CN102329638B - Gasoline and diesel oil hydrofining method - Google Patents
Gasoline and diesel oil hydrofining method Download PDFInfo
- Publication number
- CN102329638B CN102329638B CN201010519296.XA CN201010519296A CN102329638B CN 102329638 B CN102329638 B CN 102329638B CN 201010519296 A CN201010519296 A CN 201010519296A CN 102329638 B CN102329638 B CN 102329638B
- Authority
- CN
- China
- Prior art keywords
- reaction zone
- processing method
- reaction
- oil
- diesel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a gasoline and diesel oil hydrofining method. The method includes the following steps: under hydrofining conditions, the mixture of raw diesel oil and hydrogen sequentially passes through at least two reaction areas from the top of a reactor down, a feed inlet is arranged between each two reaction areas, and different natures of raw oil are respectively supplied into the reactor via the feed inlets. Since the method supplies different natures of raw oil into the feed inlets, on one hand, by utilizing the difference between weight hourly space velocities at the different feed inlets, the method can more pertinently carry out differentiated processing on different natures of raw oil, on the other hand, the supplied raw oil can take away the reaction heat of the previous reaction area, so that the temperature rise of the reactor can be decreased, consequently, each reaction area can be in an optimal reaction temperature region, and thereby the activity of catalyst can be sufficiently utilized, which can help to exert the overall performance of the catalyst and prolong the service life of the catalyst.
Description
Technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, a kind of hydrogenating desulfurization of gas, liquid, solid three-phase gas diesel oil distillate specifically, de-fragrant technique.
Background technology
Along with the raising of people's environmental consciousness and the increasingly stringent of environmental regulation, produce and use fuel for cleaning vehicle more and more to become a kind of development trend.And for the cleaning of diesel oil, desulfurization and de-aromatic hydrocarbons are its keys cleaning.
At present, in the desulfurization of diesel oil, de-fragrant technology, that hydrotreatment technology remains is main, be also the most effective technique means.Hydrotreatment technology is also varied, has successively occurred the Technologies such as single hop hydrogenation, single hop serial hydrogenation and two-stage hydrogenation.Prior art reactor is adiabatic reactor, due to reactant reaction heat release, in reactor, there is larger temperature rise, in order to make reaction, in rational temperature of reaction, carry out, conventionally reactor inlet temperature design is lower, along with the carrying out of reaction, bed temperature improves gradually, to reactor outlet temperature, reaches the highest.But along with refinery processing poor ignition quality fuel quantity is more and more, worse and worse, such temperature of reactor gradient easily causes catalyst utilization low to raw materials quality, catalyst activity can not be brought into play completely.This be because, because reactor inlet temperature is lower, it is to react at lower temperature that reaction mass entered in for some time in reactor, at this moment the sulfocompound that more easily removes of part after being removed more difficult deviate from sulfide be difficult at low temperatures further remove, this has just caused this part catalyst action under cold condition not bring into play completely.And along with the carrying out reacting, heat release gradually, in reactor, improve gradually, when arriving reactor bottom, temperature of reaction is the highest, and the at this moment reaction of reaction mass on catalyzer enters into reaction and the aromatic saturation stage of the sulfocompound that difficulty removes, and too high temperature is unfavorable for the carrying out of these reactions, the effect of catalyzer can not be brought into play equally completely, and in recent years because imported raw material oil is more and more, originate different, for same apparatus, stock oil nature difference in different times processing is larger, this just need can flexible adaptation in the processing method of processing different properties raw material.
US5114562 discloses a kind of technology of two-stage hydrogenation technique from intermediate oil production low sulfur and low aromatics product of utilizing.Its technological process is through hydrogen air lift, to remove H from first paragraph reactor liquid product out
2s and NH
3after, then heat up through heat exchange, enter into second segment reactor.This technique first reactor stream needs hydrogen air lift and heat exchange heating process comparatively complicated, and energy consumption is high.
CN02109671.6 discloses a kind of coking full fraction oil hydrogenation refining method, under middle pressure condition, charking full distillate oil contacts with Hydrobon catalyst, and reaction product is isolated gas-liquid two-phase through high score, and gas-phase product is circulated to coking full fraction oil hydrogenation refining reactor as recycle hydrogen; Liquid product enters separation column and isolates gasoline, diesel oil and wax oil.Charking full distillate oil has the advantages that hydrogenation thermal discharge is large, and bed temperature rise is larger, needs a large amount of cold hydrogen in this flow process, and catalyst in reactor bed temperature irrational distribution, is unfavorable for catalyzer long-period stable operation.
Summary of the invention
Larger for existing diesel oil hydrogenation reactor bed upper and lower temperature range, some region temperature of reaction is also unfavorable for the shortcoming that reaction is carried out smoothly, the invention provides a kind of improved gasoline and diesel hydrogenation processing method to solve existing issue.
Gasoline and diesel hydrogenation processing method of the present invention comprises:
Under hydrofining condition, the mixture autoreactor top of diesel raw material and hydrogen is downwards successively by least two reaction zones, between every two reaction zones, be provided with opening for feed, respectively from different opening for feeds toward reactor, supplement stock oil, according to top-down order, the supplementary stock oil difficulty of processing of the different feeds mouth trend that tapers off, the also hydrogen make-up simultaneously at different feeds mouth place.
According to hydrogenation method provided by the invention, described reaction zone is at least two, is preferably 3～4.Described multiple reaction zones can be distributed in a reactor, also can be distributed in two or more reactors.In general, each described reaction zone can comprise one or more beds, and a common reaction zone comprises a beds.
In gasoline and diesel hydrogenation processing method of the present invention, between each reaction zone, can blank off be isolated by bed, each reaction bed all can carry out independent operation.So just can be according to feedstock property, and the reaction bed number of product requirement choice for use, to increase the handiness of reactor processing scheme.Utilize the different feature of the each bed charging of many bed reactors reaction velocity, supplement targetedly dissimilar stock oil at different bed opening for feeds place, total principle is the stock oil difficulty of processing that injects the from top to bottom trend that tapers off.
According to the common sense of this area, it is larger that the processing complexity of common diesel raw material is affected by the source of diesel oil, in the situation that diesel raw material boiling range is close, secondary processing diesel oil is if catalytic diesel oil, coker gas oil are because it has high aromaticity content, high nitrogen content and composition is comparatively complicated, therefore, difficulty of processing will be apparently higher than straight-run diesel oil.And it is larger affected by density, boiling range, nitrogen content for its difficulty of processing of diesel raw material of same type ,～as situation, diesel raw material density is larger, the heavier difficulty of processing of boiling range is larger.In addition, compared with diesel oil, the difficulty of processing of gasoline will significantly reduce.Like this, the petrol and diesel oil raw material that this device can flexible processing different ratios.
In the inventive method, whole reactor upper and lower temperature difference is less, approaches and waits hotbed reaction.Reactor inlet is able to guarantee desulfurization, denitrogenation and aromatic saturation react the higher temperature of reaction of carrying out smoothly, opening for feed between each bed enters respectively stock oil, in charging, dilute a upper reaction bed reaction heat, make each bed all in optimal reaction temperature region, like this, the catalyst activity of each bed is fully utilized, simultaneously, reactor inlet hydrogen dividing potential drop is higher, therefore, in the first reaction zone, generally adopt secondary processing diesel oil that the aromaticity contents such as catalytic diesel oil are high as charging, be conducive to like this removing of sulfocompound of the saturated and steric hindrance of having living space of aromatic hydrocarbons wherein.And, utilize different feeds mouth place's charging air speed difference, can carry out differentiation processing to the different petrol and diesel oils at different feeds mouth place.At other different opening for feed places, because hydrogen dividing potential drop can reduce relatively, temperature is higher, is applicable to supplementing atmosphere 3rd side cut diesel oil, normal two wires diesel oil or coker gasoline and carries out hydrogenation.Certainly, also can while hydrogen make-up when different feeds mouth supplements fresh feed oil.
Under a kind of performance of the present invention, the number of described reaction zone is 4.According to reagent flow direction, be followed successively by the first reaction zone, second reaction zone, the 3rd reaction zone and the 4th reaction zone.The raw material that enters the first reaction zone is secondary processing diesel oil, as catalytic cracking diesel oil or coker gas oil; The supplementary raw material that enters second reaction zone, the 3rd reaction zone and the 4th reaction zone can be respectively atmosphere 3rd side cut diesel oil, normal two wires diesel oil and coker gasoline.
In gasoline and diesel hydrogenation processing method of the present invention, identical Hydrobon catalyst can be used in each reaction zone, also can use different Hydrobon catalysts.Hydrobon catalyst can be used commercially available prod, also can be according to the conventional knowledge preparation in this area.The activity of Hydrobon catalyst is main relevant to contained active metal component content, and the preparation method of catalyzer, the use of auxiliary agent simultaneously also affects the activity of catalyzer.The consumption of differential responses district catalyzer can according to raw material oil properties and quality product requires and catalyst property is specifically determined, general volume ratio is 1: 4～4: 1.
In gasoline and diesel hydrogenation processing method of the present invention, petrol and diesel oil raw material autoreactor top, downwards successively through at least two conversion zones, is provided with opening for feed between every two conversion zones, has respectively part fresh feed and/or hydrogen therefrom to supplement and enter.The diesel raw material effluent first general and least significant end reaction zone that enters the first reaction zone carries out heat exchange operation, after the raw material after heat exchange mixes with hydrogen, after process furnace heating, enters the first reaction zone.Least significant end reaction zone effluent goes out device and is isolated to petrol and diesel oil product.
In gasoline and diesel hydrogenation processing method of the present invention, each reaction zone reaction temperature in is all controlled at 320 ℃～400 ℃ of temperature of reaction, preferably 340 ℃～380 ℃, by adjusting furnace temperature of heating furnace and differential responses district throat-fed amount, control each reaction zone temperature in; Reaction pressure 3.0MPa～10.0MPa, preferably 4.0MPa～8.0MPa; Volume space velocity 1.0h during liquid
-1～6.0h
-1, preferably 1.5h
-1～4.0h
-1; Hydrogen to oil volume ratio 100～1000, preferably 400～800.
Compared with prior art, gasoline and diesel hydrogenation method tool of the present invention has the following advantages:
(1) in diesel oil hydrogenation technical process of the present invention, by the opening for feed arranging, supplement different properties raw material between two adjacent reaction zones, a large amount of reaction heat that can be with going on a reaction zone, play cold hydrogen effect, make reactor partial design more simple.
(2) at different opening for feeds, supplement raw material charging of different nature, super work can be switched in differential responses district.Therefore utilize different feeds mouth place's charging air speed difference, can to different properties stock oil, carry out differentiation processing more targetedly like this.
(3) replenishing when taking away reaction heat of different properties raw material makes reactor temperature distribution more even, make whole reactor upper and lower temperature difference less, approach and wait hotbed reaction, thereby can suitably improve reactor inlet temperature, at reactor inlet, be able to guarantee that desulfurization, denitrogenation and aromatic saturation react the higher temperature of reaction of carrying out smoothly.Supplementing of fresh feed, can dilute the reaction heat of a reaction zone simultaneously, makes each reaction zone all in optimal reaction temperature region, there is no overtemperature point.Like this, the catalyst activity of each reaction zone is fully utilized, thereby is conducive to bring into play the performance of integer catalyzer and the work-ing life of improving catalyzer.
Accompanying drawing explanation
Fig. 1 is a kind of principle process schematic diagram of gasoline and diesel hydrogenation processing method of the present invention.
Embodiment
In diesel oil hydrogenation technique of the present invention, the catalyzer of employing refer to there is hydrogenating desulfurization, the non-noble metal hydrogenation catalyst of hydrodenitrification, aromatic saturation function, the function of catalyzer can stress some aspect.This non-precious metal catalyst generally exists with oxidation state form before use, need to carry out prevulcanized, makes non-noble metal oxide be converted into sulfide and just has reactive behavior, and therefore, non-precious metal catalyst in use will keep sulphided state.The present invention's hydrogenation catalyst used can adopt conventional diesel oil hydrofining catalyst, generally take VI B family and/or group VIII metal as active ingredient, take aluminum oxide or silicon-containing alumina as carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Take the weight of catalyzer as benchmark, group VIB metal content is counted 8wt%～28wt% with oxide compound, and group VIII metal content is counted 2wt%～15wt% with oxide compound, and its character is as follows: specific surface is 100～650m
2/ g, pore volume is 0.15～0.8mL/g.
By reference to the accompanying drawings, gasoline and diesel hydrogenation processing method flow process of the present invention is described below:
As shown in Figure 1, in a reactor, be provided with four reaction areas from top to bottom: reaction zone 5, reaction zone 6, reaction zone 7 and reaction zone 8, each reaction zone includes a beds.Diesel raw material 1 is after interchanger 10 and product heat exchange and be mixed into reactor from the hydrogen of pipeline 9, from top to bottom by four reaction areas, under sulphided state Hydrobon catalyst exists, carries out hydrogenation reaction; Simultaneously, raw material of different nature respectively through pipeline 2, pipeline 3 and pipeline 4 to reaction zone 6, the interior supplementary fresh feed in reaction zone 7 and reaction zone 8, reaction effluent enters gas-liquid separator 11 and carries out gas-liquid separation after heat exchange, gas phase recycles through pipeline 9, liquid phase flows out through pipeline 12, through further fractionation, can obtain various hydrogenated products.
Below by embodiment, the present invention program and effect are described.
Embodiment 1～4
Adopt flow process of the present invention as Fig. 1.In following examples, use nickel-tungsten-molybdenum type Hydrobon catalyst, the composition of catalyzer and character are in Table 1, and feedstock property used is listed in table 3 in Table 2, embodiment 1～4 processing condition used, and the evaluation result of embodiment 1～4 is in Table 4.
Composition and the main character of table 1 embodiment used catalyst
| Project | Catalyzer |
| Chemical constitution, quality % | |
| MoO 3 | 6.2 |
| NiO | 12.3 |
| CoO | |
| WO 3 | 15.2 |
| Carrier | Aluminum oxide |
| Physico-chemical property | |
| Pore volume, mL/g | 0.45 |
| Specific surface area, m 2/g | 201 |
Table 2 stock oil character
Table 3 embodiment 1～4 operational condition that adopts
Table 4 embodiment 1～4 evaluation result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Sulphur content, μ g/g | 107 | 38 | 5.8 | 42 |
| Nitrogen content, μ g/g | 15 | 5 | 1.0 | 10 |
| Aromaticity content, wt% | 22.6 | 16.6 | 15.3 | 17.2 |
Claims (15)
1. a gasoline and diesel hydrogenation refining technique, described method comprises, under hydrofining condition, the mixture autoreactor top of diesel raw material and hydrogen is downwards successively by least three reaction zones, between every two reaction zones, be provided with opening for feed, respectively from different opening for feeds toward reactor, supplement stock oil, according to top-down order, the supplementary stock oil difficulty of processing of the different feeds mouth trend that tapers off.
2. according to processing method claimed in claim 1, it is characterized in that described reaction zone is 3～4.
3. according to processing method claimed in claim 1, it is characterized in that, described multiple reaction zones are distributed in a reactor, or are distributed in two or more reactors.
4. according to the processing method described in the arbitrary claim of claim 1～3, it is characterized in that, described reaction zone comprises one or more beds.
5. according to processing method claimed in claim 1, it is characterized in that, in different opening for feeds hydrogen make-up simultaneously.
6. according to processing method claimed in claim 1, it is characterized in that, between each reaction zone, can blank off be isolated by bed, independent operation all can be carried out in each reaction zone.
7. according to processing method claimed in claim 1, it is characterized in that, the number of described reaction zone is 4, according to reagent flow direction, is followed successively by the first reaction zone, second reaction zone, the 3rd reaction zone and the 4th reaction zone.
8. according to processing method claimed in claim 7, it is characterized in that, according to reagent flow direction, the raw material that enters each reaction zone is respectively secondary processing diesel oil, atmosphere 3rd side cut diesel oil, normal two wires diesel oil and coker gasoline.
9. according to processing method claimed in claim 8, it is characterized in that, described secondary processing diesel oil is catalytic cracking diesel oil or coker gas oil.
10. according to processing method claimed in claim 1, it is characterized in that, the diesel raw material that enters the first reaction zone is first carried out heat exchange operation with the effluent of least significant end reaction zone, and the diesel raw material after heat exchange enters the first reaction zone after mixing with hydrogen after process furnace heating.
11. according to processing method claimed in claim 1, it is characterized in that, described hydrofining condition is: temperature of reaction is 320 ℃～400 ℃, and reaction pressure is 3.0MPa～10.0MPa, and during liquid, volume space velocity is 1.0h
-1～6.0h
-1, hydrogen to oil volume ratio 100～1000.
12. according to processing method claimed in claim 1, it is characterized in that, by the inlet amount of adjusting furnace temperature of heating furnace and differential responses district opening for feed, controls each reaction zone temperature in.
13. according to processing method claimed in claim 1, it is characterized in that, identical or different Hydrobon catalyst is used in described reaction zone.
14. according to the processing method described in claim 13, it is characterized in that, described Hydrobon catalyst is take group vib and/or group VIII metal as active ingredient, take aluminum oxide or silicon-containing alumina as carrier; Take the weight of catalyzer as benchmark, group vib metal content is counted 8wt%～28wt% with oxide compound, and group VIII metal content is counted 2wt%～15wt% with oxide compound.
15. according to the processing method described in claim 14, it is characterized in that, described group vib metal is Mo and/or W, and group VIII metal is Co and/or Ni.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010519296.XA CN102329638B (en) | 2010-07-13 | 2010-10-20 | Gasoline and diesel oil hydrofining method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010228101.6 | 2010-07-13 | ||
| CN201010228101 | 2010-07-13 | ||
| CN201010519296.XA CN102329638B (en) | 2010-07-13 | 2010-10-20 | Gasoline and diesel oil hydrofining method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102329638A CN102329638A (en) | 2012-01-25 |
| CN102329638B true CN102329638B (en) | 2014-04-16 |
Family
ID=45481609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010519296.XA Active CN102329638B (en) | 2010-07-13 | 2010-10-20 | Gasoline and diesel oil hydrofining method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102329638B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673384B (en) * | 2015-03-02 | 2016-09-14 | 武汉凯迪工程技术研究总院有限公司 | A kind of hydrofinishing process of Low Temperature Fischer Tropsch full distillate oil fecund intermediate oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590510A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Highly desulfur and decolour method of diesel oil distillation fraction |
-
2010
- 2010-10-20 CN CN201010519296.XA patent/CN102329638B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590510A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Highly desulfur and decolour method of diesel oil distillation fraction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102329638A (en) | 2012-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102041071B (en) | Hydrogenation technology for diesel | |
| CN101210198B (en) | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material | |
| CN101747935B (en) | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons | |
| CN103059938B (en) | A kind of heavy hydrocarbon hydroprocessing method | |
| CN101294105B (en) | Hydrogenation modification method of distillate oil | |
| CN101747936B (en) | Hydrogenation method for producing high-quality low-sulfur diesel fraction | |
| CN101942330B (en) | Method for deep hydrogenation, sulfur removal and aromatics removal of diesel oil | |
| CN101942331B (en) | Gasoline and diesel oil combined hydrogenation method | |
| CN102443434B (en) | Heavy-hydrocarbon raw material hydrogenation treatment method | |
| CN102329638B (en) | Gasoline and diesel oil hydrofining method | |
| CN106753561A (en) | A kind of method of liquefied gas preparing ethylene cracking material by hydrogenation | |
| CN102465027B (en) | Hydrotreating method of heavy distillate oil | |
| CN102465021B (en) | Combined hydrogenation process for diesel oil | |
| CN102465011A (en) | Hydrotreatment method of heavy distillate oil | |
| CN101942328B (en) | Hydrogenation method for gasoline and diesel | |
| CN102041072B (en) | Diesel hydrogenation process method | |
| CN102329636B (en) | A kind of diesel hydrogenation process | |
| CN103059965B (en) | Catalytic gasoline deep hydrodesulfurizationmethod method | |
| CN102465020B (en) | Combined hydrofining method | |
| CN101942335B (en) | Gasoline and diesel oil combined hydrogenation process | |
| CN102443428B (en) | Heavy-hydrocarbon hydrogenation treatment method | |
| CN110408432A (en) | A kind of method of group technology processing poor residuum | |
| CN101942329B (en) | Diesel hydrogenation process | |
| CN103059978B (en) | Single-stage series diesel oil hydrofining method | |
| CN103773475B (en) | A kind of gas phase, Solution-Phase Combinatorial hydrogenation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |