CN101376831A - 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.During total acid value (TAN) is meant and the milligram number of 1 gram crude oil or the needed potassium hydroxide of all acidic components of petroleum fractions (KOH), unit is mgKOH/g.The acid compounds that contains in the oil mainly is that the form with naphthenic acid exists, and naphthenic acid easily reacts with the iron or the iron sulphide of 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.
Naphthenic acid in the oil is subjected to Temperature Influence bigger to the corrosive nature of equipment, almost do not having corrosive nature below 220 ℃, along with the rising of temperature, corrosive nature is strengthened gradually, corrodibility in the time of 270 ℃～280 ℃ is the strongest, raise with temperature then, corrosion begins to descend, when temperature reaches 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.By 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
At the deficiencies in the prior art, the invention provides and a kind ofly do 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 enters fixed bed hydrogenation reactor, in the presence of hydrogen and Hydrobon catalyst, carry out hydrogenation reaction, saturated and hydrogenation deacidification reaction obtains the hydrogenation effluent comprising hydrogenation of olefins.
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, described raw material is rich in the heating of the petroleum fractions of alkene and acid-containing hydrocarbon oil can be with two kinds of raw material mixing post-heating, and the furnace outlet temperature is controlled at 160～220 ℃; Also can heat mixing then respectively or enter reactor 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 dehydration and desalination or is dehydration, desalination and decalcification processing.Described distillate can be gasoline, diesel oil, kerosene, wax oil, long residuum or vacuum residuum.
Described hydrofining 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, as 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, as 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, as FF-26, the FF-26 etc. of Fushun Petrochemical Research Institute's exploitation.
Described hydrogenation reaction comprises the reaction of the saturated and hydrogenation deacidification of hydrogenation of olefins, comprises further that also hydrogenating desulfurization and hydrodenitrification etc. take off the impurity reaction.
The hydrogenation effluent 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 (as catalytic cracking charging etc.) of other oil refining apparatus.
The inventive method can also be by 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 as follows: 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 make diene hydrogenation saturated through the hydrogenation pre-treatment earlier before this raw material enters fixed bed hydrogenation reactor, 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.
Coker gasoline, catalytically cracked gasoline, catalytic cracking gasoline, olefin(e) centent is up to 30～60v% in the petroleum fractionss such as 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 contain the diolefine of 2～4wt% in this cut, because diolefine is easily condensation coking at high temperature, so common and straight-run spirit, after mixing, the petroleum fractions that olefin(e) centents such as straight-run diesel oil are low carries out hydrogenating desulfurization, denitrogenation and olefin saturation, or after carrying out the diolefine saturated hydrogenation, 90～200 ℃ of low temperature carry out hydrogenating desulfurization again, denitrogenation and olefin saturation, thus avoid diolefine condensation coking and influence catalyzer work-ing life and the device 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 problem that the present invention occurs in conjunction with the compositing characteristic that is rich in the petroleum fractions of alkene and acid-containing hydrocarbon oil and the course of processing 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 material hybrid process, 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 be rich in alkene to make acid-containing hydrocarbon oil reach required temperature of reaction, can guarantee that acid-containing raw oil enters reactor being lower than under the temperature of etching apparatus (220 ℃), thereby can avoid the corrosion of process furnace and interchanger.
5, by 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 in the Hydrobon catalyst upstream, 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; promptly the voidage along liquid phase stream direction catalyzer reduces gradually; 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 by the content of adjusting hydrogenation active metals in the catalyzer, and hydrogenation active metals content height is the catalyst activity height then, 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 classes; a kind of has been the inertia protective material of logistics distributional effects; comprise the protective material that plays the active transition effect in addition; be active ingredient generally with group vib and/or group VIII metal; with aluminum oxide or siliceous aluminum oxide is carrier; 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, 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 see Table 1.The admission space ratio of protective material, catalyst for demetalation and Hydrobon catalyst is 10%～40%:30%～80%:10%～30%.
Table 1 FZC 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; also can be seated in the reactor with Hydrobon catalyst; also the part of protective material and metal remover can be seated in the independent reactor, remainder and Hydrobon catalyst are seated in the reactor.
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 the solution 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 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 as follows: 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 sees Table 2 as high-acid crude oil character, and the character that is rich in olefin feedstock sees Table 3.The acid number of this acid-containing hydrocarbon oil is 2.82mgKOHg as shown in Table 2
-1, S content is 1.73wt%, is with the unmanageable inferior raw material of ordinary method.The olefin(e) centent of petroleum fractions that is rich in alkene as can be seen 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 for adopting coker gasoline and acid-containing hydrocarbon oil hybrid process and reduce the acid number of acid-containing hydrocarbon oil and to produce the technological process of qualified light benzine product as follows: 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 through the normal pressure water distilling apparatus cut out＜180 ℃ Q-grade gasoline cut and 180 ℃ hydrogenation deacidification oil.
Embodiment 2
This embodiment is as follows for adopting catalytic gasoline and acid-containing hydrocarbon oil hybrid process to reduce the technological process of acid number of 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 hydrofining operational condition is: hydrogen dividing potential drop 6MPa; 270 ℃ of temperature; Air speed 3.0h
-1Hydrogen to oil volume ratio 800:1.Reacted logistics through the normal pressure water distilling apparatus cut out＜180 ℃ of gasoline fractions and 180 ℃ hydrogenation deacidification oil.
Embodiment 3
This embodiment is for adopting pressure gasoline and acid-containing hydrocarbon oil hybrid process and reduce the acid number of acid-containing hydrocarbon oil and to produce the technological process of qualified light benzine product as follows: 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 through the normal pressure water distilling apparatus cut out＜180 ℃ of gasoline fractions and 180 ℃ hydrogenation deacidification oil.
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 |
| The hydrogenation deacidification oil nature | |||
| Acid number, mgKOHg -1 | 0.13 | 0.25 | 0.09 |
| Desulfurization degree, wt% | 35.6 | 18.8 | 47.2 |
Claims (12)
1, a kind of hydroprocessing process of acid-containing hydrocarbon oil 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 enters fixed bed hydrogenation reactor, in the presence of hydrogen and Hydrobon catalyst, carry out hydrogenation reaction, saturated and hydrogenation deacidification reaction obtains the hydrogenation effluent comprising hydrogenation of olefins;
Described raw material is rich in the heating of the petroleum fractions of alkene and acid-containing hydrocarbon oil can be with two kinds of raw material mixing post-heating, and the furnace outlet temperature is controlled at 160～220 ℃; Also can heat mixing then respectively or enter described hydrogenator respectively, 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,, it is characterized in that the said petroleum fractions that is rich in alkene is the petroleum fractions of olefin(e) centent 30～60v% according to the described hydroprocessing process of claim 1.
3,, it is characterized in that the said petroleum fractions that is rich in alkene is one or more in coker gasoline, catalytically cracked gasoline, catalytic cracking gasoline and the pressure gasoline according to claim 1 or 2 described hydroprocessing processs.
4, according to claim 1 or 2 described hydroprocessing processs, the total acid value that it is characterized in that described acid-containing hydrocarbon oil is greater than 0.5mgKOH/g; Described acid-containing hydrocarbon oil is crude oil or part or all of distillate wherein, and crude oil wherein is the pretreated crude oil of process, and described pre-treatment is dehydration and desalination or is dehydration, desalination and decalcification processing.
5, according to the described hydroprocessing process of claim 4, the total acid value that it is characterized in that described acid-containing hydrocarbon oil is greater than 1.0mgKOH/g.
6, according to claim 1 or 2 described hydroprocessing processs, it is characterized in that the petroleum fractions of alkene is rich in described heating and acid-containing hydrocarbon oil can be with two kinds of raw material mixing post-heating, perhaps heating is mixed into reactor then or enters reactor respectively respectively.
7,, it is characterized in that described hydrofining operational condition is: hydrogen dividing potential drop 2～20MPa according to claim 1 or 2 described hydroprocessing processs; 220～350 ℃ of temperature; Volume space velocity 0.1～10.0h during liquid
-1Hydrogen to oil volume ratio 200:1～2000:1.
8, according to claim 1,2 or 7 described hydroprocessing processs, it is characterized in that said Hydrobon catalyst is one or more in hydrogenation deacidification catalyzer, Hydrobon catalyst and the hydrodenitrogenation catalyst, with siliceous aluminum oxide or aluminum oxide is carrier, with group vib and group VIII metal is active metal component, wherein group vib is preferably molybdenum and/or tungsten, and group VIII is preferably cobalt and/or nickel; Selectivity contains one or more among auxiliary agent K, P, Mg, Zr and the Ca 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 at 0～8wt%.
9,, it is characterized in that described hydrofining operational condition is as follows: hydrogen dividing potential drop 8～20MPa according to claim 1 or 2 described hydroprocessing processs; 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.
10,, it is characterized in that the Hydrobon catalyst upstream increases protective material bed and catalyst for demetalation bed according to the described hydroprocessing process of claim 1; This protective material, metal remover and Hydrobon catalyst use along the voidage of liquid phase stream direction catalyzer and reduce gradually, the active grading loading scheme that increases gradually.
11,, it is characterized in that used protective material and catalyst for demetalation adopt heavy oil or used hydrogenation protecting agent and/or the Hydrodemetalation catalyst of residual hydrogenation according to the described hydroprocessing process of claim 10.
12, according to the described hydroprocessing process of claim 1, before the petroleum fractions that it is characterized in that being rich in alkene enters fixed bed hydrogenation reactor, 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103773437A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst grading method |
| CN103805227A (en) * | 2012-11-09 | 2014-05-21 | 长江(扬中)电脱盐设备有限公司 | Pre-treatment 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6444118B1 (en) * | 2001-02-16 | 2002-09-03 | Catalytic Distillation Technologies | Process for sulfur reduction in naphtha streams |
| CN1191332C (en) * | 2001-07-10 | 2005-03-02 | 中国石油化工股份有限公司 | Reformed oil olefine saturation hydrogenation method |
| CN1952063B (en) * | 2005-10-19 | 2010-04-28 | 中国石油化工股份有限公司 | Boiling bed residual oil hydrocracking process |
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| CN103773437A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst grading method |
| 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 |
| CN103805227A (en) * | 2012-11-09 | 2014-05-21 | 长江(扬中)电脱盐设备有限公司 | Pre-treatment process method of high acid crude oil |
| 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 |
| CN112745912A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for removing oxygen-containing compounds in Fischer-Tropsch synthesis light oil |
| 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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