CN1362494A - Residual oil hydroprocessing method - Google Patents
Residual oil hydroprocessing method Download PDFInfo
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- CN1362494A CN1362494A CN 01106016 CN01106016A CN1362494A CN 1362494 A CN1362494 A CN 1362494A CN 01106016 CN01106016 CN 01106016 CN 01106016 A CN01106016 A CN 01106016A CN 1362494 A CN1362494 A CN 1362494A
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- residual oil
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Abstract
The present invention discloses a residual oil hydrogenation treatment method, which realize the separation of partial heavier component and hydrogenation treatment process of extract oil in same reactor. Said invention uses the separation of partial heavier component to remove most of metal impurity from the residual oil, so that it can make the hydrogenation treatment equipment treat more poor residual oil, and prolong its on-stream period.
Description
The present invention relates to a kind of process for hydrogenating residual oil.Particularly residual oil is realized the method for separated from solvent and hydrotreatment process in hydrogenator.
Usually, the mixing Residual oil that obtains at the bottom of the atmospheric distillation tower is called long residuum (AR); Mixing Residual oil through obtaining at the bottom of the vacuum still is called vacuum residuum (VR).In order to make full use of petroleum resources, residual hydrocracking is one of important means of heavy (slag) oily lighting.But, in AR or VR, contain macromole colloid, bituminous matter and numerous heteroatomic compound, as sulphur, nitrogen compound, also contain heavy metal (nickel, vanadium, calcium, sodium and iron etc.), the heavy metal in the residual oil, sulphur, nitrogen and carbon residue etc. mainly are distributed in the bigger small portion cut of molecular weight.A small amount of close cut separation the heaviest in the residual oil raw material is removed, will be improved the residual hydrogenation process, improve the whole economic efficiency of device.And solvent extraction, especially supercritical extraction process are the isolating good methods of residual oil that realizes under High Temperature High Pressure.Solvent depends primarily on its molecular weight, density, molecular structure etc. to the separating power of residual oil.
The residual hydrogenation process is along with the increase of coke on the catalyzer and metal accumulation volume, rapid catalyst deactivation.Many patents of each company of various countries all adopt fixed bed catalyst classification filling technology to solve this problem.But heavy metal, suspended solid and sedimentation of coke be at the catalyzer top layer, the logistics corridor in the blocking catalyst, so that the reactor head pressure drop increases too fastly, shortens on-stream time.
For this reason, proposed or the method for industrial application has:
US4357304 has proposed first reactor and has adopted the bunker reactor technology, and catalyzer intermittently or continuously moves, and the autoreactor top adds, and is released by the bottom.Stock oil and hydrogen are entered by reactor head, discharge from the bottom.This technology shortcoming is that catalyzer and reaction raw materials are downward in the same way, can not give full play to the effect of catalyzer, causes the catalyzer waste.
A series of patents such as US5498327 and US5076908 adopt the online displacement of catalyzer (OCR) technology, and the relative adverse current with raw material of catalyzer intermittently or continuously moves from top to bottom, is added by reactor head, is released by the bottom.Stock oil and hydrogen are entered by reactor bottom, discharge from the top.This method catalyzer has obtained utilizing comparatively fully, can prolong on-stream time.But, many, the complicated operation of equipment that catalyzer adds and draws off.
In addition, Chinese patent CN1117071A discloses a kind of with the diasphaltene of residual oil elder generation, deasphalted oil is sent into the demetalization reactor again and is carried out the demetalization reaction, at last the deasphalted oil of reacted upgrading is sent into the method for hydrocracking reactor.This patent realizes diasphaltene and deasphalted oil hydrocracking in two or more unit processes.
More than many patents exist obviously different with the present invention.
The object of the invention is, separates in hydrogenator and discharges on a small quantity heavy residue oil, and this residue can be taken away most of heavy metal, sulphur, nitrogen, carbon residue and mechanical impurity etc., and all the other residual oil carry out the hydrotreatment reaction together with solvent in same reactor.To improve the residual hydrogenation operational condition, alleviate residual hydrocracking process severity, prolong on-stream time.
The present invention is provided with the separated from solvent zone according to the feature of Metal Distribution in the residual oil in molecular weight the best part narrow fraction at the residual hydrogenation reactor lower part, earlier residual oil is separated, and then carries out the hydrotreatment of residual oil.A small amount of residual oil is isolated in extracting from raw material residual oil, plays the effect of alleviating heavy metal deposition, avoiding the catalyzer duct to stop up.
Further describe the present invention below in conjunction with accompanying drawing.
Fig. 1 is the residual hydrogenation reacting flow chart that the present invention relates to.Wherein, 101 are the residual oil of process preheating and the feeding line of hydrogen; 102 is the injection pipeline of lightweight oil or solvent; 103 is residue vent pipe inferior; 104 logistics vent pipes for the residual oil of hydrotreatment, hydrogen and solvent; 105 are upflowing residual hydrogenation bed zone commonly used; 106 is the filled band; 107 is the stock oil feed zone; 108 are the remaining residual oil settling zone of extracting; 109 is the discharging area of solvent, hydrogen and hydrogenated residue.Stock oil/hydrogen sparger 110 can be set in the material feeding zone in addition so that stock oil and hydrogen in reactor inside diameter to uniform distribution.In the residual oil settling zone, solvent sparger 111 can be set, be used for uniformly distributing lightweight oil or solvent.
The implementation procedure of residual oil processing method of the present invention is (such as Fig. 1): raw material residual oil and hydrogen are by advancing Material pipeline 101 enters reactor, and solvent is entered by solvent ascending pipe 102, and 106 is interior to slag in the fill area Oil carries out solvent extraction, and the residual oil after the dissolving upwards flows simultaneously with solvent, enters hydrogenation reaction zone 105 In carry out hydrotreatment, the logistics of the residual oil after the processing, hydrogen and solvent is discharged by discharge pipe 104; Insoluble Residue oil sink down into reactor bottom, discharged by residue discharge pipe 103.
In the fill area, can fill filler, low activity catalyst or specific tube plate structure etc., act on In providing solvent and residual oil fully to contact and the place of separating, improve the solvent extraction separating effect; Wherein, exist Satisfy in the situation of separated from solvent degree requirement, should reduce 106,107,108 and 109 at reactor as far as possible 110 and 111 dispersion effect is improved, so that 105 shared volumes as far as possible in interior shared space as far as possible Greatly. In conversion zone, can be up flow type fixed catalyst bed, expanded bed, suspension bed, ebullated bed Residual hydrogenation a kind of its role is to provide the hydrogenation reaction place; Because of extent of reaction difference, it can be slag Oil hydrofinishing, hydrodesulfurization, demetalization, denitrogenation, take off carbon residue, mild hydrogenation and transform or deep hydrogenation Cracking; The upflow fixed bed residual oil demetalization of this patent recommend adoption process.
The technological parameter of this patent method is selected as follows:
Stock oil can be selected the normal pressure or the vacuum residuum of the various places of production and quality, and as Middle East residual oil, North Sea residual oil, CHARACTERISTICS OF SHENGLI VACUUM RESIDUE WITH, coal tar or shale wet goods, the stock oil of hydrotreatment is poor more, then can embody the advantage of this patent more.
The solvent of described method can select carbon atom at C
3～C
30, best C
4～C
20All kinds of hydrocarbon or the mixture of non-hydrocarbons organic compound or some kinds, as petroleum liquid vapour, light naphthar, heavy naphtha, coker gasoline, aviation kerosene, toluene, hexanaphthene or the like, be preferably petroleum liquid vapour, light naphthar, heavy naphtha, coker gasoline, aviation kerosene etc.In follow-up knockout tower, the separated recovery of solvent is reused.Selection is easy to obtain, and low-cost solvent had both helped solvent recuperation and utilized, can reduce process cost again.
In the hydrogenation reaction zone, can use existing multiple residual oil hydrocatalyst, temperature generally between 360～480 ℃, is preferably between 360～410 ℃; Pressure generally between 12.0～21.0Mpa, is preferably between 14.0～17.0Mpa; Soluble part residual oil with respect to the air speed of catalyzer generally at 0.10～2.00h
-1, be preferably in 0.25～0.85h
-1Between; Hydrogen-oil ratio is generally 100～1300: between 1 (v/v), be preferably in 600～1000: between 1 (v/v).
In the solvent extraction zone, temperature generally between 200～450 ℃, is preferably between 340～380 ℃, and extraction temperature should make the residue oil temperature of extracting be not less than the required minimum temperature of hydrogenation reaction near the temperature in the hydrogenation reaction zone; Total pressure is identical with the hydrogenation reaction zone, and the dividing potential drop of solvent is then relevant with stagnation pressure and solvent temperature, and solvent partial pressure can be adjusted by changing solvent species and temperature; The agent-oil ratio of solvent and stock oil is generally 1.00～50.0: between 100 (m/m), be preferably in 5.00～15.0: between 100 (m/m).The solvent injection rate depends on autolysis ability and residual oil output, under the prerequisite that can satisfy separation requirement, can reduce agent-oil ratio as far as possible.
The distribution of extract oil and residue oil mass.The residual oil output is determined by the performance and the economic benefit estimation situation of the quality of raw material residual oil, Impurity Distribution, hydrogenation catalyst.Suitably the operational condition in selective solvent and solvent extraction zone is controlled the residual oil that enters beds and is generally accounted for 50～100% (m) of charging, is preferably between 80～95% (m).The quantity discharged of residual oil seldom can account for 0～50% (m) of charging, preferably accounts for 5～20% (m) of raw material.
The present invention constitutes the process for hydrogenating residual oil that has reaction and separation function simultaneously by the separated from solvent zone is set in the residual hydrogenation reactor.Thereby a small amount of residual oil is isolated in extracting from raw material residual oil, plays the effect of alleviating heavy metal deposition, avoiding the catalyzer duct to stop up.Advantage is, one makes residual hydrogenation equipment can handle raw material residual oil more inferior, as metal (Ni+V) more than the 180ppm, and various normal pressures or vacuum residuum that sulphur 5.0m% is above; Its two, for same materials, prolong on-stream time; Its three, can improve the whole economic efficiency of device.The solvent that enters the hydrogenation reaction zone with soluble part residual oil can be taken away the heat that hydrogenation reaction discharges in addition, helps the hydrogenation reaction temperature controlling.
Embodiment one:
In single hose fixed bed upflowing residual hydrogenation reactor, φ 3.0mm ball-type Hydrodemetalation catalyst 300ml packs on top; The porcelain ring filler 50ml of φ 3 * 4mm packs in the bottom; The resid feed distributed areas are set between beds and the packing layer, and 150 ℃ raw material residual oil and hydrogen enter reactor herein, the long residuum of matter crude oil in the material choice Saudi Arabia (its main character sees Table 1); Be provided with the residue settling zone under the packing layer, reactor adopts two-part electric heating constant temperature salt bath that temperature of reaction is provided.In the continuous operation process, operational condition is: in the hydrodemetallation (HDM) zone, and 388 ℃ of medial temperatures, pressure 14.4Mpa, hydrogen is 800: 1 to the volume ratio of raw material, raw material residual oil is 0.55h to the air speed of catalyst for demetalation
-1In the solvent extraction zone, stagnation pressure is 14.4Mpa, and medial temperature is 365 ℃, and agent oil quality ratio is 7: 100.With the mixing oil (gasoline/diesel quality ratio is 4: 1) of raw material injection 7.0m% (with respect to raw material residual oil flow) gasoline and aviation kerosene, the residual oil of quantitatively emitting 10m% at reactor bottom.
Reaction result sees Table 1.By table 1 as seen, extract 10% residual oil out and can extract 53% sulphur, 55% nitrogen, 27% carbon residue, 53% nickel and 54% vanadium out, its technology severity be improved significantly.
Oil product main character character raw material residual oil generation oil (indistinct miscilla) sulphur before and after the reaction under table 1 embodiment one condition, m% 3.1 16.3 0.67 nitrogen, m% 0.26 1.43 0.078 Conradson carbon residue, m% 13 35 2.5 nickel, ppm 52 275 7 vanadium, ppm 28 152 5
Embodiment two:
On the basis of embodiment one reactor, φ 1.5mm ball-type Hydrodemetalation catalyst 300ml packs on top; The stainless steel Raschig ring filler 50ml of φ 5 * 4mm packs in the bottom; Solvent is selected light naphthar, and stock oil is selected the vacuum residuum (its main character sees Table 2) of Kuwait Crude Oil.Operational condition is: in the hydrodemetallation (HDM) zone, and 395 ℃ of medial temperatures, pressure 14.0Mpa, hydrogen is 700: 1 to the volume ratio of raw material, raw material residual oil is 0.65h to the air speed of catalyst for demetalation
-1In the solvent extraction zone, stagnation pressure is 14.0Mpa, and medial temperature is 345 ℃, and agent oil quality ratio is 15: 100.With the light naphthar of raw material injection 15.0m% (with respect to raw material residual oil flow), the residual oil of emitting 7m% at reactor bottom.Device and other conditions are with embodiment one.
Reaction result sees Table 2.By table 2 as seen, the residual oil of high metal like this and carbon residue content is extracted 15% residual oil out and can be extracted 51% sulphur, 60% nitrogen, 48% carbon residue, 55% nickel and 38% vanadium out, its technology severity be improved significantly.
Oil product main character before and after the reaction under table 2 embodiment two conditions
Character raw material residual oil generates oil (indistinct miscilla) sulphur, m% 5.00 16.9 0.82 nitrogen, m% 0.33 1.33 0.09 Conradson carbon residue, m% 23.13 33.12 9.81 nickel, ppm 36.6 133.0 7.0 vanadium, ppm 117.9 301.0 22.8
Embodiment three, four:
On the basis of embodiment one, embodiment three is changed to toluene with solvent, and other condition is constant.On the basis of embodiment two, embodiment four is changed to small-particle φ 0.5mm ball-type residual hydrocracking catalyzer with catalyzer, and catalyzer is in swelling state, and temperature of reaction is 450 ℃, and other condition is constant.Embodiment three and four reaction result see Table 3.
Impurity sucrose extraction project implementation example three impurity sucrose extraction embodiment four impurity sucrose extraction sulphur under table 3 embodiment three and four conditions, % 50 48 nitrogen, % 48 57 Conradson carbon residues, % 30 49 nickel, % 45 55 vanadium, % 55 37
Claims (12)
1. a process for hydrogenating residual oil is characterized in that in the hydrotreating reactor bottom separated from solvent zone being set, and earlier residual oil is separated, and then carries out the hydrotreatment of residual oil.
2. according to the described hydroprocessing process of claim 1, its technological process is that raw material residual oil and hydrogen enter reactor by feeding line 101, solvent is entered by solvent injection tube 102, in filled band 106, residual oil is carried out solvent extraction, residual oil after the dissolving upwards flows simultaneously with solvent, enter and carry out hydrotreatment in the hydrogenation reaction zone 105, the logistics of the residual oil after the processing, hydrogen and solvent is discharged by vent pipe 104; Insoluble residual oil sinks down into reactor bottom, is discharged by residue vent pipe 103.
3. according to the described hydroprocessing process of claim 2, it is characterized in that controlling the residual oil that enters hydrotreatment zone beds and account for 50～100% of charging quality, the quantity discharged of residual oil accounts for 0～50% of charging quality.
4. according to claim 2 or 3 described hydroprocessing processs, it is characterized in that controlling the residual oil that enters hydrotreatment zone beds and account for 80～95% of charging quality, the quantity discharged of residual oil accounts for 5～20% of charging quality.
5. according to the described hydroprocessing process of claim 2, wherein said solvent extraction is a supercritical extraction, and temperature of reaction is 200～450 ℃, and pressure is identical with pressure in the hydrogenation reaction zone, and agent oil quality ratio is 1.00～50.0: 100
6. according to claim 2 or 5 described hydroprocessing processs, wherein said solvent extraction is a supercritical extraction, and temperature of reaction is 340～380 ℃, and pressure is identical with pressure in the hydrogenation reaction zone, and agent oil quality ratio is 5.00～15.0: 100.
7. according to the described hydroprocessing process of claim 2, used solvent is that carbon atom is C in the wherein said solvent extraction
3～C
30All kinds of hydrocarbon, non-hydrocarbons organic compound or its mixture.
8. according to claim 2 or 7 described hydroprocessing processs, used solvent is that carbon atom is C in the wherein said solvent extraction
4～C
20All kinds of hydrocarbon, non-hydrocarbons organic compound or its mixture.
9. according to claim 2 or 7 described hydroprocessing processs, used solvent is petroleum liquid vapour, light naphthar, heavy naphtha, coker gasoline, aviation kerosene, toluene, hexanaphthene or its mixture in the wherein said solvent extraction.
10. according to claim 2 or 7 described hydroprocessing processs, used solvent is petroleum liquid vapour, light naphthar, heavy naphtha, coker gasoline, aviation kerosene or its mixture in the wherein said solvent extraction.
11. according to the described hydroprocessing process of claim 2, wherein the reaction conditions of said hydrotreatment is: temperature is 360～480 ℃, and pressure is 12.0～21.0Mpa, and soluble part residual oil is 0.10～2.00h with respect to the air speed of catalyzer
-1, hydrogen to oil volume ratio is 100～1300: 1.
12. according to claim 2 or 11 described hydroprocessing processs, wherein the reaction conditions of said hydrotreatment is: temperature is between 360～410 ℃, pressure is 14.0～17.0Mpa, and soluble part residual oil is 0.25～0.85h with respect to the air speed of catalyzer
-1Hydrogen to oil volume ratio is 600～1000: 1.
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| CNB011060166A CN1144862C (en) | 2001-01-05 | 2001-01-05 | Residual oil hydroprocessing method |
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| CNB011060166A CN1144862C (en) | 2001-01-05 | 2001-01-05 | Residual oil hydroprocessing method |
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| CN1144862C CN1144862C (en) | 2004-04-07 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942337A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Combined process for heavy oil modification |
| CN102465031A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw materials |
| CN108620118A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading and preparation method thereof |
| CN112295510A (en) * | 2019-08-01 | 2021-02-02 | 中国石油化工股份有限公司 | Reactor and application |
-
2001
- 2001-01-05 CN CNB011060166A patent/CN1144862C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942337A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Combined process for heavy oil modification |
| CN101942337B (en) * | 2009-07-09 | 2013-08-28 | 中国石油化工股份有限公司 | Combined process for heavy oil modification |
| CN102465031A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw materials |
| CN102465031B (en) * | 2010-11-04 | 2014-07-23 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw materials |
| CN108620118A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading and preparation method thereof |
| CN108620118B (en) * | 2017-03-24 | 2020-03-17 | 中国石油化工股份有限公司 | Hydrogenation modification catalyst and preparation method thereof |
| CN112295510A (en) * | 2019-08-01 | 2021-02-02 | 中国石油化工股份有限公司 | Reactor and application |
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| Publication number | Publication date |
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| CN1144862C (en) | 2004-04-07 |
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