CN101942339A - Boiling-bed residual-oil hydrocracking and catalytic-cracking combined process method - Google Patents
Boiling-bed residual-oil hydrocracking and catalytic-cracking combined process method Download PDFInfo
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Abstract
The invention discloses a boiling-bed residual-oil hydrocracking and catalytic-cracking combined process method which comprises the following steps that: a residual-oil raw material enters a boiling-bed residual-oil hydrogenation device for hydrocracking reaction after exchanging heat with a high-temperature regeneration catalyst from a catalytic cracking regenerator, total or partial boiling-bed hydrocracked tail oil enters a catalytic cracking device for cracking reaction to obtain a gasoline fraction and a diesel oil fraction, and after a catalytic cracking catalyst is regenerated, one part of the regenerated catalyst is circulated back to the catalytic cracking device, and the other part of the regenerated catalyst is used for preheating the incoming material of the boiling-bed residual oil to reaction temperature. The process characteristics of the hydrocracking and the catalytic cracking of a boiling bed are organically combined together through the combined process, respective advantages are fully exerted, the incoming material of a boiling-bed device is preheated by utilizing the high-temperature regenerated catalytic cracking catalyst, energy sources are saved, meanwhile, the heat load of a heating furnace is reduced.
Description
Technical field
The present invention relates to a kind of processing method of producing light ends oil, particularly boiling bed hydrogenation cracking and catalytic cracking process are organically combined the combined technical method of producing light ends oil by poor residuum.
Background technology
Fast development along with global economy, the quick growth of lightweight, clean fuel oil demand and former oil quality are worse and worse, heavy constituent content is more and more higher, how effectively to utilize non-renewable petroleum resources, realize residual oil lighting to greatest extent, production high value petroleum products is the current important topic that faces.
The residual oil processing technology mainly comprises hydrogenation and two kinds of technological processs of decarburization, and wherein decarbonization process mainly comprises solvent deasphalting, coking, heavy oil fluid catalytic cracking etc., and hydrogenation technique mainly comprises hydrotreatment, hydrofining, hydrocracking etc.The decarbonization process facility investment is low, but liquid product yield is low, and character is poor.The hydrogenation technique quality product is better, the liquid yield height, but owing to use high pressure reactor to cause investment higher.The residual hydrogenation technology of comparative maturity is the fixed bed residual hydrogenation at present, but this technology is subjected to the restriction of feedstock property, and to the metal of raw material, index requests such as carbon residue are relatively stricter.And boiling bed residual oil hydrogenation technique adaptability to raw material is wide, more and more is subjected to people's attention.Face quality residual oil raw material worse and worse, how decarbonization process and hydrogenation process are organically combined, realization residual oil maximum conversion and capital contribution are minimum to be the technology of being badly in need of at present.Existing hydrogenation and decarburization combination process, normally hydrogenation tail oil is sent into the decarbonization process process as fixed bed hydrogenation or boiling bed hydrogenation and catalytic cracking, solvent deasphalting or coking combination process, produce light-end products through catalytic cracking or high-temperature-coked cracking, this combination process just carries out the rational Match of material and technology according to device charging requirement, fail to give full play to the advantage of two kinds of technology.
US6447671 discloses a kind of combination process process that is used for heavily residuum hydroconversion.Detailed process is: heavy residual oil raw material and hydrogen are mixed into boiling bed hydrogenation cracking reaction district, logistics obtains lighting end and last running through tripping device behind the hydrocracking reaction, and lighting end enters distillate fixed bed hydrogenation processing section or directly enters water distilling apparatus carries out the narrow fraction cutting; Heavy constituent system after filtration enter heavy oil fixed bed hydrogenation reaction zone after removing the catalyst solid residue; Perhaps directly enter filtering system, enter heavy oil fixed bed hydrogenation processing reaction district after isolating the catalyst solid material from the effusive whole logistics in boiling bed hydrogenation cracking reaction district; Reacted all or part of logistics enters water distilling apparatus, cuts out each lighting end and heavy constituent, and the heavy constituent that wherein obtain enter catalytic cracking unit or loop back heavy-oil hydrogenation and handle or the hydrocracking reaction district.This combination process process just requires according to the charging of device and reacted logistics property carries out the rational Match of processing means, the characteristics of each COMBINED PROCESS is not given full play of.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of combination process of handling residual oil raw material is provided, give full play to the technical characterstic of each technology, make it become an organic whole, can process various inferior raw materials, maximum improves the yield and the quality of light-end products, reduces overall cost of ownership simultaneously.
Boiling bed residual oil hydrocracking of the present invention and catalytic cracking combination process comprise the steps:
A, residual oil raw material and catalytic cracked regenerated after the high temperature catalyst contact heat-exchanging, carry out finish through tripping device then and separate;
B, isolated warm sludge oil raw material and hydrogen enter the boiling bed hydrogenation cracking unit, carry out hydrocracking reaction under boiling bed hydrogenation cracking reaction condition; Reaction effluent obtains light ends oil and hydrogenation tail oil through tripping device;
The part or all of hydrogenation tail oil that c, step b obtain enters catalyst cracker and carries out catalytic cracking reaction;
The regenerated catalyst for the treatment of that d, catalyst cracker are discharged enters regenerating unit, and the catalyst recirculation behind the partial regeneration is returned catalyst cracker and carried out cracking reaction, and the catalyzer behind the partial regeneration mixes with the charging of ebullated bed device, preheating ebullated bed device raw material;
The catalytic cracking reaction product that e, step c obtain and the light ends oil of ebullated bed obtain gasoline, diesel oil distillate through water distilling apparatus.
The residual oil raw material that relates among the step a comprises that metal content is at least 150 μ g/g in the residual oil that crude distillation obtains, particularly raw material, and carbon residue is at least the poor residuum of 15wt%.Described tripping device can be centrifugal separating device or filtration unit etc., and isolated solid catalyst can all or part ofly loop back catalytic cracking regenerator.Described residual oil raw material feeding temperature is 200～360 ℃, and residual oil raw material can adopt the mode of conventional heating or heat exchange to reach above-mentioned feeding temperature.In order to suppress the excessive coking of stock oil on solid matter, can in residual oil raw material, mix an amount of hydrogen, the volume of wherein sneaking into hydrogen accounts for the 0.1v%～100v% of residual oil raw material volume, is preferably 10v%～60v%.The weight ratio of high-temperature regenerated catalyst and residual oil raw material is 2～20, be preferably 5～15, the ebullated bed device feeding temperature after the control preheating is 320～550 ℃, is preferably 420～480 ℃, heat transfer process can be generally: 0～0.5MPa carrying out near under the non-pressurized state.
Boiling bed hydrogenation catalyst described in the step b) is the hydrotreating catalyst of this area routine, and wherein the activity of such catalysts metal can be in nickel, cobalt, molybdenum or the tungsten one or more.Can comprise by weight percentage as the catalyzer composition: nickel or cobalt are 1%～20% (calculating by its oxide compound), molybdenum or tungsten are 1%～30% (calculating by its oxide compound), and carrier can be in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide or the titanium oxide one or more.The shape of catalyzer is extrudate or sphere, and bulk density is 0.4～0.9g/cm
3, particle diameter (spherical diameter or bar shaped diameter) is 0.08～1.2mm, specific surface area is 100～300m
2/ g.The operational condition of boiling bed hydrogenation process is generally: reaction pressure 6～30MPa, 400～490 ℃ of temperature of reaction, volume space velocity 0.1～5.0h during liquid
-1, hydrogen to oil volume ratio (under the standard conditions) 200～2000.Be preferably reaction pressure 15～20MPa, 420～470 ℃ of temperature of reaction, volume space velocity 0.5～2.0h during liquid
-1Hydrogen to oil volume ratio (under the standard conditions) 400～1000.Described reaction product tripping device can be high-pressure separator or flashing tower, and the temperature of cutting apart of light ends oil and hydrogenation tail oil is 350 ℃, and light ends oil comprises gasoline fraction and diesel oil distillate.
Catalytic cracking unit described in the step c comprises a reactor, a revivifier and a separation column at least.The catalytic cracking process operational condition can be identical with existing operational condition, and reaction conditions is generally: 470～570 ℃ of temperature of reaction, 1～5 second reaction times, agent weight of oil than 3～10,650～750 ℃ of regeneration temperatures.The catalytic cracking catalyst that is adopted comprises the catalytic cracking catalyst of this area routine, as silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and molecular sieve cracking catalyst, molecular sieve cracking catalyst preferably, wherein molecular sieve is optional self-contained or do not contain Y or HY molecular sieve, the super-stable Y molecular sieves that contains or do not contain rare earth, ZSM-5 series molecular sieve, the high-silica zeolite with five-membered ring structure, beta-molecular sieve or its mixture of rare earth.Adopt molecular sieve cracking catalyst active high, 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, preferably riser reactor.Technical process is generally: catalytically cracked stock injects from the riser reactor bottom, contact with fresh regenerated high temperature catalyst from revivifier, oil gas and mixture of catalysts that cracking reaction generates move up along riser reactor, finish the catalytic cracking reaction of whole stock oil.
Being used to described in the steps d treats that the regenerating unit of regeneration catalyzing cracking catalyst is preferably the two-stage regeneration device.Control the regeneration temperature of this section by the main air blower blast volume of controlling every section regenerating unit.Treating that regenerated catalyst can partly draw off after one section regenerating unit burns carbon is used for preheating residual oil bed apparatus raw material, part enters two sections regenerating units continuation burning carbon and provides regenerated catalyst for catalytic cracking unit, wherein one section regeneration temperature is 500～700 ℃, and two sections regeneration temperatures are 700～800 ℃.The regeneration catalyzing dosage that is used for preheating ebullated bed device raw material can simple computation obtain according to conditions such as the amount of ebullated bed device raw material and temperature.
Boiling bed hydrogenation tail oil described in the step e can be produced gasoline fraction and diesel oil distillate after catalytic cracking, wherein gasoline fraction is the desirable blending component of stop bracket gasoline; Diesel oil distillate can be used as the product blending component, or further hydro-upgrading.Catalytic slurry can be recycled to ebullated bed reactor and carry out cracking reaction, also can carry out other processing.
Advantage of the present invention is:
1, adopts high temperature catalyst preheating ebullated bed device charging after catalytic cracked regenerated, can alleviate process furnace thermal load or cancellation process furnace, guarantee to provide the boiling bed hydrogenation cracking required heat supply by high-temperature catalytic cracking regenerated catalyst, the more important thing is and avoided the coking problem of heavy feed stock in process furnace.
2, adopt high-temperature catalytic cracking regenerated catalyst to contact preheating, can carry out pre-treatment to residual oil raw material simultaneously, remove coking precursor such as part bituminous matter, improved the ebullated bed feed properties with the ebullated bed inferior raw material.
3, with boiling bed hydrogenation and catalytic cracking process combination, hydrogenation technique and decarbonization process are organically combined, can realize the lighting to greatest extent of residual oil, and can produce high-quality light-end products.
4, this combination process has possessed the technological merit of decarburization and hydrogenation technique simultaneously, has not only guaranteed quality product but also can reduce overall cost of ownership.
5, effectively utilize the superfluous heat of catalytic cracking system, reduce energy expenditure.
Embodiment
Below method provided by the present invention is further specified.
Residual oil raw material is after heat exchange or process furnace are preheating to 200～360 ℃, with high-temperature regenerated catalyst contact heat-exchanging to 320～550 of coming catalytic cracking ℃, be preferably 420～480 ℃, enter conventional tripping device then, as centrifuge separator or strainer etc., isolate the solid catalysis cracking catalyst in the residual oil, residual oil raw material after the heat exchange and hydrogen are mixed into ebullated bed reactor and carry out hydrocracking reaction, reactant flow is through tripping device, obtain＜350 ℃ light ends oil and＞350 ℃ hydrogenation tail oil, wherein all or part of catalyst cracker that enters of hydrogenation tail oil carries out cracking reaction, the regenerated catalyst for the treatment of behind the catalytic cracking reaction enters regenerating unit, and it is preferably the two-stage regeneration device.Control the regeneration temperature of this section by the main air blower blast volume of controlling each section regenerating unit.Treat that regenerated catalyst is used for the charging of preheating ebullated bed device through partly drawing off behind one section regenerating unit burning carbon or in burning carbon process, part enters two sections regenerating units continuation burning carbon and provides regenerated catalyst for catalytic cracking unit, wherein one section regeneration temperature is 500～700 ℃, and two sections regeneration temperatures are 700～800 ℃.Liquid product logistics behind the catalytic cracking reaction and boiling bed hydrogenation after tripping device obtain＜350 ℃ light ends oil is mixed into fractionation plant, obtains gasoline fraction and diesel oil distillate.The catalytic slurry that catalytic cracking unit is come out is circulated to ebullated bed reactor.
For further specifying all main points of the present invention, enumerate following examples, but not thereby limiting the invention.
Typical poor residuum is used in test, and its feedstock property sees Table 1.This raw material has metal content height, carbon residue height and the high characteristics of sulphur content as shown in Table 1, wherein the content of metallic nickel and vanadium is 187 μ g/g, asphalt content surpasses 8wt%, and carbon residue content is 20.7wt%, is that conventional fixed bed Residue Hydrotreating Technology is difficult to the directly poor residuum of processing.
Embodiment
Present embodiment carries out the reaction process of residual hydrogenation for the catalytic cracking combined technique that adopts boiling bed hydrogenation cracking and two-stage regeneration.At first process furnace is heated to 360 ℃ residual oil raw material and 540 ℃ of regenerated catalyst contact heat-exchangings to 440 that come one section revivifier of catalytic cracking to make charcoal to discharge in the process ℃, the two part by weight is 1: 3.4, the solidliquid mixture stream into centrifugal separator is isolated the solid catalyst in the residual oil then, residual oil raw material after the heat exchange and hydrogen are mixed into ebullated bed reactor and carry out hydrocracking reaction, reactant flow is through the high pressure-temperature separator, obtain＜350 ℃ light ends oil and＞350 ℃ hydrogenation tail oil, wherein hydrogenation tail oil enters catalyst cracker and carries out cracking reaction, the regenerated catalyst for the treatment of behind the catalytic cracking reaction enters the two-stage regeneration device, the part catalyzer that takes out in one section regenerating unit burning carbon process draws off from device and is used for the charging of preheating ebullated bed device, rest part through one section make charcoal finish after, regeneration temperature is discharged after reaching 650 ℃, enter two sections regenerating units continuation burning carbon and provide regenerated catalyst for catalytic cracking unit, wherein two sections regeneration temperatures are 750 ℃.Product stream behind the catalytic cracking reaction and boiling bed hydrogenation cracking after high-temperature high-pressure separator obtain＜350 ℃ light ends oil is mixed into atmospheric distillation plant, obtains gasoline fraction and diesel oil distillate.The catalytic slurry that catalytic cracking unit is come out all is circulated to ebullated bed reactor.
The boiling bed hydrogenation catalyst that process of the test is used as microspheroidal with the molybdenum-nickel catalyzator of aluminum oxide as carrier, wherein contain MoO in the catalyzer
3Be 15wt%, containing NiO is 4wt%.The bulk density of catalyzer is 0.75g/cm
3, surface-area is 240m
2/ g, the granules of catalyst mean diameter is 0.6mm.
FCC tests is carried out on riser fluid catalytic cracking, adopts circulating reaction-reproduction operation pattern.The CHV-1 catalyzer that catalytic cracking catalyst is produced for Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant.
Table 1 feedstock property
| Project | Residual oil raw material |
| Density (20 ℃), kg.m -3 | 1024.8 |
| Carbon residue, wt% | 20.7 |
| Metallic element | |
| Ni，μg.g -1 | 43.4 |
| V，μg.g -1 | 143.6 |
| Four proximate analyses, wt% | |
| Stable hydrocarbon | 9.9 |
| Aromatic hydrocarbon | 52.2 |
| Colloid | 29.5 |
| Bituminous matter | 8.4 |
| Boiling range, % |
| 350～520℃ | 10 |
| ＞520℃ | 90 |
Table 2 combination process test conditions
| Project | Data |
| The boiling bed hydrogenation reaction conditions | |
| The reaction stagnation pressure, MPa | 18 |
| Volume space velocity, h -1 | 2.0 |
| Temperature of reaction, ℃ | 440 |
| Hydrogen-oil ratio, v/v | 800 |
| The catalytic cracking reaction condition | |
| Temperature of reaction, ℃ | 500 |
| Reaction times, second | 2.5 |
| Agent weight of oil ratio | 1.7 |
Table 3 test-results
| Project | Data |
| Reactor product distributes (serves as to calculate benchmark with combined feed total feed weight), % | |
| Dry gas | 8.2 |
| Liquefied gas | 12.2 |
| Gasoline | 40.0 |
| Diesel oil | 33.0 |
| Coke | 3.0 |
| Externally extracting oil | 3.6 |
| Gasoline fraction character: | |
| Sulphur, μ g.g -1 | 80 |
| Nitrogen, μ g.g -1 | 31 |
| Octane value (RON) | 90 |
| Diesel oil distillate character: | |
| Sulphur, μ g.g -1 | 200 |
| Nitrogen, μ g.g -1 | 88 |
| Cetane value | 45 |
Claims (10)
1. boiling bed residual oil hydrocracking and catalytic cracking combination process comprise the steps:
A, residual oil raw material and catalytic cracked regenerated after the high temperature catalyst contact heat-exchanging, carry out finish through tripping device then and separate;
B, isolated warm sludge oil raw material and hydrogen enter the boiling bed hydrogenation cracking unit, carry out hydrocracking reaction under boiling bed hydrogenation cracking reaction condition; Reaction effluent obtains light ends oil and hydrogenation tail oil through tripping device;
The part or all of hydrogenation tail oil that c, step b obtain enters catalyst cracker and carries out catalytic cracking reaction;
The regenerated catalyst for the treatment of that d, catalyst cracker are discharged enters regenerating unit, and the catalyst recirculation behind the partial regeneration is returned catalyst cracker and carried out cracking reaction, and the catalyzer behind the partial regeneration mixes with the charging of ebullated bed device, preheating ebullated bed device raw material;
The catalytic cracking reaction product that e, step c obtain and the light ends oil of ebullated bed obtain gasoline, diesel oil distillate through water distilling apparatus.
2. in accordance with the method for claim 1, it is characterized in that: the residual oil raw material that relates among the step a comprises the residual oil that crude distillation obtains, described tripping device can be centrifugal separating device or filtration unit, and isolated solid catalyst can all or part ofly loop back catalytic cracking regenerator.
3. in accordance with the method for claim 1, it is characterized in that: the residual oil raw material feeding temperature is 200～360 ℃ among the step a, the weight ratio of high temperature regeneration catalytic cracking catalyst and residual oil raw material is 2～20, and the ebullated bed device feeding temperature after the control preheating is 320～550 ℃.
4. in accordance with the method for claim 1, it is characterized in that: mix an amount of hydrogen among the step a in residual oil raw material, the volume of sneaking into hydrogen accounts for the 0.1v%～100v% of residual oil raw material volume.
5. in accordance with the method for claim 1, it is characterized in that: the weight ratio of high temperature regeneration catalytic cracking catalyst and residual oil raw material is 5～15 among the step a, and the ebullated bed device feeding temperature after the control preheating is 420～480 ℃.
6. in accordance with the method for claim 1, it is characterized in that: the reactive metal of the described boiling bed hydrogenation catalyst of step b is one or more in nickel, cobalt, molybdenum or the tungsten, catalyzer is formed and comprised by weight percentage: by oxide compound nickel or cobalt is 1%～20%, is 1%～30% by oxide compound molybdenum or tungsten.
7. in accordance with the method for claim 1, it is characterized in that: the operational condition of step b institute boiling bed hydrogenation process is: reaction pressure 6～30MPa, 400～490 ℃ of temperature of reaction, volume space velocity 0.1～5.0h during liquid
-1, hydrogen to oil volume ratio 200～2000.
8. it is characterized in that in accordance with the method for claim 1: the catalytic cracking unit described in the step c comprises a reactor, a revivifier and a separation column at least; The catalytic cracking process operational condition is: 470～570 ℃ of temperature of reaction, 1～5 second reaction times, agent weight of oil than 3～10,650～750 ℃ of regeneration temperatures.
9. in accordance with the method for claim 1, it is characterized in that: being used to described in the steps d treats that the regenerating unit of regeneration catalyzing cracking catalyst is the two-stage regeneration device, treat that regenerated catalyst burns the carbon rear section through one section regenerating unit and draws off and be used for preheating ebullated bed device raw material, part enters two sections regenerating units continuation burning carbon and provides regenerated catalyst for catalytic cracking unit, wherein one section regeneration temperature is 500～700 ℃, and two sections regeneration temperatures are 700～800 ℃.
10. in accordance with the method for claim 1, it is characterized in that: the boiling bed hydrogenation tail oil described in the step e is produced gasoline fraction and diesel oil distillate after catalytic cracking, and catalytic slurry is recycled to ebullated bed reactor and carries out cracking reaction.
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| CN103429709A (en) * | 2011-03-23 | 2013-12-04 | 沙特阿拉伯石油公司 | Cracking system and process integrating hydrocracking and fluidized catalytic cracking |
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| CN110628462A (en) * | 2019-10-14 | 2019-12-31 | 中国石油化工股份有限公司 | Hydrocracking and catalytic cracking combined process and device |
| CN110628462B (en) * | 2019-10-14 | 2021-06-29 | 中国石油化工股份有限公司 | Hydrocracking and catalytic cracking combined process and device |
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