CN101376831B - Hydrogenation method for hydrocarbon oil containing acid - Google Patents
Hydrogenation method for hydrocarbon oil containing acid Download PDFInfo
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Abstract
The invention discloses a hydrotreatment method of acid-containing spraytex. In the method, petroleum fractions rich in olefin and the acid-containing spraytex after heated are mixed with hydrogen and fed into a fixed bed hydrogenation reactor to mainly carry out hydrogenation and deoxidation as well as olefin saturation reactions; simultaneously hydrogenation and desulfuration s well as denitrification reactions are accompanied to generate a hydrogenation effluent. In the method, two materials are mixed for hydrogenation; simultaneously the heat discharged during the hydrogenation process of the petroleum fractions rich in olefin is used for increasing the acid-containing crude oil fed in a low temperature to the needed reaction temperature as well as avoiding the device corrosion brought by the heating on the acid-containing spraytex through a heating furnace and a heat exchanger.
Description
Technical field
The invention belongs to a kind of method of hydrotreating of working method, especially high-acid crude oil of the acid-containing hydrocarbon oil under hydrogen and catalyzer situation.
Background technology
The concentration of acid or content use total acid value to represent in the oil.With the milligram number of 1 gram crude oil or the needed Pottasium Hydroxide of all acidic components of petroleum fractions (KOH), unit was mgKOH/g during total acid value (TAN) was meant.The acid compounds that contains in the oil mainly is that the form with naphthenic acid exists, and naphthenic acid is prone to iron or the iron sulphide reaction with refining equipment, causes the corrosion of refining equipments such as tower, process furnace, pipeline, interchanger.It is generally acknowledged that the total acid value in the oil surpasses 1mg KOH/g, acid corrosion will be quite serious.
Effect receives Influence of Temperature bigger to naphthenic acid in the oil to corrosion on Equipment, almost there not being corrosive nature below 220 ℃, along with the rising of temperature; Corrosive nature is strengthened gradually, and the corrodibility in the time of 270 ℃～280 ℃ is the strongest, raises with temperature then; Corrosion begins to descend, and when temperature reached 350～400 ℃ again, corrosion is aggravation again; When temperature surpasses more than 400 ℃, naphthenic acid is easy to decompose, and corrodibility reduces.
The principle of shortening deacidifying process is that the petroleum acid and the hydrogen reaction of crude oil generates hydrocarbon and water.USP5897769 has reported that (aperture 5-8.5nm) hydrogenation selectivity remove the method for oil lower molecular weight naphthenic acid to use aperture hydrogenation catalyst, and temperature of reaction is 200-370 ℃.Crude oil and hydrogen and aperture Hydrobon catalyst contact reacts, the molecular weight in the crude oil decomposes generation CO, CO less than 450 naphthenic acid
2, H
2The petroleum hydrocarbon of O and low acid number.Through the catalyzed conversion of petroleum acid, reduce the total acid value in the oil.CN1164867A proposes crude oil under the condition of gentleness (1-50bar, 100-300 ℃), adopts the method for shortening to remove naphthenic acid, but will avoid a large amount of desulphurization reaction, denitrification reaction and aromatic hydrocarbons saturated reactions, to guarantee the hydrogen-consuming volume appropriateness.Though if temperature of reaction can be avoided acid corrosion when being lower than 220 ℃,, be unfavorable for the carrying out of depickling reaction in the above-mentioned patent, more can not remove impurity such as sulphur, nitrogen because temperature of reaction is too low; If temperature of reaction is higher than 220 ℃; No matter adopt which kind of method heating high-acid crude oil, all corrode heating installation inevitably, especially these two kinds of methods include 270～280 ℃ deep-etching stage; Finally can cause damage, increase break-down maintenance number of times and the maintenance cost of oil processing equipment; Not only casualty ratio of accidents increases, and safety in production is affected, and can increase considerably investment cost.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of and does not corrode heating installation, depickling and take off the high acid-containing hydrocarbon oil hydroprocessing process of percentage of admixture.
The hydroprocessing process of acid-containing hydrocarbon oil of the present invention may further comprise the steps:
Raw material after the heating is rich in the petroleum fractions of alkene and ratio that acid-containing hydrocarbon oil with the weight ratio is 1:1～10:1 entering fixed bed hydrogenation reactor; In the presence of hydrogen and Hydrobon catalyst, carry out hydrogenation reaction; React with hydrogenation deacidification comprising hydrogenation of olefins is saturated, obtain the hydrogenation elute.
The said petroleum fractions that is rich in alkene refers to the petroleum fractions of olefin(e) centent 30～60v%, is preferably in coker gasoline, catalytically cracked gasoline, catalytic cracking gasoline and the pressure gasoline one or more.
Among the present invention, said raw material is rich in the heating of petroleum fractions and the acid-containing hydrocarbon oil of alkene can be with two kinds of raw materials mix post-heating, and the furnace outlet temperature is controlled at 160～220 ℃; Also can heat mixing then respectively or get into reactor drum respectively, the furnace outlet temperature that wherein is rich in the petroleum fractions of alkene can be controlled at 160～280 ℃, and the furnace outlet temperature of acid-containing hydrocarbon oil is controlled at 160～220 ℃.
The total acid value of described acid-containing hydrocarbon oil is greater than 0.5mgKOH/g, more preferably greater than 1.0mgKOH/g.Described acid-containing hydrocarbon oil can be crude oil or part or all of distillate wherein, and crude oil wherein can be the pretreated crude oil of process, and described pre-treatment is for dehydration and desalination or be dehydration, desalination and decalcification processing.Described distillate can be gasoline, diesel oil, kerosene, wax oil, long residuum or vacuum residuum.
Described unifining operational condition is generally: hydrogen dividing potential drop 2～20MPa; 220～350 ℃ of temperature; Volume space velocity 0.1～10.0h during liquid
-1Hydrogen to oil volume ratio 200:1～2000:1.
The Hydrobon catalyst that said fixed bed hydrogenation reaction can be adopted can be selected special hydrogenation deacidification catalyzer, can select conventional Hydrobon catalyst, also can adopt hydrodenitrogenation catalyst; Usually being carrier with the refractory inorganic oxides, being preferably siliceous aluminum oxide or aluminum oxide, is active metal component with group vib and group VIII metal, and wherein group vib is preferably molybdenum and/or tungsten, and group VIII is preferably cobalt and/or nickel.Can contain auxiliary agent in the Hydrobon catalyst, like among K, P, Mg, Zr and the Ca one or more.In the described Hydrobon catalyst, the group vib metal content is counted 3wt%～28wt% with oxide compound, and the group VIII metal content is counted 1wt%～15wt% with oxide compound, and the content of auxiliary agent is preferably 1～6wt% generally at 0～8wt%.This Hydrobon catalyst is selected according to the character of acid-containing hydrocarbon oil; When being heavy oil, residual oil or acid-containing raw oil such as acid-containing hydrocarbon oil; Can select heavy oil or residuum hydrodesulfurization catalyzer, hydrodenitrogenation catalyst, like the FZC series hydrogenating desulfurization or the hydrodenitrogenation catalyst of Fushun Petrochemical Research Institute's exploitation.When acid-containing hydrocarbon oil is wax oil, can the selective hydrocracking pretreatment catalyst, like the FF-26 of Fushun Petrochemical Research Institute's exploitation, FF-26 etc.
Described hydrogenation reaction, comprise hydrogenation of olefins saturated with hydrogenation deacidification reaction, comprise further that also hydrogenating desulfurization and hydrodenitrification etc. take off impurity and react.
The hydrogenation elute of the inventive method gained can cut out gasoline fraction and hydrogenation deacidification oil through fractionation plant, also can be after gas-liquid separation, and liquid phase is as the charging of other oil refining apparatus (like the catalytic cracking charging etc.).
The inventive method can also be through selecting the content of impurity such as sulphur, nitrogen that suitable hydrogenation purification operations condition and suitable catalyzer further reduce raw material with production premium product, and operational condition is following: hydrogen dividing potential drop 8～20MPa; 280～350 ℃ of temperature; Volume space velocity 0.1～5.0h during liquid
-1Hydrogen to oil volume ratio 1000:1～2000:1.Used Hydrobon catalyst is selected the stronger Hydrobon catalyst of denitrogenation ability, such as the FZC-42 of process residual oils type and the FH-98A of cut oil type.
Among the present invention, as if the too high levels of diolefine in the petroleum fractions that is rich in alkene, can before this raw material gets into fixed bed hydrogenation reactor, make diene hydrogenation saturated through the hydrogenation pre-treatment earlier, wherein the hydrogenation pretreatment condition be: reaction pressure: 1.0～5.0MPa; 120～240 ℃ of temperature; Air speed: 1.0～15.0h
-1Hydrogen to oil volume ratio 200:1～1000:1.
Olefin(e) centent is up to 30～60v% in the petroleum fractionss such as coker gasoline, catalytically cracked gasoline, catalytic cracking gasoline, pressure gasoline; In hydrogenation process; Can emit a large amount of reaction heat; General temperature rise is more than 100 ℃, even up to more than 130 ℃, and also contains the diolefine of 2～4wt% in this cut; Because diolefine at high temperature is prone to the condensation coking; So carry out hydrogenating desulfurization, denitrogenation and olefin saturation usually with after the low petroleum fractions of olefin(e) centents such as straight-run spirit, straight-run diesel oil is mixed, or after 90～200 ℃ of low temperature carry out the diolefine saturated hydrogenation, carry out hydrogenating desulfurization, denitrogenation and olefin saturation again, thereby avoid diolefine condensation coking and influence the work-ing life of catalyzer and install running period.And the corrodibility temperature influence of acid-containing hydrocarbon oil is very big, if in the following charging of corrosion temperature (220 ℃), though can avoid acid corrosion, its deacidification effect is bad.The present invention combines to be rich in petroleum fractions and the compositing characteristic of acid-containing hydrocarbon oil and the problem of course of processing appearance of alkene, with two kinds of raw materials mixed hydrogenation according to a certain percentage, has the following advantages:
1, with acid-containing hydrocarbon oil and the petroleum fractions mixed hydrogenation that is rich in alkene; The acid-containing raw oil that can make full use of the charging of hydrogenation of olefins process liberated heat lifting low temperature arrives required temperature of reaction, thereby satisfies the processing request of hydrogenation of olefins and acid-containing hydrocarbon oil hydrogenation deacidification simultaneously.
2, acid-containing hydrocarbon oil and the petroleum fractions mixed hydrogenation that is rich in alkene are handled, the diene content that then is rich in the petroleum fractions of alkene reduces, thereby can save the hydrogenation pretreatment unit that is rich in olefin feedstock.
3, with two kinds of raw materials mix processing, because the olefin saturation liberated heat passes to acid-containing hydrocarbon oil, and then the hydrogenation deacidification reaction takes place, can avoid reaction process that bigger temperature rise is arranged effectively.
4, utilize the petroleum fractions reaction liberated heat that is rich in alkene to make acid-containing hydrocarbon oil reach required temperature of reaction, can guarantee that acid-containing raw oil is being lower than entering reactor drum under the temperature of etching apparatus (220 ℃), thereby can avoid the corrosion of process furnace and interchanger.
5, through selecting suitable catalyzer and operational condition, the product of production premium simultaneously.
Embodiment
When metallic impurity such as iron, vanadium, nickel in the acid-containing hydrocarbon oil that is adopted and soil content when higher (such as heavy oil, residual oil or acid-containing raw oil); In order to prolong the work-ing life of Hydrobon catalyst; Keep advantages of high catalytic activity; Usually increase protective material bed and catalyst for demetalation bed at the Hydrobon catalyst upper reaches, used protective material and catalyst for demetalation can adopt heavy oil or used hydrogenation protecting agent and the Hydrodemetalation catalyst of residual hydrogenation.For the dirty ability of the appearance that increases catalyzer; The running period of extension fixture; This protective material, metal remover and Hydrobon catalyst use the catalyst loading scheme of grating usually, and promptly the voidage along liquid phase stream direction catalyzer reduces gradually, and activity increases gradually; Preferred 2～10 kinds of different voidages and the active catalyzer of using can use 3～4 kinds for easy to operate.Described beds voidage is generally 0.2～0.7, and the space rate variance of adjacent catalyst bed layer is 0.05～0.35, and preferred 0.1～0.2.Activity of such catalysts generally obtains through the content of hydrogenation active metals in the adjustment catalyzer, and hydrogenation active metals content height then catalyst activity is high, and hydrogenation active metals content is low, and then catalyst activity is low.Adjacent catalyst bed layer active metallic content can differ 1%～10%, and preferred 2%～8%.Wherein protective material is divided into several types; A kind of has been the inertia protective material of logistics distributional effects; Comprising the protective material that plays the active transition effect in addition, is active ingredient with group vib and/or group VIII metal generally, is carrier with aluminum oxide or siliceous aluminum oxide; The group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.In the weight of catalyzer, the group vib metal content is counted 0.5wt%～20wt% with oxide compound, and the group VIII metal content is counted 0.5wt%～10wt% with oxide compound, and shape can be Raschig ring, huge saddle ring, porous ball or different cylindricality.It is that the metals content impurity in the raw material is reduced that metal remover mainly acts on; The poisoning that minimizing causes the rear portion catalyzer; Be active ingredient generally with group vib and/or group VIII metal; With aluminum oxide or siliceous aluminum oxide is carrier, and the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.In the weight of catalyzer, the group vib metal content is counted 1wt%～20wt% with oxide compound, and the group VIII metal content is counted 0.5wt%～10wt% with oxide compound, and shape can be right cylinder, trifolium shape, Herba Galii Bungei or spherical etc.FZC series residual hydrogenation protective material and catalyst for demetalation that above-mentioned protective material and metal remover can adopt Fushun Petrochemical Research Institute's research and development, Fushun new and high-tech development zone catalyst plant to produce are seen table 1.The admission space ratio of protective material, catalyst for demetalation and Hydrobon catalyst is 10%～40%:30%～80%:10%～30%.
Table 1FZC series residual hydrogenation protective material and catalyst for demetalation
| Kind | Function | Shape | Diameter/mm | Voidage/% | Active |
| FZC-100 | Protective material | The seven apertures in the human head ball | 16 | 55 | Low |
| FZC-102 | Protective material | Raschig ring | 5.0 | 51 | Low |
| FZC-103 | Protective material | Raschig ring | 3.5 | 47 | Lower |
| FZC-200 | Catalyst for demetalation | Herba Galii Bungei | 1.3 | 42 | Lower |
| FZC-201 | Catalyst for demetalation | Herba Galii Bungei | 1.3 | 42 | Higher |
| FZC-204 | Catalyst for demetalation | Herba Galii Bungei | 1.3 | 42 | Higher |
Described protective material and catalyst for demetalation can be seated in the independent reactor drum; Also can be seated in the reactor drum with Hydrobon catalyst; Also can the part of protective material and metal remover be seated in the independent reactor drum, remainder and Hydrobon catalyst are seated in the reactor drum.
Among the present invention, bed voidage definition and mensuration:
Wherein: catalyst volume=catalyst quality/catalyst particle density
The catalyst particle density measuring method adopts mercury displacementmethod to measure (being the conventional criteria method).
For further specifying scheme of the present invention and effect, enumerate following examples.The per-cent that relates to all is weight percentage.
Wherein fixed bed hydrogenation uses the catalyzer of grading loading to comprise among the embodiment: the protective material FZC-102 (bed voidage 0.51 of reactor drum top filling Fushun Petrochemical Research Institute Development and Production; Molybdenum oxide 4%, nickel oxide 2%), the catalyst for demetalation FZC-201 of stage casing filling is a Herba Galii Bungei shape (bed voidage 0.42; Consist of: molybdenum oxide 8%; Nickel oxide 2%, catalyzer pore volume are 0.9ml/g, and specific surface area is 150m
2/ g); The Hydrobon catalyst A of reactor lower part filling is a cloverleaf pattern, and its character is following: bed voidage 0.28, and molybdenum oxide 18%, nickel oxide 6%, catalyzer pore volume are 0.6ml/g, specific surface area is 220m
2/ g.Catalyzer FZC-102:FZC-201 wherein: catalyst A is 30:40:30.
The acid-containing hydrocarbon oil raw material that embodiment uses is seen table 2 as high-acid crude oil character, and the character that is rich in olefin feedstock is seen table 3.Can know that by table 2 acid number of this acid-containing hydrocarbon oil is 2.82mgKOHg
-1, S content is 1.73wt%, is with the unmanageable inferior raw material of ordinary method.The olefin(e) centent that can find out the petroleum fractions that is rich in alkene from table 3 is up to 35～50v%, and sulphur and nitrogen content are also higher.
Table 2 high-acid crude oil character
| Project | Data |
| Density (20 ℃), kg.m -3 | 0.9404 |
| Carbon residue, wt% | 7.1 |
| Viscosity (38 ℃), mm 2·s -1 | 500.6 |
| S，wt％ | 1.73 |
| N，wt％ | 0.32 |
| Nickel and vanadium, μ g.g -1 | 2.5 |
| Iron, μ g.g -1 | 1.8 |
| Acid number, mgKOHg -1 | 2.82 |
| < 350 ℃ of yields, wt% | 9.5 |
| 350～500 ℃ of yields, wt% | 24.8 |
| 500 ℃ of yields, wt% | 65.7 |
Table 3 is rich in the petroleum fractions of alkene
| Project | Coker gasoline | Catalytic gasoline | Pressure gasoline |
| Density (20 ℃)/kg.m -3 | 0.7132 | 0.7231 | 0.7152 |
| The boiling range scope/℃ | 41～176 | 40～166 | 50～172 |
| Sulphur content, μ g.g -1 | 1300 | 2400 | 3200 |
| Nitrogen content, μ g.g -1 | 127 | 100 | 156 |
| Group composition, v% | |||
| Alkane | 46.5 | 28.7 | 52.1 |
| Alkene | 40.1 | 52.9 | 35.4 |
| Naphthenic hydrocarbon | 10.4 | 0 | 11.4 |
| Aromatic hydrocarbons | 3.0 | 18.4 | 1.1 |
Embodiment 1
This embodiment is following for the acid number that adopts coker gasoline and acid-containing hydrocarbon oil hybrid process reduction acid-containing hydrocarbon oil and the technological process of producing qualified light benzine product: coker gasoline and acid-containing hydrocarbon oil are heated to after 245 ℃ and 210 ℃ the weight ratio with 4:1 respectively mix; Be mixed into fixed bed hydrogenation reactor with hydrogen then; Carry out hydrogenation reaction, comprise that hydrogenation of olefins is saturated, hydrogenation deoxidation, hydrogenating desulfurization and hydrodenitrification reaction.The hydroprocessing condition is: hydrogen dividing potential drop 15MPa; 300 ℃ of temperature; Air speed 1.0h
-1Hydrogen to oil volume ratio 1200:1.Reacted logistics cuts out the hydrogenation deacidification oil of < 180 ℃ Q-grade gasoline cut with>180 ℃ through the normal pressure water distilling apparatus.
Embodiment 2
This embodiment is for adopting catalytic gasoline following with the technological process of the acid number of acid-containing hydrocarbon oil hybrid process reduction acid-containing hydrocarbon oil: with catalytic gasoline and acid-containing hydrocarbon oil with the weight ratio Hybrid Heating to 200 of 4.6:1 ℃; Be mixed into fixed bed hydrogenation reactor with hydrogen then; Carry out hydrogenation reaction, comprise that hydrogenation of olefins is saturated, hydrogenation deacidification, hydrogenating desulfurization and hydrodenitrification reaction.The unifining operational condition is: hydrogen dividing potential drop 6MPa; 270 ℃ of temperature; Air speed 3.0h
-1Hydrogen to oil volume ratio 800:1.Reacted logistics cuts out the hydrogenation deacidification oil of < 180 ℃ gasoline fraction with>180 ℃ through the normal pressure water distilling apparatus.
Embodiment 3
This embodiment is following for the acid number that adopts pressure gasoline and acid-containing hydrocarbon oil hybrid process reduction acid-containing hydrocarbon oil and the technological process of producing qualified light benzine product: pressure gasoline and acid-containing hydrocarbon oil are heated to after 260 ℃ and 220 ℃ the weight ratio with 3.7:1 respectively mix; Be mixed into fixed bed hydrogenation reactor with hydrogen then and carry out hydrogenation reaction, comprise that hydrogenation of olefins is saturated, hydrogenation deacidification, hydrogenating desulfurization and hydrodenitrification reaction.The hydroprocessing condition is: hydrogen dividing potential drop 15MPa; 320 ℃ of temperature; Volume space velocity 1.5h during liquid
-1Hydrogen to oil volume ratio 1500:1.Reacted logistics cuts out the hydrogenation deacidification oil of < 180 ℃ gasoline fraction with>180 ℃ through the normal pressure water distilling apparatus.
Table 4 reaction result
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Gasoline property | |||
| Sulphur content, μ g.g -1 | 150 | 700 | 120 |
| Nitrogen content, μ g.g -1 | 3.1 | 27.5 | 2.1 |
| Olefin(e) centent, v% | 5.6 | 8.7 | 2.3 |
| Hydrogenation deacidification oiliness matter | |||
| Acid number, mgKOHg -1 | 0.13 | 0.25 | 0.09 |
| Desulfurization degree, wt% | 35.6 | 18.8 | 47.2 |
Claims (11)
1. the hydroprocessing process of an acid-containing hydrocarbon oil may further comprise the steps:
Raw material after the heating is rich in the petroleum fractions of alkene and the ratio entering fixed bed hydrogenation reactor that acid-containing hydrocarbon oil with weight ratio is 1: 1～10: 1; In the presence of hydrogen and Hydrobon catalyst, carry out hydrogenation reaction; React with hydrogenation deacidification comprising hydrogenation of olefins is saturated, obtain the hydrogenation elute; The described petroleum fractions that is rich in alkene is the petroleum fractions of olefin(e) centent 30～60v%; The total acid value of described acid-containing hydrocarbon oil is greater than 0.5mgKOH/g; Described Hydrobon catalyst is one or more in hydrogenation deacidification catalyzer, Hydrobon catalyst and the hydrodenitrogenation catalyst; The operational condition of said hydrogenation reaction is: hydrogen dividing potential drop 2～20MPa, 220～350 ℃ of temperature, volume space velocity 0.1～10.0h during liquid
-1, hydrogen to oil volume ratio 200: 1～2000: 1;
Said raw material is rich in the petroleum fractions of alkene and the heating of acid-containing hydrocarbon oil is with two kinds of raw materials mix post-heating, and the furnace outlet temperature is controlled at 160～220 ℃; Perhaps heating mixes then or gets into described hydrogenator respectively respectively, and the furnace outlet temperature that wherein is rich in the petroleum fractions of alkene is controlled at 160～280 ℃, and the furnace outlet temperature of acid-containing hydrocarbon oil is controlled at 160～220 ℃.
2. according to the described hydroprocessing process of claim 1, it is characterized in that the described petroleum fractions that is rich in alkene is one or more in coker gasoline, catalytically cracked gasoline, catalytic cracking gasoline and the pressure gasoline.
3. according to the described hydroprocessing process of claim 1; It is characterized in that described acid-containing hydrocarbon oil is crude oil or part or all of distillate wherein; Crude oil wherein is the pretreated crude oil of process, and described pre-treatment is for dehydration and desalination or be dehydration, desalination and decalcification processing.
4. according to the described hydroprocessing process of claim 1, the total acid value that it is characterized in that described acid-containing hydrocarbon oil is greater than 1.0mgKOH/g.
5. according to the described hydroprocessing process of claim 1, it is characterized in that described Hydrobon catalyst is is carrier with siliceous aluminum oxide or aluminum oxide, be active metal component with group vib and group VIII metal; In the described Hydrobon catalyst, the group vib metal content is counted 3wt%～28wt% with oxide compound, and the group VIII metal content is counted 1wt%～15wt% with oxide compound.
6. according to the described hydroprocessing process of claim 1, it is characterized in that described Hydrobon catalyst is is carrier with siliceous aluminum oxide or aluminum oxide, be active metal component with group vib and group VIII metal; Contain among auxiliary agent K, P, Mg, Zr and the Ca one or more in the described Hydrobon catalyst; In the described Hydrobon catalyst, the group vib metal content is counted 3wt%～28wt% with oxide compound, and the group VIII metal content is counted 1wt%～15wt% with oxide compound, and the content of auxiliary agent is to 8wt% greater than 0.
7. according to claim 5 or 6 described hydroprocessing processs, it is characterized in that described group vib is molybdenum and/or tungsten, group VIII is cobalt and/or nickel.
8. according to the described hydroprocessing process of claim 1, it is characterized in that the operational condition of said hydrogenation reaction is following: hydrogen dividing potential drop 8～20MPa; 280～350 ℃ of temperature; Volume space velocity 0.1～5.0h during liquid
-1Hydrogen to oil volume ratio 1000: 1～2000: 1, described Hydrobon catalyst is selected the strong Hydrobon catalyst of hydrodenitrification ability.
9. according to the described hydroprocessing process of claim 1, it is characterized in that the Hydrobon catalyst upper reaches increase protective material bed and catalyst for demetalation bed; This protective material, catalyst for demetalation and Hydrobon catalyst use along the voidage of liquid phase stream direction catalyzer and reduce gradually, the active grading loading scheme that increases gradually.
10. according to the described hydroprocessing process of claim 9, it is characterized in that used protective material and catalyst for demetalation adopt heavy oil or used hydrogenation protecting agent and the Hydrodemetalation catalyst of residual hydrogenation.
11. according to the described hydroprocessing process of claim 1; Before it is characterized in that being rich in the petroleum fractions entering fixed bed hydrogenation reactor of alkene; Earlier make diene hydrogenation saturated through the hydrogenation pre-treatment, wherein the hydrogenation pretreatment condition is: reaction pressure: 1.0～5.0MPa; 120～240 ℃ of temperature; Air speed: 1.0～15.0h
-1Hydrogen to oil volume ratio 200: 1～1000: 1.
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| CN103773437B (en) * | 2012-10-24 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst grading method |
| CN103805227B (en) * | 2012-11-09 | 2016-12-21 | 长江(扬中)电脱盐设备有限公司 | A kind of pretreatment process method of high-acid crude oil |
| CN110295057A (en) * | 2018-03-22 | 2019-10-01 | 中国石油化工股份有限公司 | A kind of using plasma is carried out to distillate plus the technique of hydrogen |
| CN112745912B (en) * | 2019-10-30 | 2022-05-03 | 中国石油化工股份有限公司 | Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil |
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| CN1394937A (en) * | 2001-07-10 | 2003-02-05 | 中国石油化工股份有限公司 | Reformed oil olefine saturation hydrogenation method |
| CN1802423A (en) * | 2001-02-16 | 2006-07-12 | 催化蒸馏技术公司 | Process for sulfur reduction in naphtha streams |
| CN1952063A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Boiling bed residual oil hydrocracking process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802423A (en) * | 2001-02-16 | 2006-07-12 | 催化蒸馏技术公司 | Process for sulfur reduction in naphtha streams |
| CN1394937A (en) * | 2001-07-10 | 2003-02-05 | 中国石油化工股份有限公司 | Reformed oil olefine saturation hydrogenation method |
| CN1952063A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Boiling bed residual oil hydrocracking process |
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