CN102465031B - Hydrotreating method for heavy hydrocarbon raw materials - Google Patents
Hydrotreating method for heavy hydrocarbon raw materials Download PDFInfo
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Abstract
The invention discloses a hydrotreating method for heavy hydrocarbon raw materials. According to the invention, a fixed bed hydrogenation reactor is employed; at least two catalyst beds are arranged in the fixed bed hydrogenation reactor; a solvent is introduced at least from one gap formed by two adjacent catalyst beds and is mixed with reacting materials, and light components are extracted; the light components are introduced out from the reactor in an extraction and separation area between two adjacent catalyst beds, and heavy components enter into next catalyst bed for further reaction; extracted oil can directly enter into a gasoline/diesel hydrogenation device so as to obtain qualified gasoline/diesel and can also enter into an FCC main fractionating column for fractionation so as to obtain a crude product which enters into the gasoline/diesel hydrogenation device so as to obtain qualified gasoline/diesel. The method provided in the invention can effectively reduce pressure drop of beds in fixed bed hydrotreatment, prolong the service life of a catalyst, improve a total conversion rate of a fixed bed hydrogenation apparatus and enhance treating capacity of an apparatus under the condition of a same conversion rate, thereby creating greater benefits for an enterprise.
Description
Technical field
The present invention relates to a kind of heavy-hydrocarbon raw material hydrogenation treatment method, particularly heavy hydrocarbon feeds removing impurities matter separates with light, heavy oil the hydroprocessing process simultaneously carrying out.
Background technology
Along with day by day becoming of crude oil is bad, it is heavy to become and increase day by day to light-end products demand, heavy oil lighting has become oil refining worker's main task.Heavy-oil hydrogenation upgrading is one of main method of heavy oil lighting, not only can slough in a large number the detrimental impurity such as metal in residual oil, sulphur, nitrogen, the low boiling component can also make heavily, slag oil crack being high value.
At present, the Residue Hydrotreating Technology of industrialization or technology maturation has fixed bed, moving-bed, ebullated bed and the large class of suspension bed four in the world, and wherein fixed-bed process is most widely used, also the most ripe.Though moving-bed, ebullated bed and suspension bed can be processed inferior heavy oil, complicated operation and investment are higher, the less stable of device.Fixed bed hydrogenation technology is to fill in different reactors or different bed equipped the catalyst grade of difference in functionality, and residual oil raw material contacts with catalyzer during by bed and carries out hydrogenation reaction.The deficiency of this Residue Hydrotreating Technology is that stock oil is had to strict restriction, along with the increase of coke on catalyzer and metal deposition, rapid catalyst deactivation, particularly contain a large amount of impurity particularly when inferior heavy oil, the residual oil raw material of carbon residue and metal in processing, beds easily stops up, in addition, it is to be determined by catalyzer and stock oil substantially that the product of fixed bed hydrogenation device distributes, and is difficult to adjust with turn of the market.At present, the optimization that has catalyst performance is mainly concentrated in the improvement of fixed bed hydrogenation device, and the grading loading of different performance catalyzer, with the work-ing life of further extending catalyst and the on-stream time of hydrogenation unit.
CN1335369 discloses improving one's methods of a kind of heavy, resid Fixed Bed Hydrotreating Technology, the method first adopts heavily, residual oil relaxes thermally splitting and generates the middle phase of residual oil, then centre is separated, remove more bituminous matter and/or the part colloid of metal content in resid feed, its metal content is reduced, then carry out hydrotreatment.The shortcoming of this technique be not only in the middle of the heat cracking reaction degree of depth and residual oil the formation of phase be difficult to control, and be difficult to ensure stock oil in reactor from top to bottom until reactor outlet be all in the middle of phase.
CN1362494 discloses a kind of process for hydrogenating residual oil, and the method arranges separated from solvent region in hydrotreating reactor bottom, and the heavy component in residual oil is separated and discharged, and remaining oil carries out hydrotreatment.The shortcoming of this technique be when on the one hand heavy constituent is extracted out because pressure is high, must carry a large amount of light constituents and cause the loss of light oil, light oil carries out cracking reaction repeatedly and has reduced liquid receipts in reactor on the other hand.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of heavy-hydrocarbon raw material hydrogenation treatment method, the inventive method has deep conversion heavy hydrocarbon feeds, and extends the advantages such as hydrogenation unit running life.
Heavy-hydrocarbon raw material hydrogenation treatment method of the present invention comprises following content: adopt fixed bed hydrogenation reactor, two beds are at least set in fixed bed hydrogenation reactor, between at least one adjacent catalyst bed layer, introduce solvent, solvent mixes with reaction mass and light constituent is extracted, light constituent is drawn reactor by extracting disengaging zone at adjacent two catalyst bed interlayers, and heavy constituent enters next beds and continues reaction.
In the inventive method, heavy hydrocarbon feeds can be the raw material of various poor qualities, heavy, as the residual oil of various crude oil, heavy crude, liquefied coal coil, coal tar wet goods.Beds in fixed bed hydrogenation reactor is generally 3～5, and hydrotreating catalyst can use the catalyzer of this area routine, can use a kind of hydrotreating catalyst according to the character of raw material, also can use multiple hydrotreating catalyst.Those skilled in the art will know that, hydrotreating catalyst is preferably by the order grading loading along reduce successively in reagent flow direction aperture, active metal component raises successively, concrete catalyzer can be selected commercial goods catalyzer, also can prepare by this area ordinary method.Hydrotreating catalyst is generally taking aluminum oxide as carrier, taking one or more in W, Mo, Ni, Co as hydrogenation activity component.
In the inventive method, hydrotreatment reaction conditions is generally: temperature of reaction is 360-480 DEG C, and reaction pressure is 10.0-21.0MPa, and feed volume air speed is 0.1-2.0h
-1, reactor inlet hydrogen to oil volume ratio is 500: 1-1500: 1.Concrete operations condition can be adjusted definite according to feedstock property and required reaction depth.
In the inventive method, between adjacent two beds, can adopt cold hydrogen control temperature of reaction, also can be by cold oil control temperature of reaction, in order to dissolve the bituminous matter in heavy constituent, preferably adopt cold oil control temperature of reaction, cold oil is as all kinds of oil plants of C20～C40 or its mixture, and cold oil introduction volume is determined by the bed top temperature of design.Cold oil is preferably the residual oil after fluid catalytic cracking decant oil, the hydrotreatment of this device etc.
In the inventive method, solvent is propane and/or butane, and the solvent load of adjacent two catalyst bed interlayers is 5%～50% of stock oil charging quality, preferably 10%～30%.Solvent carries out extracting separation in the extracting disengaging zone in reactor to the light constituent producing in reaction process, and the light constituent extracting is drawn reactor.Solvent can together be introduced reactor with cold oil, also can introduce respectively reactor.Extracting disengaging zone in reactor is the suitable way such as natural subsidence or centrifugal settling.
In the inventive method, extract at the different positions of reactor the light oil that in stock oil hydrotreatment process, cracking produces out, improve transformation efficiency with the contact probability that increases remaining heavy feed stock and catalyzer; Below cold miscella inlet, solvent extraction region is set and carries out extracting in device, extract the light oil after extracting out a mouthful extraction from light oil, the injection of cold miscella can suppress the overreaction of heavy, asphaltene in vacuum residues and blocking catalyst aperture by reducing temperature of reaction on the one hand, the bituminous matter of separating out on the other hand can solubilizing reaction process and slow down catalyzer coking and blocking bed, extend the running period of follow-up residual hydrogenation process, in addition the light oil in reaction mixture is carried out to solvent extraction and realize light, heavy oil separating.The inventive method not only can be optimized the operation of follow-up fixed bed hydrogenation treatment process, expands the source of fixed bed hydrogenation raw material, and can also greatly extend the running life of fixed bed hydrogenation device.
Specifically, compared with prior art, tool has the following advantages the inventive method:
1, inject the technique of cold miscella dilution residual hydrogenation resultant of reaction by employing, the highly active part bituminous matter that reaction can be generated and intermediate product is partly dissolved and suitably cooling and reduce its activity, thereby delay catalyzer coking and blocking bed, in taking off beavy metal impurity by hydrogenation reaction, extend the work-ing life of hydrogenation catalyst, extend the running period of hydrotreater.Adaptability to raw material is wider, has expanded the source of raw material.
2, solvent add can realization response product in weight oil separating, avoid light oil drastic cracking, improve the liquid of residual hydrogenation and receive, the economic benefit of taking out high device.
3, by adopting the technique of extracting continuously the light oil after solvent extraction at reactor different positions out, reclaim the good light oil of part quality, improve the utilization ratio of residual oil, and the touch opportunity of remaining heavy oil and catalyzer is increased and improved the transformation efficiency of residual oil.
4, reaction product liberated heat is absorbed by cold oil, therefore need not inject cold hydrogen lowers the temperature to product, save energy consumption, and the injection of cold oil makes reactor beds laminar flow regime more stable, flow distribution is more even, thereby whole reactor temperature of reaction from top to bottom can be kept evenly, and reaction is difficult for temperature runaway, be easy to control.
5,, by residual hydrocracking technique, make residual oil after treatment be more suitable for the use in downstream unit.
Brief description of the drawings
Fig. 1 is processing method schematic flow sheet of the present invention.
1 is the residual oil through heating and the feeding line of hydrogen;
2,3,4, the 5 injection pipelines that are respectively first to fourth beds cold oil and solvent;
6,7,8,9 lightweight oils that are respectively first to fourth beds are extracted pipeline out;
14,15,16,17 mixing regions that are respectively cold oil and solvent and the reactant of first to fourth beds;
10,11,12, the 13 solvent extraction disengaging zone that are respectively first to fourth beds, both extracting separated regions of weight component.
Embodiment
In heavy-hydrocarbon raw material hydrogenation treatment method of the present invention, adopt the light oil arranging in heavy hydrocarbon feeds hydrotreatment process after cold miscella inlet and solvent extraction to extract mouth out, realize on the one hand light, heavy oil separating, improve bottoms conversion and treatment capacity, on the other hand because part bituminous matter has been dissolved in the injection of cold oil, slow down beds coking speed, take off most metal by the hydrogenation reaction gradually of each bed and realize fixed bed hydrogenation processing reaction, light oil and heavy oil separating are also realized, avoid light oil deep hydrogenation and improved liquid product yield.
Specifically, first the temperature of residual oil raw material and hydrogen mixture is heated to the required temperature of reaction, entering fixed-bed reactor the first beds reacts again, the first beds outlet arranges cold oil and solvent mixture, with the first catalyst bed reaction product hybrid cooling and carry out solvent extraction, the light constituent that extracting obtains is drawn reactor, and heavy constituent enters the second beds and proceeds reaction until reactor outlet.The injection of cold miscella has suitably reduced the temperature of heavy oil, suppress the excessive fragmentation reaction of heavy oil, the bituminous matter that heavy oil is about to separate out has been dissolved in the injection of cold oil simultaneously, prevents the obstruction of catalyzer aperture, can the light oil in reaction product be carried out solvent extraction and be extracted out in addition.
The main operational condition of hydrotreating reactor is cold miscella character and injection rate.On the impact of residual hydrocracking clearly, cold oil is stronger to the bitum solvability in reactant for cold oil character and injection rate, and beds is more not easy to stop up; The injection rate of cold oil is larger, the mixed temperature of cold oil and mixture is lower, more can suppress bitum overreaction, prevent bituminous matter coking, but simultaneous temperature can not be too low, react needed temperature otherwise can not reach next bed residual hydrocracking, affect hydrotreatment effect and transformation efficiency; Solvent is larger to the solubleness of light oil, and weight oil separating effect is better.The temperature of therefore reacting required according to residual hydrocracking in the present invention is determined the injection rate of cold oil, determines the add-on of solvent according to cracking reaction degree, and the add-on of solvent and light oil have a suitable ratio.The mixing temperature of cold oil and solvent is generally 150～250 DEG C.
Further illustrate the present invention below in conjunction with accompanying drawing.
The implementation procedure of residual hydrocracking process of the present invention is: stock oil and hydrogen are heated to residual hydrogenation through process furnace and react after required temperature, enter reactor by feeding line 1, after the first bed reaction, in 14 regions and cold oil and solvent, make material cooling, after mixing, entering 10th district carries out solvent extraction and realizes light oil and heavy oil separating, light oil is extracted out from pipeline 6, remaining heavy oil enters the second bed generation hydrogenation reaction, then carry out mixing of reaction product and cold oil and solvent in 15 regions, after carrying out solvent extraction to 11 regions, light oil is extracted out from pipeline 7, remaining heavy oil enters the 3rd bed generation hydrogenation reaction, then carry out mixing of reaction product and cold oil and solvent in 16 regions, after carrying out solvent extraction to 12 regions, light oil is extracted out from pipeline 8, remaining heavy oil enters four bed generation hydrogenation reactions.
The high efficient mixed of mixing tank realization response product and cold oil and solvent can be set in 14,15,16,17 regions, strengthen solvent extraction effect; At 10,11,12,13 region division solvent extraction apparatus, can be extracting case or extracting tank etc.
Different raw materials and different hydrotreatments require corresponding different operating parameterss, and the present invention can change amount and the operational condition that light oil extracted amount and cold oil and solvent are injected according to feedstock property.
The processing parameter of this patent method is selected as follows:
Stock oil can be selected normal pressure or vacuum residuum, and the bituminous matter in residual oil is relatively many, more can embody the advantage of this patent.
The cold oil of described method can be selected all kinds of oil plants of C30 left and right and composition thereof, and preferably narrow fraction oil, is convenient to dissolved bitumen matter, also can install charging with this, convenient operation, and solvent can be propane etc.The light oil of extracting out can remove vapour, diesel oil hydrofining.
In solvent extraction region, material is in higher temperature, and the high residual oil viscosity of temperature is low, be easier to realize the extracting separation of light oil, heavy oil, but separation temperature will be controlled at below the coking temperature of residual oil; Total pressure is identical with hydrogenation reaction region pressure, prevents the coking of residual oil.The extracted amount of light oil depends on the degree of slag oil crack, will make slag oil crack degree relatively relax in reaction process, improves on the one hand liquid and receives, and makes on the other hand the temperature of reaction that enters next bed be easy to control.
In cold oil and solvent mixture injection zone, temperature generally, between 360-400 DEG C, by the controlling of injecting quantity of cold oil, is tried one's best close to the temperature in of reactor feed, the injection of cold oil will be controlled bitum reactive behavior effectively, and dissolves the bituminous matter that part is separated out.Therefore the mixed temperature of cold oil and reaction product is lower, better to bitum restraining effect, but temperature can not be too low, otherwise can make the temperature in of next bed not reach the required temperature of reaction of residual hydrogenation.
Below in conjunction with embodiment, this technological invention scheme is elaborated, but the present invention is not subject to the restriction of following embodiment.
Embodiment raw material used is residual oil, and its character is shown in Table 1, and hydrotreating catalyst A character used is shown in Table 2, and the liquid product character after separation is shown in Table 3.
Embodiment 1
Fixed bed residual hydrogenation reactor is established three beds altogether, and three bed catalyst type are identical with consumption, the first bed generation hydrogenation reaction that residual oil and hydrogen enter fixed-bed reactor after heating, and reaction conditions is as follows: temperature---and 360 DEG C; Pressure 15.0MPa, resid feed volume space velocity 0.5h
-1; Reactor inlet hydrogen-oil ratio is 1300 (V/V).Solvent is propane, and cold oil is 320～420 DEG C of petroleum fractionss, and solvent and cold oil are introduced in the first bed and the outlet of the second bed.Each bed solvent amount of quoting is 15% of raw material charging quality.It is 360 DEG C that each beds temperature in is all controlled.
From test-results, in the light oil reclaiming by the method, foreign matter content is lower, can be used as the charging of gasoline and diesel hydrogenation device, has improved utilization ratio and the treatment capacity of residual oil, thereby improves the economic benefit of refinery.
The main property of table 1 raw material
| Feedstock property | |
| Sulphur, wt% | 3.5 |
| Nitrogen, wt% | 0.24 |
| Conradson carbon residue, wt% | 15 |
| Ni，μg/g | 48 |
| V，μg/g | 26 |
Table 2 catalyzer main character and composition
| Catalyst A | |
| Metal composition | |
| CoO，wt％ | 1.0 |
| NiO，wt％ | 7.5 |
| MoO 3，wt％ | 10 |
| WO 3，wt％ | 1.5 |
| Character | |
| Specific surface, m 2/g | 150 |
| Pore volume, ml/g | 0.75 |
| Pore distribution | |
| 5-10nm | 10 |
| 10-20nm | 15 |
| ＞20nm | 75 |
Product main character after table 3 hydrotreatment
| Product property | Extract oil out | Raffinate oil |
| Sulphur, wt% | 0.71 | 1.2 |
| Nitrogen, wt% | 0.05 | 0.16 |
| Conradson carbon residue, wt% | / | 8 |
| Ni，μg/g | ＜1 | 9.5 |
| V，μg/g | ＜1 | 5.4 |
Claims (7)
1. a heavy-hydrocarbon raw material hydrogenation treatment method, adopt fixed bed hydrogenation reactor, two beds are at least set in fixed bed hydrogenation reactor, it is characterized in that: between at least one adjacent catalyst bed layer, introduce solvent, solvent mixes with reaction mass and light constituent is extracted, light constituent is drawn reactor by extracting disengaging zone at adjacent two catalyst bed interlayers, and heavy constituent enters next beds and continues reaction; Adjacent two beds adopt cold oil control temperature of reaction; Cold oil is all kinds of oil plants or its mixture of C20～C40.
2. it is characterized in that in accordance with the method for claim 1: the beds in fixed bed hydrogenation reactor is 3～5.
3. in accordance with the method for claim 1, it is characterized in that: hydrotreatment temperature of reaction is 360-480 DEG C, reaction pressure is 10.0-21.0MPa, and feed volume air speed is 0.1-2.0h
-1, reactor inlet hydrogen to oil volume ratio is 500: 1-1500: 1.
4. it is characterized in that in accordance with the method for claim 1: solvent is propane and/or butane.
5. according to the method described in claim 1 or 4, it is characterized in that: the solvent load of adjacent two catalyst bed interlayers is 5%～50% of stock oil charging quality.
6. according to the method described in claim 1 or 4, it is characterized in that: the solvent load of adjacent two catalyst bed interlayers is 10%～30% of stock oil charging quality.
7. in accordance with the method for claim 1, it is characterized in that: solvent carries out extracting separation in the extracting disengaging zone in reactor to the light constituent producing in reaction process, and the light constituent extracting is drawn reactor; Solvent and cold oil are together introduced reactor, or introduce respectively reactor.
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| CN201010536258.5A CN102465031B (en) | 2010-11-04 | 2010-11-04 | Hydrotreating method for heavy hydrocarbon raw materials |
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| CN105586069B (en) * | 2014-10-22 | 2017-05-24 | 中国石油化工股份有限公司 | A solvent extraction method |
| CN105733674B (en) * | 2014-12-07 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of method that inverted sequence is hydrocracked |
| CN112705118B (en) * | 2019-10-25 | 2022-07-12 | 中国石油化工股份有限公司 | Heavy oil hydrogenation reactor and hydrogenation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0832958A1 (en) * | 1996-09-24 | 1998-04-01 | Institut Francais Du Petrole | Process and apparatus for the production of low sulphur catalytically cracked gasolines |
| CN1362494A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Residual oil hydroprocessing method |
| CN1362478A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Heavy hydrocarbon hydroprocessing technique |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0832958A1 (en) * | 1996-09-24 | 1998-04-01 | Institut Francais Du Petrole | Process and apparatus for the production of low sulphur catalytically cracked gasolines |
| CN1362494A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Residual oil hydroprocessing method |
| CN1362478A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Heavy hydrocarbon hydroprocessing technique |
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