CN102234530B - Heavy oil vacuum deep-drawing grading-partition catalytic cracking combined process method - Google Patents
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Abstract
The invention relates to a combined process method of heavy oil vacuum deep-drawing classification-partition catalytic cracking; a set of pressure-reducing deep-drawing device is additionally arranged beside an atmospheric distillation device or an atmospheric and vacuum distillation device, the inlet temperature of the raw material is 360-460 ℃, the temperature of the top of the tower is 40-150 ℃, the absolute pressure of the top of the tower is 5-50 mmHg, the temperature of the bottom of the tower is 360-420 ℃, the theoretical plate of the pressure-reducing deep-drawing tower is 5-20, the distillation range is less than 520-620 ℃, and the residual carbon weight value is less than 2-4 percent, so that the raw material is high-quality catalytic; the distillation range is more than 520-620 ℃, and the residual carbon weight value is more than 2-4 percent, and the catalyst is poor-quality catalytic raw material; respectively sending high-quality catalytic raw materials and poor-quality catalytic raw materials into two independent reaction zones arranged in a catalytic cracking unit, and converting under respective optimized process conditions; the method avoids the adsorption competition between the inferior raw material and the high-quality raw material and the retardation effect on the reaction, and obviously improves the yield of the light oil.
Description
Technical field
The present invention relates to a kind of heavy oil decompression deep drawing classification that improves the Rfcc Feedstock transformation efficiency-regional catalytic cracking combined technical method, belong to the Petroleum Processing Technology field.
Background technology
Catalytic cracking process is the Main Means of light materialization of heavy oil, is the important production process of the light-end products such as liquefied petroleum gas (LPG), gasoline, diesel oil.Traditional catalytically cracked material is mainly the vacuum distillate that in refinery, atmospheric and vacuum distillation unit provides, due to the continuous growth to the lightweight oil demand and the raising of crude oil price, utilize catalytic cracking technology processing heavy raw oil to become the important selection of oil refining enterprise to increase economic efficiency as atmospheric residue, vacuum residuum and diasphaltene residual oil.
At present, processing for heavy raw oil, for example, except carbon residue and the low especially paraffinic base of heavy metal content (especially content of vanadium) decompression (Daqing Vacuum Residue) can directly enter catalytic cracking unit processing (Resid Fcc Technology For Processing Daqing Vacuum Residue, Wu Xiuzhang, Yang Baokang, refining of petroleum and chemical industry, 2001,32 (8): 6～10; Several key measures of swallowization vacuum residue catalytic device regeneration system transformation, Song Yichang, Ling Yiqun, Liang Fengyin, refining of petroleum and chemical industry, 2002,33 (5): 20～23), the residual oil of the overwhelming majority is all partly to mix in vacuum distillate to enter catalytic cracking unit processing, and the ratio of mixing is subject to the strict restriction of carbon residue in residual oil, heavy metal and hydrogen richness, and this has also seriously limited the ability of utilizing the direct process residual oils of catalytic cracking unit.
Utilize atmospheric and vacuum distillation unit optimization to improve the vacuum distillate extracting rate, be the direction of numerous refineries raising self level of processing for catalytic cracking unit provides many as far as possible high quality raw material always.In recent years, in order to improve total extracting rate and oil quality, there is pair crude oil atmospheric vacuum distillation technology to carry out improved report both at home and abroad.More typical technology has: change High Efficient Column Internals; Optimization of Heat Exchanger Networks; Improve the pumped vacuum systems of vacuum distillation tower; Primary tower is opened side line; Primary tower changes flashing tower into; Set up vacuum flasher between ordinary decompression column, ordinary decompression column is set up stripping section; Two atmospheric tower flow processs; Two vacuum distillation tower flow processs; Dry distillation technology etc.This type of technology has disclosed at CN1061080C, CN1054312C, CN1620120A, CN1344780A, CN1194070C, CN101376068A etc.These patented technologies are from improving the crude oil extracting rate, can for example, for downstream secondary processing device (catalytic cracking, hydrocracking, delayed coking) provides more raw material, this has brought into play great function for the time processing ability of strengthening atmospheric and vacuum distillation unit in refinery.But, consider the singularity of catalytic cracking unit feed properties, utilize atmospheric and vacuum distillation unit to carry high quality raw material as much as possible for catalytic cracking unit, this still also has further improved space for atmospheric and vacuum distillation unit.
At present, each company of great oil refining is less than 8～10wt% to carbon residue substantially both at home and abroad, heavy metal Ni (nickel)+V (vanadium) is less than 25～30 μ g/g as the direct restricted condition of charging of present stage catalytic cracking, and this is because the impurity such as the contributive gum asphalt of carbon residue, heavy metal are caused to very large negative impact to catalyst levels and the product yield of catalyzed cracking processing process.For the catalytic cracking charging, the impurity overwhelming majority such as these colloids, bituminous matter and heavy metal are present in the residual oil raw material from atmospheric and vacuum distillation unit, and this is also to have caused current catalytic cracking unit to mix the major cause that refining residual oil difficulty is large, it is poor that product distributes.Yet, research in recent years shows, if from boiling range, the Catalytic Cracking Residual Oil raw material from atmospheric and vacuum distillation unit is deeply distinguished, these residual oil can further be separated into two portions, part hydrogen richness is high, contain a large amount of saturated minute and fragrance minute, mostly concentrate on<520～620 ℃ of temperature ranges interior (the boiling range scope of this part cut of raw material that the different places of production and base belong to there are differences) of its boiling range scope, be easy to transform component because this part cut comprises under a large amount of catalytic cracking reaction conditions, so this part cut can be called the high-quality fcc raw material; And a part contains a large amount of polycyclic aromatic hydrocarbonss, condensed-nuclei aromatics, heavy metal and gum asphalt in addition, its boiling range scope concentrates on mostly>520～620 ℃ of temperature ranges in, because comprising under wide variety of conventional heavy oil catalytic cracking reaction condition, this part material is difficult to transform component, and also can the conversion of high quality raw material be affected greatly, so this part cut can be called fcc raw material inferior.
For high-quality or fcc raw material inferior, the larger difference of boiling range scope and chemical structure and composition has determined that there is larger difference in their reactivity worth.Be in particular in: the non-hydrocarbons of condensed ring, condensed-nuclei aromatics and condensed ring naphthenic hydrocarbon high adsorption capacity and speed of reaction is low, and, with a little less than the mononuclear aromatics of longer side chain and macromole isoparaffin, naphthenic hydrocarbon adsorptive power and speed of reaction is high, this has just caused competitive adsorption between different hydrocarbons and to the retardation of reaction.Once high adsorption capacity and at first low condensed ring non-hydrocarbons, the condensed-nuclei aromatics of speed of reaction occupy catalyst surface, their speed of reaction are slow, be difficult for desorption, even condensation becomes coke and covers catalyst surface, cause catalyst deactivation, this has just had a strong impact on other and has been easy to the reaction efficiency of cracking hydrocarbons.And for the high quality raw material of heavy oil catalytically cracking equipment, wherein contain a large amount of components that is easy to conversion under the catalytic cracking reaction condition, if this part raw material and the inferior raw material that contains a large amount of non-hydrocarbons, condensed-nuclei aromatics together charging react, pernicious absorption competition and the retardation to reacting certainly will occur in same reaction zone, and the reaction that result can affect whole raw material transforms.
On the other hand, condensed ring non-hydrocarbons, condensed-nuclei aromatics and gum asphalt speed of reaction a large amount of in inferior raw material are low, and reaction times that need to be longer just can reach desirable depth of conversion.The reaction times of conventional riser reactor is controlled at the 3s left and right, high quality raw material part for easy conversion, this reaction times is suitable, but for the inferior raw material part, this reaction times is nowhere near, cause a large amount of non-transformed heavy constituents thoroughly to be adsorbed on spent agent and be brought into stripping stage, after these heavy constituent parts are out entered settling vessel by stripping, easy condensation is got off, cause the settling vessel coking, another part is brought in revivifier and burns as coke (" the some of heavy oil catalytic cracking reaction course are familiar with again---the proposition of " the control Catalytic Cracking Technique of Heavy Oil MZCC of Novel multi association " ". Gao Jinsen, spring is bright, Lu Chunxi, filoplume, oil Refining Technologies and engineering, 2006, 36 (12): 1-6, ), also seriously reduced yield of light oil and the liquid yield of heavy oil catalytic cracking process.
Yet, the raw material that at present from atmospheric and vacuum distillation unit, enters heavy oil catalytically cracking equipment processing is not distinguished from fractions consisting and reactivity worth thereof, all to adopt the form of mixing refining that various raw materials are mixed and enter catalytic cracking unit, and transformed in same reactor He under the same process condition, result is due to the reactivity worth difference of high-quality and fcc raw material inferior and react the inconsistent of step, cause reaction depth not optimize and the phase mutual interference, had a strong impact on the catalytic cracking transformation efficiency of whole raw material.
Summary of the invention
The purpose of this invention is to provide a kind of decompression deep drawing device that utilizes the raw material that enters heavy oil catalytically cracking equipment is further separated to classification, be cut into the high-quality part that is rich in the easy process element of catalytic cracking unit and the part inferior that contains a large amount of polycyclic aromatic hydrocarbonss, condensed-nuclei aromatics, heavy metal and gum asphalt, then make it enter respectively the catalytic cracking unit reactor assembly for its separate reaction zones provided, and the method transformed under the processing condition of each self-optimizing.The method can effectively be avoided the pernicious absorption competition that occurs between component inferior and suitable cracking high-quality component in the heavy fcc raw material and the retardation to reacting, also overcome the problem of part inferior reaction depth deficiency in conventional riser reactor of raw material simultaneously, significantly improve lightweight oil and liquid yield, solve to a certain extent plant catalytic cracking stock in poor quality problem day by day.
To achieve these goals, a kind of heavy oil decompression deep drawing classification provided by the invention-regional catalytic cracking combined technical method comprises the steps:
At first, set up a set of decompression deep drawing device at conventional atmospheric distillation plant or atmospheric and vacuum distillation unit side, making after distillation the atmospheric residue that obtains or vacuum residuum be introduced into this decompression deep drawing device before entering catalytic cracking unit processing further separates, requirement according to catalytic cracking unit to the charging classification, the operating procedure condition of this decompression deep drawing device is: the feed(raw material)inlet temperature is 360～460 ℃, preferably 375～445 ℃, tower top temperature is 40～150 ℃, absolute pressure of top of the tower 5～50mmHg, column bottom temperature is 360～420 ℃, decompression deep drawing tower theoretical tray is 5～20.Establish the high-quality fcc raw material of lateral line withdrawal function boiling range<520～620 ℃ at decompression deep drawing tower, and the carbon residue of controlling this extraction raw material is less than 2～4wt%; Extract the fcc raw material inferior of boiling range scope>520～620 ℃ out at the bottom of decompression deep drawing tower, and the carbon residue of controlling this extraction raw material is greater than 2～4wt%;
Then, the decompression isolated high-quality fcc raw material of deep drawing device and fcc raw material inferior are sent into respectively in the catalytic cracking unit reactor assembly to the separate reaction zones that is respectively high-quality fcc raw material and fcc raw material inferior setting, and transformed under the processing condition of each self-optimizing.
In above-mentioned steps, for the decompression deep drawing device of setting up, comprise preheating oven, tower body, tower tray or filler, and vaccum-pumping equipment;
In above-mentioned steps, the fcc raw material for the isolated high-quality of decompression deep drawing device, require the boiling range scope to be less than 520～620 ℃, and carbon residue is less than 2～4wt%; Fcc raw material for the isolated poor quality of decompression deep drawing device, require the boiling range scope to be greater than 520～620 ℃, and carbon residue is greater than 2～4wt%;
In above-mentioned steps, catalyzed cracking processing method and apparatus for high-quality and fcc raw material inferior, proposed to set up on conventional catalytic cracking unit two independently reaction zone carry out the Grading And Zoning catalytic cracking, and to the application, applied on the same day relevant patent, name is called: a kind of riser tube catalytic unit and application of processing heavy oil: by main riser tube and secondary riser tube, form two independently reactors, main riser tube top riser tube is one and radially with the bottom riser tube of main riser tube, radially waits outlet section large or that dwindle, the bottom riser tube is provided with and promotes steam-in, inferior heavy oil entrance and regenerator sloped tube, the hole enlargement riser tube is in the optional position at 20～95% places of main riser tube height, hole enlargement riser tube height accounts for 20～75% of main riser tube height, the diameter ratio of hole enlargement riser tube and main riser tube bottom riser tube is (1.0～3.0): 1, the interface of secondary riser tube and main riser tube is in the middle and lower part of the hole enlargement riser tube of main riser tube.A kind of heavy oil regional catalytic cracking device and application: by riser reactor and combined reactor, form two independently reactors, bottom is connected with regenerator bottoms with the regenerated catalyst guiding valve by catalyst transport respectively, and riser reactor is connected with oil-gas separator respectively with combined reactor top; Combined reactor consists of fast bed and conveying bed, and fast bed is arranged on the bottom of carrying bed, is highly 1～50% of combined reactor height, and fast bed is (1.0～3.0) with carrying a diameter ratio: 1; Chilling agent import is arranged on fast bed top.A kind of method and apparatus of heavy oil tandem subregion staged catalytic cracking: catalytic cracking riser reactor is divided into independently reaction zone of two of reaction zone and lower reaction zones, lower reaction zone is fast bed or with the hole enlargement riser tube of vertical sleeve tubular type structure, hole enlargement riser tube structure with vertical sleeve tubular type structure is: inner tube, outer tube is divided into inside and outside two isolated areas by lower reaction zone, a circle distributor around inner tube is established in the annular space bottom formed in inner and outer tubes, the ratio of inner tube cross-sectional area and annular space cross-sectional area is 1: (0.1～10), lower reaction zone virtual height is 1～50% of whole riser reactor height.The application's heavy oil decompression deep drawing grading technology can be combined with above-mentioned regional catalytic cracking technique.
The accompanying drawing explanation
The process flow sheet that Fig. 1 is the embodiment of the present invention 1.
The process flow sheet that Fig. 2 is the embodiment of the present invention 2.
Embodiment
Embodiment 1
The visible Fig. 1 of flow process of the present invention, be summarized as follows: on atmospheric distillation plant 1 side, set up a set of decompression deep drawing device 2, enter from the atmospheric residue 3 of sending at the bottom of atmospheric tower the decompression deep drawing device 2 that theoretical plate number is 5～20, then in the feed(raw material)inlet temperature, be 360～460 ℃ (preferably 375～445 ℃), tower top temperature is 40～150 ℃, absolute pressure of top of the tower 5～50mmHg, under the condition that column bottom temperature is 360～420 ℃, separated, establish lateral line withdrawal function boiling range scope<520～620 ℃ at decompression deep drawing tower, carbon residue is less than the high-quality fcc raw material 4 of 2～4wt%, extraction boiling range scope at the bottom of decompression deep drawing tower>520～620 ℃, carbon residue is greater than the fcc raw material inferior 5 of 2～4wt%, the I reaction zone 61 that high-quality fcc raw material 4 enters catalytic cracking unit 6 is reacted, and the II reaction zone 62 that fcc raw material 5 inferior enters catalytic cracking unit 6 is reacted, oil gas 7 after reacting completely enters next technological process.
The visible Fig. 2 of flow process of the present invention, be summarized as follows: on atmospheric and vacuum distillation unit 11 sides, set up the decompression deep drawing device 2 that a set of theoretical plate number is 5～20, it is 360～460 ℃ (preferably 375～445 ℃) in the feed(raw material)inlet temperature that the vacuum residuum 3 of sending from VACUUM TOWER BOTTOM enters decompression deep drawing device 2, tower top temperature is 40～150 ℃, absolute pressure of top of the tower 5～50mmHg, under the condition that column bottom temperature is 360～420 ℃, separated, establish lateral line withdrawal function boiling range scope<520～620 ℃ at decompression deep drawing tower, carbon residue is less than the high-quality fcc raw material 4 of 2～4wt%, extraction boiling range scope at the bottom of decompression deep drawing tower>520～620 ℃, carbon residue is greater than the fcc raw material inferior 5 of 2～4wt%, the I reaction zone 61 that high-quality fcc raw material 4 enters catalytic cracking unit 6 is reacted, and the II reaction zone 62 that fcc raw material 5 inferior enters catalytic cracking unit 6 is reacted, oil gas 7 after reacting completely enters next technological process.
The present invention is that a kind of decompression deep drawing device that utilizes further separates the raw material that enters heavy oil catalytically cracking equipment, be cut into the high-quality part that is rich in the easy process element of catalytic cracking unit and the part inferior that contains a large amount of polycyclic aromatic hydrocarbonss, condensed-nuclei aromatics, heavy metal and gum asphalt, then make it enter respectively the method transformed in catalytic cracking unit reactor differential responses district.The method can effectively be avoided the pernicious absorption competition that occurs between component inferior and suitable cracking high-quality component in the heavy fcc raw material and the retardation to reacting, also overcome the problem of part inferior reaction depth deficiency in conventional riser reactor of raw material simultaneously, significantly improve lightweight oil and liquid yield, solve to a certain extent plant catalytic cracking stock in poor quality problem day by day.
For verifying effect of the present invention, adopt the technical process shown in Fig. 1, utilize decompression deep drawing device that atmospheric residue (character is in Table 1) further is separated into to high quality raw material and inferior raw material, then enter respectively in the regional catalytic cracking device as separately independently in reaction zone of its setting, and reacted under optimum processing condition at it, the optimization reaction conditions adopted separately is as shown in table 2, with conventional heavy oil fluid catalytic cracking, compare, adopt this patented technology can make yield of light oil improve 1.7 percentage points, liquid yield improves 2.0 percentage points, dry gas and coke yield obviously reduce.Detailed product distributes can be in Table 3.
Table 1 heavy oil feedstock character
| Project | Raw material before fractionation | Inferior raw material | High quality raw material |
| Density (20 ℃) kg/m 3 | 0.9206 | 0.9962 | 0.8954 |
| Carbon residue, wt% | 5.79 | 17.14 | 2.00 |
| Ultimate analysis | |||
| Hydrogen richness, wt% | 87.18 | 88.18 | 86.85 |
| Carbon content, wt% | 12.02 | 10.32 | 12.58 |
| Sulphur content, wt% | 0.38 | 0.42 | 0.37 |
| Nitrogen content, wt% | 0.36 | 0.61 | 0.27 |
| Hydrocarbon group composition analysis | |||
| Stable hydrocarbon, wt% | 60.26 | 36.30 | 68.24 |
| Aromatic hydrocarbons, wt% | 24.69 | 38.48 | 20.09 |
| Colloid, wt% | 13.12 | 20.32 | 10.72 |
| Bituminous matter, wt% | 1.94 | 4.90 | 0.95 |
| Ni content, ug/g | 10.6 | 29.3 | 4.3 |
| V content, ug/g | 7.4 | 16.4 | 4.4 |
Table 2 technological condition
Table 3 main products distributes
| Product distributes and character | The prior art scheme | The present invention program |
| H 2S | 0.5 | 0.7 |
| Fuel gas | 4.1 | 3.2 |
| Liquefied gas | 15.3 | 15.6 |
| Gasoline | 44.7 | 45.9 |
| Diesel oil | 25.3 | 25.8 |
| Clarified oil | 1.8 | 1.3 |
| Coke | 8.3 | 7.5 |
| Add up to | 100.0 | 100.0 |
Claims (1)
1. heavy oil decompression deep drawing classification-regional catalytic cracking combined technical method is characterized in that:
Set up a set of decompression deep drawing device at atmospheric distillation plant or atmospheric and vacuum distillation unit side, making after distillation the atmospheric residue that obtains or vacuum residuum be introduced into this decompression deep drawing device before entering catalytic cracking unit processing further separates, the operating procedure condition of decompression deep drawing device is: the feed(raw material)inlet temperature is 360～460 ℃, tower top temperature is 40～150 ℃, absolute pressure of top of the tower 5～50mmHg, column bottom temperature is 360～420 ℃, decompression deep drawing tower theoretical tray is 5～20, establish the high-quality fcc raw material of lateral line withdrawal function boiling range<520～620 ℃ at decompression deep drawing tower, the carbon residue gravimetric value of controlling this extraction raw material is less than 2～4%, extract the fcc raw material inferior of boiling range scope>520～620 ℃ out at the bottom of decompression deep drawing tower, and the carbon residue gravimetric value of controlling this extraction raw material is greater than 2～4%,
Then, the decompression isolated high-quality fcc raw material of deep drawing device and fcc raw material inferior are sent into respectively in the catalytic cracking unit reactor assembly to the separate reaction zones that is respectively high-quality fcc raw material and fcc raw material inferior setting, and transformed under the processing condition of each self-optimizing;
Described catalytic cracking unit is: by riser reactor and combined reactor, form two independently reactors, bottom is connected with regenerator bottoms with the regenerated catalyst guiding valve by catalyst transport respectively, and riser reactor is connected with oil-gas separator respectively with combined reactor top; Combined reactor consists of fast bed and conveying bed, and fast bed is arranged on the bottom of carrying bed, is highly 1～50% of combined reactor height, and fast bed is (1.0～3.0) ︰ 1 with carrying a diameter ratio; Chilling agent import is arranged on fast bed top;
Perhaps described catalytic cracking unit is: catalytic cracking riser reactor is divided into independently reaction zone of two of reaction zone and lower reaction zones, lower reaction zone is fast bed or with the hole enlargement riser tube of vertical sleeve tubular type structure, hole enlargement riser tube structure with vertical sleeve tubular type structure is: inner tube, outer tube is divided into inside and outside two isolated areas by lower reaction zone, a circle distributor around inner tube is established in the annular space bottom formed in inner and outer tubes, the ratio of inner tube cross-sectional area and annular space cross-sectional area is 1:(0.1～10), lower reaction zone virtual height is 1～50% of whole riser reactor height.
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| CN106753508B (en) * | 2017-03-22 | 2023-12-19 | 中国石油大学(华东) | Pressure-reducing deep drawing tower for fractionation |
| CN114437754B (en) * | 2020-10-19 | 2023-10-10 | 中国石油化工股份有限公司 | Method for producing low-sulfur marine residue fuel oil by using low-sulfur paraffin-based crude oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786400A (en) * | 1984-09-10 | 1988-11-22 | Farnsworth Carl D | Method and apparatus for catalytically converting fractions of crude oil boiling above gasoline |
| CN1262306A (en) * | 1999-01-28 | 2000-08-09 | 中国石油化工集团公司 | Hydrogenation and catalystic cracking combined process for residual oil |
| JP4223690B2 (en) * | 2001-02-21 | 2009-02-12 | 財団法人 国際石油交流センター | Fluid catalytic cracking method of heavy oil |
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2010
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|---|---|
| CN102234530A (en) | 2011-11-09 |
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