CN1769393A - A kind of residual oil processing method - Google Patents
A kind of residual oil processing method Download PDFInfo
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- CN1769393A CN1769393A CN 200410050704 CN200410050704A CN1769393A CN 1769393 A CN1769393 A CN 1769393A CN 200410050704 CN200410050704 CN 200410050704 CN 200410050704 A CN200410050704 A CN 200410050704A CN 1769393 A CN1769393 A CN 1769393A
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- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000005336 cracking Methods 0.000 claims abstract description 10
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- 239000012263 liquid product Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 4
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- 238000004523 catalytic cracking Methods 0.000 claims description 31
- 238000012545 processing Methods 0.000 claims description 30
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- 230000008569 process Effects 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 23
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- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000007667 floating Methods 0.000 claims description 12
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- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
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- 239000007795 chemical reaction product Substances 0.000 claims description 7
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- 239000000203 mixture Substances 0.000 abstract description 7
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- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- -1 contains fixed bed Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 239000000084 colloidal system Substances 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- 239000003337 fertilizer Substances 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 3
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- 238000011020 pilot scale process Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 101100059658 Mus musculus Cetn4 gene Proteins 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
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- 101100493820 Caenorhabditis elegans best-1 gene Proteins 0.000 description 1
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a method of dealing leavings. The method includes: first, treat part of the raw leavings entering the hydrogenation unit of the fixed bed, then, crack the hydrogenation leavings entering the FCC unit, deal the mixture of part FCC circulating oil and the left raw leavings entering hydrogenation unit of the suspended bed, fractionate the final liquid product and the left FCC circulating oil treated as activating agent in atmospheric and vacuum distillation unit, and treat said vacuum distillate oil circulated to fixed bed hydrogenation unit and FCC unit individually. Comparing with present techniques, said method not only increases the flexibility of disposing feeding of hydrogenation device, but also improves the disposing ability and the total liquid recovery rate of the catalytic and cracking units, and improves the recovery rate of distillate oil at the same time.
Description
Technical field
The present invention relates to a kind of processing and treating method of heavy hydrocarbon.In particular, relate to a kind ofly utilize combination process to handle to contain the inferior heavy of high bituminous matter, colloid, sulphur, nitrogen and metals content impurity, the method for residual oil.
Background technology
As everyone knows, world's crude oil becomes heavy gradually, becomes bad in recent years, adds that environmental regulation is more and more stricter to the requirement of oil product, and it is more and more important that residual hydrocracking seems.Yet because inferior heavy, residual oil density is big, viscosity is high and be rich in impurity element such as a large amount of metals, sulphur, nitrogen and undesirable components such as colloid, bituminous matter, causes its hydrotreatment difficulty to be far longer than distillate.
The at present industrial technology that is used for handling inferior heavy, residual oil mainly contains fixed bed, suspension bed, ebullated bed and moving-bed, wherein fixed bed be most widely used general, also be the most sophisticated technology.But the fixed bed hydrogenation treatment technology has the shortcoming of itself: catalyzer is shorter work-ing life, and feedstock property generally can not be too bad, otherwise can be forced to because of the quick generation of the too fast inactivation of catalyzer and bed pressure drop stop work.Compare with it, the suspension bed hydrogenation process technology can be in higher space velocity, under operational conditions such as low operating pressure, the degree of depth transforms poor-quality heavy residuum, produce lighter secondary processing of raw material, and this technology can the extremely bad mink cell focus of working properties, so the suspension bed hydrogenation process technology also is the integral part of heavy residual oil transformation technology.
In general, the slag oil cracking rate of heavily residual hydrocracking technology of fixed bed is lower, and main purpose is to supply raw materials for downstream raw material lighting device such as devices such as catalytic cracking or coking.By hydrotreatment, sulphur, nitrogen, metal impurities content and carbon residue in the poor residuum are obviously reduced, thereby obtain the charging that raw material lighting device in downstream can receive.
US4,713,221 disclose a kind of combination process of mink cell focus hydrotreatment, promptly on the residual hydrogenation of routine and catalytic cracking combined basis, the heavy cycle oil of catalytic cracking is circulated to residual hydrogenation equipment, and carries out hydrogenation after residual oil mixes, enter catalytic cracking unit again.But this technology has only been considered the lighting of the treatable residual oil of residual hydrocracking device, by the processing again of catalytic cracking turning oil being increased the yield of light oil.
A kind of heavy hydrocarbon feeding and hydrogenating process has been described among the CN1335371A, this method is that residual oil is faced hydrogen thermally splitting and organic combination of fixed bed residual hydrocracking technology, heavier hydrocarbon feeds is at first at suspension bed or similarly raw material is relaxed in the reactor to face hydrogen thermally splitting pre-treatment, and then enters the fixed bed hydrogenation treatment unit and carry out hydrotreatment.But when adopting this method to handle poor-quality heavy residuum, owing to increased operating units such as system pressure adjusting and gas-liquid-solid three-phase separation, so operation easier is bigger, handiness is relatively poor.
Summary of the invention
Purpose of the present invention is exactly at above-mentioned the deficiencies in the prior art, develop the inferior heavy of a kind of high metal, high Conradson carbon residue, sulphur and nitrogen content, the treatment process of residual oil, this method not only can be produced the lower boiling purpose product cut oil such as petroleum naphtha, intermediate oil and vacuum gas oil of a large amount of low impurity contents, and can obviously improve the yield of lower boiling purpose product cut oil.
Residual oil treatment process of the present invention may further comprise the steps:
The part of A, residual oil raw material enters the fixed bed hydrogenation processing unit, reacts in the presence of hydrogen and hydrogenation catalyst, separates liquid product and obtains light-end products and the normal slag of hydrogenation;
The normal slag of hydrogenation described in B, the steps A enters catalytic cracking (FCC) unit and carries out cracking reaction, obtains gas phase, raw gasline, gas oil, heavy cycle oil and slurry oil;
The residual oil raw material of C, remainder with mix to the described FCC turning oil of small part after enter the floating bed hydrogenation processing unit and handle, gained liquid product and remainder FCC turning oil enter the atmospheric and vacuum distillation unit and carry out fractionation, obtain light-end products, vacuum distillate and vacuum residuum, described vacuum distillate enters the fixed bed hydrogenation processing unit respectively and the FCC unit is handled.
In the above-mentioned steps, the weight ratio that raw material residual oil enters fixed bed hydrogenation processing unit and floating bed hydrogenation processing unit is 1: 9～7: 3, is preferably 3: 7～6: 4.
The condition of the described fixed bed hydrogenation treating processes of the inventive method is as follows usually: adopt hydrogenation catalyst to be meant the single catalyst or the combination catalyst of functions such as having weight, residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking.These catalyzer generally all are to be carrier with porous refractory inorganic oxides such as aluminum oxide, the oxide compound of group vib and/or VIII family metal such as Mo, Co, Ni etc. is an active ingredient, described heavy oil hydrogenating treatment catalyst, generally, the content of its metal oxide is: NiO 0.5wt%～9.6wt%, MoO
30～25wt%.Catalyst system therefor of the present invention optionally adds other various auxiliary agents such as P, Si, elements such as F, B.For example CEN, the FZC series of being produced by Fushun Petrochemical Research Institute pilot scale base weighs, residuum hydrogenating and metal-eliminating catalyst, and ZTN, the ZTS catalyst series produced by first fertilizer plant of Qilu Petrochemical company just belong to this class catalyzer.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst are wherein arranged, and the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst successively.Technology with these several catalyst mix fillings is also arranged certainly.Common operational condition is as follows: absolute pressure is 10MPa～25MPa, and preferred 12MPa～18MPa, temperature are 300 ℃～450 ℃, preferred 350 ℃～430 ℃; Volume space velocity and hydrogen dividing potential drop are to select according to the characteristic for the treatment of material and the transformation efficiency and the refining depth of requirement during liquid; Volume space velocity is generally 0.1h during liquid
-1～5.0h
-1, 0.15h preferably
-1～2h
-1Hydrogen to oil volume ratio is 100～5000, is preferably 500～2000.
The catalytic cracking technology that the described catalytic cracking of the inventive method can use those skilled in the art to be familiar with, catalytic cracking reaction product can access dry gas, liquefied gas, raw gasline, gas oil, heavy cycle oil and catalytic slurry through fractionation.Above-mentioned dry gas, liquefied gas, raw gasline, gas oil generally can directly go out device and carry out next step the refining product that is processed into.Part heavy cycle oil can be used as the activator of intensifying distillation, with the liquid-phase mixing after the suspension bed residual oil hydrogenation processing, enter the atmospheric and vacuum distillation unit, wherein heavy cycle oil enters among the step C 0～90wt% that the normal unitary ratio of vacuum fractionation accounts for total heavy cycle oil amount, is preferably 40wt%～60wt%.The adding of activator makes the productive rate of distillate not be significantly increased when adding activator.The operational condition of described catalytic cracking unit is generally: temperature is 450～580 ℃, preferably 480 ℃～550 ℃; The agent weight of oil is than 5～25, and preferably 5～20; With 0.1 second～10 seconds duration of contact of catalyzer, best 1 second～5 seconds; Pressure 0.1MPa～0.5MPa.The catalytic cracking catalyst that is adopted comprises the catalyzer that is generally used for catalytic cracking, as silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and molecular sieve cracking catalyst, molecular sieve cracking catalyst preferably, this is because the active height of molecular sieve cracking catalyst, green coke is few, gasoline yield height, transformation efficiency height.The reactor of described catalytic cracking unit can be the catalyst cracker of various types, and preferably riser reactor or riser tube add the bed reactor.Technical process is generally: stock oil injects from the riser reactor bottom, contact with high temperature catalyst from the fresh regenerated of revivifier, the oil gas that cracking reaction generates and the catalyst mixture of deposit coke move up along riser reactor, finish the catalytic cracking reaction of whole stock oil.
The described floating bed hydrogenation treatment technology of the inventive method can be any attainable floating bed hydrogenation treatment technology, can use catalyzer, also can not use catalyzer.Catalyzer of the present invention, comprise oil-soluble catalyst and water-soluble catalyst that all are suitable for hydrogenation of residual oil suspended bed, for example, oil-soluble catalyst has iron cpd and coal dust are ground made iron-coal paste shape catalyzer in oil, water-soluble catalyst such as molybdenum phosphate aqueous solution catalyzer, Mo, Ni, P water-soluble catalyst etc.The present invention preferably uses water-soluble catalyst.The addition of oil-soluble catalyst or water-soluble catalyst is generally 0.01wt%～0.5wt% with the total restatement of reactor heavy hydrocarbon charging, is preferably 0.02wt%～0.1wt%.Temperature of reaction is generally 370 ℃～500 ℃, is preferably 410 ℃～480 ℃; Reaction pressure is generally 8.0MPa～20.0MPa, is preferably 14.0MPa～18.0MPa; Volume space velocity is generally 0.5h during liquid
-1～5h
-1, be preferably 1.0h
-1～5h
-1Hydrogen to oil volume ratio is generally 500～2000, is preferably 800～1500.
The weight ratio that vacuum distillate described in the step C enters catalytic cracking unit and fixed bed hydrogenation processing unit is 2: 8～9: 1, is preferably 3: 7～7: 3.
The fractionation operation that fractionation operation described in the step C is promptly conventional.
It is generally acknowledged that residual oil is a colloid system, bituminous matter phase colloidal particle or micella core are present in the residual oil.With the bituminous matter is the center, adds the solvated layer that is attached to it, has formed supramolecular chelation structure unit, has constituted the disperse phase of solution.With the bituminous matter is the formed this supramolecular structure of core, then be the solvated layer that hangs down aromatic hydrocarbons and form than the small molecules hydrocarbon around it, and the aromaticity freestone heart successively decreases.Theoretical investigation and experimental result show, in heavy residual oil, add the activator that is rich in aromatic hydrocarbons, just can regulate supramolecular structure and chelation structure cell size, increase the solvency power of dispersion medium in the vacuum residuum, change micellar particle diameter and association strength, when the chelation structure cell size diminishes, under distillation condition, the surface tension of the vapour-liquid phase of this raw material diminishes, cause the acute variation of evaporation bubble size and solvation thin layer, identical hydro carbons disperses again, goes thereby impel more hydro carbons to import in the boiling process, makes the gain in yield of distilled oil.Therefore, by the method for intensifying distillation, can increase the yield of light-end products significantly.
Compared with prior art, the present invention is owing to adopted the organic associating of fixed bed hydrogenation processing, floating bed hydrogenation treatment process, adopting heavy catalytic cycle oil simultaneously is activator, not only increase present residual hydrogenation equipment and handled the handiness of charging, and improved the processing power of catalytic cracking unit and the total liquid yield of device, can significantly improve the yield of distillate simultaneously; In addition, also effectively utilize the low value-added byproduct of catalytic cracking, both made present catalytic cracking unit operation more flexible, improved the resid feed character of fixed bed device again, prolonged the work-ing life of fixed bed catalyst.In a word, high lighting heavy, residual oil raw material that the present invention has not only realized, and can also obviously improve the yield of light-end products, realized the reasonable utilization of petroleum resources.
The present invention is applicable to normal slag and the processing that subtracts slag, is particularly useful for the poor residuum processing treatment process of high metal, high carbon residue, high condensed ring material, high nitrogen-containing.
Description of drawings
Fig. 1 is the simple and easy schematic flow sheet of the embodiment of the invention;
Fig. 2 is the simple and easy schematic flow sheet of comparative example of the present invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further details.
As shown in Figure 1, fresh feed residual oil 1 part with mix from the part vacuum distillate 13 of normal vacuum fractionation unit 11 and hydrogen 2 after enter fixed bed hydrogenation processing unit 4, in the presence of hydrogenation catalyst, carry out hydrotreatment, after fractionation, fractionate out hydrogen-rich gas 5, gasoline fraction 6, diesel oil distillate 7 and long residuum 8.Long residuum 8 with enter catalytic cracking unit 18 after part vacuum distillate 13 from normal vacuum fractionation unit 11 mixes and handle, in the presence of cracking catalyst, carry out cracking reaction, the liquid-phase product of gained is after fractionation, fractionate out dry gas 19, liquefied gas 20, naphtha fraction 21, diesel oil distillate 22, heavy cycle oil 23 and catalytic slurry 24, wherein dry gas 19, liquefied gas 20, naphtha fraction 21, diesel oil distillate 22 directly goes out device, heavy cycle oil 23 parts enter normal vacuum fractionation unit 11 as the activator of intensifying distillation, rest part with enter floating bed hydrogenation processing unit 9 after the remainder of fresh feed residual oil 1 mixes.After liquid product after floating bed hydrogenation is handled adds activator (being the heavy cycle oil 23 among the present invention), finish fractionation process in normal vacuum fractionation unit 11, fractionate out hydrogen-rich gas 12, gasoline fraction 15, diesel oil distillate 16, vacuum distillate 13 and vacuum residuum 14.Described hydrogen-rich gas 12 returns hydrogenation unit again after washing, purification, gasoline fraction 15, diesel oil distillate 16 can go out device and be further processed, and vacuum distillate 13 partly or entirely is used to enter catalytic cracking unit 18.
For further specifying all main points of the present invention, enumerate following examples.
On residue fixed-bed and hydrogenation of residual oil suspended bed testing apparatus, mix small-sized lifting tubular type catalytic cracking unit and continuous fractionation device and test.The used catalyzer of wherein residue fixed-bed hydropyrolysis experiment device is to be heavy, the residuum hydrogenating and metal-eliminating catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base of CEN, FZC series, by ZTN, ZTS series weight, residual hydrogenation denitrogenation, the desulfurization catalyst of first fertilizer plant of Qilu Petrochemical company production.The order of catalyst loading is hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst.The Hydrodemetalation catalyst that uses in this test is CEN-5, CEN-6; Protective material is CEN-2, CEN-4, FZC-16 (over current protection agent); Hydrobon catalyst ZTS-01, ZTS-02, ZTS-03; Hydrodenitrogenation catalyst ZTN-01.Filling ratio between each catalyzer is:
CEN-2∶FZC-16∶CEN-4∶CEN-5∶CEN-6∶ZTS-01∶ZTS-02∶ZTS-03∶ZTN-01＝1∶1.25∶1.5∶2.62∶7.8∶6.63∶0.69∶0.87∶11(V/V)。
The suspension bed residual oil hydrogenation testing apparatus is the catalyzer of this test with the 9 prepared catalyzer of embodiment among the CN 1045307C then, and this catalyzer is a water-soluble catalyst, and it contains Mo is that 5.6wt%, Ni are that 0.7wt%, P/Mo atomic ratio are 0.087.The catalyzer usage quantity is that benchmark is 0.024wt% with heavy hydrocarbon charging gross weight.
The employed catalyzer of catalytic cracking unit is RHZ200 (Qilu Petrochemical company of China Petrochemical Corporation catalyst plant is produced).The catalytic cracking unit operational condition is: temperature is 505 ℃, and pressure is 0.13MPa, and agent weight of oil ratio is 5.5, and finish duration of contact is 1.2 seconds.
The stock oil character of using sees Table 1, and schema is seen Fig. 1.
The operational condition that fixed bed hydrogenation is handled is as follows: temperature is 393 ℃; Pressure is 15.4MPa; Hydrogen to oil volume ratio is 758; Air speed is 0.30h
-1Recycle hydrogen purity is 95v%.
The reaction conditions of suspension bed is as follows: temperature is 405 ℃; Pressure is 16.0MPa; Hydrogen to oil volume ratio is 1000; Recycle hydrogen purity is 95v%.
The dispensed weight ratio of residual oil raw material 1 is the fixed bed charging: suspension bed charging=3: 7;
The weight ratio that vacuum distillate 13 enters fixed bed hydrogenation unit 4 and FCC unit 18 is 6: 4;
The weight ratio that heavy cycle oil 23 enters normal vacuum fractionation unit 11 and suspension bed unit 9 is 4: 6.
Under above-mentioned experiment condition, the productive rate of gas, raw gasline, gas oil and vacuum residuum sees Table 2 in the technical solution of the present invention.
Comparative example 1
Fig. 2 is a comparative example schematic flow sheet of the present invention: raw material residual oil 1 with enter residue fixed-bed hydrotreatment unit 4 after hydrogen 2 mixes, after fractionation, obtain hydrogen-rich gas 5, gasoline fraction 6, diesel oil distillate 7 and long residuum 8, described long residuum 8 enters FCC unit 18 and handles, the dry gas 19, liquefied gas 20, raw gasline 21, gas oil 22 and the catalytically cracked oil 24 that generate go out device, heavy cycle oil 23 enters the fixed bed hydrogenation processing unit, catalytically cracked oil 24 does not carry out other conversions again, calculates by unconverted oil during material balance.
This tests raw materials used residual oil with embodiment 1.
Raw material residual oil carries out hydrotreatment, and the hydrogenation catalyst of fixed bed hydrogenation device filling and device operational condition are with embodiment 1.
The liquid efflunent of reactor enters atmospheric tower and carries out the normal pressure fractionation.
The normal slag of hydrogenation directly carries out catalytic cracking, and catalyzer that catalytic cracking unit is used and device operational condition are with embodiment 1.
The product of comparative example 1 process residual oils distributes and sees Table 2.
Table 1 stock oil main character
| Project | Character | Project | Character |
| Density (20 ℃), g/cm 3 | 0.998 | Fe，μg/g | 13.8 |
| Elementary composition | Ca，μg/g | 33.8 | |
| S，wt％ | 2.52 | Saturated part, wt% | 14.5 |
| N，wt％ | 0.8 | Fragrance part, wt% | 34.8 |
| Carbon residue, wt% | 15.6 | Colloid, wt% | 47.2 |
| Ni，μg/g | 78.0 | Bituminous matter, wt% | 3.5 |
| V，μg/g | 32.2 |
Table 2 embodiment 1 distributes with the product of comparative example 1
| | Comparative example 1 | |
| Charging: | ||
| Raw material, wt% | 100 | 100 |
| The hydrogen consumption, wt% | 1.90 | 1.32 |
| Product: | ||
| Gas phase, wt% | 5.30 | 6.69 |
| Raw gasline, wt% | 50.50 | 44.50 |
| Gas oil, wt% | 29.40 | 27.40 |
| Unconverted oil, wt% | 11.20 | 16.20 |
| Coke, wt% | 5.10 | 5.90 |
| Loss, wt% | 0.40 | 0.63 |
The light oil yield of combination process of the present invention exceeds 8.0wt% than the light oil yield of the existing technology in the comparative example 1 as can be seen from Table 2, and low respectively 5.0wt% of the yield of unconverted oil and coke and 0.8wt%.
On residue fixed-bed and hydrogenation of residual oil suspended bed testing apparatus, to mix small-sized lifting tubular type catalytic cracking unit and continuous fractionation device and test, schema is seen Fig. 1.The complete series catalyst for hydrotreatment of residual oil of fixed bed hydrogenation processing unit filling Fushun Petrochemical Research Institute exploitation carries out the residual hydrocracking test.The filling situation of each anticatalyzer is: one instead loads CEN-2, CEN4, FZC-16, CEN-5, CEN6 from top to bottom, filling ratio (V) is: 1: 1.5: 2.2: 2.4: 13, two instead load FZC-301 from top to bottom, and the filling ratio (V) of two reactors is 50: 50.Above-mentioned CEN-2, CEN4, FZC-16, CEN-5, CEN-6 catalyzer are to be produced by Fushun Petrochemical Research Institute pilot scale base, and FZC-301 is produced by first fertilizer plant of Qilu Petrochemical company.With Saudi Arabia's residual oil is raw material, and the main character of stock oil is listed in table 3.
And catalyzer that the suspension bed residual oil hydrogenation testing apparatus is adopted and consumption thereof are with embodiment 1.
The employed catalyzer of catalytic cracking unit is with embodiment 1, and its operational condition is: temperature is 508 ℃, and pressure is 0.13MPa, and agent weight of oil ratio is 5.8, and finish duration of contact is 1.5 seconds.
The operational condition that fixed bed hydrogenation is handled is: reaction pressure 14.0MPa, and 393 ℃ of temperature of reaction, hydrogen-oil ratio is 650 (v/v), volume space velocity 0.235h during liquid
-1(to residual oil raw material).
The reaction conditions of suspension bed is as follows: temperature is 415 ℃, and pressure is 16.0MPa, and hydrogen to oil volume ratio is 1000, and recycle hydrogen purity is 95v%.
The dispensed weight ratio of stock oil is the fixed bed charging: suspension bed charging=7: 3;
The weight ratio that vacuum distillate 13 enters fixed bed unit 4 and FCC unit 18 respectively is 8: 2;
The weight ratio that heavy cycle oil 23 enters normal vacuum fractionation unit 11 and suspension bed unit 9 is 6: 4;
Under above-mentioned experiment condition, the material balance of process residual oils of the present invention sees Table 4.
Embodiment 3
On residue fixed-bed and hydrogenation of residual oil suspended bed testing apparatus, to mix small-sized lifting tubular type catalytic cracking unit and continuous fractionation device and test, schema is seen Fig. 1.Fixed bed hydrogenation processing unit catalyst loading scheme is with embodiment 2, and stock oil is with embodiment 2.
And catalyzer that the suspension bed residual oil hydrogenation testing apparatus is adopted and consumption thereof are with embodiment 1.
The employed catalyzer of catalytic cracking unit is with embodiment 1, and its operational condition is with embodiment 2.
The operational condition that fixed bed hydrogenation is handled is with embodiment 2.
The reaction conditions of suspension bed is with embodiment 2.
The dispensed weight ratio of stock oil is the fixed bed charging: suspension bed charging=7: 3;
The weight ratio that vacuum distillate 13 enters fixed bed unit 4 and FCC unit 18 respectively is 8: 2;
Under above-mentioned experiment condition, the material balance of the inventive method process residual oils sees Table 4.
Comparative example 2
Comparative example 2 equipment therefors are with comparative example 1, raw material residual oil, and the hydrogenation catalyst and the operational condition of the filling of fixed bed hydrogenation device, catalyzer that catalytic cracking unit is used and operational condition are all with embodiment 2.
The product of comparative example 2 distributes and sees Table 4.
Table 3 stock oil main character
| Density (20 ℃)/kg/m 3 | 995.9 |
| CCR，wt％ | 14.67 |
| S，wt％ | 4.42 |
| N，wt％ | 0.32 |
| Metal (Ni+V) content, μ g/g | 140.5 |
The material balance of table 4 embodiment 2
| | Embodiment 3 | Comparative example 2 | |
| Charging: | |||
| Raw material, wt% | 100 | 100 | 100 |
| The hydrogen consumption, wt% | 2.20 | 2.20 | 1.68 |
| Product: | |||
| Gas phase, wt% | 5.00 | 5.00 | 4.35 |
| Raw gasline, wt% | 46.50 | 45.40 | 43.80 |
| Gas oil, wt% | 31.40 | 30.20 | 27.53 |
| Unconverted oil, wt% | 13.30 | 15.60 | 17.80 |
| Coke, wt% | 5.40 | 5.40 | 7.60 |
| Loss, wt% | 0.60 | 0.60 | 0.60 |
As can be seen from Table 4, the embodiment 2 of combination process of the present invention and 3 compares with the existing technology in the comparative example 2, light oil yield exceeds 6.57wt% and 4.27wt% respectively, and low respectively 4.5wt% of unconverted oil yield and 2.2wt%, low respectively 2.2wt% of coke yield and 2.2wt%.
Claims (7)
1, a kind of residual oil treatment process may further comprise the steps:
The part of A, residual oil raw material enters the fixed bed hydrogenation processing unit, reacts in the presence of hydrogen and hydrogenation catalyst, separates liquid product and obtains light-end products and the normal slag of hydrogenation;
The normal slag of hydrogenation described in B, the steps A enters the FCC unit and carries out cracking reaction, obtains gas phase, raw gasline, gas oil, turning oil and slurry oil;
The residual oil raw material of C, remainder with mix to the described FCC turning oil of small part after enter the floating bed hydrogenation processing unit and handle, gained liquid product and remainder FCC turning oil enter the atmospheric and vacuum distillation unit and carry out fractionation, obtain light-end products, vacuum distillate and vacuum residuum, described vacuum distillate enters the fixed bed hydrogenation processing unit respectively and the FCC unit is handled;
The weight ratio that wherein said raw material residual oil enters fixed bed hydrogenation processing unit and floating bed hydrogenation processing unit is 1: 9～7: 3; The ratio that described vacuum distillate enters fixed bed hydrogenation processing unit and catalytic cracking unit is 2: 8～9: 1; It is 0～90wt% of heavy cycle oil total amount that described FCC turning oil enters the unitary ratio of normal vacuum fractionation.
2, residual oil treatment process according to claim 1, the weight ratio that described raw material residual oil enters fixed bed hydrogenation processing unit and floating bed hydrogenation processing unit is 3: 7～6: 4, the weight ratio that described vacuum distillate enters FCC unit and fixed bed hydrogenation processing unit is 3: 7～7: 3, and it is the 40wt%～60wt% of heavy cycle oil total amount that described FCC turning oil enters the unitary ratio of normal vacuum fractionation.
3, residual oil treatment process according to claim 1 and 2, the operational condition of described fixed bed hydrogenation processing unit is: absolute pressure 10MPa～25MPa, temperature is 300 ℃～450 ℃, volume space velocity 0.1h during liquid
-1～5.0h
-1, hydrogen to oil volume ratio is 100～5000.
4, residual oil treatment process according to claim 1 and 2, the reaction conditions of described floating bed hydrogenation processing unit is: temperature of reaction is 370 ℃～500 ℃, and reaction pressure is 8.0MPa～20.0MPa, volume space velocity is 0.5h during liquid
-1～5h
-1, hydrogen to oil volume ratio is 500～2000.
5, residual oil treatment process according to claim 1 and 2, the unitary operational condition of described FCC is: temperature is 450 ℃～580 ℃, the agent weight of oil is than 5～25, with 0.1 second～10 seconds duration of contact of catalyzer; Pressure 0.1MPa～0.5MPa.
6, residual oil treatment process according to claim 1 and 2, described floating bed hydrogenation process is used catalyzer, or does not use catalyzer, described catalyst pack oil scraper dissolubility catalyzer and water-soluble catalyst.
7, residual oil treatment process according to claim 6, when using catalyzer, the usage quantity of described catalyzer is that benchmark is 0.01wt%～0.5wt% with heavy hydrocarbon charging gross weight.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453544A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Residual oil hydrotreating and catalytic cracking combined method |
| CN102732311A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking combined method for residuum |
| CN102732314A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking combined method for residuum |
| CN102732315A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
| CN102732313A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
| CN102732312A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01131297A (en) * | 1987-08-03 | 1989-05-24 | Res Assoc Petroleum Alternat Dev<Rapad> | Treatment of heavy oil |
-
2004
- 2004-10-29 CN CNB2004100507046A patent/CN100569924C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453544A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Residual oil hydrotreating and catalytic cracking combined method |
| CN102453544B (en) * | 2010-10-15 | 2013-11-06 | 中国石油化工股份有限公司 | Residual oil hydrogenation treatment and catalytic cracking combination method |
| CN102732311A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking combined method for residuum |
| CN102732314A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking combined method for residuum |
| CN102732315A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
| CN102732313A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
| CN102732312A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking deeply-combined method for residuum |
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