CN1189538C - Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material - Google Patents
Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material Download PDFInfo
- Publication number
- CN1189538C CN1189538C CNB001305670A CN00130567A CN1189538C CN 1189538 C CN1189538 C CN 1189538C CN B001305670 A CNB001305670 A CN B001305670A CN 00130567 A CN00130567 A CN 00130567A CN 1189538 C CN1189538 C CN 1189538C
- Authority
- CN
- China
- Prior art keywords
- reactor
- liquid
- phase separator
- coal
- fraction
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 100
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 59
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 57
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 57
- 239000002994 raw material Substances 0.000 title claims abstract description 55
- 238000007670 refining Methods 0.000 title description 5
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 title 1
- 239000007788 liquid Substances 0.000 claims abstract description 101
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 62
- 230000003197 catalytic effect Effects 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 238000009835 boiling Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 239000003245 coal Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 39
- 238000006555 catalytic reaction Methods 0.000 claims description 35
- 150000002431 hydrogen Chemical class 0.000 claims description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 17
- 238000004904 shortening Methods 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 239000013502 plastic waste Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003250 coal slurry Substances 0.000 claims description 5
- 239000012263 liquid product Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 23
- 239000000295 fuel oil Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003476 subbituminous coal Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 and in this reactor Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a multi-stage catalytic hydrogenation method. In a back mixing catalytic reactor of the first stage, the raw material reacts with an iron base catalyst; effluent is decompressed, vapor fractions and liquid fractions are removed from the top, and the heavy liquid fractions are inputted into a back mixing catalytic reactor of the second stage; in the catalytic reactor of the first stage and the catalytic reactor of the second stage, the temperature is from 700 to 850 DEG F, the hydrogen partial pressure is from 1000 to 3500 psig, and the air speed is from 20 to 80 lb. /hr/ft<3>. The vapor removed from the effluent of the first reactor and the second reactor is mixed with light fractions, and the mixture is introduced into a streamline fixed bed catalytic hydrogenation processor for removing heteroatoms to prepare naphtha and intermediate distillate or full distillation range distillate. The bottom fractions of a separator are distilled in stepwise air pressure and vacuum; liquid hydrocarbon products are discharged, heavy fractions are circulated and concentrated, and hydrocarbon liquid with a low boiling point is provided.
Description
The present invention is the application number No.08/742 that submitted on November 1st, 1996,541 part renewal application, and No.08/742, and 541 is the application number No.08/609 that submitted on February 23rd, 1996,759 part renewal application.
Technical field
The present invention relates to the multistage catalysis method of heavy hydrocarbon feeds hydrogenation and hydrocracking, this method is produced the low boiling hydrocarbon liquid feul by using the ferrum-based catalyst of high dispersing.The invention particularly relates to so multistage shortening method, promptly streamline catalytic hydroprocessing step is adopted in coal, heavy crude residual oil, plastic waste and their combination.
Background technology
Permitted just to know that various iron containing compoundses are (as pyrite (FeS many years ago
2) and red soil (Fe
2O
3)) can in coal hydrogenation and liquifying method, be used as catalyzer.These iron catalyst compound particles are usually with in the coal-slurry oil attitude feedstream that is added in the reactor upstream of operation under the high-temperature and high-pressure conditions on a small quantity.Yet, because the efficient of these known iron-based catalytic compounds is lower usually, this mainly is because their initial surface area is lower, high-caliber dispersity can not be provided under reaction conditions, therefore develop the shortening conversion method of coal and heavy crude residual oil raw material in the past in 30 years, adopt particulate vector type catalyst bed in the reactor usually.These carried catalysts can be to contain a small amount of one or more to be deposited on the bead or the extrusion molding thing of the active co catalyst metal (as cobalt, molybdenum or nickel) on the inert support material (as aluminum oxide or silicon-dioxide).That these granule type carriers can be used for maintaining is temperature required, in the down-type fixed-bed reactor or upflowing fluidized-bed reactor under the reaction conditions of pressure and air speed.
Although these particulate vector type catalyzer (as be deposited on aluminum oxide or the silica supports cobalt-molybdenum or nickel-molybdenum) and the shortening conversion method that adopts carried catalyst provide preferable effect for the hydrogenation and the hydrocracking of coal and heavy oil feedstock, but some shortcomings of these particulate vector type catalyzer are, they are relatively poor with contacting of raw material, and because the rapid inactivation that pollution caused of the metal (as iron, nickel, titanium and vanadium) that sedimentation of coke contains on catalyzer and in the raw material.U.S. Patent No. 4,136,013 (Moll etc.) disclose a kind of emulsion-type metal catalyst that is used for hydrogenation process, but it also has the shortcoming that catalytic activity is low, catalyst levels is high.Under the disclosed catalyst levels level of patent of Moll etc., the catalyzer cost is too high, unless reclaim catalyzer and reuse from unconverted raw material.U.S. Patent No. 4,077,867 and 4,134,825 (Bearden etc.) disclose the decentralized slurry attitude catalyzer of the containing metal-carbon of original position formation, and this catalyzer is called " M-Coke ", can be used for the hydrocracking of coal, heavy oil and composition thereof.The catalyzer of Bearden etc. is mainly based on molybdenum, and molybdenum than the iron costliness many.U.S. Patent No. 4,486,293 (Garg) disclose the co-catalyst combination of a kind of iron and VI family or group VIII non-ferrous metal, make gelatin liquefaction with the water-soluble salt of co-catalyst metal in awarding the hydrogen solvent.
Know, the catalyzer that makes from the salt of water-soluble precursor usually can be under the gelatin liquefaction condition sintering, thereby can lose the required high degree of dispersion of high catalytic activity.U.S. Patent No. 5,168,088 (Utz etc.) disclose a kind of uniqueness pass through with iron oxide precipitation on the matrix of coal when improving in gelatin liquefaction the method for decentralized slurry attitude catalyzer.But this deposition method of catalyst precipitation on whole coal raw material generally acknowledged that for commercial-scale production be difficulty and very expensive.Therefore, the form of catalyzer and composition also need to do further improvement, to being used for the catalyst hydrogenation treatment process of various carbon raw materials, also require further improvement in particular for the method for highly active, the environmental sound of shortening conversion process, the cheap iron oxide based catalyzer of decentralized.
The present invention is used for the improving one's methods of hydrogenation of heavy hydrocarbon feeds such as coal, comminuted coal, and with the slurry of the ferrum-based catalyst that contains high dispersing, import chopped-off head backmixing reactor under suitable high temperature and pressure condition with hydrogen, make the coal reaction, the high molecular carbonaceous material is decomposed into lower molecular weight, low-sulfur and low boiling hydrocarbon overhead product and gas.The direct catalytic liquefaction method that was used for coal and heavy oil in the past has tangible difference, because they use the particulate vector type catalyzer in fixed-bed type reactor or fluid bed-type of reactor system.The hydrogenation method of some coals depended on coal slurry shape oil separating in the past, provided to award the hydrogen solvent liquid in the reactor.But the existing known hydrogenation method that is used for heavy hydrocarbon pressure does not comprise the maximization of combination of process steps provided by the invention and catalyst activity and reactor kinetics.
Known, the carbonaceous material deposition occurs in gelatin liquefaction reactor assembly that is not mechanical backmixing and the fluidized bed type system that uses particulate vector type catalyzer, and the aging rapidly and inactivation of catalyzer is difficult to operation.Yet, the present invention is by adding the iron-based gel-type or the liquid-type catalyzer of new high dispersing continuously to two reactor, these problems have been avoided, can be used for and contain the fixed-bed catalytic hydrotreating reactor combination of supported catalyst, but the lightweight of this catalyzer hydrotreatment front liquefaction step or the overhead product fraction of medium boiling spread, the carrier hydrotreating catalyst is not exposed in unconverted heavy residue and the ash from coal, and the deactivation rate minimum of catalyzer.In addition, to the coal of low-grade elevated oxygen level, and the two reactor method that does not have the intermediate stage phase separation step, do not wish that hydrogen consumption increases the unwanted light C of generation when the oxygen in the raw material is converted into water and in second section catalyticreactor
1-C
3Gas.Yet, by the method for the shortening with intermediate phase separating step is provided, can overcome shortcoming of the prior art, therefore, because the contained oxygen of coal raw material is with CO
2Remove and reduced the consumption of hydrogen, fixed-bed catalytic hydrotreatment and molecular sieve under the lesser temps are reformed to be removed the lightweight overhead product.And, remove light fraction at middle separating step, can improve the kinetics of second section catalyticreactor by improving heavy oil and the concentration of the liquid that is derived from raw coal and the hydrogen dividing potential drop that enters second section.Although some known liquefaction and oily hydrogen addition technology have been used for streamline fixed-bed catalytic hydrotreating step, but the combination adopted among the present invention and order are not provided, and the catalytic reactor system that is used for the biggest ground hydrogenation, molecule reformation and removes heteroatomic and two backmixing high dispersing combines the production with the overhead product that makes most worthy.Employing the present invention can be from heavy hydrocarbon feeds such as coal, oil and the high-quality clean fuel liquid of plastic waste High-efficient Production, and this is that known various processes can't be predicted or expect.
The content of invention
One aspect of the present invention provides a kind of hydrogenation of heavy carbon raw material and multistage catalysis method that hydrocracking prepares the low boiling hydrocarbon product liquid of being used for, and described method comprises the following steps:
(a) ferrum-based catalyst of carbon raw material and high dispersing and hydrogen are reacted in first section backmixing catalyticreactor, first reactor effluent that contains steam and liquid fraction stream is provided, the reaction conditions that keeps in the reactor is: temperature is 370-460 ℃, the hydrogen dividing potential drop is the 6.89-24.12MPa gauge pressure, and the reactor air speed is 320-1280kg/h/m
3, catalytic amount is 500-15 with respect to raw material, 000wppm iron;
(b) flowing out logistics with described first in successive primary and secondary interlude phase separator is separated and is steam and liquid fraction, logistics of separator top and bottoms are provided, remaining elementary interlude phase separator bottom liquid fraction is further reacted, second reactor effluent that contains steam and liquid fraction stream is provided;
(c) the described second reactor effluent stream is separated is steam and liquid fraction, the second phase separator top logistics and bottom liquid fraction are provided, the second phase separator top fraction stream and described secondary interlude phase separator bottom fraction logistics are merged, the fraction logistics of the described merging of catalytic hydroprocessing in online fixed-bed catalytic hydrotreating reactor provides the product liquid after the hydrotreatment;
(d) distillation is discharged the low boiling hydrocarbon product liquid from the liquid fraction of described second phase separator from this process.
In a better example of the present invention, described carbon raw material is a particulate coal, and reaction conditions is: temperature is 400-450 ℃, and the hydrogen dividing potential drop is the 8.26-20.6MPa gauge pressure, and air speed is 400-1000kg/h/m
3Reactor volume.
In a better example of the present invention, described first section temperature of reactor is than low 10-50 ℃ of second section temperature of reactor.
In a better example of the present invention, described first section temperature of reactor is than second section high 10-50 of temperature of reactor ℃.
In a better example of the present invention, the reaction conditions of described fixed-bed catalytic hydrotreating reactor is: temperature is 260.02-426.7 ℃, and the hydrogen dividing potential drop is the 5.516-20.684MPa gauge pressure, and the reactor air speed is 0.2-5.0/h.
In a better example of the present invention, carbon raw material is selected from the mixture of mixture, heavy crude residual oil and miscellaneous plastic waste material of mixture, coal and miscellaneous plastic waste material of coal, heavy crude residual oil, coal and heavy crude residual oil or the mixture of coal, heavy crude residual oil and miscellaneous plastic waste material.
In a better example of the present invention, described ferrum-based catalyst is that pH is the ionic liquid of 0.1-3.0.
In a better example of the present invention, under reduced pressure distill from the liquid fraction of described second phase separator stream, the overhead stream of underpressure distillation is circulated to described online catalytic hydroprocessing reactor.
In a better example of the present invention, separate described first section reactor effluent stream with external phase in the described secondary intermediate phase separator at described elementary interlude phase separator, form secondary interlude phase separator top logistics and elementary interlude phase separator bottoms; Described secondary interlude phase separator top logistics is further processed to reclaim appropriate hydrocarbon gas and hydrogen, and described elementary interlude phase separator bottoms flows in described second section backmixing catalyticreactor.
In a better example of the present invention, the reaction conditions of described second section backmixing catalyticreactor is: temperature 415.59-454.48 ℃, hydrogen dividing potential drop are the 5.516-20.684MPa gauge pressure.
In a better example of the present invention, described method also comprises the outflow logistics of further processing catalytic hydroprocessing reactor, removes C
1-C
3Gas, CO
2, NH
3And H
2S impurity, and the hydrogen of purification is provided, be used for being circulated back at least one reactor of described first and second sections reactors.
In a better example of the present invention, distillatory bottom liquid fraction in the step (d) is looped back described first section backmixing catalyticreactor.
In a better example of the present invention, further distillatory bottom liquid fraction stream and reclaims extra heavy hydrocarbon liquid product removing solid in the procedure of processing (d).
In a better example of the present invention, under reduced pressure distill liquid fraction stream from described second phase separator, the overhead stream of underpressure distillation is looped back described online catalytic hydroprocessing reactor, the bottoms of at least a portion underpressure distillation is looped back coal slurrying step.
Another aspect of the present invention relates to a kind of multistage shortening and hydroconversion process that is used for coal, described method is used the ferrum-based catalyst of high dispersing, separate and online catalytic hydroprocessing in conjunction with intermediate phase, so that the productive rate of low boiling hydrocarbon product liquid reaches maximum, described method comprises the following steps:
(a) with coal particle in the iron-based ionic-liquid catalyst of hydrocarbon pulpous state oil and high dispersing and first section backmixing reactor that hydrogen is imported pressurization, described reactor contains liquid and the hydrogen that is derived from coal; With the coal raw material is benchmark, and described catalyzer provides 500-15,000wppm iron;
(b) described blended coal slurry material, dispersed catalyst and hydrogen are reacted in described first section backmixing reactor, the reaction conditions that catalyticreactor keeps is: temperature is 398.92-437.81 ℃, the hydrogen dividing potential drop is the 8.27-20.68MPa gauge pressure, air speed is 320.6-1284.8 kilogram coal/hour/cubic metre reaction volume, with heating and shortening coal, first reactor effluent that is derived from coal that makes the partial hydrogenation that contains steam and liquid fraction and hydrocracking flows;
(c) take out first reactor effluent stream that contains steam and liquid fraction, this logistics pressure is reduced the 0.345-3.45MPa gauge pressure, described first reactor effluent that is separated in elementary interlude phase separator flows, and forms steam and lightweight top fraction and the logistics of elementary interlude phase separator bottom liquid; The described lightweight that further is separated in secondary interlude phase separator top fraction forms overhead vapor stream and bottom liquid stream;
(d) described elementary interlude phase separator bottoms is fed second section catalyticreactor with other hydrogen, described second section reactor keeps reaction conditions to be: temperature is 415.59-454.48 ℃, the hydrogen dividing potential drop is the 6.894-17.24MPa gauge pressure, further hydrocracking described liquid bottom fraction wherein forms second reactor effluent stream that contains steam and low boiling hydrocarbon liquid fraction;
(e) in second phase separator, the described second reactor effluent stream is separated and is top steam and light liquid fraction and bottom liquid fraction, will merge from the overhead vapor of second phase separator and the bottom stream of light weight fluid fraction and described secondary interlude phase separator; The steam and the light weight fluid fraction of the described merging of catalytic hydroprocessing in online fixed-bed type catalytic hydroprocessing reactor with further hydrogenation and remove heteroatoms, provide the product liquid after the hydrotreatment;
(f) with continuous normal pressure and underpressure distillation step, distillation is from the described bottom liquid fraction of described second phase separator; And the logistics of at least a portion vacuum distilling bottom liquid is circulated back to coal slurrying step;
(g) from process, reclaim appropriate hydrocarbon gas and the spissated C of lower boiling
4The hydrocarbon product liquid of-398.92 ℃ of fractions.
In a better example of the present invention, described method also comprises the outflow logistics of further processing catalytic hydroprocessing reactor, removes C
1-C
3Gas, CO
2, NH
3And H
2S impurity, and the hydrogen of purification is provided, be used to be circulated back to described first and second sections reactors.
In a better example of the present invention, further process the logistics of described round-robin vacuum distilling bottom liquid, Gu remove solid by liquid/filtration method or selectivity critical solvent partition method, to reclaim additional hydrocarbon liquid.
Description of drawings
With reference to following accompanying drawing the inventive method is described.
Fig. 1 is the schematic flow sheet that is used for the multistage catalysis method of heavy carbon raw material hydrogenation, it uses dispersive iron-based powder, gel or ion liquid type catalyzer in the isolating two sections backmixing reactors of intermediate phase are arranged, perhaps contain the fixed bed hydrogenation treatment reactor of particulate vector type catalyzer;
Fig. 2 is the schematic flow sheet that another kind is used for the multistage shortening method of particulate coal raw material.
Embodiment
The invention provides a kind of multistage catalysis method, can be used for hydrogen conversion and refining hydrocarbon feedstocks and comprise coal, heavy oil, plastic waste and their combination, be mainly used in and produce lower boiling cleaning hydrocarbon liquid fuel product.Particularly, the invention provides the hydrogen conversion method of the hydrocarbon of the stable ferrum-based catalyst that uses high dispersing, this catalyzer can be added in the hydrocarbon feed equably, as is added to coal-slurry oil material or heavy oil feedstock.Hydrocarbon feed and dispersed catalyst are passed through preheating, and send into first section backmixing catalyticreactor with hydrogen, and in this reactor, raw material is by hydrogenation and hydrocracking.First section reaction conditions is: temperature 370-460 ℃ (700-850), hydrogen dividing potential drop be 6.89-24.12MPa (gauge pressure) (1000-3500psig), air speed is 320-1280kg/h/m
3(20-80l/h/ft
3).Catalyzer is dispersive iron-based gel or powder slurries shape catalyzer, the catalyzer (being incorporated herein by reference) described in the United States Patent (USP) provisional application 08/742/541 of application on November 1st, 1996.Perhaps catalyzer can be iron-based ion type liquid or liquid-gel catalyst, its pH is 0.1-3.0, described in the United States Patent (USP) provisional application " the iron-based liquid catalyst that is used for the hydrotreatment carbon raw material " of application on January 28th, 1999 (being incorporated herein by reference).The general preferred iron-based ion liquid type catalyzer that uses pH as 0.1-0.5.First section catalyst reactor amount with respect to fresh hydrocarbon raw material in the reactor, should be 200-15, and 000wppm with respect to fresh material, is 500-10 preferably, 000wppm.
Flow out fluid pressure 0.345-3.45MPa gauge pressure (50-500psig) from first of first section reactor, feed elementary interlude phase separator, take out wherein hydrocarbon vapour and light liquid flow from the top, the logistics of taking out feeds secondary interlude phase separator, further removes light hydrocarbon gas and other steam that does not conform to demand in the hydrocarbon liquid fraction stream on the lenient side.From described elementary interlude phase separator, discharge residual bottom flow, feed second section backmixing catalyticreactor of lower pressure, with further hydrocracking hydrocarbon liquid fraction in the presence of the ferrum-based catalyst of high dispersing.If desired, can directly inject other catalyzer,, keep 500-10, the 000wppm concentration of iron so that with respect to wherein raw material at second section reactor.Second section reaction conditions is: temperature 398.92-482.26 ℃ (750-900), hydrogen dividing potential drop are 5.516-20.684MPa gauge pressure (800-3000psig).
Second effluent fluid from second section backmixing catalyticreactor is separated in second phase separator.A key character of the present invention is, low boiling hydrocarbon steam that takes out from the second phase separator top and light weight fluid fraction mix with the light weight fluid fraction that takes out from secondary interlude phase separator, two groups of materials flows of blended feed online fixed-bed catalytic hydrotreating reactor with existing lesser temps and hydrogen dividing potential drop, removing heteroatoms, and further hydrogenation and refining (polish) gently distillate the liquid feul that fraction becomes cleaning.The adoptable reaction conditions of fixed-bed catalytic hydrotreating reactor is 260.02-426.7 ℃ of (500-800) temperature, 5.516-20.684MPa gauge pressure (800-3,000psig) hydrogen dividing potential drop, and 0.2-5.0h
-1Air speed.The catalyzer that uses in the catalytic hydroprocessing reactor is known particulate state hydrotreating catalyst, as the cobalt-molybdenum on the alumina supporter or nickel-molybdenum.
Fraction is distilling under normal pressure and the vacuum pressure subsequently step by step at the bottom of the liquid that contains no conversion hydrocarbon of discharging from second phase separator, reclaim high boiling point oil product, and the vacuum distilling substrate fraction that will contain part exhausted ferrum-based catalyst is partially recycled to reactor at least, with further hydrocracking.If desired, Gu further handle vacuum distilling substrate fraction, make the hydrocarbon slurry flow that contains heavy solids that other heavy oil product and suitable burning or partial oxidation produce the required hydrogen of this method by the separation of selectivity critical solvent or liquid/filtration step.
The invention provides a kind of improved multistage catalysis method, be used for the hydrotreatment heavy hydrocarbon feedstocks, make the low boiling hydrocarbon liquid product, by using two sections dispersed catalyst reactors and successive primary and secondary interlude phase separator and online fixed-bed catalytic hydrotreating reactor, with raising overhead product productive rate and quality, and by improving second section reactor kinetics with hydrotreatment C
4-398.92 ℃ of (750) overhead products, and oxygen is removed as carbonic acid gas, rather than form water and consume hydrogen.In the past to the shortening method unique balance provided by the invention of carbon raw material, i.e. the combination of following several things: in reactor, use iron-based pulp-like catalyzer, the intermediate phase of high dispersing separate with remove the light hydrocarbon steam, online pressurization static bed catalytic hydrocarbon treatment step is removed the round-robin selectivity only to make the high boiling liquid fraction by the liquid of second section reactor and vacuum distilling substrate.Hydrocarbon product liquid quality height of the present invention can be used for producing or making up the fuel of making redistribution.This catalytic two sections, the advantage of the dispersion shortening method of backmixing have overcome and have used the fixed bed of particulate vector catalyzer and the complicacy of ebullated bed reactor system, easily control the temperature rise of reactor, avoided the flow distribution inequality in the carbon distribution and metal refining and backmixing slurry reactor on catalyzer.Although this method is specially adapted to the shortening of coal raw material, also can be used for containing the raw material of heavy oil resistates, plastic waste and their combination.Through the laboratory in 25-50 kilogram coal raw material/sky long run test operation, verified by the present invention especially in conjunction with the economical effectiveness of the economic method that operation out of the ordinary provided.
The invention provides a kind of improved multistage catalysis method that is used for liquefaction, hydrogenation, hydrocracking and the hydrotreatment of coal and/or other heavy hydrocarbon feeds, this method is used the ferrum-based catalyst of high dispersing in two reactor, and uses supported catalyst in direct-connected online fixed bed hydrogenation treatment reactor.As shown in Figure 1, provide the particulate coal raw material 10, provide heavy hydrocarbon pulpous state oil or raw material 11, both and the 12 finely divided ferrum-based catalysts that provide or iron-based ionic liquid or liquid-gel catalyst mix.Coal, heavy-hydrocarbon oil and catalyzer contain the part used catalyst with some and mix along the turning oil of having handled that pipeline 13 transmits in mixing tank 14.Mixed coal, oil and iron-based dispersive or ionic-liquid catalyst pressurize in 15 places, and send into preheater 17 with 16 new hydrogen that provide and recycle hydrogen.Raw material after the heating is upwards imported first section backmixing catalyticreactor 20, dissolves in this reactor, hydrocracking and hydroconversion reactions.Reactor 20 can be with suitable interior pump circulation device 21, or carries out mechanical backmixing by the mechanically mixing device of other suitable pressurized reactor.The reaction conditions of reactor 20: temperature is 371.14-454.48 ℃ (700-850 a °F), and the hydrogen dividing potential drop is 6.89-24.12MPa gauge pressure (1000-3500psig), and air speed is 320.6-1284.4 kilogram charging/m
3-h (20-80lb charging/ft
3-h), with respect to new raw material, catalytic amount is a 200-15000wppm iron.Reaction conditions is that temperature is 398.92-437.81 ℃ (750-820 a °F) preferably, and the hydrogen dividing potential drop is 8.27-20.68MPa gauge pressure (1200-3000psig).
From first effluent fluid 22 of first section catalyticreactor 20 in valve 23 decompression 0.345-3.45MPa gauge pressures (50-500psig), feed the elementary interlude phase separator 24 of heat, take out steams and low boiling hydrocarbon overhead product as top materials flow 25 from separator 24, and it is fed secondary interlude phase separator 26, so that top hydrocarbon vapour fraction 27 and bottom liquid fraction 28 to be provided.Mix with the other hydrogen 16a from preheater 17a as required from the remaining heavy bottom liquid stream 29 of elementary interlude phase separator 24, feed second section catalyticreactor 30, generally under temperature, carry out further hydrocracking reaction than reactor 20 high 5.5-28 ℃ (10-50).Adopt in second section catalyticreactor and be connected to the downtake road 31 that internal circulation pump 32 comprises flow distribution plate 32a, or adopt same effectively backmixing flowage structure to carry out backmixing.Second section reaction conditions preferably: temperature is 415.59-454.48 ℃ (780-850 a °F), and the hydrogen dividing potential drop is 6.894-17.24MPa gauge pressure (1000-2500psig).
, feed in second phase separator 34 of heat in valve 33a place decompression 0.345-3.45MPa gauge pressure (50-500psig) from second effluent fluid 33 of second section catalyticreactor 30, be used on the top 35 places and remove steam and light fraction, and end liquid flow 39 is provided.Come the light hydrocarbon liquid bottom stream 28 of the secondary interlude phase separator 26 of self-heating to combine with top materials flow 35 from second phase separator 34, bonded fluid 36 is provided, fluid 36 Input Online fixed-bed catalytic hydrotreating reactors 38, the latter is used to remove reactions such as heteroatoms, hydrogenation and molecule reformation, produces the hydrocarbon product stream 40 of cleaning.The reaction conditions preferably that is used for fixing a catalytic hydroprocessing device 38: temperature is 287.8-398.92 ℃ (550-750 a °F), and the hydrogen dividing potential drop is 5.516-17.24MPa gauge pressure (800-2500psig), and air speed is 0.2-2.0/hr.Product stream 40 from hydrotreating reactor 38 cools off at 41 places, reduces pressure at valve 42 places, and is separated in product separator 44 places, and top steam flow 45 is provided.Steam flow 45 feeds air processing unit 46 with steam flow 27, removes C at 47 places
1-C
3Gas, CO
2, unwanted H
2S, ammonia and water vapor.Remove these unwanted emptying gas at 47 places.Hydrogen after 48 places purify is circulated back to first and second sections reactors 20 and 30 respectively as air- flow 16 and 28, and the hydrogen make-up that provides with the 48a place merges in case of necessity.
Bottom liquid materials flow 39 from second phase separator 34 is reduced pressure at valve 39a place, and with distilling at air distillation still 50 from the fluid 49 that distillates after the hydrotreatment of product separator 44, make top IBP-400 (IBP-204 ℃) logistics 51,400-650 (204-343 ℃) logistics 52 and bottom liquid logistics 53.Bottoms 53 feeds vacuum tower 54, makes top 650-975 (343-524 ℃) vacuum gas oil logistics 55 and spissated heavy residual bottom stream 56, and it contains the form circulation of part dispersive ferrum-based catalyst with materials flow 13.
If necessary, special in the coal raw material that contains ash content, spissated bottom flow 56 can turn to and filter or separate further by the selective solvent at device 58 by liquid/solid and handle via valve 57, reclaims heavier heavy oil and incorporates recycle stream 13 into 60.The concentrated bottom flow 59 that contains ash content, no conversion hydrocarbon and some relict catalysts can be led to partial oxidation step (not marking), to make the required hydrogen of present method.
In the another kind of method shown in Figure 2, before the fluid 19 and the coal raw material 10 of premix were imported main mixing tank 14, heavy circulating liquid 13 was in advance at first mixing tank, 18 places and heavy oil feedstock 11 and catalyzer 12 premixs.Top vacuum gas oil stream 55 from vacuum tower 54 mixes the online catalytic hydroprocessing reactor 38 of back feeding with the light fraction stream 36 that merges, and further to carry out the hydrotreatment reaction, produces other low-boiling point liquid product 40.In the decompression of valve 39b place, directly feed vacuum tower 54 from the bottom liquid stream 39 of separator 34, combine with liquid flow 56, circulate as logistics 13 from the heavy liquid flow 53 of atmospheric distillation tower 50.
Further describe the present invention by the following examples, these embodiment do not constitute limitation of the scope of the invention.
Embodiment 1
To multistage shortening method of the present invention, the intermediate phase separating step is provided between the two-stage catalytic reactor, to remove steam and light fraction, provide useful result.To containing the low grade coal raw material of higher concentration oxygen, in the method, be with CO
xRemove deoxidation, rather than H
2O, thus demand can be reduced to hydrogen.In addition, produce less C
1-C
3Appropriate hydrocarbon gas is because minimum to the hydrocracking of the liquid starting material of second section catalyticreactor.To U.S.'s sub-bituminous coal raw material, adopt two kinds of similar catalysis two-stage hydrogenation methods, to have the intermediate phase separating step and not this step compare, important comparative result is listed in the table below 1.
Table 1
| The comparative approach result, weight %MAF coal | There is not the isolating previous method of intermediate phase | Have middle to isolating the inventive method |
| C 1-C 3Gas | 7.3 | 6.5 |
| C 4-C 7 | 4.1 | 4.1 |
| C 4-975 resistatess | 59.4 | 61.6 |
| 975 resistatess | 2.0 | 2.2 |
| CO x | 2.3 | 5.3 |
| Water | 19.4 | 17.1 |
| H 2Consumption | 7.4 | 7.5 |
These results show: essentially identical about operational condition and liquid yield under, for the inventive method of intermediate phase separating step is arranged, reduced light C
1-C
3Gas, CO
xZ obviously increases, and reduces the water that produces.
To two-stage hydrogenation method relatively, with bituminous coal Illinois #6 coal raw material, under the identical operations condition, in the middle of having to separating and not having intermediate phase to separate to operate, comparative approach the results are shown in table 2.
Table 2
| The comparative approach result | CMSL-02 | CMSL-05 |
| Middle separating step | Do not have | Have |
| Relative response intensity (relative reaction severity) | 1.1 | 1.25 |
| C 4-975 productive rates, weight %MAF coal | 76 | 78 |
| 975 resistatess transform weight %MAF coal | 91 | 94 |
| H 2Consumption, weight %MAF coal | 8.3 | 8.0 |
These results show: by removing steam and light fraction, C at middle separating step
4The conversion of the productive rate of-975 liquid products and remaining fraction (975) obviously improves, because improved the concentration that is derived from the intermediate product liquid of raw coal in second section reactor, and the hydrogen consumption is lowered with meeting the requirements.
Embodiment 2
To the mixing raw material of 35% (weight) sub-bituminous coal and 65% (weight) Hondo petroleum residual oil, adopt catalysis two reactor hydrogenation method, to having and not having intermediate section from comparing.The results are shown in following table 3.
Table 3
| The productive rate of normalizing, weight %MAF raw material | Do not have intermediate section from | Have intermediate section from |
| Relative response intensity | 43 | 46 |
| C 1-C 3Gas | 6.2 | 7.3 |
| C 4-C 7Liquid | 9.7 | 9.3 |
| Petroleum naphtha (C 4-3250°F) | 17.7 | 21.6 |
| Middle distillate (350-650) | 31.5 | 37.3 |
| Heavy overhead product (650-975) | 26.7 | 20.1 |
| Resistates (975) | 10.4 | 7.5 |
| The method performance, weight %MAF raw material | ||
| Coal transforms | 92.6 | 95.7 |
| 975 resistatess transform | 85.4 | 89.8 |
| C 4-975 product productive rates | 75.8 | 79.1 |
| H 2Consumption | 4.45 | 4.78 |
By these results as can be known, under same reaction conditions, when using the intermediate phase separating step, generally can obtain the transformation efficiency of higher coal and resistates raw mix, and higher C
4-975 product productive rates.This improvement mainly is owing to improved the reaction kinetics of liquid starting material in second section reactor.
Embodiment 3
Being used for the streamline catalytic hydrogenation step at the outflow steam fraction of the combination two reactor of this two-stage hydrogenation method, is the very effective and economic step that is used for reducing content of heteroatoms and product oil aromatic hydrocarbons.The heat release of the hydrogenation of coal or heavy-hydrocarbon oil raw material, and can be effective to the streamline hydrogenator from the high hydrogen dividing potential drop that the front reactor obtains, and can reach the obvious raising of product oil price value, improve.List in table 4 to being derived from the typical comparative result of making the streamline shortening of the petroleum naphtha fraction that obtains in the two-stage catalytic reactor operation of raw material with sub-bituminous coal:
Table 4: the quality of the petroleum naphtha fraction behind the streamline hydrogenation
| The streamline hydrogenation | Do not have | Have |
| ° ApI proportion | 36.2 | 39.9 |
| Carbon, weight % | 86.6 | 86.3 |
| Hydrogen, weight % | 13.3 | 13.7 |
| Nitrogen, wppm | 1,280 | 9 |
| Sulphur, wppm | 230 | 14 |
| The mid-boiling point temperature, °F | 421 | 401 |
| Hydrogen/carbon ratios | 1.85 | 1.91 |
Can know naphtha products after the hydrotreatment by above-mentioned comparison, compare to have higher ° of api gravity of requirement and obvious less nitrogen and sulphur content with naphtha products without hydrotreatment.
The comparative result that is presented at the performance variation that requires between the hydrocarbon feed of streamline catalytic hydroprocessing step and the product after the hydrotreatment is listed in table 5.
Table 5
| The logistics characteristic | Raw material to hydrotreater | Product after the hydrotreatment | ||||
| Proportion, ° API | 39.6 | 46.2 | ||||
| Carbon, weight % | 86.2 | 83.2 | ||||
| Hydrogen, weight % | 13.2 | 12.9 | ||||
| Sulphur, wppm | 297 | 9 | ||||
| Nitrogen, wppm | 161 | 1 | ||||
| Boiling spread, °F | IBP-350 | 350-650 | IBP-350 | 350-650 | ||
| Paraffin, weight % | 24.3 | 12.2 | 22.8 | 13.7 | ||
| Alkene, weight % | 0.3 | - | 0.5 | - | ||
| Cycloalkanes, weight % | 67.0 | 48.2 | 69.3 | 55.7 | ||
| Aromatic hydrocarbons, weight % | 8.4 | 39.6 | 7.4 | 30.6 | ||
| Cetane index | 38.0 | 39.5 | ||||
| Cetane value | - | 39.0 | ||||
Can be known by top comparative result, raw material is used the streamline hydrotreatment, almost can remove whole heteroatomss, sulphur and nitrogen have reduced aromatic hydrocarbons, simultaneously for the fraction of two boiling ranges, and the corresponding increase of cycloalkanes.Therefore, two sections combined methods of catalysis are in being useful on the centre of removing steam and light fraction isolating segmentation backmixing reactor, use iron-based dispersive slurry catalyst system, streamline fixed bed hydrogenation treatment step can be produced the product with premium properties, and reduces running cost.
Embodiment 4
Table 6 is listed known catalysis two-stage liquification (CTSL) method of using two sections sealing coupling ebullated bed reactors, use the direct comparison of catalysis two-stage reaction method of the iron-based slurry catalyst of high dispersing with the present invention, boiling reactor contains particulate vector type catalyzer or disperse type catalyzer separately, and method of the present invention has intermediate phase to separate and be used for the streamline catalytic hydroprocessing step of sub-bituminous coal.
Table 6
Two sections gelatin liquefactions of the catalysis of sub-bituminous coal
| Process is arranged | The carrier granule catalyzer | Dispersed catalyst iron/molybdenum | Gel catalyst TMIron/molybdenum/phosphorus |
| Functional symbol | CC-1 | CMSL-6 | PB-04 |
| Intermediate phase separates | Do not have | Do not have | Have |
| The streamline hydrotreatment | Do not have | Do not have | Have |
| Performance characteristic, weight % MAF coal | |||
| C 1-C 3Gas | 8.0 | 8.0 | 7.9 |
| CO x | 0.5 | 4.5 | 6.5 |
| H 2O | 18.5 | 14.0 | 12.1 |
| Coal transforms | 86.4 | 94.1 | 93.2 |
| C 4-975 liquid fraction | 62.6 | 63.1 | 67.5 |
| 975°F +Liquid fraction | 84.8 | 83.0 | 89.4 |
| H 2Consumption | 7.7 | 7.1 | 7.2 |
As shown in Table 6, catalysis two-stage hydrogenation method of the present invention comprises that intermediate phase separates and streamline catalytic hydroprocessing step, and described method makes CO
xObviously increase, the water of generation obviously reduces, and also improves the productive rate and the percentage transformation efficiency of product overhead product, does not increase the hydrogen consumption.Adopt the inventive method, make every barrel of Yue Wei $28/bbl of projected cost of oil production by the coal raw material, and use the known catalysis two-stage method of the sealing coupling reactor of supported catalyst to be $32-38$/bbl separately.
Although briefly described the present invention, should understand in scope and can carry out various modifications and changes described method by claims definition by embodiment preferably.
Claims (22)
1. one kind is used for the hydrogenation of heavy carbon raw material and the multistage catalysis method that hydrocracking prepares the low boiling hydrocarbon product liquid, and described method comprises the following steps:
(a) ferrum-based catalyst of carbon raw material and high dispersing and hydrogen are reacted in first section backmixing catalyticreactor, first reactor effluent that contains steam and liquid fraction stream is provided, the reaction conditions that keeps in the reactor is: temperature is 370-460 ℃, the hydrogen dividing potential drop is the 6.89-24.12MPa gauge pressure, and the reactor air speed is 320-1280kg/h/m
3, catalytic amount is 500-15 with respect to raw material, 000wppm iron;
(b) flowing out logistics with described first in successive primary and secondary interlude phase separator is separated and is steam and liquid fraction, logistics of separator top and bottoms are provided, remaining elementary interlude phase separator bottom liquid fraction is further reacted, second reactor effluent that contains steam and liquid fraction stream is provided;
(c) the described second reactor effluent stream is separated is steam and liquid fraction, the second phase separator top logistics and bottom liquid fraction are provided, the second phase separator top fraction stream and described secondary interlude phase separator bottom fraction logistics are merged, the fraction logistics of the described merging of catalytic hydroprocessing in online fixed-bed catalytic hydrotreating reactor provides the product liquid after the hydrotreatment;
(d) distillation is discharged the low boiling hydrocarbon product liquid from the liquid fraction of described second phase separator from this process.
2. multistage catalysis method as claimed in claim 1, its feature are that also described carbon raw material is a particulate coal, and reaction conditions is: temperature is 400-450 ℃, and the hydrogen dividing potential drop is the 8.26-20.6MPa gauge pressure, and air speed is 400-1000kg/h/m
3Reactor volume.
3. multistage catalysis method as claimed in claim 1, its feature are that also described first section temperature of reactor is than low 10-50 ℃ of second section temperature of reactor.
4. multistage catalysis method as claimed in claim 1, its feature are that also described first section temperature of reactor is than second section high 10-50 of temperature of reactor ℃.
5. multistage catalysis method as claimed in claim 1, its feature are that also the reaction conditions of described fixed-bed catalytic hydrotreating reactor is: temperature is 260.02-426.7 ℃, and the hydrogen dividing potential drop is the 5.516-20.684MPa gauge pressure, and the reactor air speed is 0.2-5.0/h.
6. multistage shortening method as claimed in claim 1, its feature is that also carbon raw material is a coal.
7. multistage catalysis method as claimed in claim 1, its feature are that also carbon raw material is a heavy crude residual oil.
8. multistage catalysis method as claimed in claim 1, its feature are that also carbon raw material is the mixture of coal and heavy crude residual oil.
9. multistage catalysis method as claimed in claim 1, its feature are that also described carbon raw material is the mixture of coal and miscellaneous plastic waste material.
10. multistage catalysis method as claimed in claim 1, its feature are that also described carbon raw material is the mixture of heavy crude residual oil and miscellaneous plastic waste material.
11. multistage catalysis method as claimed in claim 1, its feature are that also described carbon raw material is the mixture of coal, heavy crude residual oil and miscellaneous plastic waste material.
12. multistage catalysis method as claimed in claim 1, its feature are that also described ferrum-based catalyst is that pH is the ionic liquid of 0.1-3.0.
13. multistage catalysis method as claimed in claim 1 is characterized in that under reduced pressure distilling the liquid fraction stream from described second phase separator, and the overhead stream of underpressure distillation is circulated to described online catalytic hydroprocessing reactor.
14. multistage catalysis method as claimed in claim 1, it is characterized in that separating described first section reactor effluent stream with external phase in the described secondary intermediate phase separator, form secondary interlude phase separator top logistics and elementary interlude phase separator bottoms at described elementary interlude phase separator; Described secondary interlude phase separator top logistics is further processed to reclaim appropriate hydrocarbon gas and hydrogen, and described elementary interlude phase separator bottoms flows in described second section backmixing catalyticreactor.
15. multistage catalysis method as claimed in claim 1 is characterized in that the reaction conditions of described second section backmixing catalyticreactor is: temperature 415.59-454.48 ℃, hydrogen dividing potential drop are the 5.516-20.684MPa gauge pressure.
16. multistage catalysis method as claimed in claim 1 is characterized in that described method also comprises the outflow logistics of further processing catalytic hydroprocessing reactor, removes C
1-C
3Gas, CO
2, NH
3And H
2S impurity, and the hydrogen of purification is provided, be used for being circulated back at least one reactor of described first and second sections reactors.
17. multistage catalysis method as claimed in claim 1 is characterized in that distillatory bottom liquid fraction in the step (d) is looped back described first section backmixing catalyticreactor.
18. multistage catalysis method as claimed in claim 1 is characterized in that in the further procedure of processing (d) distillatory bottom liquid fraction stream removing solid, and reclaims extra heavy hydrocarbon liquid product.
19. multistage catalysis method as claimed in claim 1, it is characterized in that under reduced pressure distilling liquid fraction stream from described second phase separator, the overhead stream of underpressure distillation is looped back described online catalytic hydroprocessing reactor, the bottoms of at least a portion underpressure distillation is looped back coal slurrying step.
A 20. multistage shortening and hydroconversion process that is used for coal, described method is used the ferrum-based catalyst of high dispersing, separate and online catalytic hydroprocessing in conjunction with intermediate phase, so that the productive rate of low boiling hydrocarbon product liquid reaches maximum, described method comprises the following steps:
(a) with coal particle in the iron-based ionic-liquid catalyst of hydrocarbon pulpous state oil and high dispersing and first section backmixing reactor that hydrogen is imported pressurization, described reactor contains liquid and the hydrogen that is derived from coal; With the coal raw material is benchmark, and described catalyzer provides 500-15,000wppm iron;
(b) described blended coal slurry material, dispersed catalyst and hydrogen are reacted in described first section backmixing reactor, the reaction conditions that catalyticreactor keeps is: temperature is 398.92-437.81 ℃, the hydrogen dividing potential drop is the 8.27-20.68MPa gauge pressure, air speed is 320.6-1284.8 kilogram coal/hour/cubic metre reaction volume, with heating and shortening coal, first reactor effluent that is derived from coal that makes the partial hydrogenation that contains steam and liquid fraction and hydrocracking flows;
(c) take out first reactor effluent stream that contains steam and liquid fraction, this logistics pressure is reduced the 0.345-3.45MPa gauge pressure, described first reactor effluent that is separated in elementary interlude phase separator flows, and forms steam and lightweight top fraction and the logistics of elementary interlude phase separator bottom liquid; The described lightweight that further is separated in secondary interlude phase separator top fraction forms overhead vapor stream and bottom liquid stream;
(d) described elementary interlude phase separator bottoms is fed second section catalyticreactor with other hydrogen, described second section reactor keeps reaction conditions to be: temperature is 415.59-454.48 ℃, the hydrogen dividing potential drop is the 6.894-17.24MPa gauge pressure, further hydrocracking described liquid bottom fraction wherein forms second reactor effluent stream that contains steam and low boiling hydrocarbon liquid fraction;
(e) in second phase separator, the described second reactor effluent stream is separated and is top steam and light liquid fraction and bottom liquid fraction, will merge from the overhead vapor of second phase separator and the bottom stream of light weight fluid fraction and described secondary interlude phase separator; The steam and the light weight fluid fraction of the described merging of catalytic hydroprocessing in online fixed-bed type catalytic hydroprocessing reactor with further hydrogenation and remove heteroatoms, provide the product liquid after the hydrotreatment;
(f) with continuous normal pressure and underpressure distillation step, distillation is from the described bottom liquid fraction of described second phase separator; And the logistics of at least a portion vacuum distilling bottom liquid is circulated back to coal slurrying step;
(g) from process, reclaim appropriate hydrocarbon gas and the spissated C of lower boiling
4The hydrocarbon product liquid of-398.92 ℃ of fractions.
21. multistage catalysis method as claimed in claim 20 is characterized in that described method also comprises the outflow logistics of further processing catalytic hydroprocessing reactor, removes C
1-C
3Gas, CO
2, NH
3And H
2S impurity, and the hydrogen of purification is provided, be used to be circulated back to described first and second sections reactors.
22. multistage catalysis method as claimed in claim 20, its feature also are further to process the logistics of described round-robin vacuum distilling bottom liquid, Gu remove solid by liquid/filtration method or selectivity critical solvent partition method, to reclaim additional hydrocarbon liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001305670A CN1189538C (en) | 2000-09-28 | 2000-09-28 | Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001305670A CN1189538C (en) | 2000-09-28 | 2000-09-28 | Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1345910A CN1345910A (en) | 2002-04-24 |
| CN1189538C true CN1189538C (en) | 2005-02-16 |
Family
ID=4594200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001305670A Expired - Fee Related CN1189538C (en) | 2000-09-28 | 2000-09-28 | Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1189538C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482580A (en) * | 2009-08-19 | 2012-05-30 | Ifp新能源公司 | Direct coal liquefaction with integrated product hydrotreating and catalyst cascading |
| CN104419436A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct coal liquefaction process using inferior oil |
| CN104419438A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct liquefaction process of coal mixed with medium and low temperature coal tar |
| CN104419439A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Two-stage hydrogenation based direct coal liquefaction process |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7938952B2 (en) * | 2008-05-20 | 2011-05-10 | Institute Francais Du Petrole | Process for multistage residue hydroconversion integrated with straight-run and conversion gasoils hydroconversion steps |
| CN104918698B (en) * | 2013-07-18 | 2016-10-12 | 中国石油大学(北京) | A kind of iron-based hydrogenation catalyst and application thereof |
| CN111944554A (en) * | 2020-08-12 | 2020-11-17 | 中国科学院青岛生物能源与过程研究所 | Homogeneous hydrogenation method for producing biodiesel by using liquid catalyst |
-
2000
- 2000-09-28 CN CNB001305670A patent/CN1189538C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482580A (en) * | 2009-08-19 | 2012-05-30 | Ifp新能源公司 | Direct coal liquefaction with integrated product hydrotreating and catalyst cascading |
| CN102482580B (en) * | 2009-08-19 | 2015-01-28 | Ifp新能源公司 | Direct coal liquefaction with integrated product hydrotreating and catalyst cascading |
| CN104419436A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct coal liquefaction process using inferior oil |
| CN104419438A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct liquefaction process of coal mixed with medium and low temperature coal tar |
| CN104419439A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Two-stage hydrogenation based direct coal liquefaction process |
| CN104419439B (en) * | 2013-08-29 | 2016-08-17 | 任相坤 | A kind of direct coal liquefaction process of two-stage hydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1345910A (en) | 2002-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6190542B1 (en) | Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds | |
| EP1783194B1 (en) | A process for direct liquefaction of coal | |
| JP4874977B2 (en) | Recycling method of active slurry catalyst composition in heavy oil upgrade | |
| KR102093454B1 (en) | Integrated ebullated-bed process for whole crude oil upgrading | |
| CN102041084B (en) | Heavy hydrocarbon hydrogenation combined process | |
| CN101045884A (en) | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil | |
| CN1187523A (en) | Heavy hydrocarbon fraction converting process relating to hydrogenation demetalization in catalyst bubbling bed | |
| CN1093871C (en) | Multi-step converting catalyzing process for heavy hydrocarbon fraction | |
| CN101067089A (en) | Shale oil producing process | |
| CN1916112A (en) | Method for deep processing coal tar | |
| CN101074381A (en) | Hydrogenation for processing and utilizing coal tar | |
| CN1189538C (en) | Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material | |
| CN1297635C (en) | Process for preparing naphtha materials special for ethylene production device by using Fisher-Tropsch synthetic products | |
| CN1903984A (en) | Hydrogenation method for coal tar processing and its equipment | |
| CN100345945C (en) | Two-stage hydrocracking method for increasing yield of middle distillate oil | |
| CN1175090C (en) | Method for producing the clean diean diesel oil with low sulfur and low arene | |
| CN1132913C (en) | Process for preparing jet fuel and/or diesel oil or tail oil | |
| CN1940030A (en) | Hydrogenation cracking method of high-output diesel oil from high-nitrogen content heavy raw material | |
| CN102041082B (en) | Process of hydrogenation of heavy oil feedstock | |
| CN100351346C (en) | Medium pressure hydrocracking process for preparing jet fuel | |
| CN1446888A (en) | Suspension bed hydrocracking technique for producing gasoline with high octane number and diesel oil with high cetane number simultaneously | |
| CN101434867A (en) | Suspension bed residual oil hydrogenation-catalytic cracking combined technological process | |
| CN103540356B (en) | Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefins and diesel oil | |
| CN102071059A (en) | Multistage hydrogenation method for heavy hydrocarbon | |
| CN108865253A (en) | The method of coal Direct Hydrogenation liquefaction richness production aromatic hydrocarbons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1045710 Country of ref document: HK |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050216 Termination date: 20180928 |