (equivalent to the primary fractionation treatment of the light product by the hydrogenation reactor), and may be further refined by gas-liquid separation and other treatments.
The gas-liquid separator may be one or more of hot high fraction, hot low fraction, cold high fraction and cold low fraction, and may be assembled with hydrogenation reactor, fractionating tower, etc. by conventional method in the art. The hydrogenation reactor of the present invention may be a conventional hydrogenation reactor in the art, such as a high pressure resistant hollow cylinder device without any internal components, or a high pressure resistant reaction device with one or more sections of circulating internal components or other internal components, etc.
The method of the present invention is particularly useful for upgrading heavy oil feedstocks having relatively high carbon residue values, relatively high heavy metal (e.g., nickel (Ni), vanadium (V), etc.) contents, and relatively high sulfur and nitrogen contents, and in one embodiment, the heavy oil feedstock has a conradson carbon residue value (CCR) of greater than 10 wt%, and/or a total heavy metal content of greater than 150 μ g/g. Specifically, the heavy oil feedstock may be, for example, one or more of low-quality heavy oil such as heavy oil, super heavy oil, oil sand bitumen, atmospheric heavy oil, vacuum residue, FCC oil slurry, and solvent deoiled bitumen, and derived low-quality heavy oil such as heavy tar and residue generated in a coal pyrolysis or liquefaction process, heavy oil generated in dry distillation of oil shale, and low-temperature pyrolysis liquid product in biomass.
The implementation of the invention has at least the following beneficial effects:
compared with the existing hydrogenation processes such as a suspension bed and the like, the heavy oil hydrogenation process has the advantages of high conversion rate of heavy oil raw materials, mild and non-harsh conditions such as operating pressure and the like, simple process flow and the like, has the advantages of easiness in operation, low cost and the like, and is beneficial to industrial production and application.
Drawings
FIG. 1 is a flow chart of a heavy oil upgrading process according to an embodiment of the present invention;
description of reference numerals:
1: a infinitesimal generating device; 2: a hydrogenation reactor; 3: a gas-liquid separator; 4: a distillation column; a: hydrogen gas; b: a heavy oil feedstock mixed with a catalyst; c: a mixed gas of cracked gas and hydrogen; d: a gasoline fraction; e: a diesel fraction; f: a wax oil fraction; g: tail oil.
Detailed Description
The present invention will be described in more detail with reference to examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
Example 1
This example provides a method for converting heavy oil into light oil, as shown in fig. 1, in which hydrogen gas a and a heavy oil raw material b mixed with a catalyst are introduced into a micro-element generating apparatus 1 to be subjected to a dispersion treatment, thereby obtaining a micro-element dispersion system in which hydrogen gas is dispersed in the heavy oil raw material in the form of bubbles having an average size of not more than 500 μm; the infinitesimal dispersion system enters a hydrogenation reactor 2 for hydrogenation reaction (the hydrogenation reaction system in the hydrogenation reactor is a dispersion system in which hydrogen is dispersed in heavy oil raw materials by bubbles of not more than 500 microns) to obtain a lightweight product; the light product enters a gas-liquid separator 3 for gas-liquid separation to respectively obtain a gas-phase component (mixed gas c of cracked gas and hydrogen) and a liquid-phase component; the liquid phase component enters a distillation tower 4 for fractionation to respectively obtain a gasoline fraction d below 200 ℃, a diesel fraction e at 200-350 ℃, a wax oil fraction f at 350-500 ℃ and tail oil g above 500 ℃; wherein, the hydrogen in the mixed gas c is separated and mixed with fresh hydrogen for recycling.
Specifically, in the present embodiment, the infinitesimal generating device 1 is a venturi-type infinitesimal generating device; the first infinitesimal dispersion enters the hydrogenation reactor 2 from the top of the hydrogenation reactor.
Application examples
In the following test examples 1 and 2 and comparative examples 1 and 2, the heavy oil feedstock used was Sinkiang vacuum residue, the properties of which are shown in Table 1; the catalyst is a heterogeneous catalyst formed by loading iron element on activated carbon (carbon powder), and the mass fraction of the iron element in the catalyst is 5%.
Test example 1 and test example 2
Experimental example 1 and experimental example 2 were carried out by the method for upgrading heavy oil of example 1, and conditions such as hydrogen bubble size (micro-scale), operating pressure, reaction temperature, space velocity, hydrogen-oil ratio, and mass ratio of the catalyst to the heavy oil feedstock (catalyst addition amount) of the dispersoid in the hydrogenation reactor are shown in table 2, and product distribution in the product of hydrogenation reaction (upgraded product) is shown in table 3.
Comparative examples 1 and 2
The heavy oil raw material is subjected to a lightening treatment by a conventional suspension bed hydrogenation process, conditions such as the size of hydrogen bubbles (infinitesimal scale), the operating pressure, the reaction temperature, the space velocity, the hydrogen-oil ratio, the mass ratio of the catalyst to the heavy oil raw material (catalyst addition amount) and the like dispersed in the suspension bed reactor are shown in table 2, and the product distribution in the product of the hydrogenation reaction (lightening product) is shown in table 3.
TABLE 1 heavy oil feedstock Properties
TABLE 2 reaction conditions
| Item | Test example 1 | Test example 2 | Comparative example 1 | Comparative example 2 |
| Infinitesimal scale, mum | 210 | 500 | 5000 | 5000 |
| Operating pressure, MPa | 13 | 13 | 13 | 22 |
| Reaction temperature of | 457 | 457 | 457 | 459 |
| Weight hourly space velocity, h-1 | 0.4 | 0.4 | 0.4 | 0.4 |
| Hydrogen to oil ratio, Nm3/m3 | 1200 | 1200 | 1200 | 2278 |
| The addition amount of the catalyst is wt% | 1.2 | 1.2 | 1.2 | 1.2 |
TABLE 3 Main product distribution
| Product distribution, wt% | Test example 1 | Test example 2 | Comparative example 1 | Comparative example 2 |
| Cracked gas | 3.9 | 4.1 | 4.8 | 2.1 |
| Gasoline (gasoline) | 11.6 | 8.5 | 5.3 | 21.7 |
| Diesel oil | 28.2 | 25.1 | 17.1 | 43.2 |
| Wax oil | 46.3 | 42.9 | 35.3 | 23.4 |
| Tail oil | 9.8 | 17.5 | 33.7 | 9.2 |
| Coke | 0.2 | 1.9 | 3.8 | 0.4 |
| Total up to | 100.0 | 100 | 100.0 | 100.0 |
| Conversion rate | 90.2％ | 82.50％ | 66.3％ | 90.8％ |
The results show that at lower hydrogen to oil ratios (1200 Nm)3/m3) Under the conditions of operating pressure (13MPa) and the like, the test example 1 and the test example 2 can achieve excellent lightening effect, and the conversion rate of heavy oil raw materials is up to more than 82.5 percent and is far higher than that of the traditional suspension bed process (such as a comparative example 1); the traditional suspension bed hydrogenation process has very poor light-weight effect under the conditions of lower pressure, hydrogen-oil ratio and the like, and the high pressure (22MPa) and high hydrogen-oil ratio (2278 Nm) as in comparative example 2 are often needed to improve the light-weight effect3/m3) Conditions, further shown by the experimental example 1 and the comparative example 2, the experimental example 1 can still reach the conditions of the comparative example under the conditions of hydrogen-oil ratio, operation pressure and the like which are far lower than those of the comparative example 22 equivalent heavy oil raw material conversion rate and lower coke yield, which shows that the heavy oil lightening method can greatly reduce the conditions of operation pressure, hydrogen-oil ratio and the like, and has very obvious advantages compared with the conventional suspension bed and other hydrogenation processes; in addition, in the lightening process of the test examples 1 and 2, the whole system runs stably, and the method also has the advantages of simple process flow, easiness in operation and the like, and further ensures that the heavy oil lightening method is beneficial to practical industrial application.
Claims (10)
1. A method for lightening heavy oil, comprising: hydrogen and heavy oil raw materials mixed with a catalyst enter a hydrogenation reactor, and a lightweight product is obtained through hydrogenation reaction; wherein, the system for realizing the hydrogenation reaction is a dispersion system in which hydrogen is dispersed in the heavy oil raw material by bubbles with the size not more than 500 microns.
2. A lightening process according to claim 1, wherein hydrogen gas and hydrogen gas obtained by subjecting said heavy oil feedstock to dispersion treatment by a micro-generator are introduced into a hydrogenation reactor as a first micro-dispersion system in which bubbles having a size of not more than 500 μm are dispersed in said heavy oil feedstock, thereby forming said dispersion system;
alternatively, the first and second electrodes may be,
dispersing a portion of the hydrogen gas and the heavy oil feedstock by a first infinitesimal generation device to form a second infinitesimal dispersion system in which the hydrogen gas is dispersed in the heavy oil feedstock in bubbles having a size of not more than 500 microns; allowing the second infinitesimal dispersion to enter the hydrogenation reactor from the bottom of the hydrogenation reactor; meanwhile, the rest part of hydrogen is processed by a second infinitesimal generator and enters the hydrogenation reactor from the bottom of the hydrogenation reactor to form the dispersion system together with the second infinitesimal dispersion system.
3. A lightening process according to claim 2, wherein said first infinitesimal dispersion enters the hydrogenation reactor from the top or bottom of the hydrogenation reactor.
4. A method for weight reduction according to claim 2 or 3, wherein said infinitesimal generating device is at least one selected from the group consisting of a microporous ceramic membrane infinitesimal generating device, a Venturi-type infinitesimal generating device, and an ultrasonic cavitation device.
5. A lightening process according to claim 1 or 2, wherein said bubbles have a size of 10 to 500 μm.
6. A lightening process according to claim 1, wherein the conditions of said hydrogenation reactor are: the operating pressure is 6-15 MPa, the reaction temperature is 420-480 ℃, and the weight hourly space velocity is 0.1-1.5 h-1The hydrogen-oil ratio is 600-2500 Nm3/m3。
7. A lightening process according to claim 1 or 5, wherein the catalyst is present in an amount of 0.5 to 3.0% by mass based on the heavy oil feedstock.
8. A lightening process according to claim 1 or 5, wherein said catalyst is selected from at least one of a homogeneous hydrogenation catalyst and a heterogeneous hydrogenation catalyst; wherein the content of the first and second substances,
the homogeneous hydrogenation catalyst is selected from at least one of oil-soluble catalyst and water-soluble catalyst;
the heterogeneous hydrogenation catalyst comprises a carrier and a metal component loaded on the carrier, wherein the carrier is selected from at least one of coal dust and activated carbon, and the metal component is selected from at least one of Fe, Co, Mo and Zn.
Preferably, in the heterogeneous catalyst, the mass content of the metal component is 1-10%.
9. A lightening method according to claim 1 or 6, further comprising: and (3) separating the light products, and returning the separated tail oil to the hydrogenation reactor for circular processing, wherein the circulation ratio is controlled to be 0.1-0.7.
10. A lightening process according to any one of claims 1 to 9, wherein the heavy oil feedstock is one or a mixture of more of heavy oil, ultra-heavy oil, oil sand bitumen, atmospheric heavy oil, vacuum residue, FCC slurry oil, solvent de-oiled bitumen, heavy tar and residue from coal pyrolysis or liquefaction processes, heavy oil from dry distillation of oil shale, and low temperature pyrolysis liquid products from biomass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011118954.4A CN114381303A (en) | 2020-10-19 | 2020-10-19 | Heavy oil lightening method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011118954.4A CN114381303A (en) | 2020-10-19 | 2020-10-19 | Heavy oil lightening method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114381303A true CN114381303A (en) | 2022-04-22 |
Family
ID=81193186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011118954.4A Pending CN114381303A (en) | 2020-10-19 | 2020-10-19 | Heavy oil lightening method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114381303A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393524A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Process for lightening heavy oil or residual oil |
| CN203451487U (en) * | 2013-09-17 | 2014-02-26 | 李方 | Raw oil suspended bed hydrogenation device |
| CN110484296A (en) * | 2019-09-02 | 2019-11-22 | 南京中汇能源科技研发中心 | A kind of adverse current type multiphase flow hydrocracking heavy oil technique |
| CN111482139A (en) * | 2019-01-29 | 2020-08-04 | 南京大学 | Up-down opposite flushing type residual oil hydrogenation fluidized bed micro-interface strengthening reaction device and method |
-
2020
- 2020-10-19 CN CN202011118954.4A patent/CN114381303A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393524A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Process for lightening heavy oil or residual oil |
| CN203451487U (en) * | 2013-09-17 | 2014-02-26 | 李方 | Raw oil suspended bed hydrogenation device |
| CN111482139A (en) * | 2019-01-29 | 2020-08-04 | 南京大学 | Up-down opposite flushing type residual oil hydrogenation fluidized bed micro-interface strengthening reaction device and method |
| CN110484296A (en) * | 2019-09-02 | 2019-11-22 | 南京中汇能源科技研发中心 | A kind of adverse current type multiphase flow hydrocracking heavy oil technique |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100434496C (en) | Two-way combined process of wax-oil hydrogenation treatment and catalytic cracking | |
| CN102796559B (en) | Method and the device of oil fuel are produced in hydrocracking | |
| CN101987972B (en) | Method for processing inferior crude oil through combined processes | |
| CN105567316B (en) | Inferior heavy oil processing and treating method | |
| CN102051221B (en) | Method for more producing light oil by using hydrocarbon oil | |
| CN102041084A (en) | Heavy hydrocarbon hydrogenation combined process | |
| CN1119397C (en) | Hydrogenation and catalystic cracking combined process for residual oil | |
| CN109777500B (en) | Gas-liquid countercurrent two-stage hydrocracking method | |
| CN108659882B (en) | Heavy oil hydrogenation method and hydrogenation system thereof | |
| CN107557064B (en) | Coal tar combined bed hydrogenation method and system for coal tar combined bed hydrogenation | |
| CN101538481A (en) | Improved hydrotreatment and catalytic cracking combination method for hydrocarbon oil | |
| CN112538370B (en) | Method and device for coupling hydro-pressurized catalytic cracking of heavy oil with coke gasification | |
| CN114381303A (en) | Heavy oil lightening method | |
| CN114381300A (en) | Heavy oil lightening method | |
| CN114437813A (en) | Heavy oil lightening method | |
| CN114381299A (en) | Heavy oil lightening method | |
| CN114381302A (en) | Heavy oil lightening method | |
| CN114437812A (en) | Heavy oil lightening method | |
| CN114381298A (en) | Heavy oil lightening method | |
| CN116328663A (en) | Slurry bed reactor, poor-quality oil slurry bed hydrocracking system and method | |
| CN101875856B (en) | Wax oil hydrogenated treatment and catalytic cracking combined method | |
| CN112745952B (en) | Method and system for processing aromatic-rich distillate oil | |
| CN114381301A (en) | Heavy oil lightening method coupled with hydrogen donor | |
| CN103540356A (en) | Low-grade heavy oil catalytic conversion process for increasing yield of low-carbon olefins and diesel oil | |
| CN114381297A (en) | Heavy oil lightening method with circulation dispersion state |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220422 |