CN1335368A - Heavy oil and residual oil hydrogenating process - Google Patents
Heavy oil and residual oil hydrogenating process Download PDFInfo
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Abstract
Before the heavy oil and residual oil hydrogenating reaction system, one section of adsorbing and filtering agent bed layer or one combination of one section of adsorbing and filtering agent bed layer and one section of adsorbing and filtering catalyst bed layer is used. This can eliminate the suspended particles in the material oil as possible and eliminate the ferrous sulfide produced by the iron naphthenate in the material oil and most of the coke producing matters, and this can decrease the scale formation in the hydrogenation system and thus produced shutdown times.
Description
The present invention relates to heavily, residual oil shortening technology, the stock oil pretreatment process of especially heavy, residual oil catalytic hydrogenation process.
Heavy and to the increase day by day of light-end products demand along with becoming day by day of crude oil, many comprehensive refinerys have all been built up residual hydrogenation equipment in succession both at home and abroad.The needs that refinery improves light oil yield, obtains maximum economic benefit have been satisfied in the operation of these residual hydrogenation equipments on the one hand, have also satisfied the environmental legislation requirement of increasingly stringent on the other hand.Wherein the fixed bed Residue Hydrotreating Technology has advantages such as flow process is simple, investment is little, easy to operate and industrialized unit is more, but also there is shortcoming in it, that be exactly processing during poor quality oil the easy fouling of beds of lead reactor result in blockage, produce differential pressure, cause stopping work.Therefore, the fixed bed residual hydrogenation equipment has at least the lead reactor inner catalyst once be cast aside the top or changed operation in the middle of each running period.Expend a large amount of shutting down expense and catalyst costs, influenced the economic benefit of residual hydrogenation equipment greatly.
As everyone knows, residual oil is a kind of material the most complicated in the oil product, it not only contains colloid, the bituminous matter of complex construction and composition, and the micro-metals Fe, the Ni that exist of crude oil itself, V etc. and compounds such as S, N also nearly all are present in the residual oil, and impurity such as the corrosion product that upstream device is come, coke also mainly concentrate in the residual oil.Therefore, the easy fouling of lead reactor beds of residual hydrogenation equipment is stopped up.Though the fouling reason of each different residual hydrogenation equipments varies, the fouling mechanism of residual hydrogenation equipment has general character: precipitation and polymerization.
Precipitation: inevitably have large amount of organic and inorganics class particle in the raw material residual oil.The inorganic salt that do not purify when wherein inorganics may carry out desalination to crude oil for Iron sulfuret, upstream device and other corrosion products etc.; Polymkeric substance that organism may produce by radical polymerization, metal-catalyzed polymerization and non-free radical polymerization for upstream device and coke etc.And the catalyst themselves in the residual hydrogenation equipment lead reactor is exactly a strainer, the mechanical impurity that enters reactor is all had filteration, so contained mechanical impurity can be deposited in the catalyzer space of reactor head bed in the residual oil raw material.The device start of run only can be tackled the macrobead greater than the catalyzer gap, forms gradually after the filter cake, and small-particle also is blocked, thereby generates the filter cake of one deck densification, causes reactor plugs, differential pressure to rise.And polymerization mainly is because of containing many complex mixtures with polymerization coke forming property in the residual oil, and Conradson carbon residue promptly is to show to contain what one of index of coking tendency material in the residual oil.The polymerization that residual oil takes place under the high temperature is a kind of reaction of complexity, and can be divided into following three classes by mechanism: radical polymerization, metal-catalyzed polymerization, non-free radical polymerization, wherein metal-catalyzed polymerization is main.The metal that can play the catalyzed polymerization effect has Fe, Cu, Ni, V, Zn, Ca etc., but document (RDS stock oil deironing-FEROSEP " petro-technology " (day) Vol.17 in 1994) thinks that the essential substance of residual hydrogenation reactor head bed fouling is an Iron sulfuret, and find through experiment: Ni, V mainly are present in the inside of catalyst for demetalation, Iron sulfuret exists only between the granules of catalyst, and the very thin film of one deck around the formation granules of catalyst, coke mainly is present between the catalyzer, and the concentration between the Iron sulfuret particle is the highest.Document (RDS stock oil deironing-FEROSEP " petro-technology " (day) Vol.17 in 1994) carries out electron microscope scanning and the analysis of X ray micro-detector to the spent catalyst that turned round at Japanese chamber blue refinery RDS device, finds that coke is that core generates with the Iron sulfuret particulate.Fushun Petrochemical Research Institute also analyzes the top bed powder dirt sample and the catalyzer of the lead reactor of the VRDS device of Qilu Petroleum Chemical Corporation Institute, find heavy metal iron class material major sedimentary at the outside surface of granules of catalyst, surface (testing) that coke mainly is present in catalyzer, Iron sulfuret with x-ray photoelectron spectroscopy mainly with pyrrhotite (Fe
0.95What S) form existed (with X-ray diffraction test), dirty sample mainly consists of Iron sulfuret and coke, and wherein Iron sulfuret is maximum.Therefore, Iron sulfuret and coke precursor are to cause the major cause of reactor fouling, and wherein Iron sulfuret is topmost, and it is self blocking catalyst bed not only, but also the reaction of the green coke of catalysis residual oil generates coke and comes the blocking catalyst bed.Iron sulfuret in the beds mainly contains two kinds of sources: the sulfur corrosion product of the iron that upstream device is come, the iron naphthenate in the crude oil generate under the condition that hydrogen exists.
In order to solve the scale problems of residual hydrogenation equipment, from precipitation and two kinds of mechanism of polymerization of causing the beds fouling, each major oil companies has taked multiple measure to solve the device scale problems.
It is the efficient raw material strainer of 25 μ m that Chevron company has used precision, but owing to the filter design reason, cause easily in it and leak, in addition can not the easy green coke material of effective elimination and crude oil in the Iron sulfuret that in the presence of hydrogen, generates of iron naphthenate, still can induce reaction the fouling of device beds very soon (can be referring to " winning refining science and technology ", 1999,2,7～11).
The OCR technology that Chevron company is newly developed can reach the purpose that reduces pressure drop by the part fouling catalyzer with the continuous metathesis reactor of raw catalyst bottom, but its complex process, investment is big, difficult operation, and the catalyzer that uses is expensive.
Japan chamber blue refinery RDS device adopts stock oil deferrization process (FEROSEP), with in the raw material with normal magnetic Fe
7S
8The Iron sulfuret that form exists utilizes electromagnetic field to be removed, but non magnetic iron class can not remove with easy green coke material, still can make the lead reactor beds fouling of residual hydrogenation equipment.(referring to RDS stock oil deironing-FEROSEP " petro-technology " (day) Vol.17 in 1994)
The HYVAHL-F technology with guard reactor that ELF company, IFP and Total SA develop jointly also can solve the beds blockage problem.Filling protecting materials and Hydrodemetalation catalyst in guard reactor, wherein the loading amount of catalyst for demetalation accounts for guard reactor volumetrical 60%, and the decreasing ratio of metals such as Ni, V is very high.The physico-chemical property of protecting materials is: granular size is 3～10mm, surface-area＜1m
2/ g does not have active metal component, does not have hydrogenating desulfurization and metal removal activity.The physico-chemical property of Hydrodemetalation catalyst is: granular size is 1.2～6mm, surface-area 80～180m
2/ g, active metal component are Mo/MoNi, have high metal removal activity and low desulphurizing activated.The patent characteristics of this technology are: 2 of guard reactor operated by rotary motion, and 1 operation, 1 is standby or handle spent catalyst or be used for filling, sulfuration of raw catalyst etc.But it is too much that the workload of this technology loading and unloading catalyzer reaches switching times greatly, not only can cause the investment of its equipment and catalyzer bigger, and the control difficulty is big, and give to produce and also make troubles.(can referring to the mink cell focus catalyzed conversion international conference data of holding 13-17 day in April, 1997-" Recent Developments in Fixed Bed Catalytic ResidueUpgrading ") at California, USA San Francisco
In order to improve the deficiency of above-mentioned pre-treatment residual oil method and technology, the invention provides a kind of simple, easy to operate, attached filtering pre-treatment residual oil method of double suction efficiently.
Technical scheme of the present invention is as follows:
Heavy residual oil raw material at first passes through pre-treatment, mixes with hydrogen then, after the process heating reaches desired reaction temperature, enters in the residual hydrogenation reactive system and reacts, and reactant enters separation system to be separated; Described preprocessing process be heavy residual oil raw material through heat exchange reach temperature required after, enter the adsorption filtration system that absorption filter agent is housed, the operational condition of described adsorption filtration is: 100～320 ℃ of temperature, volume space velocity is 2.0～8.5h during liquid
-1, working pressure 0.1～0.3MPa.
Described heavy residual oil raw material is mixing with hydrogen, after the process heating reaches desired reaction temperature, enter react in the beds before, preferably entering the adsorption filtration catalysis system that the adsorption filtration catalyzer is housed again carries out further adsorption filtration and removes impurity, the operational condition of described adsorption filtration beds is: temperature is 340～390 ℃, and volume space velocity is 2.0～8.5h during liquid
-1, hydrogen to oil volume ratio 500～1500, working pressure 8.0～16.0Mpa is identical with the residual hydrogenation equipment system pressure.
The absorption filter agent that is loaded in the adsorption filtration bed of the present invention can be selected from spent catalyst, gac, molecular sieve of porous refractory inorganic oxides such as aluminum oxide etc., residual oil device or other catalysis oil refining apparatus etc.The pore volume distribution of described absorption filter agent is preferably diameter accounts for pore volume at least greater than the macropore of 100nm 10% (better be 15%～45%, preferably 35%～45%); Surface-area is at 50m
2/ g～200m
2Between/the g, be preferably at 80m
2/ g～150m
2/ g, best is at 100m
2/ g～120m
2/ g, can several apertures in the scope of about 20～100nm, pore volume (mercury penetration method) is at 0.7～1.2cm
3Between/the g, average particulate diameter 3.5～5.0mm is preferably at 4.0～5.0mm, and best is at 4.5～5.0mm.The present invention is the adsorption filtration effect that utilizes absorption filtering material, filters the suspended particulate (especially iron content particle) that upstream device is come, and also has the material of easy green coke etc.The operational condition of this adsorption filtration bed is: temperature is generally at 100～320 ℃, and 150～300 ℃ preferably, be preferably in 200～300 ℃, this temperature can obtain by the weight behind the hydrogenation, residual oil and stock oil heat exchange, does not need other thermal source, invests little, easy to control; Air speed is generally at 2.0～8.5h
-1, be 3.5～8.5h preferably
-1, that best is 4.5～8.0h
-1, working pressure is 0.1～0.3Mpa.According to device needs, stock oil character and use the cost of catalyzer, two beds can be set switch and use, add back-purge system or the disposable discharge of catalyzer.If an adsorption filtration bed is set, so when the filter bed layer need be changed, because of adsorption filtration dosage required for the present invention is few, it is rapid to change agent, can allow the temporary transient by-passing of stock oil, takes all factors into consideration, and two beds are set, and to switch uses more preferably.
Adsorption filtration beds of the present invention filling be to be carrier with the porous refractory inorganic oxides, with VIB (as W, Mo) and/or group VIII (as Co, Ni) metal component is the catalyzer or the spent catalyst of active ingredient, has the hydrogenating function spent catalyst as residual hydrogenation equipment or other catalysis oil refining apparatus exhausted.The pore volume distribution of described adsorption filtration catalyzer 10% (better be 15%～45%, preferably 35%～45%) that to be diameter account for pore volume at least greater than the macropore of 100nm; Surface-area is at 50m
2/ g～200m
2Between/the g, be preferably 80m
2/ g～150m
2/ g, that best is 100m
2/ g～120m
2/ g, can several apertures in the scope of about 20～100nm, pore volume (mercury penetration method) is at 0.7～1.2cm
3Between/the g, average particulate diameter 3.5～5.0mm is preferably 3.5～4.5mm, and that best is 4.2～4.5mm.What the above-mentioned adsorption filtration support of the catalyst of the present invention was the most frequently used is aluminum oxide.This aluminum oxide can prepare with any method in common.For example, preparing the method for catalyst oxidation alumina supporter of the present invention can be referring to the United States Patent (USP) the 4179408th (date of publication on December 18th, 1979) of the United States Patent (USP) of Laine etc. No. 4392987 (12 days July nineteen eighty-three of date of publication) and Sanchez etc.After this, can be by pickling process commonly used in any suitable method, particularly catalyst preparation technology, the catalyst component that the catalyzer of this beds is required joins on the alumina supporter.Be applicable to that catalyst component of the present invention has vib metal (especially molybdenum and tungsten) and/or VIII family metal (especially cobalt and nickel).The amount of catalyst component (by the metal oxide compound) is preferably between about 0.5～4.5%, and the kind of catalyzer is at least a kind of, can increase a plurality of beds as required.This bed is the chemisorption cake filtration effect that utilizes catalyzer, and further absorption filters the material of easy green coke etc., and the Iron sulfuret that also has the iron naphthenate in the crude oil to generate in the presence of hydrogen makes stock oil obtain maximum the purification.The operational condition of this beds be temperature generally at 340～390 ℃, 350～385 ℃ preferably, be preferably in 360～385 ℃, this temperature is obtained by the charging process furnace, does not need to build in addition process furnace; Air speed is generally at 2.0～8.5h
-1, be 3.5～8.5h preferably
-1, that best is 4.5～8.0h
-1Hydrogen to oil volume ratio is generally 500～1500, is preferably 600～1200, and best is 700～1000, and working pressure is 8.0～16.0Mpa.According to device needs, stock oil character and use the cost of catalyzer, two beds can be set switch and use or only be provided with a beds, add back-purge system or with the disposable discharge of catalyzer.If a beds is set, so when beds need be changed, because of catalytic amount required for the present invention is few, it is rapid to change agent, can allow the temporary transient by-passing of stock oil.Take all factors into consideration, the scheme that two beds switching uses are set is more preferably.
For prevent that suspended particulate (especially iron content particle) the initiation stock oil that upstream device is come from a large amount of green cokes reactions taking place in process furnace, two kinds of adsorption filtration beds that filter among the bed must be provided with, and the adsorption filtration beds can determine whether according to needs, the stock oil character of device being provided with, take all factors into consideration, be provided with simultaneously two bed better effects if some.
Described residual hydrogenation reactive system can be the various Technologies that are applicable to residual hydrogenation, as the fixed bed residual hydrogenation, and suspension bed residual oil hydrogenation, moving-bed residual hydrogenation, boiling bed residual oil hydrogenation etc.With more sophisticated fixed bed hydrogenation reaction technology at present is example, and its process conditions is: hydrogen pressure 1.0～20.0MPa, be preferably 5.0～18.0MPa, and that best is 8.0～16.0MPa; 260～450 ℃ of temperature are preferably 320～440 ℃, and best is 360～430 ℃; Volume space velocity 0.2～5h during liquid
-1, be preferably 0.2～3h
-1, that best is 0.2～2h
-1Hydrogen to oil volume ratio 300～2500 is preferably 400～2000, and best is 500～1500.The heavy residual oil hydrocatalyst that adopts be meant have weight, the single catalyst or the series catalyst of residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking function.These catalyzer generally all are to be carrier with porous, inorganic refractory oxide such as aluminum oxide, the oxide compound of group vib and/or VIII family metal oxide such as W, Mo, Co, Ni etc. is an active ingredient, the catalyzer that optionally adds other various auxiliary agents such as P, Si, elements such as F, B, for example CEN, the FZC series of being produced by Fushun Petrochemical Research Institute pilot scale base weighs, residuum hydrogenating and metal-eliminating catalyst, and ZTN, the ZTS catalyst series produced by first fertilizer plant of Qilu Petrochemical company just belong to this class catalyzer.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst are wherein arranged, and the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking catalyst successively.Technology with these several catalyst mix fillings is also arranged certainly.
The present invention is applicable to normal slag and the pre-treatment that subtracts slag, is particularly useful for the residual oil pre-treatment of high metal, high granule content, high carbon residue, high condensed ring material.
Compared with prior art, characteristics of the present invention are: use simultaneously by adopting one section absorption filter agent bed or one section absorption filter agent bed and one section adsorption filtration beds, not only can farthest remove the suspended particle that carries in the stock oil, but also can remove Iron sulfuret and the most of easily material of green coke that the iron naphthenate in the crude oil generates, at utmost reduce the fouling of residual hydrogenation reactive system reactor, reduce the shutting down number of times that because of fouling cause of device in running period.
Fig. 1 is the schematic flow sheet that adsorption filtration bed and adsorption filtration catalyst bed layered scheme are set simultaneously of the present invention.
For further specifying all main points of the present invention, be elaborated below in conjunction with drawings and Examples.
As shown in Figure 1, residual oil raw material is through after the heat exchange, reach temperature required and enter the first adsorption filtration bed 2 with the form at upper reaches through pipeline 1, filter back stock oil enters charging oil pump 4 through pipeline 3, reach behind the required pressure to mix jointly and enter process furnace 7 through pipeline 6 with high pressure hydrogen by the heat exchange of pipeline 5, be heated to the temperature required parallel feeding of reaction through pipeline streamed second adsorption filtration beds 9 that enters 8 or more, filter parallel feeding afterwards enters fixed bed residual hydrogenation reactor 11 through pipeline 10.
Embodiment 1～6
In the test of Jie Shaoing, four kinds of absorption filtering materials or catalyst A, B, C, D have been used below.
A is the inertia alumina balls, and diameter accounts for 40% of particle pore volume greater than the macropore of 100nm, and surface-area is 130m
2/ g (BET nitrogen adsorption method), can the scope of a few about 60～90nm in aperture in, pore volume (mercury penetration method) is at 0.9～1.1cm
3Between/the g, particle diameter is 4.7mm.
B is the acidic alumina ball, and diameter accounts for 40% of particle pore volume greater than the macropore of 100nm, and surface-area is 130m
2/ g, particle diameter are 4.7mm, can the scope of a few about 60～90nm in aperture in, pore volume (mercury penetration method) is at 0.9～1.1cm
3Between/the g, infrared acidity is 0.4mmo1/g.
C is a catalyzer, and carrier is the wide aperture gama-alumina, supports nickel and makes active metal component, and metal content is 1.2w% (in NiO).Diameter accounts for 40% of particle pore volume greater than the macropore of 100nm in the catalyzer, and surface-area is 130m
2/ g, can the scope of a few about 60～90nm in aperture in, pore volume (mercury penetration method) is at 0.9～1.1cm
3Between/the g, particle diameter is 4.3mm.
D is a catalyzer, and carrier is the wide aperture gama-alumina, supports nickel, molybdenum is made active metal component, and metal content is that 0.5w% (in NiO), 1.7w% are (with MoO
3Meter).Diameter accounts for 40% of particle pore volume greater than the macropore of 100nm in the catalyzer, and surface-area is 130m
2/ g,, particle diameter is 4.3mm.
These embodiment mainly investigate the adsorption filtration ability of adsorption filtration bed.Employed stock oil character sees Table-1, and operational condition and reaction result see Table-2.
The main character of table-1 stock oil
| Project | Stock oil |
| Elementary composition | |
| S，w％ | ????2.52 |
| N，w％ | ????0.80 |
| Metal content | |
| Ni，μg/g | ????48.0 |
| V，μg/g | ????2.2 |
| Fe，μg/g | ????13.8 |
| Ca，μg/g | ????33.8 |
| Ash content, μ g/g | ????150 |
| Benzene insoluble, μ g/g | ????400 |
| Four components | |
| Saturated part, w% | ????14.5 |
| Fragrance part, w% | ????34.8 |
| Colloid, w% | ????47.2 |
| Bituminous matter, w% | ????3.5 |
The operational condition of table-2 adsorption filtration beds and filter back oil analysis result
| Project | ??????????1 | ??????????2 | ???????????3 | |||
| Temperature, ℃ | ?????????220 | ?????????250 | ??????????280 | |||
| Air speed, h -1 | ?????????4.5 | ?????????5.0 | ??????????6.0 | |||
| Filtering medium | ????A | ????B | ????A | ????B | ????A | ????B |
| Generate oil nature | ||||||
| Elementary composition | ||||||
| S，w％ | ????2.46 | ????2.38 | ????2.47 | ????2.35 | ????2.44 | ????2.28 |
| N，w％ | ????0.77 | ????0.76 | ????0.79 | ????0.76 | ????0.78 | ????0.74 |
| Metal content | ||||||
| Ni，μg/g | ????47.1 | ????45.2 | ????47.2 | ????44.5 | ????46.4 | ????43.0 |
| V，μg/g | ????2.15 | ????2.06 | ????2.15 | ????2.03 | ????2.12 | ????1.96 |
| Fe，μg/g | ????9.5 | ????9.1 | ????9.5 | ????8.9 | ????9.3 | ????8.5 |
| Ca，μg/g | ????33.0 | ????31.8 | ????33.1 | ????31.3 | ????32.6 | ????30.3 |
| Benzene insoluble | ????0 | ????0 | ????0 | ????0 | ????0 | ????0 |
| Four components | ||||||
| Saturated part, w% | ????14.5 | ????14.5 | ????14.5 | ????14.5 | ????14.5 | ????14.5 |
| Fragrance part, w% | ????34.2 | ????33.2 | ????33.6 | ????31.9 | ????33.0 | ????30.2 |
| Colloid, w% | ????46.5 | ????45.1 | ????46.6 | ????44.7 | ????46.1 | ????43.1 |
| Bituminous matter, w% | ????3.0 | ????2.4 | ????3.1 | ????2.1 | ????2.7 | ????2.0 |
The operational condition of continuous table-2 adsorption filtration beds and filter back oil analysis result
| Project | ???????????4 | ??????????5 | ???????????6 | |||
| Temperature, ℃ | ??????????280 | ?????????280 | ??????????300 | |||
| Air speed, h -1 | ??????????7.0 | ?????????8.0 | ??????????8.0 | |||
| Filtering medium | ??A | ????B | ????A | ????B | ????A | ????B |
| Generate oil nature | ||||||
| Elementary composition | ||||||
| S，m％ | ??2.45 | ????2.30 | ????2.47 | ????2.34 | ????2.46 | ????2.30 |
| N，m％ | ??0.78 | ????0.75 | ????0.79 | ????0.76 | ????0.78 | ????0.75 |
| Metal content | ||||||
| Ni，ppm | ??46.8 | ????43.5 | ????47.2 | ????44.4 | ????46.9 | ????43.5 |
| V，ppm | ??2.13 | ????1.99 | ????2.15 | ????2.02 | ????2.14 | ????1.99 |
| Fe，ppm | ??9.5 | ????8.7 | ????9.5 | ????8.9 | ????9.5 | ????8.7 |
| Ca，ppm | ??32.8 | ????30.6 | ????33.1 | ????31.2 | ????32.9 | ????30.6 |
| Benzene insoluble | ??0 | ????0 | ????0 | ????0 | ????0 | ????0 |
| Four components | ||||||
| Saturated part, w% | ??14.5 | ????14.5 | ????14.5 | ????14.5 | ????14.5 | ????14.5 |
| Fragrance part, w% | ??33.2 | ????30.5 | ????33.6 | ????30.9 | ????33.4 | ????30.6 |
| Colloid, w% | ??46.3 | ????43.4 | ????46.6 | ????43.9 | ????46.4 | ????43.3 |
| Bituminous matter w% | ??2.9 | ????2.3 | ????3.1 | ????2.7 | ????2.9 | ????2.4 |
Following examples are mainly investigated the collaborative adsorption filtration ability of adsorption filtration bed and adsorption filtration beds.The employed catalyzer of adsorption filtration beds is C, D.Stock oil character sees Table-1, and operational condition and reaction result see Table-3.
The operational condition of table-3 adsorption filtrations bed/adsorption filtration beds and filter back oil analysis result
| Project | ???????????1 | ??????????2 | ??????????3 | |||
| The adsorption filtration bed | ||||||
| Temperature, ℃ | ??????????220 | ?????????250 | ?????????280 | |||
| Air speed, h -1 | ??????????4.5 | ?????????5.0 | ?????????6.0 | |||
| Filtering medium | ????A | ????B | ????A | ????B | ????A | ????B |
| The adsorption filtration beds | ||||||
| Temperature, ℃ | ??????????360 | ?????????365 | ?????????370 | |||
| Air speed, h -1 | ??????????4.5 | ?????????5.0 | ?????????6.0 | |||
| Hydrogen-oil ratio, | ??????????700 | ?????????800 | ?????????800 | |||
| Pressure, MPa | ??????????10.0 | ?????????10.0 | ?????????14.0 | |||
| Catalyzer | ????C | ????D | ????C | ????D | ????C | ????D |
| Generate oil nature | ||||||
| Elementary composition | ||||||
| S，w％ | ???1.98 | ????1.77 | ????1.94 | ????1.70 | ????1.86 | ????1.56 |
| N，w％ | ???0.71 | ????0.69 | ????0.72 | ????0.68 | ????0.72 | ????0.66 |
| Metal content | ||||||
| Ni，μg/g | ???39.2 | ????35.2 | ????38.5 | ????33.9 | ????36.8 | ????31.2 |
| V，μg/g | ???1.77 | ????1.58 | ????1.74 | ????1.52 | ????1.70 | ????1.45 |
| Fe，μg/g | ???5.2 | ????3.7 | ????4.8 | ????3.3 | ????4.9 | ????3.2 |
| Ca，μg/g | ???26.4 | ????25.4 | ????26.5 | ????25.0 | ????26.0 | ????23.8 |
| Benzene insoluble | ???0 | ????0 | ????0 | ????0 | ????0 | ????0 |
| Four components | ||||||
| Saturated part, w% | ???15.8 | ????16.3 | ????16.7 | ????16.9 | ????17.5 | ????17.9 |
| Fragrance part, w% | ???33.6 | ????32.5 | ????33.0 | ????31.1 | ????32.3 | ????29.5 |
| Colloid, w% | ???43.2 | ????40.9 | ????43.0 | ????40.2 | ????42.2 | ????38.5 |
| Bituminous matter, w% | ???2.2 | ????2.2 | ????2.1 | ????1.3 | ????1.8 | ????1.2 |
The operational condition of continuous table-3 adsorption filtrations bed/adsorption filtration beds and filter back oil analysis result
| Project | ???????????4 | ???????????5 | ???????????6 | |||
| The adsorption filtration bed | ||||||
| Temperature, ℃ | ??????????280 | ??????????280 | ??????????300 | |||
| Air speed, h -1 | ??????????7.0 | ??????????8.0 | ??????????8.0 | |||
| Filtering medium | ????A | ????B | ????A | ????B | ????A | ????B |
| The adsorption filtration beds | ||||||
| Temperature, ℃ | ??????????370 | ??????????380 | ??????????380 | |||
| Air speed, h -1 | ??????????6.0 | ??????????7.0 | ??????????7.0 | |||
| Hydrogen-oil ratio, | ??????????900 | ??????????900 | ??????????1000 | |||
| Pressure, MPa | ??????????14.0 | ??????????15.0 | ??????????15.0 | |||
| Catalyzer | ????C | ????D | ????C | ????D | ????C | ????D |
| Generate oil nature | ||||||
| Elementary composition | ||||||
| S，w％ | ????1.86 | ????1.57 | ????1.82 | ????1.53 | ????1.81 | ????1.50 |
| N，w％ | ????0.72 | ????0.67 | ????0.73 | ????0.75 | ????0.72 | ????0.67 |
| Metal content | ||||||
| Ni，μg/g | ????37.1 | ????31.6 | ????35.4 | ????29.7 | ????35.1 | ????29.1 |
| V，μg/g | ????1.71 | ????1.48 | ????1.68 | ????1.44 | ????1.68 | ????1.42 |
| Fe，μg/g | ????5.02 | ????3.29 | ????5.0 | ????3.3 | ????5.0 | ????3.2 |
| Ca，μg/g | ????26.2 | ????24.5 | ????26.4 | ????24.9 | ????26.3 | ????24.5 |
| Benzene insoluble | ????0 | ????0 | ????0 | ????0 | ????0 | ????0 |
| Four components | ||||||
| Saturated part of w% | ????18.5 | ????19.0 | ????19.5 | ????20.2 | ????20.6 | ????21.1 |
| Fragrance part, w% | ????32.5 | ????29.7 | ????32.9 | ????30.1 | ????32.6 | ????29.7 |
| Colloid, w% | ????45.9 | ????38.6 | ????42.2 | ????38.8 | ????41.7 | ????37.9 |
| Bituminous matter, w% | ????1.9 | ????1.3 | ????1.9 | ????1.4 | ????1.7 | ????1.2 |
Claims (10)
1, a kind of heavy, process for hydrogenating residual oil, heavy, residual oil raw material at first passes through pre-treatment, mixes with hydrogen then, after the process heating reaches desired reaction temperature, enters in the residual hydrogenation reactive system and reacts, and reactant enters separation system to be separated; It is characterized in that described preprocessing process be heavy residual oil raw material through heat exchange reach temperature required after, entering the adsorption filtration system that absorption filter agent is housed filters, the operational condition of described adsorption filtration is: 100～320 ℃ of temperature, volume space velocity is 2.0～8.5h during liquid
-1, working pressure 0.1～0.3Mpa.
2, according to described heavy, the process for hydrogenating residual oil of claim 1, it is characterized in that described heavy residual oil raw material is mixing with hydrogen, after the process heating reaches desired reaction temperature, enter react in the beds before, also will enter the bed that the adsorption filtration catalyzer is housed carries out further adsorption filtration and removes impurity, the operational condition of described adsorption filtration beds is: temperature is 340～390 ℃, and volume space velocity is 2.0～8.5h during liquid
-1, hydrogen to oil volume ratio 500～1500, working pressure 8.0～16.0Mpa.
3,, it is characterized in that described absorption filter agent is selected from the spent catalyst of porous, inorganic refractory oxide, molecular sieve, gac, residual oil device or other catalysis oil refining apparatus according to described heavy, the process for hydrogenating residual oil of claim 1.
4, according to the described weight of claim 1, process for hydrogenating residual oil, it is characterized in that described absorption filter agent pore distribution is diameter and accounts for 10% of pore volume at least greater than the macropore of 100nm, surface-area is at 50m
2/ g～200m
2Between/the g, can several apertures in the scope of about 20～100nm, pore volume is at 0.7～1.2cm
3Between/the g, average particulate diameter 3.5～5.0mm.
5, according to the described weight of claim 1, process for hydrogenating residual oil, it is characterized in that described adsorption filtration system is provided with two covers, both switch use.
6,, it is characterized in that described adsorption filtration part also is provided with back-purge system according to the described weight of claim 1, process for hydrogenating residual oil.
7, according to described heavy, the process for hydrogenating residual oil of claim 2, it is characterized in that described adsorption filtration catalyzer is is carrier with the porous refractory inorganic oxides, is the catalyzer or the spent catalyst of active ingredient with VIB in the periodic table of elements and/or VIII family metallic element.
8, according to described heavy, the process for hydrogenating residual oil of claim 2, it is characterized in that described adsorption filtration catalyst pores is distributed as diameter and accounts for 10% of pore volume at least greater than the macropore of 100nm, surface-area is at 50m
2/ g～200m
2Between/the g, can several apertures in the scope of about 20～100nm, pore volume is at 0.7～1.2cm
3Between/the g, average particulate diameter 3.5～5.0mm.
9, according to described heavy, the process for hydrogenating residual oil of claim 2, it is characterized in that described adsorption filtration catalysis system is provided with two covers, switch and use.
10,, it is characterized in that described adsorption filtration catalysed partial also is provided with back-purge system according to described heavy, the process for hydrogenating residual oil of claim 2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110714 CN1107713C (en) | 2000-07-24 | 2000-07-24 | Heavy oil and residual oil hydrogenating process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110714 CN1107713C (en) | 2000-07-24 | 2000-07-24 | Heavy oil and residual oil hydrogenating process |
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| Publication Number | Publication Date |
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| CN1335368A true CN1335368A (en) | 2002-02-13 |
| CN1107713C CN1107713C (en) | 2003-05-07 |
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ID=4580693
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00110714 Expired - Lifetime CN1107713C (en) | 2000-07-24 | 2000-07-24 | Heavy oil and residual oil hydrogenating process |
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| CN (1) | CN1107713C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1312256C (en) * | 2003-10-31 | 2007-04-25 | 中国石油化工股份有限公司 | Distillate oil hydrodeacidifying method |
| CN102344827A (en) * | 2010-08-05 | 2012-02-08 | 中国石油化工股份有限公司 | Hydrogenation method for catalytic cracking heavy cycle oil |
| CN102732304A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Naphtha hydrogenation reaction device capable of prolonging running period and naphtha hydrogenation reaction method |
| CN102911728A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Naphtha hydrogenation reaction system apparatus and hydrogenation reaction method |
| CN103013567A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing needle coke material by catalytic cracking slurry |
| CN101684414B (en) * | 2008-09-27 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid and high-calcium crude oil |
| WO2018004743A1 (en) * | 2016-06-28 | 2018-01-04 | Chevron U.S.A. Inc. | Regeneration of an ionic liquid catalyst by hydrogenation using a macroporous noble metal catalyst |
| CN107670699A (en) * | 2016-08-01 | 2018-02-09 | 北京华石联合能源科技发展有限公司 | A kind of heavy oil floating bed hydrogenation catalyst using complex carrier |
| CN111534328A (en) * | 2020-05-12 | 2020-08-14 | 武汉科林化工集团有限公司 | Inferior high-olefin cracking carbon nine-fraction hydrogenation process |
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| CN1312256C (en) * | 2003-10-31 | 2007-04-25 | 中国石油化工股份有限公司 | Distillate oil hydrodeacidifying method |
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| CN102344827A (en) * | 2010-08-05 | 2012-02-08 | 中国石油化工股份有限公司 | Hydrogenation method for catalytic cracking heavy cycle oil |
| CN102344827B (en) * | 2010-08-05 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method for catalytic cracking heavy cycle oil |
| CN102732304B (en) * | 2011-04-15 | 2014-07-23 | 中国石油化工股份有限公司 | Naphtha hydrogenation reaction device capable of prolonging running period and naphtha hydrogenation reaction method |
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| CN102911728B (en) * | 2011-08-01 | 2014-07-23 | 中国石油化工股份有限公司 | Naphtha hydrogenation reaction system apparatus and hydrogenation reaction method |
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| CN103013567B (en) * | 2011-09-28 | 2015-02-25 | 中国石油化工股份有限公司 | Method for preparing needle coke material by catalytic cracking slurry |
| WO2018004743A1 (en) * | 2016-06-28 | 2018-01-04 | Chevron U.S.A. Inc. | Regeneration of an ionic liquid catalyst by hydrogenation using a macroporous noble metal catalyst |
| US9956553B2 (en) | 2016-06-28 | 2018-05-01 | Chevron U.S.A. Inc. | Regeneration of an ionic liquid catalyst by hydrogenation using a macroporous noble metal catalyst |
| GB2564597A (en) * | 2016-06-28 | 2019-01-16 | Chevron Usa Inc | Regeneration of an ionic liquid catalyst by hydrogenation using a macroporous noble metal catalyst |
| US11000839B2 (en) | 2016-06-28 | 2021-05-11 | Chevron U.S.A. Inc. | Regeneration of an ionic liquid catalyst by hydrogenation using a macroporous noble metal catalyst |
| GB2564597B (en) * | 2016-06-28 | 2022-04-20 | Chevron Usa Inc | Regeneration of an ionic liquid catalyst by hydrogenation using a macroporous noble metal catalyst |
| CN107670699A (en) * | 2016-08-01 | 2018-02-09 | 北京华石联合能源科技发展有限公司 | A kind of heavy oil floating bed hydrogenation catalyst using complex carrier |
| CN107670699B (en) * | 2016-08-01 | 2021-04-13 | 北京华石联合能源科技发展有限公司 | Heavy oil suspension bed hydrogenation catalyst adopting composite carrier |
| CN111534328A (en) * | 2020-05-12 | 2020-08-14 | 武汉科林化工集团有限公司 | Inferior high-olefin cracking carbon nine-fraction hydrogenation process |
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