CN114381299A - Heavy oil lightening method - Google Patents
Heavy oil lightening method Download PDFInfo
- Publication number
- CN114381299A CN114381299A CN202011118881.9A CN202011118881A CN114381299A CN 114381299 A CN114381299 A CN 114381299A CN 202011118881 A CN202011118881 A CN 202011118881A CN 114381299 A CN114381299 A CN 114381299A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- hydrogen
- infinitesimal
- heavy oil
- catalyst
- 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 126
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 207
- 239000001257 hydrogen Substances 0.000 claims abstract description 111
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 111
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 98
- 239000006185 dispersion Substances 0.000 claims abstract description 88
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 42
- 239000000047 product Substances 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims description 50
- 239000003921 oil Substances 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 33
- 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
- 238000012545 processing Methods 0.000 claims description 10
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000012528 membrane 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
- 230000000694 effects Effects 0.000 abstract description 12
- 239000012071 phase Substances 0.000 description 31
- 239000007791 liquid phase Substances 0.000 description 24
- 239000000725 suspension Substances 0.000 description 24
- 238000004517 catalytic hydrocracking Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 14
- 230000005484 gravity Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- -1 organic acid salt Chemical class 0.000 description 11
- 239000000571 coke Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005194 fractionation Methods 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
- 239000007790 solid phase Substances 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
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 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
- 239000006227 byproduct Substances 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
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization 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
- 230000002349 favourable effect Effects 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
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 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
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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: carrying out a first hydrogenation reaction on a first part of hydrogen and a heavy oil raw material mixed with a catalyst in a first hydrogenation reactor to obtain a first hydrogenation reaction product; carrying out a second hydrogenation reaction on the first hydrogenation reaction product and a second part of hydrogen in a second hydrogenation reactor to obtain a second hydrogenation reaction product; wherein, the system for realizing the first hydrogenation reaction is a first dispersion system that a first part of hydrogen is dispersed in the heavy oil raw material by bubbles with the size not more than 500 microns; the second hydrogenation system is a second dispersion system in which a second part of hydrogen is dispersed in the first hydrogenation product by bubbles with the size of not more than 500 microns. The method for lightening the heavy oil has good lightening effect on the heavy oil raw material.
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 powderAnd the vulcanized micro-mesoporous lanthanum ferrite (the content is 0.2 to 8 weight percent). 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: carrying out a first hydrogenation reaction on a first part of hydrogen and a heavy oil raw material mixed with a catalyst in a first hydrogenation reactor to obtain a first hydrogenation reaction product; carrying out a second hydrogenation reaction on the first hydrogenation reaction product and a second part of hydrogen in a second hydrogenation reactor to obtain a second hydrogenation reaction product; wherein, the system for realizing the first hydrogenation reaction and the system for realizing the second hydrogenation reaction are respectively dispersion systems 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 cascade (two-stage) hydrogenation reactors (namely a first hydrogenation reactor and a second hydrogenation reactor) to lighten heavy oil raw materials, and respectively forms a dispersion system (also can be called as a dispersion flow form) taking a liquid phase (heavy oil raw material/first hydrogenation reaction product) as a continuous phase and a catalyst and highly dispersed hydrogen bubbles with micron scale (not more than 500 microns) as a discrete phase under the reaction state in the two hydrogenation reactors, the reactor with the system or the form is called as a dispersion bed hydrogenation reactor, hydrogenation reaction is carried out under the dispersion system state, heavy oil, the catalyst and hydrogen can be fully contacted, the conversion rate and the yield of the light oil raw material are remarkably improved, the condensation and coking of the heavy oil raw material can be inhibited, and simultaneously, because all the raw materials are fully contacted, the hydrogenation reaction can be carried out under the conditions of lower operation pressure and the like, so that the reaction condition is more moderate, and the energy consumption and the cost are saved; in addition, a two-stage reactor is adopted in a matching manner, so that two-stage hydrogenation reaction can be flexibly regulated and controlled, and the improvement of the lightening efficiency is further ensured.
It is understood that the hydrogen bubbles dispersed in the heavy oil feedstock or the first hydrogenation reaction product described above are similar to spheres, and the above dimensions generally refer to the diameter of the hydrogen bubbles, and the methods of measurement and control are conventional. The present invention can disperse hydrogen in the form of bubbles with the size not greater than 500 microns in the heavy oil raw material or the first hydrogenation reaction product by using the conventional material micro-dispersion or bubble generation method in the art, for example, the present invention can specifically use the conventional bubble generation device (or referred to as infinitesimal generation device) in the art to perform micro-dispersion treatment on the feed, so that the hydrogen entering the hydrogenation reactor and the heavy oil raw material or the first hydrogenation reaction product perform 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 or first hydrogenation reaction product) 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 a separate feeding portion) is fed separately, the infinitesimal generator (e.g., a third infinitesimal generator or a sixth infinitesimal generator described below) may be generally embedded 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., an oil phase in a second infinitesimal dispersion system or an oil phase in a fifth 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 first part of hydrogen and hydrogen obtained by processing a heavy oil raw material by a first infinitesimal generator (i.e., a first part of hydrogen) may enter a first hydrogenation reactor as a first infinitesimal dispersion system in which bubbles with a size of not greater than 500 micrometers are dispersed in the heavy oil raw material, so as to form a first dispersion system (i.e., the first dispersion system in the first hydrogenation reactor is formed by entering the first hydrogenation reactor from the first infinitesimal dispersion system). 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 simultaneously along the gravity field and liquid phase is simultaneously along the gravity field, or gas phase is simultaneously along the gravity field and liquid phase is simultaneously along the gravity field). As a preferred embodiment, the first infinitesimal dispersion system can generally enter the first hydrogenation reactor from the top or the bottom of the first hydrogenation reactor, and under the process conditions of the invention, the flow form of the liquid phase in the first hydrogenation reactor and solid phase materials such as coke and the like generated by the reaction and included 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 portion of the first portion of hydrogen (or a portion of the first portion of hydrogen, which is referred to as "part 1 a" hydrogen for convenience of description) and the heavy oil feedstock may be subjected to a second infinitesimal generation device to form a second infinitesimal dispersion in which hydrogen (i.e., part 1a hydrogen) is dispersed in the heavy oil feedstock in the form of bubbles having a size of no greater than 500 μm; feeding the second infinitesimal dispersion into the first hydrogenation reactor; meanwhile, the rest part of the first part of hydrogen (for convenience of description, the 1b part of hydrogen) is treated by the third infinitesimal generator and enters the first hydrogenation reactor to form a first dispersion system together with the second infinitesimal dispersion system (namely, the 1b part of hydrogen is treated by the third infinitesimal generator and enters the first hydrogenation reactor to form bubbles with the size of not more than 500 microns and is dispersed in the oil phase of the second infinitesimal dispersion system to form the first dispersion system). Specifically, the second infinitesimal device firstly disperses the 1a part of hydrogen in the heavy oil raw material in bubbles with the size not more than 500 microns to form the second infinitesimal dispersion system, and then feeds the second infinitesimal dispersion system; the third infinitesimal generation means disperses the hydrogen of part 1b (i.e. the hydrogen of the single feed portion) in the oil phase in the second infinitesimal dispersion entering the first hydrogenation reactor in the form of bubbles of size not greater than 500 microns, thus forming the first dispersion described above. Wherein the hydrogen of the part 1a accounts for 10% to 90% of the total feeding amount (mass) of the hydrogen of the first part, and further may be 20% to 50% or 20% to 40%, for example, in a specific embodiment, 30% of the hydrogen of the first part and the heavy oil raw material mixed with the catalyst may be passed through a second infinitesimal generator to form a second infinitesimal dispersion, and the second infinitesimal dispersion is fed into the first hydrogenation reactor, and simultaneously the remaining (i.e. 70%) of the hydrogen of the first part is passed through the second infinitesimal generator to be treated into the first hydrogenation reactor and then fed into the first dispersion together with the second infinitesimal dispersion to form the first dispersion; the second infinitesimal dispersion system and the part 1b of hydrogen can enter the first hydrogenation reactor from one or more of the top, the middle, the bottom and the like of the first hydrogenation reactor, and the specific entering positions can be the same or different.
Similarly, in an embodiment of the present invention, the second part of hydrogen and the hydrogen obtained by processing the first hydrogenation reaction product by the fourth infinitesimal generator (i.e. the second part of hydrogen) may enter the second hydrogenation reactor as a fourth infinitesimal dispersion system in which bubbles with a size not greater than 500 micrometers are dispersed in the first hydrogenation reaction product, so as to form the second dispersion system (i.e. the second dispersion system in the second hydrogenation reactor is formed by the fourth infinitesimal dispersion system entering the second 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 (oil to be reacted, generated light oil and the like) in the fourth infinitesimal dispersion system can be the same (uniform gravity field or uniform inverse gravity field) or opposite (gas phase is in the gravity field and liquid phase is in the inverse gravity field, or gas phase is in the gravity field and liquid phase is in the gravity field). As a preferred embodiment, the fourth infinitesimal dispersion system can generally enter the second hydrogenation reactor from the top or the bottom of the second hydrogenation reactor, and under the process conditions of the invention, the flow form of the liquid phase in the second hydrogenation reactor and solid phase materials such as coke and the like generated by the reaction and contained in the liquid phase is close to the ideal plug flow, which is beneficial to the reaction and the operation stability of the whole system.
Alternatively, in another embodiment, a portion of the second portion of hydrogen (or a portion of the second portion of hydrogen, referred to as part 2a hydrogen for convenience of description) and the first hydrogenation reaction product may be subjected to dispersion treatment by a fifth infinitesimal generation device to form a fifth infinitesimal dispersion system in which hydrogen (i.e., part 2a hydrogen) is dispersed in the first hydrogenation reaction product as bubbles having a size of not greater than 500 μm; feeding the fifth infinitesimal dispersion system into a second hydrogenation reactor; meanwhile, the remaining part of the second part of hydrogen (for convenience of description, referred to as part 2b hydrogen) is treated by the sixth infinitesimal generator and enters the second hydrogenation reactor to form the second dispersion system together with the fifth infinitesimal dispersion system (i.e. part 2b of hydrogen is treated by the sixth infinitesimal generator and enters the second hydrogenation reactor to form bubbles with the size of not more than 500 micrometers, and the bubbles are dispersed in the oil phase of the fifth infinitesimal dispersion system to form the second dispersion system). Specifically, the fifth infinitesimal device firstly disperses the 2a part of hydrogen in the first hydrogenation reaction product in bubbles with the size not more than 500 microns to form the fifth infinitesimal dispersion system, and then feeds; the sixth infinitesimal generation means disperses the 2b part of the hydrogen (i.e. the hydrogen of the single feed portion) in the oil phase in the fifth infinitesimal dispersion entering the second hydrogenation reactor in bubbles having a size not greater than 500 microns, thus forming the above-mentioned second dispersion. Wherein the hydrogen of the 2a part accounts for 10-90% of the total feeding amount (mass) of the hydrogen of the second part, and further can be 20-50% or 20-40%, for example, in a specific embodiment, 30% of the hydrogen of the first part and the heavy oil raw material mixed with the catalyst can be processed by a fifth infinitesimal generating device to form a fifth infinitesimal dispersion system, the fifth infinitesimal dispersion system enters the second hydrogenation reactor, and simultaneously the remaining (i.e. 70%) of the hydrogen of the first part is processed by a sixth infinitesimal generating device to enter the second hydrogenation reactor to form the second dispersion system together with the fifth infinitesimal dispersion system; the fifth infinitesimal dispersion system and the part 2b of hydrogen can enter the first hydrogenation reactor from one or more of the top, the middle, the bottom and the like of the first hydrogenation reactor, and the specific entering positions can be the same or different.
Specifically, the above-mentioned infinitesimal generating device (i.e. the first infinitesimal generating device to the sixth infinitesimal generating device) may be at least one selected from 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 microcell generator having a pore diameter of 100 μm (wherein the pore diameter of the microporous ceramic membrane is 100 μm), the gaseous phase (e.g., hydrogen as described above) enters the liquid phase (e.g., the heavy oil feedstock or the first hydrogenation reaction product as described above) through the microporous ceramic membrane to form bubbles, which are also believed to have an average size of about 100 μm; 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. In specific implementation, the first infinitesimal generating device to the sixth infinitesimal generating device can be the same or different.
In the present invention, unless otherwise specified, "first", "second", "third", "fourth", "fifth", "sixth", and the like are merely for convenience of description to explain or explain the embodiments more clearly, and do not imply a sequence of forming the system or a sequence of using the system.
Considering the weight reduction effect, the system operation stability, the operation difficulty and other factors comprehensively, in the present invention, the size of the hydrogen bubbles may be 10-500 μm, and further may be 50-350 μm, such as 100-300 μm or 150-250 μm.
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.
In the process of the hydroconversion of the heavy oil raw material, besides the cracking reaction of hydrocarbons, reactions such as hydrodesulfurization, denitrification, demetalization and the like generally occur, the requirements of the two on reaction conditions are often different, compared with the former (namely the cracking reaction of hydrocarbons), the latter reaction is relatively fast, and the required reaction conditions are relatively mild.
Through further research, the invention can strengthen reactions of desulfurization, denitrification, demetalization and the like in the first hydrogenation reactor, strengthen hydrocarbon cracking reaction in the second hydrogenation reactor, and is beneficial to further improving the conversion rate of heavy oil raw materials and the yield of light oil products and reducing the generation of byproducts such as coke and the like. Specifically, in one embodiment of the present invention, the conditions of the first hydrogenation reactor (i.e., the first hydrogenation reaction conditions) may be: the operation pressure is 6-15MPa, further 8-15MPa or 8-13MPa, the reaction temperature is 390-450 ℃, further 400-430 ℃ and the weight hourly space velocity is 0.5-3.0h-1Further, it can be 0.8-2.5h-1For example, it may be 0.8-1.5h-1The hydrogen-oil ratio is 400-1800Nm3/m3Further 600-1500Nm3/m3Or 600 + 1300Nm3/m3For example, it can be 800-1300Nm3/m3Or 1000-1300Nm3/m3(ii) a And/or, the conditions of the second hydrogenation reactor (i.e., the second hydrogenation reaction conditions) may be: the operation pressure is 6-15MPa,further 8-15MPa or 8-13MPa, the reaction temperature is 420-480 ℃, further 450-470 ℃ and 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/m3. In particular implementation, the reaction temperature of the first hydrogenation reactor is generally lower than the reaction temperature of the second hydrogenation reactor, and/or the weight hourly space velocity of the first hydrogenation reactor is greater than the weight hourly space velocity of the second hydrogenation reactor. The reaction conditions not only can pertinently strengthen different types of reactions and improve the lightening efficiency of the heavy oil, but also are 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 (referred to as the first 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%.
In specific implementation, a catalyst (denoted as a second catalyst) may be introduced into the reaction system of the second hydrogenation reactor to further improve the second hydrogenation effect, for example, the second catalyst may be directly input into the second hydrogenation reactor, or the first hydrogenation product is first mixed with the second catalyst (even if the second catalyst is mixed in the first hydrogenation product) and then enters the second hydrogenation reactor. In an embodiment of the present invention, a second catalyst may be mixed in the first hydrogenation reaction product, and then the first hydrogenation reaction product mixed with the second catalyst and a second portion of hydrogen gas are subjected to dispersion treatment by the fourth or fifth infinitesimal generator, so that the obtained corresponding infinitesimal dispersion (the fourth or fifth infinitesimal dispersion) enters the second hydrogenation reactor.
In general, the amount of the second catalyst added may be 0.5 to 3.0% by mass, further 0.8 to 2.3% by mass, for example, 0.8 to 1.5% by mass or 1 to 1.3% by mass of the first hydrogenation product.
The above-mentioned catalysts (i.e. the first catalyst and the second catalyst) may be hydrogenation catalysts having hydrogenation activity and/or coking-inhibiting property, which are conventional in the art, and may be, for example, at least one selected from homogeneous hydrogenation catalysts and heterogeneous hydrogenation catalysts, wherein the homogeneous hydrogenation catalysts may be selected from at least one selected from oil-soluble catalysts and water-soluble catalysts, the raw material composition of the heterogeneous hydrogenation catalysts includes a carrier and a metal component (denoted as a first metal component) supported on the carrier, the carrier may be selected from at least one selected from coal dust and activated carbon, and the metal component may be selected from 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 practice, the first catalyst and the second catalyst may be the same or different.
In the above process, when the catalyst is a homogeneous hydrogenation catalyst, the dispersion system in the hydrogenation reactor is generally 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 with the heavy oil feedstock (or the first hydrogenation reaction product) by a method conventional in the art to form the above-mentioned heavy oil feedstock mixed with the catalyst (i.e., the first catalyst) (or to form the first hydrogenation reaction product mixed with the second catalyst), which is not particularly limited. In specific implementation, the catalyst is generally dispersed or dissolved in the heavy oil raw material (or the first hydrogenation reaction product) as uniformly as possible, for example, when a heterogeneous hydrogenation catalyst or other catalyst that is not soluble in the heavy oil raw material (or the first hydrogenation reaction product) is used, the catalyst can form a micro-element structure such as solid particles with micron scale (e.g., with the size equivalent to that of the hydrogen bubbles) and be uniformly dispersed in the heavy oil raw material (or the first hydrogenation reaction product), so that a uniformly distributed dispersion system with an oil phase as a continuous phase and highly dispersed hydrogen bubbles with micron scale and catalyst particles as discrete phases is formed in the two-stage hydrogenation reactor, and the reaction and the lightening effect are facilitated.
In general, the second hydrogenation reaction product (i.e. the light product) from the second 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, it may further include: separating the second hydrogenation reaction product, returning the separated tail oil to the second hydrogenation reactor for circular processing, and controlling the circulation ratio (the mass ratio of the tail oil to the first hydrogenation reaction product) to be 0.1-0.7, further 0.2-0.5, so as to be beneficial to the total conversion effect 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 second hydrogenation reactor may be first introduced into a gas-liquid separator or other device for gas-liquid separation to obtain a gas-phase component (mainly a mixed gas of cracked gas and hydrogen gas) 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 second hydrogenation reactor, and the products flowing out from each position may generally have different fraction distributions (equivalent to the light product being subjected to the primary fractionation treatment by the second hydrogenation reactor), and may be further refined by further gas-liquid separation, etc.
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 reactors (i.e. the first hydrogenation reactor and the second hydrogenation reactor) of the present invention may be conventional hydrogenation reactors 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., and the first hydrogenation reactor and the second hydrogenation reactor may be the same or different.
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 (up to 85 percent or even more than 90 percent or 92 percent), 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 first infinitesimal generating device; 1': a fourth infinitesimal generating device; 2: a first hydrogenation reactor; 2': a second hydrogenation reactor; 3. a gas-liquid separator; 4. a distillation column; d: a heavy oil feedstock mixed with a catalyst; e 1: a first portion of hydrogen; e 2: a second portion of hydrogen; f 1: a first hydrogenation reaction product; f 2: a second hydrogenation reaction product; g: a gasoline fraction; h: a diesel fraction; i: a wax oil fraction; j: tail oil; k: a mixture of cracked gas and hydrogen.
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 embodiment provides a method for converting heavy oil into light oil, as shown in fig. 1, feeding a first portion of hydrogen e1 and a heavy oil raw material d mixed with a first catalyst into a first infinitesimal generating device 1 for dispersion treatment, so as to obtain a first infinitesimal dispersion system in which hydrogen is dispersed in the heavy oil raw material as bubbles with an average size of not more than 500 micrometers, and feeding the first infinitesimal dispersion system into a first hydrogenation reactor 2 for a first hydrogenation reaction (the system of the first hydrogenation reaction is a first dispersion system), so as to obtain a first hydrogenation reaction product f 1; allowing the first hydrogenation reaction product f1 and a second part of hydrogen e2 to enter a fourth infinitesimal generation device 1 'for dispersion treatment to obtain a fourth infinitesimal dispersion system in which hydrogen is dispersed in the first hydrogenation reaction product by bubbles with the average size of no more than 500 micrometers, and allowing the fourth infinitesimal dispersion system to enter a second hydrogenation reactor 2' for second hydrogenation reaction (the second hydrogenation reaction system is a second dispersion system) to obtain a second hydrogenation reaction product f 2; the second hydrogenation reaction product f2 enters a gas-liquid separator 3 for gas-liquid separation to respectively obtain a gas-phase component (a mixed gas K of cracked gas and hydrogen) and a liquid-phase component; and the liquid phase component enters a distillation tower 4 for fractionation to respectively obtain a gasoline fraction g below 200 ℃, a diesel oil fraction h between 200 and 350 ℃, a wax oil fraction i between 350 and 500 ℃ and tail oil j above 500 ℃.
Specifically, in the present embodiment, the above-described infinitesimal generating device (i.e., the first infinitesimal generating device 1 and the second infinitesimal generating device 1') is a venturi-type infinitesimal generating device; the first infinitesimal dispersion system enters the first hydrogenation reactor 2 from the top of the first hydrogenation reactor, and the fourth infinitesimal dispersion system enters the second hydrogenation reactor 2' from the top of the second hydrogenation reactor; in the process, the first hydrogenation reaction product f1 is mixed with a second catalyst and then enters a fourth infinitesimal generation device 1'; and separating hydrogen from the mixed gas K, and mixing the hydrogen with fresh hydrogen for recycling.
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 first catalyst and the second catalyst are heterogeneous catalysts formed by loading iron element on activated carbon (carbon powder), and the mass fraction of the iron element in the catalysts 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, wherein the conditions of hydrogen bubble size (infinitesimal scale), operating pressure, reaction temperature, space velocity, hydrogen-oil ratio, mass ratio of the first catalyst to the heavy oil feedstock (first catalyst addition amount), mass ratio of the second catalyst to the first hydrogenation product (second catalyst addition amount), and the like of the dispersoid in the hydrogenation reactors (i.e., the first hydrogenation reactor and the second hydrogenation reactor) are shown in table 2, and the product distribution in the product of the second hydrogenation (upgrading product) is shown in table 3.
Comparative examples 1 and 2
The heavy oil raw material is subjected to a lightening treatment by using 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 (first catalyst) to the heavy oil raw material (first 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
TABLE 3 Main product distribution
| Product distribution, wt% | Test example 1 | Test example 2 | Comparative example 1 | Comparative example 2 |
| Cracked gas | 3.2 | 3.5 | 4.8 | 2.1 |
| Gasoline (gasoline) | 21.8 | 20.3 | 5.3 | 21.7 |
| Diesel oil | 43.6 | 41.6 | 17.1 | 43.2 |
| Wax oil | 23.6 | 22.8 | 35.3 | 23.4 |
| Tail oil | 7.7 | 11.2 | 33.7 | 9.2 |
| Coke | 0.1 | 0.6 | 3.8 | 0.4 |
| Total up to | 100 | 100.0 | 100.0 | 100 |
| Conversion rate | 92.30％ | 88.8％ | 66.30％ | 90.80％ |
The results show that under the conditions of lower operating pressure (13MPa) and the like, the experimental example 1 and the experimental example 2 can achieve excellent lightening effect, the conversion rate of the heavy oil raw material is up to more than 88%, and is far higher than that of the traditional suspension bed process (such as the comparative example 1); the traditional suspension bed hydrogenation process has very poor lightening effect under the conditions of lower pressure and the like, and comparison is often needed if the lightening effect is improvedExample 2 high pressure (22MPa), high hydrogen to oil ratio (2278 Nm)3/m3) The conditions further show through test example 1 and comparative example 2 that test example 1 can achieve higher conversion rate of heavy oil raw materials under the conditions such as the operating pressure far lower than that of comparative example 2, and has lower coke yield, which shows that the heavy oil lightening method of the invention can greatly reduce the conditions such as the operating pressure, and has very obvious advantages compared with the conventional hydrogenation processes such as a suspended bed, and the like; 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: carrying out a first hydrogenation reaction on a first part of hydrogen and a heavy oil raw material mixed with a catalyst in a first hydrogenation reactor to obtain a first hydrogenation reaction product; carrying out a second hydrogenation reaction on the first hydrogenation reaction product and a second part of hydrogen in a second hydrogenation reactor to obtain a second hydrogenation reaction product;
wherein, the system for realizing the first hydrogenation reaction is a first dispersion system that a first part of hydrogen is dispersed in the heavy oil raw material by bubbles with the size not more than 500 microns; the second hydrogenation system is a second dispersion system in which a second part of hydrogen is dispersed in the first hydrogenation product by bubbles with the size of not more than 500 microns.
2. A lightening process according to claim 1, wherein a first portion of hydrogen and hydrogen from said heavy oil feedstock being treated by a first infinitesimal generating device are introduced into a first hydrogenation reactor as a first infinitesimal dispersion of bubbles having a size of not more than 500 microns dispersed in said heavy oil feedstock to form said first dispersion;
or dispersing a part of the first part of hydrogen and the heavy oil raw material by a second infinitesimal generating device to form a second infinitesimal dispersion system in which hydrogen is dispersed in the heavy oil raw material in bubbles with the size of not more than 500 micrometers; passing the second infinitesimal dispersion into a first hydrogenation reactor; meanwhile, the rest part of the first part of hydrogen is processed by a third infinitesimal generator and enters a first hydrogenation reactor to form the first dispersion system together with the second infinitesimal dispersion system.
3. A lightening method according to claim 1 or 2,
enabling a second part of hydrogen and hydrogen obtained by processing the first hydrogenation reaction product through a fourth infinitesimal generation device to enter a second hydrogenation reactor in a fourth infinitesimal dispersion system in which bubbles with the size not larger than 500 micrometers are dispersed in the first hydrogenation reaction product, so as to form a second dispersion system;
or dispersing a part of the second part of hydrogen and the first hydrogenation reaction product by a fifth infinitesimal generation device to form a fifth infinitesimal dispersion system in which hydrogen is dispersed in the first hydrogenation reaction product in the form of bubbles with the size of not more than 500 micrometers; passing said fifth infinitesimal dispersion into a second hydrogenation reactor; meanwhile, the rest part of the second part of hydrogen is processed by a sixth infinitesimal generator and enters a second hydrogenation reactor to form the second dispersion system together with the fifth infinitesimal dispersion system.
4. A lightening process according to claim 2 or 3, wherein the first infinitesimal dispersion enters the first hydrogenation reactor from the top or bottom thereof; and/or the fourth infinitesimal dispersion enters the second hydrogenation reactor from the top or the bottom of the second hydrogenation reactor.
5. A method of weight reduction according to any one of claims 2 to 4, 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.
6. A lightening process according to claim 1 or 5, wherein said bubbles have a size of 10 to 500 μm.
7. A lightening process according to claim 1, wherein the conditions of said first hydrogenation reactor are: the operation pressure is 6-15MPa, the reaction temperature is 390-450 ℃, and the weight hourly space velocity is 0.5-3.0h-1The hydrogen-oil ratio is 400-1800Nm3/m3；
And/or the presence of a gas in the gas,
the conditions of the second hydrogenation reactor are as follows: the operating pressure is 6-15MPa, 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。
8. A lightening process according to claim 1 or 7, wherein the catalyst is present in an amount of 0.5 to 3.0% by mass based on the heavy oil feedstock.
9. A lightening process according to claim 1 or 8, 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%.
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 |
|---|---|---|---|
| CN202011118881.9A CN114381299A (en) | 2020-10-19 | 2020-10-19 | Heavy oil lightening method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011118881.9A CN114381299A (en) | 2020-10-19 | 2020-10-19 | Heavy oil lightening method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114381299A true CN114381299A (en) | 2022-04-22 |
Family
ID=81193619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011118881.9A Pending CN114381299A (en) | 2020-10-19 | 2020-10-19 | Heavy oil lightening method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114381299A (en) |
Citations (3)
| 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 |
| 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 CN202011118881.9A patent/CN114381299A/en active Pending
Patent Citations (3)
| 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 |
| 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 | |
| CN102041084B (en) | Heavy hydrocarbon hydrogenation combined process | |
| CN103627434B (en) | A kind of catalyst cracking method with hydrotreatment combinations produce propylene | |
| CN103265971A (en) | Heterogeneous coal tar suspension bed hydrogenation method | |
| CN102051221B (en) | Method for more producing light oil by using hydrocarbon oil | |
| CN109777500B (en) | Gas-liquid countercurrent two-stage hydrocracking method | |
| CN1119397C (en) | Hydrogenation and catalystic cracking combined process for residual oil | |
| CN107557064B (en) | Coal tar combined bed hydrogenation method and system for coal tar combined bed hydrogenation | |
| CN108659882B (en) | Heavy oil hydrogenation method and hydrogenation system thereof | |
| CN101434867A (en) | Suspension bed residual oil hydrogenation-catalytic cracking combined technological process | |
| CN1446888A (en) | Suspension bed hydrocracking technique for producing gasoline with high octane number and diesel oil with high cetane number simultaneously | |
| CN103540356B (en) | A kind of inferior heavy oil catalytic conversion process improving low-carbon alkene and diesel yield | |
| CN114381299A (en) | Heavy oil lightening method | |
| CN114381302A (en) | Heavy oil lightening method | |
| CN112745952B (en) | Method and system for processing aromatic-rich distillate oil | |
| CN101875856B (en) | Wax oil hydrogenated treatment and catalytic cracking combined method | |
| CN114381303A (en) | Heavy oil lightening method | |
| CN114381300A (en) | Heavy oil lightening method | |
| CN114437813A (en) | Heavy oil lightening method | |
| CN116328663A (en) | Slurry bed reactor, poor-quality oil slurry bed hydrocracking system and method | |
| CN114437812A (en) | Heavy oil lightening method | |
| CN114381298A (en) | Heavy oil lightening method | |
| CN1144863C (en) | Heavy hydrocarbon feeding and hydrogenating process | |
| CN102876370B (en) | Hydrocracking method of residual oil |
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 |
Application publication date: 20220422 |
|
| RJ01 | Rejection of invention patent application after publication |