CN1331992C - Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues - Google Patents
Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues Download PDFInfo
- Publication number
- CN1331992C CN1331992C CNB2003801090397A CN200380109039A CN1331992C CN 1331992 C CN1331992 C CN 1331992C CN B2003801090397 A CNB2003801090397 A CN B2003801090397A CN 200380109039 A CN200380109039 A CN 200380109039A CN 1331992 C CN1331992 C CN 1331992C
- Authority
- CN
- China
- Prior art keywords
- heavy
- materials flow
- distillation
- diasphaltene
- oil
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 109
- 230000008569 process Effects 0.000 title claims abstract description 53
- 238000004821 distillation Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 19
- 239000010779 crude oil Substances 0.000 title abstract description 4
- 239000003921 oil Substances 0.000 claims abstract description 76
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000571 coke Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 239000000295 fuel oil Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 71
- 239000007789 gas Substances 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 30
- 238000011010 flushing procedure Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 239000004615 ingredient Substances 0.000 claims description 15
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 238000007701 flash-distillation Methods 0.000 claims description 9
- 239000010426 asphalt Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000005111 flow chemistry technique Methods 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000011269 tar Substances 0.000 abstract 2
- 238000007324 demetalation reaction Methods 0.000 abstract 1
- 239000000727 fraction Substances 0.000 abstract 1
- 229910052976 metal sulfide Inorganic materials 0.000 abstract 1
- 239000002358 oil sand bitumen Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000012071 phase Substances 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000005864 Sulphur Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 241000772415 Neovison vison Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 241000212978 Amorpha <angiosperm> Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Abstract
Process for the conversion of heavy feedstocks selected from heavy crude oils, distillation residues, heavy oils coming from catalytic treatment, thermal tars, oil sand bitumens, various kinds of coals and other high-boiling feedstocks of a hydrocarbon origin known as black oils, by the combined use of the following three process units: hydroconversion with catalysts in slurry phase (HT), distilla tion or flash (D), deasphalting (SDA), comprising the follow ing steps: mixing at least part of the heavy feedstock and/or at least most of the stream containing asphaltenes obtained in the deasphalting unit with a suitable hydrogenation catalyst and sending the mixture obtained to a hydrotreatment reactor (HT) into which hydrogen or a mixture of hydrogen and H2S is charged; sending the stream containing the hydrotreatment reaction product and the catalyst in dispersed phase to one or more distillation or flash steps (D) whereby the different frac tions coming from the hydrotreatment reaction are separated; recycling at least part of the distillation residue (tar) or liquid leaving the flash unit, containing the catalyst in dispersed phase, rich in metal sulfides produced by demetallation of the feedstock and possibly coke, to the deasphalting zone (SDA) in the presence of solvents, optionally also fed with at least a fraction of the heavy feedstock, obtaining two streams, one consisting of deasphalted oil (DAO) and the other containing asphaltenes, characterized in that the stream containing the hydrotreatment reaction product and the catalyst in dispersed phase, before being sent to one or more distillation or flash steps, is subjected to a high pressure separation pre-step in order to obtain a light fraction and a heavy fraction, the heavy fraction alone being sent to said distillation step(s) (D).
Description
The present invention relates to a kind of method that heavy feed stock is transformed, heavy crude, oil sands bitumen, distillation residue and various coal are arranged in the described heavy feed stock, adopting the mixture flow that suitably connects and form with fresh feed and converted product is three main technique unit of charging: transform heavy feed stock unit, distillation unit and diasphaltene unit with disperse phase state catalyst hydrogenation, increase lightweight overhead product, petroleum naphtha and a gas oil post-processing unit in three formants
Basically can realize heavy crude, oil sands bitumen and petroleum residual oil are converted into the purpose of liquid product by two kinds of methods: a kind of method only adopts heater means, and the opposing party's rule will be passed through hydrotreating step.
Present research mainly concentrates on hydrotreatment because heat treating method by product particularly coke (with respect to raw material, the quantity that obtains is greater than 30% (weight)) dispose and there are some problems converted product aspect of poor quality.
Hydroprocessing process is in the presence of hydrogen and suitable catalyzer raw material to be handled.
Hydroconversion process in the market is with fixed-bed reactor or ebullated bed reactor and is carried on the catalyzer that the transition metal (Mo, W, Ni, Co etc.) on the silica (or equivalent material) constitutes by one or more usually.
Fixed-bed process is having sizable problem aspect the special heavy feed stock of handling high heteroatoms, metal and asphalt content, because these impurity can make rapid catalyst deactivation.
Developed and the multiple ebullated bed technology that is used to handle these raw materials of industrialization, their performance is interesting, but very complicated and expense is high.
Can be with the hydroprocessing technique of disperse phase state catalyzer operation and to solve the shortcoming of using fixed bed or ebullated bed technology to run into an attractive terms of settlement is provided.In fact, the advantage that slurry process can be big with feed flexibility combines with conversion and upgrading aspect high-performance, from the viewpoint of technology, will make them more simple in principle.
The granules of catalyst form very little with median size and that can effectively be scattered in medium that is characterized as of slurry process exists, so hydrogenation process is simpler and play a greater role in all positions of reactor.Significantly reduced the coke growing amount, the product of upgrading raw material are higher mutually.
The powder that catalyzer is can size enough little or the form of oil soluble precursor are introduced.In one situation of back,, in its reaction process or suitably, form activity of such catalysts form (being generally metallic sulfide) on the spot after the pre-treatment by compound used therefor is carried out the pyrolysated method.
The metal component of disperse phase catalyzer is generally one or more transition metal (preferred Mo, W, Ni, Co or Ru).Molybdenum and tungsten have more satisfactory performance (N.Panariti et al., Appl.Catal.A:Gen.2000,204,203) than nickel, cobalt or ruthenium even than vanadium and iron.
Though the use of disperse phase catalyzer has solved the listed most of problem of above-mentioned technology, but still there are some shortcomings relevant with the products obtained therefrom quality with the life-span of catalyst themselves.
In fact, from the viewpoint and environmental influence two aspects of economy, the working conditions of these catalyzer (type of precursor, concentration etc.) is epochmaking.
Catalyzer can use in " one way " process layout by lower concentration (hundreds of ppm), but in this case, common upgrading deficiency (November 1995,35 for A.Delbianco et al., Chemtech) to reaction product.When mode was operated, the quality that obtains product was much better with high active catalyst (for example molybdenum) and high concentration catalyst (thousands of ppm metal), but must catalyzer to be circulated.
Leave reactor catalyzer can with traditional method for example decant, centrifugation or filtration method separate with hydrotreatment products obtained therefrom (preferably the base product from reactor downstream obtains) and reclaim (US-3240718, US-4762812).The described catalyzer of a part just loops back hydrogenation process without further processing.But the catalyzer that adopts known hydroprocessing process to reclaim decreases than the activity of live catalyst usually, must have suitable regeneration step to recover catalytic activity and makes the described catalyst recirculation of at least a portion return hydrotreating reactor.And from the viewpoint of technology, these method expenses that reclaim catalyzer are high and extremely complicated.
The level of conversion height that above-mentioned all hydroconversion process can reach will depend on raw material and used technology type, but in any case, can produce some unconverted residual oil (being called tar here) under the limit of stability condition, according to circumstances different its amounts can be 15% to 85% of initial feed.This product is used for producing oil fuel, pitch or is used as the raw material of gasification.
In order to improve total level of conversion of residuum (cracking) process, the various flow processs of a large amount of tar circulation step in the cracking unit that makes have more or less been proposed to comprise.Adopting catalyzer to be scattered in the hydroconversion process of slurry phase, the circulation of tar is reclaimed catalyzer, for this reason, same applicant has described a kind of the acquisition in the high-quality product under the condition that does not produce residual oil (sludgeless oil oil refining apparatus) in IT-95A001095, make the catalyzer of recovery just be recycled to the method for hydrotreating reactor without other regeneration step.
This method may further comprise the steps:
Heavy crude or distillation residue are mixed with the hydrogenation catalyst that is fit to, and the gained mixture sent into hydrogen or hydrogen and H are housed
2The hydrotreating reactor of S mixture;
The distillation zone is sent in the materials flow that will comprise hydrotreatment reaction product and disperse phase state catalyzer, isolates volatile components (petroleum naphtha or gas oil);
Therefore the high boiling component that distilation steps obtains is sent into the diasphaltene step, produce two bursts of materials flows, one comprises deasphalted oil (DAO), and another strand comprises bituminous matter, disperse phase state catalyzer and presumable coke and be rich in metal from initial feed;
With at least 60% preferred at least 80% comprise bituminous matter, disperse phase state catalyzer and may coke be rich in the metal materials flow be recycled to the hydrotreatment district.
As described in the patent application IT-MI2001A-001438, again find thereafter, with regard to above-mentioned these methods, when the hydrocarbon mixture with heavy crude or oil sands bitumen upgrading one-tenth complexity further changes into the raw material of component oil process to be used as, can use different process layouts.
The described heavy feed stock method for transformation of patent application It-MI2001A-001438 is used in combination following three technique units: catalyzer is in hydrocracking unit (HT), distillation or flash evaporation unit (D), diasphaltene unit (SDA) of slurry phase, it is characterized in that three unit are to begin operation with the mixture flow that fresh feed and cycle stock are formed, and adopt following steps:
At least a portion heavy feed stock is sent into the diasphaltene section (SDA) that has solvent, make two bursts of materials flows, one is made of deasphalted oil (DAO), and another strand then is made of bituminous matter;
The bituminous matter materials flow is mixed with the remainder heavy feed stock of not sending into the diasphaltene district and suitable hydrogenation catalyst, and the gained mixture delivered to be filled with hydrogen or hydrogen and H
2The hydrotreating reactor of S mixture (HT);
One or more distillation or flash distillation step (D) are sent in the materials flow that will contain hydrotreatment reaction product and disperse phase state catalyzer, thereby isolate volatile components, and the gas, petroleum naphtha and the gas oil that generate in the hydrotreatment reaction are wherein arranged;
With leave flash evaporation unit comprise rich metallic sulfide that disperse phase state catalyzer, raw material demetalization step generated and may coke and the 60wt% at least of the distillation residue (tar) of various carbonaceous residues or liquid preferably at least 80wt% more preferably at least 95wt% be recycled to the diasphaltene district.
Usually need wash the bituminous matter materials flow of leaving diasphaltene section (SDA), in hydrotreating reactor, can not accumulate too much, and under the situation of catalyst deactivation, shift out a part of catalyzer and substitute with live catalyst so that guarantee these elements.But when catalyzer can keep it active for a long time, normally do not need to do like this, but must will wash for above-mentioned reasons the time, though obviously some catalyzer far away complete deactivation also must abandon.In addition, though compare with other hydroprocessing techniques, the quantity (with respect to the 0.5-4% of raw material) of flushing materials flow is extremely limited, and they still exist sizable utilization or handling problems.
When the heavy component of the complicated hydrocarbon mixture that this process must be produced (distillation Tata at the bottom of) when carrying out the catalytic cracking unit raw material of hydrocracking (HC) and fluid catalystic cracking (FCC) simultaneously, described application particularly suitable.
Catalytic hydrogenation unit (HT) and being used in combination of extraction process (SDA) can make the diasphaltene well cuts produced (metal, sulphur, nitrogen, contain the carbonaceous residue) content low, thereby can handle in catalytic cracking process easilier.
But what will consider is that the petroleum naphtha of hydrotreatment unit direct production and gas oil still contain many impurity (sulphur, nitrogen ...), under any circumstance all must handle, so that make the finished product again on the other hand.
Have now found that, can be by inserting an additional C
2-500 ℃, preferred C
5-350 ℃ of component second aftertreatment hydrogenation sections come patent application IT-MI2001A-001438 and the described two kinds of methods of patent application IT-95A001095 (all introducing present patent application as a reference) are further improved.
The second aftertreatment hydrogenation section is to the C from still-process upstream high-pressure separator
2-500 ℃ of components, preferred C
5-350 ℃ of components are carried out further hydrotreatment.
Target of the present invention is to be selected from the method that heavy crude, distillation residue, the heavy oil from the catalytic treatment process, thermal tar, oil sands bitumen, various coal and some other heavy feed stock that is derived from the hydro carbons high boiling point raw material that is called dirty oil transform, present method has been used in combination following three technique units: adopt hydrocracking (HT) unit, distillation (D) unit, diasphaltene (SDA) unit of slurry phase state catalyzer, may further comprise the steps:
● at least a portion heavy feed stock and/or most of at least asphaltenes materials flow that obtains in the diasphaltene unit are mixed with suitable hydrogenation catalyst, and the mixture that obtains delivered to charge into hydrogen or hydrogen and H
2The hydrotreating reactor of S mixture (HT);
● one or more distillation or flash distillation step (D) are sent in the materials flow that will contain hydrotreatment reaction product and disperse phase state catalyzer, thereby will separate from the different components of hydrotreatment reaction;
● contain disperse phase state catalyzer with what at least a portion was left flash evaporation unit, the distillation residue (tar) of rich metallic sulfide that raw material demetalization process generates and possibility coke or liquid circulation are to the diasphaltene district (SDA) that has solvent, optional also have at least a portion heavy feed stock as charging, obtain two bursts of materials flows, another strand is made of bituminous matter by deasphalted oil (DAO) formation for one, described method is characterised in that: the materials flow that contains hydrotreatment reaction product and disperse phase state catalyzer wanted advanced horizontal high voltage to separate pre-treatment step before being sent to one or more distillation or flash distillation step, obtain light component and heavy component, separately heavy component is delivered to described distilation steps (D).
The light component that the high pressure separating step obtains can be delivered to the hydrotreatment section, generates to contain C
1-C
4Gas and H
2S than light constituent and contain the heavy component of the petroleum naphtha and the gas oil of hydrotreatment.
Insert a C
2-500 ℃ of components, preferred C
5The method of-350 ℃ of component second aftertreatment hydrogenation sections has been developed the possibility that this component is utilized with the hydrogen near the hydrotreating reactor elevated pressures, can obtain following benefit:
It can be met the fuel of the harshest sulphur content specification requirement (＜10-50ppm sulphur) by the oils raw material production capacity in next life that is rich in sulfur-bearing, and is improving to some extent aspect other characteristics of diesel engine gas oil such as density, polycyclic aromatic hydrocarbon content and the cetane value;
There is not stability problem in the distillate of producing.
The reaction output object of hydrotreating reactor (HT) is carried out pre-separation in that to carry out hydrofinishing process on the fixed bed be the separator operated under by one or more high pressure and high temperature.The heavy that takes out from the bottom is partly delivered to main distillation unit, and the part that take out at the top is C
2-500 ℃ of components, preferred C
5-350 ℃ of components are delivered to second treatment zone that has high pressure hydrogen, wherein reactor is fixed-bed reactor, typical desulfurization/dearomatization catalyst is housed, so that obtain the product of low sulfur content very and low nitrogen content, low overall consistency, concerning the gas oil fraction of being paid close attention to, its cetane value increases simultaneously.
The hydrotreatment section is made up of one or more tandem reactor usually; Available then distillation method makes the petroleum naphtha and the diesel engine gas oil that meets fuel specification of complete desulfurization with the further fractionation of this system's product.
Described fixed bed hydrogenation desulfurized step uses typical gas oil hydrogenating desulfurization fixed bed catalyst usually, this catalyzer or also may be catalyst mixture or be assembled with various different properties catalyzer reactor by significantly reducing the hydrogenation degree of sulphur and nitrogen content, raising raw material, thereby reduce the density of gas oil fraction and improve cetane value, the method that reduces the generation of coke simultaneously makes light component obtain making with extra care considerably.
Catalyzer contains the pars amorpha based on aluminum oxide, silicon oxide, silica-alumina and various inorganic oxide mixtures usually, and the hydrogenating desulfurization component deposits on it with hydrogenation reagent and (ins all sorts of ways).The nickel and/or cobalt on being deposited on the amorphous material carrier, be the used typical catalyst of this generic operation based on the catalyzer of molybdenum or tungsten.
Hydrogenation aftertreatment reaction is to carry out under absolute pressure is lower than the pressure of first hydrotreating step slightly, is generally 7-14MPa, preferred 9-12MPa; The hydrogenating desulfurization temperature is 250-500 ℃, preferred 280-420 ℃; Temperature depends on required desulfurization level usually.In the time will controlling the products obtained therefrom quality, air speed is another important parameter: it can be 0.1-5 hour
-1, preferred 0.2-2 hour
-1
Mix with raw material send into materials flow amounts of hydrogen at 100-5000Nm
3/ m
3, preferred 300-1000Nm
3/ m
3Between.
Except the second aftertreatment hydrogenation section, also can choose wantonly has flushing materials flow second an aftertreatment section in addition.
The described second hydrogenation section is that aftertreatment is carried out in the flushing materials flow, so that significantly reduce its quantity, makes the still activated catalyst recirculation of at least a portion return hydrotreating reactor.
In the case, product is separated into solid ingredient and liquid ingredient, from liquid ingredient, shifts out described solvent subsequently being called the processing section that suitable solvent is delivered in the asphaltenes materials flow of washing materials flow from diasphaltene section (SDA).
Optional flushing effluent (preferably accounting for the 0.5-10% (volume) of fresh feed) processing section is made up of solvent (toluene or gas oil or other are rich in the aromatic component materials flow) de-oiling step and liquid ingredient and solid ingredient separating step.
The described liquid ingredient of at least a portion can be sent into:
" fuel oil sump ", former state is sent into or is isolated behind the solvent and/or after adding suitable diluent and sends into;
And/or former state is sent into hydrotreating reactor (HT).
Under some particular cases, solvent can be identical with diluted liquid.
But solid ingredient treated as such, or more favourable way is it to be sent to transition metal or transition-metal catalyst institute containing metal (for example molybdenum) are carried out the selective recovery processing (with respect to other metals that exist in the raw material residual oil, nickel and vanadium) and the optional materials flow that will be rich in transition metal (molybdenum) loop back hydrotreating reactor (HT).
Compare with traditional method, this comprehensive treatment method has following advantage:
The quantity of flushing component significantly reduces;
Most of flushing component can become oil fuel by the method upgrading of isolating metal and coke;
Owing to have at least a part to be recycled from the selective recovery treatment step molybdenum that comes together, thus in the first hydrotreating step raw material with the quantity minimizing of live catalyst.
The de-oiling step is that the flushing materials flow is handled, its representative is minimized from the bituminous matter component of the heavy feed stock first hydrotreater diasphaltene section (SDA), and solvent for use is wanted to bring the organic compound of maximum possible into liquid phase and with metallic sulfide, coke with contain carbonaceous residue (be insoluble to toluene or similarly product) than infusible and stay solid phase.
The component of considering metalline might spontaneous combustion under drying conditions very, and therefore reasonably way is to operate in the inert atmosphere that contains the least possible oxygen and moisture.
In this de-oiling step, preferably use all kinds of SOLVENTS; Wherein can mention be in the gas oil that for example produced of hydrocarbon raw material that aromatic solvent for example obtains in toluene and/or dimethylbenzene concoction, the device or the refinery available hydrocarbon raw material for example from the unitary light cycle of FCC or from the unitary hot gas oil of visbreaking/thermally splitting.
Can promote operating rate by improving temperature and reaction times within the specific limits, but because economic cause, it is unsuitable that over-drastic improves.
Service temperature depends on the pressure condition of solvent for use and employing; But the temperature range of recommendation is 80-150 ℃; Reaction times can be 0.1-12 hour, did not wait in preferred 0.5-4 hour.
The volume ratio of solvent/flushing materials flow also is the important parameter that will consider, can be at 1-10 (volume/volume), preferred 1-5, more preferably change between 1.5-3.5.
In case the blended stage finishes between solvent and flushing materials flow, just this output object sent into liquid phase and solid phase segregation section keeping under the agitation condition.
This step working method can be one of industrial practice working method commonly used, for example decant, centrifugation or filtration method.
Then liquid phase is delivered to solvent stripping and recovery zone, solvent cycle is backwashed and is washed materials flow first treatment step (de-oiling).It is preferably that remaining heavy component is used for refinery because in fact this materials flow containing metal and sulphur content are not lower.If for example handle operation with gas oil, then a part of described gas oil can be stayed in the heavy product, makes it meet the specification requirement of fuel oil sump.
Perhaps liquid phase is recycled to hydrogenator.
Solid part can in statu quo be disposed, or handles selective recovery will loop back the catalyzer (molybdenum) of hydrotreating reactor in addition.
In fact, found by with metal-free heavy feed stock such as a part from the unitary deasphalted oil of the own diasphaltene of device (DAO) add above-mentioned solid mutually in and described system mixed with acidified water (carrying out acidifying with mineral acid usually), nearly all molybdenum is remained in the organic phase, and other metal of most of amount move into water.Two-phase can be easy to separate, and preferably organic phase is recycled to hydrotreating reactor thereafter.
Solid is scattered in the capacity organic phase mutually the deasphalted oil of same process (for example from), to wherein adding acidified water.
The ratio of water and organic phase can be 0.3-3 and does not wait; The pH value of water can be 0.5-4, preferred 1-3 does not wait.
Can handle all kinds of heavy feed stocks: they are optional to be derived from the hydro carbons high boiling point raw material that this specialty often is called dirty oil from heavy crude oil, oil sands bitumen, all kinds of coal, distillation residue, bottom product, thermal tar (for example from visbreaking or similar heat treatment process) from the heavy cycle oil of for example catalytic cracking treating processes of mink cell focus of catalytic treatment process, hydrocracking treating processes and other.
With regard to processing condition commonly used, can be with reference to defined terms in patent application IT-MI2001A-001438 and IT-95A001095.
IT-95A001095 is described according to patent application, all heavy feed stocks can be mixed with the hydrogenation catalyst that is fit to, send into hydrotreating reactor (HT) then, but will be with at least 60%, preferred at least 80% asphaltenes and also contain disperse phase state catalyzer and may coke and the materials flow of being rich in from the initial feed metal be recycled to the hydrotreatment district.
IT-MI2001A-001438 is described according to patent application, with a part of heavy feed stock and most of at least asphaltenes and also contain disperse phase state catalyzer and materials flow that may coke mixes with suitable hydrogenation catalyst, and send into hydrotreating reactor, and the heavy feed stock of remainder is sent into the diasphaltene section.
Described in patent application IT-MI2001A-001438, the materials flow (being made of described bituminous matter substantially) of most of at least asphaltenes is mixed with the hydrogenation catalyst that is fit to, and send into hydrotreating reactor, and all heavy feed stocks are sent into the diasphaltene section.
When diasphaltene section (SDA) is returned in the distillation residue (tar) that only a part is left flash evaporation unit or liquid circulation, with the described distillation of at least a portion residual content or flash distillation residual oil is optional send into hydrotreating reactor from the asphaltenes materials flow of diasphaltene section (SDA) with at least a portion.
Used catalyzer is selected from the precursor (metal derivative of metal ring alkyl salt, phosphoric acid, metal carbonyl etc.) that can decompose on the spot or is selected from based on one or more transition metal premolding compound of Ni, Co, Ru, W and Mo for example, because of latter's catalytic activity height, so be preferred.
In metal or the many metal concentrations that exists in the hydroconversion reactions device, the catalyst concn scope is 300-20000ppm, preferred 1000-10000ppm.
Hydrotreating step preferably 370-480 ℃, more preferably 380-440 ℃ and 3-30MPa, more preferably carry out under the 10-20MPa.
Hydrogen is sent into reactor, can be downwards and upwards flow two kinds of modes and preferred above stream mode operation.Described gas can be sent into the different sections of reactor.
Distilation steps is preferably at 0.0001-0.5MPa, more preferably carry out under the reduced pressure of 0.001-0.3MPa scope.
Hydrotreating step can be made up of one or more reactor of operating in the afore mentioned rules condition and range.The part distillate of producing in first reactor can be recycled to the reactor of back.
By hydro carbons or non-hydrocarbons (C for example
3-C
6Alkane or isoparaffin) the solvent extraction diasphaltene step of carrying out normally carries out under 40-200 ℃ of range temperature and 0.1-7MPa scope pressure.Also can be made of one or more section with identical or different solvent operation, solvent recovery step can divide a step or multistep to carry out under subcritical or super critical condition, makes deasphalted oil (DAO) and residual oil can further carry out fractionation like this.
The materials flow that contains deasphalted oil (DAO) can be chosen wantonly and mix with distillate with former state as synthetic crude, or as the raw material of fluid catalystic cracking or hydrocracked, treated process.
Preferably the characteristic of based on crude (metal content, sulphur and nitrogen content, contain the carbonaceous residue) is adjusted by with heavy oil residue or send into the diasphaltene unit or send into the hydrotreatment unit or send into the feeding manner that two unit change whole process simultaneously:
Send into the heavy oil residue (fresh feed) of hydrotreatment section and will send to ratio between the deasphalting heavy oil residue, described ratio is preferably 0.01-100, more preferably 0.1-10 even more preferably 1-5;
Send into the fresh feed of diasphaltene section and the recycle ratio between tar, described ratio is preferably at 0.01-100, more preferably change between 0.1-10;
Send into the fresh feed and the bitum recycle ratio of hydrotreatment section, described ratio can according to above-mentioned these than change change;
Send into the tar and the bitum recycle ratio of hydrotreatment section, described ratio can change according to the change of aforementioned ratio.
This handiness is particularly useful to full-scale development diasphaltene unit (reduce and disperse nitrogen and remove aromatic hydrocarbons) and the complementary characteristic of hydrogenation unit (the high decreasing ratio of metal and sulphur).
The stability of the type of based on crude, the materials flow of studying and the quality of products obtained therefrom (also relevant with the concrete treatment step in downstream), fresh feed is sent into the mark of diasphaltene section and hydrotreatment section and can be adjusted by best mode.
When the complicated hydrocarbon mixture heavy component (base product product) of process institute output is raw material as the catalytic cracking unit of carrying out hydrocracking (HC) and fluid catalytic cracking (FCC) simultaneously, described application particularly suitable.
The keying action of catalytic hydrogenation unit (HT) and extraction process (SDA) can make the deasphalted oil of being produced have low impurity (metal, sulphur, nitrogen, contain the carbonaceous residue) content, thereby easilier handles in catalytic cracking process.
Hereinafter provide an embodiment preferred of the present invention, but never should think restriction the scope of the invention itself by accompanying drawing 1.
Heavy feed stock (1) or its at least a portion (1a) are sent into diasphaltene unit (SDA), operate by the solvent extraction means.
Make two bursts of materials flows from diasphaltene unit (SDA): one is the materials flow (2) that contains deasphalted oil (DAO), and another is the materials flow (3) of asphaltenes.
Will except that the asphaltenes materials flow of flushing materials flow (4) with remedy with flushing materials flow (4) loss aequum add live catalyst (5), do not send into the diasphaltene section a part of heavy feed stock (1b), do not send into a part of tar (24) of diasphaltene section (SDA) and choose wantonly from the materials flow (15) of washing thing processing section (further specifying hereinafter) and mix, formation materials flow (6) is delivered to and is charged into hydrogen (or hydrogen and H
2The S mixture) hydrotreating reactor of (7) (HT).Reactor is left in the materials flow (8) that contains hydrogenation products and disperse phase state catalyzer, carries out fractionation earlier in the separator (HP Sep) of one or more high top pressure operation.Cat head component (9) is sent into fixed bed hydrogenation treatment reactor (HDTC
5-350), generation contains C
1-C
4Gas and H
2The light component of S (10) and contain hydrotreated naphtha and the C of gas oil
5-350 ℃ of components (11).Heavy component (12) leaves the high-pressure separator bottom, and carries out fractionation in separation column (D), isolates vacuum gas oil (13) from the distillation residue that contains dispersion state catalyzer and coke.This materials flow is called tar (14), and major part (25) it is whole or except that said components (24) is recycled to diasphaltene reactor (SDA).
Flushing materials flow (4) can be sent into hydrotreatment section (de-oiling) with solvent (16), form the mixture (17) of liquid containing component and solid ingredient.Described mixture is sent into solids treatment section (solids constituent from), therefrom isolate solid effluent (18) and liquid efflunent (19), the latter is delivered to solvent recuperation section (solvent recuperation).Send recovered solvent (16) back to the de-oiling section, and heavy effluent (20) in statu quo or after adding possible diluted liquid (21) is delivered to oil fuel fractionation process (22).
Solid ingredient (18) but former state dispose, or as hereinafter with described in the embodiment, choose wantonly and it is delivered to other treatment zone (filter cake processing), the component that is rich in molybdenum (15) that obtains to send to the component (23) that does not contain molybdenum substantially of disposal and will loop back hydrotreating reactor.
For the present invention is described better, some embodiment hereinafter are provided, but never should be with them as limitation of the scope of the invention.
Embodiment 1
Carry out following experiment by schema shown in Figure 1.
The diasphaltene step
Raw material: 300 grams are from the vacuum residuum (table 1) of Ural crude oil
Diasphaltene reagent: 2000 milliliters of liquid propane (re-extract three times)
Temperature: 80 ℃
Pressure: 35 crust
Show 1:500 ℃
+The characteristic of Ural vacuum residuum
| API severe | 10.8 |
| Sulphur (% (weight)) | 2.6 |
| Nitrogen (% (weight)) | 0.7 |
| Conradson carbon residue (% (weight)) | 18.9 |
| Ni+V(ppm) | 80+262 |
Hydrotreating step
Reactor: 3000 milliliters, steel, suitable shape also is equipped with magnetic stirrer
Catalyzer: 3000ppm raw material that Mo/ adds, use molybdenum naphthenate as precursor
Temperature: 410 ℃
Pressure: 16MPa hydrogen pressure
The residence time: 4 hours
The flash distillation step
Implement (T=120 ℃) with a liquid evaporation laboratory equipment
Experimental result
Circulate fully by making experiment for the first time be added catalyzer, carry out 10 continuous diasphaltene experiments, each is tested and all uses by Ural residual oil (fresh feed) with by the C of preceding step
3The raw material that the long residuum that bituminous matter hydrotreatment reaction obtains is formed.For each step, be with a certain amount of by Ural vacuum residuum (fresh feed) and diasphaltene unit gained C
3The raw material that bituminous matter is formed is sent into autoclave, so that the total mass of institute's charging feed (fresh feed+round-robin C
3Bituminous matter) reaches 300 initial values that restrain.
Under these operational conditions, the ratio between fresh feed amount and the circulation products amount is 1: 1.
Hereinafter provide last circulation back and discharge the related data (with respect to the % (weight) of raw material) of materials flow.
Gas: 7%
Petroleum naphtha (C
5-170 ℃): 8%
Atmospheric gas oil (AGO, 170-350 ℃): 17%
Deasphalted oil (VGO+DAO): 68%
The bituminous matter materials flow of reclaiming when experiment finishes contains metal Ni and the sulfide of V and the coke that resid feed total amount about 1% (weight) in relative Ural is measured that generates in whole catalyzer of sending at first, 10 the hydrotreatment reaction process.In described embodiment, do not need to carry out the rinse step of recycle stream.Table 2 is listed the characteristic of products therefrom.
Table 2: the experiment reaction product characteristic of pressing embodiment 1
| Sulphur (% (weight)) | Nitrogen (% (weight)) | Proportion (grams per milliliter) | RCC (% (weight)) | Ni+V (ppm) | |
| Petroleum naphtha C 5-170℃ | 0.06 | 450 | 0.768 | - | - |
| AGO 170-350℃ | 0.52 | 2100 | 0.870 | - | - |
| VGO+DAO | 1.45 | 2500 | 0.938 | 3 | 1 |
Embodiment 2
According to flow process shown in Figure 1, the product that leaves the high-pressure separator top is sent into fixed-bed reactor, with the reagent materials flow charging that flows downward.Reactor is equipped with a kind of typical commercially available Hydrobon catalyst based on molybdenum and nickel.
Operational condition is as follows:
LHSV:0.5 hour
-1
Hydrogen pressure: 10MPa
Temperature of reactor: 390 ℃
Table 3 illustrates the quality of fixed-bed reactor charging and makes the quality of product.
Show 3:500 ℃
+Ural residual oil is handled the C that obtains
5The hydrotreatment of-350 ℃ of components
| Raw material | Product | |
| Proportion (grams per milliliter) | 0.8669 | 0.8294 |
| Mononuclear aromatics (% (weight)) | 30.1 | 19.5 |
| Double ring arene (% (weight)) | 8.3 | 1.2 |
| Thrcylic aromatic hydrocarbon (% (weight)) | 2.8 | 0.4 |
| Polycyclic aromatic hydrocarbons (% (weight)) | 11.1 | 1.6 |
| Sulphur (ppm) | 5300 | 37 |
| Nitrogen (ppm) | 2280 | 3 |
| Distillation curve | ||
| T 10(℃) | 187 | 145 |
| T 50(℃) | 271 | 244 |
| T 90(℃) | 365 | 335 |
Embodiment 3
Restrain from 500 ℃ in Ural residual oil 20.7
+The flushing materials flow of conversion system (composition that table 4 is listed) was handled 3 hours down at 100 ℃ with 104 gram toluene (weight ratio of solvent/flushing materials flow is 5).The component that obtains is filtered.Collect 3.10 gram solids (composition that table 5 is listed) and 17.60 and restrain mink cell focuses (evaporation remove toluene after), listed in its metal content such as the table 6.
Table 4: handle 500 ℃ from Ural residual oil
+The characteristic of flushing materials flow
| Proportion (grams per milliliter) | 1.1 |
| S (% (weight)) | 2.4 |
| Mo (% (weight)) | 0.68 |
| Ni (% (weight)) | 0.12 |
| V (% (weight)) | 0.36 |
| Fe (% (weight)) | 0.07 |
Table 5: 500 ℃ in the O for toluene Ural residual oil of using by oneself
+Solid (filter cake) characteristic of flushing materials flow
| C (% (weight)) | 82.0 |
| H (% (weight)) | 3.9 |
| S (% (weight)) | 4.8 |
| Mo (% (weight)) | 4.1 |
| Ni (% (weight)) | 0.6 |
| V (% (weight)) | 2.2 |
| Fe (% (weight)) | 0.4 |
Table 6: to from 500 ℃ in Ural residual oil
+The flushing materials flow for the treatment of processes handle come together and metal content in the heavy oil
| Mo(ppm) | 10 |
| Ni(ppm) | 26 |
| V(ppm) | 23 |
| Fe(ppm) | 10 |
Embodiment 4
Adopt embodiment 3 described same steps as, 10.6 gram flushing materials flows (the listed composition of table 4) are handled with 62 milliliter gas oils (in the Ural residual hydrocracking experimentation that is undertaken by top embodiment 1 described step output and the listed quality of table 2 is arranged), the ratio of gas oil/flushing materials flow is 5, and is to carry out operation in 6 hours under 130 ℃.The component of output is carried out centrifugation (5000 rev/mins).Collect 1.78 gram solids (the listed composition of table 7) and 8.82 and restrain mink cell focuses (evaporation remove gas oil after).
Table 7: handle 500 ℃ of Urals with gas oil
+The flushing resulting solid of materials flow (filter cake) characteristic
| Mo (% (weight)) | 3.43 |
| Ni (% (weight)) | 0.53 |
| V (% (weight)) | 1.75 |
Embodiment 5
1.0 gram solid residues (obtain from embodiment 3 described treating processess, form and list in table 5) are handled with the mixture of the deasphalted oil (DAO) of 50 milliliters of acidified waters (pH=2) and 50 milliliters of listed compositions of table 8.
70 ℃ after following 24 hours, decant goes out liquid phase, and the metal in the two-phase is analyzed.
All the molybdenum of amount (＞99%) is stayed organic phase, and finds nickel and vanadium at aqueous phase, and its quantity corresponds respectively to percentage extraction 23.5% and 24.4%.
The organic phase that will contain molybdenum is then sent to the hydrotreatment experiment with fresh Ural residual oil, is undertaken by the step that embodiment 1 describes, and molybdenum keeps its catalytic activity character.
Table 8: from 500 ℃ of Urals
+The DAO characteristic of residual oil treating processes
| Sulphur (% (weight)) | Nitrogen (ppm) | Proportion (grams per milliliter) | RCC (% (weight)) | Ni+V (ppm) | |
| DAO | 1.02 | 2100 | 0.934 | 3 | ＜1 |
Embodiment 6
Adopt the same steps as of describing with embodiment 5, but be to use gas oil (referring to embodiment 1) (replacing DAO) and the acidified water (pH=2) that produces in the Ural residual hydrocracking process.
All the molybdenum of amount is stayed in the organic phase, and finds nickel and vanadium at aqueous phase, and it is 41.0% and 26.8% that its quantity corresponds respectively to percentage extraction.
Claims (36)
1. an energy will be selected from the method that heavy crude, distillation residue, the heavy oil from the catalytic treatment process, thermal tar, oil sands bitumen, various coal and some other heavy feed stock that is derived from the hydro carbons high boiling point raw material that is called dirty oil transform, described method is used in combination following three technique units: adopt hydrocracking unit, distillation or flash evaporation unit, the diasphaltene unit of slurry phase state catalyzer, may further comprise the steps:
● the materials flow of at least a portion heavy feed stock and/or most of at least asphaltenes that obtains in the diasphaltene unit is mixed with suitable hydrogenation catalyst, and the mixture that obtains delivered to charge into hydrogen or hydrogen and H
2The hydrotreating reactor of S mixture;
● one or more distillation or flash distillation step are sent in the materials flow that will contain hydrotreatment reaction product and disperse phase state catalyzer, thereby will separate from the different components of hydrotreatment reaction;
● contain rich metallic sulfide that disperse phase state catalyzer, raw material demetalization process generate and distillation residue that may coke or liquid circulation to the diasphaltene district that has solvent with what at least a portion was left flash evaporation unit, optional also have at least a portion heavy feed stock as charging, obtain two bursts of materials flows, one is made of deasphalted oil and another strand is made of bituminous matter;
Be characterised in that: the materials flow that contains hydrotreatment reaction product and disperse phase state catalyzer wanted advanced horizontal high voltage to separate pre-treatment step before being sent to one or more distillation or flash distillation step, obtain light component and heavy component, separately heavy component is delivered to described distilation steps.
2. contain C by the process of claim 1 wherein that the light component that the high pressure separating step is obtained sends into the second hydrogenation aftertreatment section, generating
1-C
4Gas and H
2S than light constituent and contain hydrotreated naphtha and the heavy component of gas oil.
3. by the method for claim 2, wherein hydrogenation aftertreatment reaction is what to carry out under the pressure of 7-14MPa scope.
4. by at least one method among the claim 1-3, wherein all heavy feed stocks to be mixed with the hydrogenation catalyst that is fit to, and send into hydrotreating reactor, and asphaltenes that will at least 60% and also contain disperse phase state catalyzer and may coke and the materials flow of being rich in from the initial feed metal be recycled to the hydrotreatment district.
5. by the method for claim 4, wherein general at least 80% asphaltenes materials flow is recycled to the hydrotreatment district.
6. press the method for claim 1, wherein with a part of heavy feed stock and most of at least asphaltenes and also contain disperse phase state catalyzer and materials flow that may coke mixes with suitable hydrogenation catalyst, and send into hydrotreating reactor, and the heavy feed stock of remainder is sent into the diasphaltene section.
7. by the process of claim 1 wherein, constitute by described bituminous matter substantially, mix with the hydrogenation catalyst that is fit to, and send into hydrotreating reactor, and all heavy feed stocks are sent into the diasphaltene section most at least asphaltenes materials flow.
8. by the process of claim 1 wherein that distillation residue or liquid circulation that a part is left flash evaporation unit go back to the diasphaltene district and the described distillation or the flash distillation residual oil of at least a portion residual content are sent into hydrotreating reactor.
9. by the method for claim 8, wherein at least a portion distillation or flash distillation residual oil are sent into hydrotreating reactor with at least a portion from the asphaltenes materials flow of diasphaltene section.
10. by the process of claim 1 wherein that the distillation residue with at least 80 weight % is recycled to the diasphaltene district.
11. by the method for claim 10, wherein the distillation residue with at least 95 weight % is recycled to the diasphaltene district.
12. by the process of claim 1 wherein that the residual content distillation residue that at least a portion is not recycled to the diasphaltene district is recycled to the hydrotreatment section.
13. by the process of claim 1 wherein that distilation steps carries out under the reduced pressure of 0.0001-0.5MPa scope.
14. by the method for claim 13, wherein distilation steps carries out under the reduced pressure of 0.001-0.3MPa scope.
15. by the process of claim 1 wherein that hydrotreating step carries out under 370-480 ℃ of range temperature and 3-30MPa pressure.
16. by the method for claim 15, wherein hydrotreating step carries out under the pressure of the temperature of 380-440 ℃ of scope and 10-20MPa scope.
17. by the process of claim 1 wherein that the diasphaltene step carries out under the pressure of the temperature of 40-200 ℃ of scope and 0.1-7MPa.
18. by the process of claim 1 wherein that deasphalting solvent is C
3-C
7Light paraffins.
19. by the process of claim 1 wherein the diasphaltene step under subcritical or super critical condition, divide one or multistep carry out.
20. by the process of claim 1 wherein that the materials flow that deasphalted oil constitutes carries out fractionation with traditional distillation method.
21. by the process of claim 1 wherein that the materials flow that deasphalted oil is constituted mixes with separated products after the distilation steps condensation.
22. by the process of claim 1 wherein that but hydrogenation catalyst is decomposition of precursors or the premolding compound based on one or more transition metal.
23. by the method for claim 22, wherein transition metal is a molybdenum.
24. by the process of claim 1 wherein that the concentration of catalyzer in the hydroconversion reactions device is 300-20000ppm by the metal concentration that exists.
25. by the method for claim 24, wherein the concentration of catalyzer in the hydroconversion reactions device is 1000-10000ppm.
26. method by claim 1, wherein the part that is called the asphaltenes materials flow of washing materials flow from the diasphaltene section to be sent into the treatment zone of suitable solvent, so that product is separated into solid ingredient and liquid ingredient, from liquid ingredient, shift out described solvent subsequently.
27., wherein wash materials flow R amount and be the 0.5-10 volume % of fresh feed by the method for claim 26.
28. by the method for claim 26, wherein from the liquid ingredient of flushing treatment zone in statu quo or isolate solvent and/or add and be fit to dilution and send into later in the oil fuel component with liquid with at least a portion.
29., wherein at least a portion is recycled to hydrotreating reactor from the liquid ingredient that washes treatment zone by the method for claim 28.
30. by the method for claim 26, wherein the solvent that uses in flushing materials flow processing section is aromatic solvent or that produce or that refinery provides the certainly gas oil mixture of present method.
31. by the method for claim 30, wherein aromatic solvent is toluene and/or xylene mixture.
32. by the method for claim 26, wherein the volume ratio of solvent/flushing materials flow is 1-10.
33. by the method for claim 32, wherein the volume ratio of solvent/flushing materials flow is 1-5.
34. by the method for claim 33, wherein the volume ratio of solvent/flushing materials flow is 1.5-3.5.
35. by the method for claim 26 and 22, the solid ingredient that wherein will handle product is delivered to the treating processes of the contained transition metal of further selective recovery hydrogenation catalyst.
36., wherein the transition metal that reclaims is recycled to hydrotreating reactor by the method for claim 35.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2002A002713 | 2002-12-20 | ||
| ITMI20022713 ITMI20022713A1 (en) | 2002-12-20 | 2002-12-20 | PROCEDURE FOR THE CONVERSION OF HEAVY CHARGES SUCH AS |
| ITMI2003A000692 | 2003-04-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1738890A CN1738890A (en) | 2006-02-22 |
| CN1331992C true CN1331992C (en) | 2007-08-15 |
Family
ID=35927894
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801090397A Expired - Lifetime CN1331992C (en) | 2002-12-20 | 2003-12-12 | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
| CNB2003801069625A Expired - Lifetime CN100497548C (en) | 2002-12-20 | 2003-12-12 | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801069625A Expired - Lifetime CN100497548C (en) | 2002-12-20 | 2003-12-12 | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN1331992C (en) |
| IT (1) | ITMI20022713A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216432A (en) * | 2008-11-15 | 2011-10-12 | 环球油品公司 | Integrated solvent deasphalting and slurry hydrocracking process |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100122932A1 (en) * | 2008-11-15 | 2010-05-20 | Haizmann Robert S | Integrated Slurry Hydrocracking and Coking Process |
| US9481835B2 (en) | 2010-03-02 | 2016-11-01 | Meg Energy Corp. | Optimal asphaltene conversion and removal for heavy hydrocarbons |
| CN102989495B (en) * | 2011-09-14 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation modifying catalyst and preparation method thereof and heavy oil hydrogenation modifying method |
| CN102989486B (en) * | 2011-09-14 | 2015-10-28 | 中国石油化工股份有限公司 | Heavy-oil hydrogenation modifying catalyst and preparation method thereof and heavy oil hydrogenation modifying method |
| CN103059915B (en) * | 2011-10-21 | 2015-04-29 | 中国石油化工股份有限公司 | Poor-quality heavy oil hydro-upgrading method |
| BR112014017582A8 (en) * | 2012-01-17 | 2017-07-04 | Meg Energy Corp | conversion of high yield and low complexity heavy hydrocarbons |
| US9200211B2 (en) | 2012-01-17 | 2015-12-01 | Meg Energy Corp. | Low complexity, high yield conversion of heavy hydrocarbons |
| CN103789036B (en) * | 2012-10-26 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of inferior heavy oil combinational processing method |
| CN103789027B (en) * | 2012-10-26 | 2015-04-29 | 中国石油化工股份有限公司 | Modifying method for heavy oil hydrogenating |
| AU2014221152A1 (en) | 2013-02-25 | 2015-09-17 | Meg Energy Corp. | Improved separation of solid asphaltenes from heavy liquid hydrocarbons using novel apparatus and process ("IAS") |
| ITMI20131137A1 (en) | 2013-07-05 | 2015-01-06 | Eni Spa | PROCEDURE FOR REFINING THE CRUDE |
| CN114774162B (en) * | 2016-10-18 | 2024-03-19 | 马威特尔有限责任公司 | Method for converting hydrocarbon feed, integrated process, fuel and use thereof |
| CN110114445A (en) * | 2016-12-28 | 2019-08-09 | 国际壳牌研究有限公司 | Method for producing middle distillate |
| US10752847B2 (en) * | 2017-03-08 | 2020-08-25 | Saudi Arabian Oil Company | Integrated hydrothermal process to upgrade heavy oil |
| CN110734783A (en) * | 2018-07-19 | 2020-01-31 | 中山市亿鼎杰纳米科技有限公司 | Processing method of inferior heavy oil |
| WO2020065522A1 (en) | 2018-09-25 | 2020-04-02 | Eni S.P.A. | Process for the hydroconversion of heavy oil products with recycling |
| IT201800020818A1 (en) * | 2018-12-21 | 2020-06-21 | Eni Spa | PROCESS OF HYDROCONVERSION OF MIXTURES OF POLYMERS |
| CN111686796B (en) * | 2020-07-06 | 2023-11-10 | 中国石油天然气集团公司 | Oil sand asphalt non-hydrogenation viscosity-reducing modification catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5242578A (en) * | 1989-07-18 | 1993-09-07 | Amoco Corporation | Means for and methods of deasphalting low sulfur and hydrotreated resids |
| CN1398953A (en) * | 2001-07-06 | 2003-02-26 | 艾尼股份公司 | Converting process of heavy material, such as heavy raw oil and distilled residue |
| CN1400997A (en) * | 2000-02-15 | 2003-03-05 | 埃克森美孚研究工程公司 | Heavy feed upgrading based on solvent deasphalting and followed method of slurry hydroprocessing of asphalt from solvent deasphalting |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4454023A (en) * | 1983-03-23 | 1984-06-12 | Alberta Oil Sands Technology & Research Authority | Process for upgrading a heavy viscous hydrocarbon |
| CA1222471A (en) * | 1985-06-28 | 1987-06-02 | H. John Woods | Process for improving the yield of distillables in hydrogen donor diluent cracking |
| IT1275447B (en) * | 1995-05-26 | 1997-08-07 | Snam Progetti | PROCEDURE FOR THE CONVERSION OF HEAVY CRUDE AND DISTILLATION DISTILLATION RESIDUES |
| FR2753984B1 (en) * | 1996-10-02 | 1999-05-28 | Inst Francais Du Petrole | METHOD FOR CONVERTING A HEAVY HYDROCARBON FRACTION INVOLVING HYDRODEMETALLIZATION IN A BUBBLE BED OF CATALYST |
| FR2753982B1 (en) * | 1996-10-02 | 1999-05-28 | Inst Francais Du Petrole | MULTI-STAGE CATALYTIC PROCESS FOR CONVERTING A HEAVY HYDROCARBON FRACTION |
| CN1152945C (en) * | 2000-10-26 | 2004-06-09 | 中国石油化工股份有限公司 | Process for refining and coverting residual oil |
-
2002
- 2002-12-20 IT ITMI20022713 patent/ITMI20022713A1/en unknown
-
2003
- 2003-12-12 CN CNB2003801090397A patent/CN1331992C/en not_active Expired - Lifetime
- 2003-12-12 CN CNB2003801069625A patent/CN100497548C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5242578A (en) * | 1989-07-18 | 1993-09-07 | Amoco Corporation | Means for and methods of deasphalting low sulfur and hydrotreated resids |
| CN1400997A (en) * | 2000-02-15 | 2003-03-05 | 埃克森美孚研究工程公司 | Heavy feed upgrading based on solvent deasphalting and followed method of slurry hydroprocessing of asphalt from solvent deasphalting |
| CN1398953A (en) * | 2001-07-06 | 2003-02-26 | 艾尼股份公司 | Converting process of heavy material, such as heavy raw oil and distilled residue |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216432A (en) * | 2008-11-15 | 2011-10-12 | 环球油品公司 | Integrated solvent deasphalting and slurry hydrocracking process |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI20022713A1 (en) | 2004-06-21 |
| CN100497548C (en) | 2009-06-10 |
| CN1738890A (en) | 2006-02-22 |
| CN1729275A (en) | 2006-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100489061C (en) | Integrated process for the conversion of feedstocks containing coal into liquid products | |
| CN101068908B (en) | Process for the conversion of heavy charges such as heavy crude oils and distillation residues | |
| CN1331992C (en) | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues | |
| CN100467575C (en) | Converting process of heavy material, such as heavy raw oil and distilled residue | |
| US8017000B2 (en) | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues | |
| US8123932B2 (en) | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues | |
| CN101558139B (en) | Process for the total conversion of heavy feedstocks to distillates | |
| CN101098949B (en) | Process for the conversion of heavy charge stocks such as heavy crude oils and distillation residues | |
| CN101553555B (en) | Process for the total conversion of heavy feedstocks to distillates | |
| CN102051221B (en) | Method for more producing light oil by using hydrocarbon oil | |
| CN104995284A (en) | Method for converting a heavy hydrocarbon feedstock incorporating selective deasphalting with recycling of the deasphalted oil | |
| CN115916928A (en) | Heavy oil upgrading process using hydrogen and water | |
| CN103339232B (en) | By decon, in ebullated bed hydrocracking and the conversion by air distillation fractionation comprise the method for the hydrocarbon feed of shale oil | |
| AU2002358182B2 (en) | Process for the conversion of heavy charges such as heavy crude oils and distillation residues | |
| CA2149595C (en) | Process for the conversion of a residual hydrocarbon oil | |
| CN112745952A (en) | Method and system for processing aromatic-rich distillate oil | |
| CN114437808B (en) | Method and system for processing heavy oil | |
| CN112745946B (en) | Method and system for processing heavy raw oil | |
| CN116024006A (en) | Hydrocracking method of deasphalted oil | |
| CN116024007A (en) | Hydrocracking method of inferior raw oil | |
| CN109486522A (en) | A kind of method and system producing fuel oil, aviation kerosine and diesel oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20070815 |
|
| CX01 | Expiry of patent term |