CN106256884A - A kind of diesel hydrogenation for removal sulphur and the method for decolouring - Google Patents
A kind of diesel hydrogenation for removal sulphur and the method for decolouring Download PDFInfo
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Abstract
A kind of diesel hydrogenation for removal sulphur and the method for decolouring, diesel raw material oil enters reactor together with hydrogen, hydrogenation reaction is carried out under the effect of hydrogenation catalyst I, reactor effluent enters high pressure hot separator after heat exchange, high pressure hot separator bottom filling active metal is the hydrogenation catalyst II of cobalt-molybdenum, the liquid phase stream of high pressure hot separator isolated is extracted out bottom high pressure hot separator, obtains hydrogasoline and hydrogenated diesel oil after cooled, fractional distillation.The present invention have employed the hydrogenation catalyst II that active metal is cobalt-molybdenum in high pressure hot separator, and not only the hydrogen utilization ratio of hydrodesulfurization reaction is higher, and when ultra-deep hydrodesulfuration by H2The inhibitory action of S is less, straight-run diesel oil or secondary processing diesel oil inferior can be processed, produce the sulfur content ultra-low-sulphur diesel less than 10ppm, it is not necessary to independent hydrogenation decoloring reaction device, just can complete to be hydrogenated with decoloring reaction, make product A STM D1500 colourity less than 1.0.
Description
Technical field
The invention belongs to the method for hydrocarbon oil refining under conditions of there is hydrogen, more specifically, be a kind of
Diesel hydrogenation for removal sulphur and discoloration method.
Background technology
Along with the quickening of diesel oil of vehicle trend in world wide, the demand of future diesel will be further
Increase.But, containing oxysulfide (SO in the waste gas of discharge after diesel combustionX), nitrogen oxides
(NOX) and the substantial amounts of harmful substance such as particulate matter (PM).These materials not only form city and week
The acid rain of Region In Yanbian, the ozone layer of the destruction earth, it is also possible to cause human carcinogen.Car tail to be reduced
SO in gasX、NOXWith the discharge capacity of the pollutant such as PM, the sulfur content in diesel oil to be reduced,
Also need to reduce the arene content in diesel oil.
To this end, diesel oil standard increasingly stringent in world wide, the low-sulfur of production environment close friend or super-low sulfur
Diesel oil has become countries in the world government and the problem of oil refining enterprise's most attention.The bavin of Europe IV discharge standard
Oil, it is stipulated that sulfur content is less than 50 μ g/g, polycyclic aromatic hydrocarbon (double ring arene and the above aromatic hydrocarbons of dicyclo) quality
Mark is less than 11%；And the diesel oil of Euro V emissions, it is stipulated that sulfur content is further lowered into being less than
10μg/g.As can be seen here, in world wide, the development trend of diesel quality is: constantly reduce diesel oil
Sulfur content, reduces arene content and density the most further, improves Cetane number, the tightest to meet
The Abgasgesetz of lattice.
Hydrofinishing is sulfur, the Main Means of nitrogen heteroatom in removing raw material, in certain temperature, pressure
Under power, hydrogen and raw material react on a catalyst, sulfide and nitride be separately converted to hydrogen sulfide and
Ammonia.Produce sulfur content and be less than 50 μ g/g, the ultra-low-sulphur diesel of even 10 μ g/g, generally require raising behaviour
Make the severity of condition, as improved reaction temperature, make the sulfur content in product touch the mark requirement, but
This will result in oil product form and aspect problem.General diesel oil distillate can because of containing nitride in faint yellow, along with
Hydrogenation reaction must occur, and these hetero atoms can be removed, and diesel product color is thin out even becomes colourless.
But when ultra-deep hydrodesulfuration, high reaction temperature can cause product to present the fluorescent yellow green of band,
This is primarily due at high temperature there occurs the reactions such as condensation, dehydrogenation, generates instability, is easily polymerized
Free radical, form that color is relatively deep and the composition of difficult removing.In order to keep the color of diesel product,
Have been proposed for being controlled by routine techniques the reaction condition of hydrodesulfurization, or introducing is used for improving face
The hydrotreating of color is as the subsequent step of hydrodesulfurization, in order to improve the color of diesel oil.These are conventional
Technology is as follows:
CN1115387C discloses the process for deeply desulfurizing fractional oil of a kind of low hydrogen consumption, bavin in the method
Oil raw material is 2～7h with hydrogen in hydrogen dividing potential drop 2.0～8.0MPa, temperature 320～440 DEG C, liquid hourly space velocity (LHSV)-1、
Contacting with Hydrobon catalyst under conditions of hydrogen-oil ratio 200～700v/v, reaction effluent in temperature is
200～290 DEG C, liquid hourly space velocity (LHSV) 4～10h-1Under conditions of contact with Hydrobon catalyst.Use the party
Method, can produce the sulfur content diesel product less than 300 μ g/g, and improve diesel product colourity.
CN1115390C discloses a kind of medium pressure hydrogenation Porous deproteinized bone method of diesel oil distillate, in the method
Diesel raw material and hydrogen enter the first reactor, temperature 330～390 DEG C, hydrogen dividing potential drop 6.0～9.0MPa,
Liquid hourly space velocity (LHSV) 0.3～1.0h-1, contact with Hydrobon catalyst under conditions of hydrogen-oil ratio 400～700v/v,
Entering aromatic hydrocarbons saturated reaction, the first reactor effluent enters the second reactor, in temperature
250～290 DEG C, hydrogen dividing potential drop 6.0～9.0MPa, liquid hourly space velocity (LHSV) 1.5～5.0h-1, hydrogen-oil ratio 400～700v/v
Under conditions of contact with Hydrobon catalyst, improve reaction logistics color.
CN100443571C discloses the method for hydrotreating of a kind of diesel fraction deep desulfurization and decolouring,
In the method, raw oil and hydrogen are mixed into the first hydrotreating reactor, and its reaction product enters
High pressure hot separator, isolated liquid phase stream and hydrogen are mixed into the second hydrotreating reactor
Hydroconversion reaction zone, top, carries out deep hydrodesulfurizationof reaction；The isolated gas gas-phase objects of high pressure hot separator
The middle part of the second hydrotreating reactor is entered, at this with the second hydrotreating reactor after flowing through cooling
The mixing of top product after enter hydroconversion reaction zone, bottom, carry out being hydrogenated with decoloring reaction.Use the method,
Can produce sulfur content meet Europe III, Europe IV discharge standard require fine-quality diesel oil, simultaneously its
ASTM D1500 colourity is less than 1.0.
CN1824736B discloses a kind of ultra-low-sulphur diesel for preparing the color property with improvement
Two-step method, in the method, reaction pressure be 40～80,000 grams/cm, reaction temperature be
330～380 DEG C, liquid hourly space velocity (LHSV) be 0.1～2.0h-1, under conditions of hydrogen-oil ratio 150～1000v/v to hydrocarbon ils
Carry out deep hydrodesulfurizationof, prepare the product of hydrodesulfurization；It is 40～80 kilograms/square in reaction pressure
Centimetre, reaction temperature be 230～320 DEG C, liquid hourly space velocity (LHSV) be 4～10h-1, hydrogen-oil ratio 150～1000v/v
Under conditions of, the product of described hydrodesulfurization is carried out hydrotreating, improves product colour.
But, on the one hand this several method above-mentioned can not produce the sulfur content diesel oil less than 10 μ g/g and produce
Product, are on the other hand all two-stage methods, and every section of reaction are required for bigger hydrogen-oil ratio, it means that the
Two-stage nitration improves the hydrotreating reaction of colourity and must carry out in reactor, and equipment investment is big.
Summary of the invention
The technical problem to be solved is, produces sulfur content less than 10 μ g/g's in prior art
During diesel product, the colourity of product is higher, and colour stability is poor.
The method that the present invention provides, including:
(1) diesel raw material oil enters reactor together with hydrogen, and hydrogen to oil volume ratio is
100～1000Nm3/m3, under the effect of hydrogenation catalyst I, carry out hydrogenation reaction,
(2) reactor effluent enters high pressure hot separator, the behaviour of high pressure hot separator after heat exchange
As condition it is: temperature 240～360 DEG C, pressure 3.0～15.0MPa, reactor effluent isolated liquid
Phase logistics and gaseous stream, gained liquid phase stream is urged by the hydrogenation that active metal is cobalt-molybdenum from top to down
The bed of agent II, during liquid, volume space velocity is 5.0～20.0h-1, one is introduced from high pressure hot separator bottom
Stock hydrogen gas stream, described hydrogen gas stream to lower and on be the hydrogenation catalyst of cobalt-molybdenum by active metal
The bed of II,
(3) liquid phase stream of high pressure hot separator isolated is extracted out by bottom high pressure hot separator, warp
Hydrogasoline and hydrogenated diesel oil, the gas gas-phase objects of high pressure hot separator isolated is obtained after cooling, fractional distillation
Flow through high pressure hot separator top to extract out, recycle after treatment；
Described hydrogenation catalyst II contains carrier and loads cobalt on the carrier and molybdenum, described load
Body is aluminium oxide and/or silica-alumina, and described hydrogenation catalyst II employing comprises the following steps
Method prepares: with a kind of impregnation liquid dipping carrier, dipping is obtained solid matter and is dried, described
Impregnation liquid contains at least one cobalt compound, at least one molybdate compound, at least one is containing phosphatization
Compound and citric acid, in described impregnation liquid, the concentration of cobalt compound in terms of cobalt element is
0.01-0.1g/mL, the concentration of the molybdate compound counted with molybdenum element is as 0.05-0.4g/mL, with P elements
The concentration of the phosphorus-containing compound of meter is 0.005-0.1g/mL, and the concentration of citric acid is 0.05-0.5g/mL,
With ultraviolet-visible spectrum analysis and characterization, λ≤1 of described impregnation liquid, λ is in ultraviolet-visible spectrum 517
The ratio of spectral peak peak height at spectral peak peak height and 772 ± 10nm at ± 10nm.
Described diesel raw material oil is selected from straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking
The mixture of one or more in diesel oil.
The present invention enters reactor, instead by oily for diesel raw material together with after the hydrogen mixing of excess far away
Answer and contact with hydrogenation catalyst I in device, carry out that hydrodesulfurization, hydrodenitrogeneration, alkene is saturated, aromatic hydrocarbons
Saturated and cracking etc. reacts, the most sulfur-containing compound of removing and nitrogen-containing compound, step (1)
In gained reactor effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.In reactor, mistake far away
Hydrogen and the liquid phase of amount are fully contacted, and hydrogen is sufficiently dissolved in liquid phase, at reactor exit,
The hydrogen dissolved in liquid phase is close to the state of saturated dissolving.
In the reactor, under standard state, hydrogen to oil volume ratio is 100～1000Nm3/m3, preferably
200～600Nm3/m3, further preferably 250～400Nm3/m3.Reactor can be one or more,
It can be one or more bed in reactor.
The reaction condition of reactor is: average reaction temperature is 320～420 DEG C, preferably 340～410 DEG C,
Further preferably 350～400 DEG C, pressure 3.0～15.0MPa, preferably 5.0～12.0MPa, further preferably 6.0～
10.0MPa, volume space velocity 0.5～6.0h during liquid-1, preferably 0.8～4.0h-1, further preferably 1.0～3.0h-1。
In reactor, the hydrogenation catalyst I of filling is for being supported in unformed aluminium oxide and/or silica-alumina supports
Group vib base metal and/or the non-noble metal catalyst of VIII, wherein group vib base metal
For Mo and/or W, VIII base metal is Ni and/or Co.
This method completes major part sulfide and most in the hydrogenation reactor of step (1)
The removing of nitride, has only remained the sulfide being most difficult to remove on a small quantity, and in high reaction temperatures
Some substance that show colors produced.In step (2), above-mentioned reactor effluent, through heat exchange, enters
High pressure hot separator.
The operating condition of described high pressure hot separator is: temperature 240～360 DEG C, preferably 280～340 DEG C,
Further preferably 300～340 DEG C, pressure 3.0～15.0MPa, preferably 5.0～12.0MPa, further preferably 6.0～
10.0MPa。
Described high pressure hot separator bottom arranges the bed of the hydrogenation catalyst II that filling active metal is cobalt-molybdenum
Layer, is provided above vapor-liquid separation tower tray at hydrogenation catalyst II bed, the entrance of reactor effluent
It is arranged on the top of gas-liquid separation tower tray, after reactor effluent enters high pressure hot separator, passes through vapour
Liquid separation tray isolated liquid phase stream and gaseous stream, the liquid phase stream of gained passes through from top to down
Active metal is the bed of the hydrogenation catalyst II of cobalt-molybdenum, and during its liquid, volume space velocity is preferably
6.0～15.0h-1, further preferably 8.0～12.0h-1.Described liquid phase stream has dissolved the hydrogen reaching saturation
Gas and a certain amount of hydrogen sulfide, the liquid phase stream of gained from top to down, with high air speed, by dress
Fill out the hydrogenation catalyst II bed that the active metal in high pressure hot separator is cobalt-molybdenum, carry out further
Hydrogenation reaction, removing residue sulfide also improves product colourity.
The present inventor studies discovery, and hydrogen sulfide has significantly suppression to ultra-deep desulfurization reaction
Effect, when dissolving a certain amount of hydrogen sulfide in liquid phase stream, can significantly reduce difficult removing sulfide
Hydrodesulfurization speed.In order to solve the problems referred to above, the present invention introduces one from high pressure hot separator bottom
Hydrogen gas stream, described hydrogen gas stream to lower and on by the bed of hydrogenation catalyst II, and with pass through
The liquid phase stream of hydrogenation catalyst II bed inversely contacts, and described hydrogen gas stream is also at vapor-liquid separation tower
With liquid phase stream counter current contacting in dish so that the concentration of hydrogen sulfide in liquid phase stream, divide along thermal high
From the axial direction of device, top-down it is gradually lowered, when liquid phase stream arrives hydrogenation catalyst II bed
Time above Ceng, the concentration of hydrogen sulfide dissolved in liquid phase stream is the lowest.Due to, the present invention is significantly
Reduce the concentration of hydrogen sulfide in liquid phase stream, and have employed by the less work of hydrogen sulfide inhibitory action
Property metal is the hydrogenation catalyst II of cobalt-molybdenum, so that ultra-deep on hydrogenation catalyst II bed adds
Hydrogen desulphurization reaction speed is greatly improved.The sulfur content of raw oil is reduced in hydrogenation reactor by the present invention
To 50 below μ g/g, in high pressure hot separator, complete to remain the removing of sulfide so that product sulfur contains
Amount is reduced to 10 below μ g/g, and improves oil product color.
The hydrogen gas stream that step (2) is injected by high pressure hot separator bottom, the volume under its standard state
Flow is in high pressure hot separator 5～200 times of liquid phase stream, preferably 10～100 times, further preferably 20～50
Times.
Described hydrogenation catalyst II uses the method comprised the following steps to prepare: by one dipping immersion
Stain carrier, obtains solid matter by dipping and is dried, and described impregnation liquid contains at least one containing cobalt
Compound, at least one molybdate compound, at least one phosphorus-containing compound and citric acid, described impregnation liquid
In the concentration of cobalt compound counted with cobalt element as 0.01-0.1g/mL, in terms of molybdenum element containing molybdenum
The concentration of compound is 0.05-0.4g/mL, and the concentration of the phosphorus-containing compound in terms of P elements is
0.005-0.1g/mL, the concentration of citric acid is 0.05-0.5g/mL, with ultraviolet-visible spectrum analysis and characterization,
λ≤1 of described impregnation liquid, λ is spectral peak peak height and 772 at 517 ± 10nm in ultraviolet-visible spectrum
The ratio of spectral peak peak height at ± 10nm.
This preferred embodiment in, it is preferable that in described impregnation liquid in terms of cobalt element containing cobalt
The concentration of compound is 0.02-0.09g/mL, such as 0.05-0.08g/mL；Molybdate compound in terms of molybdenum element
Concentration be 0.08-0.35g/mL, such as 0.1-0.25g/mL；Phosphorus-containing compound in terms of P elements dense
Degree is 0.007-0.08g/mL, such as 0.01-0.03g/mL；The concentration of citric acid is 0.05-0.4g/mL,
Such as 0.08-0.25g/mL, with ultraviolet-visible spectrum analysis and characterization, the λ=0-0.95 of described impregnation liquid,
It is highly preferred that λ=0-0.80.
According to this preferred embodiment, described impregnation liquid can use following methods to prepare: (1) will
Cobalt compound, molybdate compound, phosphorus-containing compound and citric acid mix with water, and dissolving is reacted into molten
Liquid；(2) solution that step (1) obtains is reacted 0.5 hour-200 hours at a temperature of 60-300 DEG C；
Wherein, the consumption of each component in making the impregnation liquid finally given the content of each component meet previously described
Requirement is as the criterion.In step (2), described temperature is preferably 75-200 DEG C, more preferably 80-150 DEG C,
Such as 80-120 DEG C.In step (2), the time of described reaction is preferably 1-100 hour, more preferably
2-50 hour, such as 1-10h.Step (2) can be carried out in hermetic container (such as autoclave),
Can also carry out in open system.
According to this preferred embodiment, described cobalt compound is selected from water miscible cobalt compound,
Such as, the salt containing cobalt metal component, the oxide containing cobalt metal component and the hydrogen-oxygen containing cobalt metal component
One or more in compound.The instantiation of described cobalt compound can include but not limited to
The nitrate of cobalt, the chloride of cobalt, the sulfate of cobalt, the formates of cobalt, the acetate of cobalt, cobalt
Phosphate, the citrate of cobalt, the oxalates of cobalt, the carbonate of cobalt, the subcarbonate of cobalt, cobalt
Hydroxide, the phosphate of cobalt, the phosphide of cobalt, the sulfide of cobalt, the aluminate of cobalt, cobalt
One or more in the oxide of molybdate, the tungstates of cobalt and cobalt.Preferably, described contain
Cobalt compound be the oxalates of cobalt, the carbonate of cobalt, the subcarbonate of cobalt, the hydroxide of cobalt,
One or more in the oxide of the phosphate of cobalt, the molybdate of cobalt, the tungstates of cobalt and cobalt.
It is highly preferred that the subcarbonate that described cobalt compound is cobalt and/or the carbonate of cobalt.
According to this preferred embodiment, described molybdate compound is selected from water miscible molybdate compound,
Such as, the salt containing molybdenum component and/or the oxide containing molybdenum component.Described molybdate compound
Instantiation can include but not limited to the one or two in ammonium molybdate, the heteropolyacid salt of molybdenum and molybdenum oxide
More than Zhong.
According to this preferred embodiment, described phosphorus-containing compound can be phosphoric acid, ammonium dihydrogen phosphate,
One or more in diammonium phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate, preferably phosphoric acid.
According to this preferred embodiment, silicon oxide and the content of aluminium oxide in described silica-alumina
Can be conventional selection.Preferably, in described silica-alumina, the content of silicon oxide can be 2-45
Weight %, preferably 5-40 weight %, more preferably 5-30 weight %, such as 10-20 weight %；
The content of aluminium oxide can be 55-98 weight %, preferably 60-95 weight %, more preferably
70-95 weight %, such as 80-90 weight %.
According to this preferred embodiment, described dipping can be saturated dipping, it is also possible to soak for excess
Stain.Usually, impregnation liquid by volume can be 0.5-10:1 with the ratio of carrier by weight,
It is preferably 0.7-8:1.When described dipping is excess dipping, in the mixture that dipping obtains, there is trip
In the presence of exsolution liquid, before being dried, preferably include the step filtered, dissociate with removing
Solution.
According to this preferred embodiment, described being dried can be carried out under normal conditions.Usually,
Described be dried can 100-300 DEG C, carry out at a temperature of preferred 120-280 DEG C.Described dry holding
The continuous time can be 1-12 hour, preferably 2-8 hour.In a preferred embodiment, it is dried
After product can use directly as catalyst, it is also possible to use as catalyst after carrying out roasting.
Described roasting can be carried out under normal conditions.Usually, the temperature of described roasting can be
350-550 DEG C, preferably 400-500 DEG C.The persistent period of described roasting can be 1-8 hour, excellent
Elect 2-6 hour as.
One of the present invention preferred embodiment in, described hydrogenation catalyst II, it is also possible to contain
Any performance not affecting catalyst maybe can improve the material of catalyst performance.As the groups such as boron can be contained
Point, to count and on the basis of catalyst by element, the content of boron is less than 10 weight %, preferably 0.5-6
Weight %.
In high pressure hot separator, the liquid product of reactor is made to complete ultra-deep under high air speed
Spend hydrodesulfurization reaction and improve product colourity.This is compared with traditional hydrodesulfurization, discoloration method
Not only reducing the usage amount of catalyst, it is thus also avoided that the use of decoloring reaction device, the equipment that decreases is thrown
Money, uses hydrogenation catalyst II, and not only the hydrogen utilization ratio of hydrodesulfurization reaction is higher, and super
By H during deep hydrodesulfurizationof2The inhibitory action of S is less, completes under hydrogen to oil volume ratio that can be the lowest
Diesel oil ultra-deep hydrodesulfuration and decolouring.
In step (3), the liquid phase stream of high pressure hot separator isolated is through at the bottom of high pressure hot separator
Portion extracts out, obtains hydrogasoline and hydrogenated diesel oil after cooled, fractional distillation, and high pressure hot separator separates
The gaseous stream arrived is extracted out through high pressure hot separator top, recycles after treatment.Through depriving hydrogen sulphide
Gaseous stream after process is recycled into reactor inlet, it is possible to by entering heat bottom high pressure hot separator
High-pressure separator.
The method using the present invention to provide, can process straight-run diesel oil or secondary processing diesel oil inferior (includes
Coker gas oil, catalytic diesel oil) or the mixing raw material of above-mentioned raw materials, produce sulfur content and be less than 10 μ g/g,
The ASTM D1500 colourity ultra-low-sulphur diesel product less than 1.0.
The hydrotreating reaction of second segment in prior art is separated coupling with the high pressure of gas, liquid by the present invention
Carry out in being combined in a separation equipment, decrease equipment investment.Using active metal is the hydrogenation of cobalt-molybdenum
Catalyst II, not only the hydrogen utilization ratio of hydrodesulfurization reaction is higher, and at ultra-deep hydrodesulfuration
Time by H2The inhibitory action of S is less, completes that diesel oil is ultra-deep to be added under hydrogen to oil volume ratio that can be the lowest
Hydrogen desulfurization and decolouring.The present invention compared with Ultra-deep Desulfurization of Diesel Fuels, discoloration method compares, it is not necessary to
Independent hydrogenation decoloring reaction device, and can complete under high-speed, low hydrogen/gasoline ratio hydrodesulfurization and
Decoloring reaction, saves investment and operating cost.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of the method for the diesel hydrogenation for removal sulphur that provides of the present invention and decolouring.
Detailed description of the invention
The method provided the present invention below by accompanying drawing is further described, but the most therefore limits
The present invention processed, eliminates much equipment, such as pump, heat exchanger, compressor etc. in figure.
As it is shown in figure 1, raw oil is mixed through pipeline 2 with hydrogen partial through pipeline 1, heated stove 4
Heated transportation, in hydrogenation reactor 5, surpasses under conditions of hydrogen and hydrogenation catalyst I exist
Deep hydrodesulfurizationof reacts.Gained reactor effluent in pipeline 6 is transported to high pressure hot separator 7,
In course of conveying reactor effluent through heat exchanger heat exchange to suitable temperature.From pipeline 6
Reactor effluent enters from the middle and upper part of high pressure hot separator 7, and reactor effluent enters thermal high
After separator, by vapor-liquid separation tower tray 12 isolated liquid phase stream and gaseous stream, the liquid of gained
Phase logistics flows through the hydrogenation catalyst II bed 11 that active metal is cobalt-molybdenum from top to down；Another strand of hydrogen
Gas logistics by pipeline 8 from high pressure hot separator 7 bottom enter, to lower and on by active metal be
The hydrogenation catalyst II bed 11 of cobalt-molybdenum, inversely contacts with liquid phase stream.High pressure hot separator separates
The liquid phase effluent of gained enters subsequent processing units through pipeline 9 and obtains hydrogasoline and hydrogenated diesel oil.
The separating obtained gas phase effluent of high pressure hot separator is extracted out through pipeline 10.Hydrogen partial can be as supplementing
Hydrogen is entered the catalyst bed interlayer of reactor 5 by pipeline 3.
The method that the present invention will be provided by the following examples, is further described, but not because of
This and limit the present invention.
Embodiment and comparative example use a kind of Middle East high-sulfur straight(-run) diesel distillate as raw oil A, one
The miscella of Middle East high-sulfur straight(-run) diesel distillate and catalytic cracking diesel oil fraction as raw oil B, its base
This character is listed in table 1.
Product designation RS-2000 of hydrogenation catalyst used therein C in embodiment and comparative example reactor,
Product designation RS-2000 of comparative example high pressure hot separator hydrogenation catalyst used therein C, hydrogenation catalyst
Product designation RS-1100 of agent D, is Sinopec catalyst branch company and produces.
Embodiment thermal high Disengagement zone hydrogenation catalyst used therein D1 is prepared by following steps:
In following example, ultraviolet-visible light analysis of spectrum (UV-Vis), use U.S. Perkin-Elmer
The Lambda35 type multi-functional spectrophotometry instrument of company, in light neon source, measures wavelength
286nm, slit width 1.0nm, sample detection time 4.5min, the experiment bar of detection step-length 2.0s
Solution ultra-violet absorption spectrum in the range of 450-900nm is measured under part.
In following example, in catalyst, the content of each element is analyzed, and uses and manages commercially available from Japan
The 3271E type Xray fluorescence spectrometer learning electric machine industry Co., Ltd. measures.
Hydrogenation catalyst II used in embodiment uses following methods to prepare.
(1) weigh respectively 27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6
Gram citric acid is put in 55mL deionized water, is heated to 80 DEG C and is stirred dissolving 1 hour, obtains
Brownish red settled solution.This solution is put in beaker, be heated to 90 DEG C and under agitation constant temperature 8 little
Time, add water to 85mL, obtain clarifying impregnation liquid S1.The λ value of impregnation liquid S1, cobalt (Co),
The concentration (g/mL) of molybdenum (Mo), phosphorus (P) and citric acid (CTA) is listed in Table 1.
Table 1
| Co(g/mL) | Mo(g/mL) | P(g/mL) | CTA(g/mL) | λ | |
| S1 | 0.05 | 0.21 | 0.017 | 0.09 | 0.78 |
(2) by 2000 grams of aluminium hydrate powders (dry glue powder that Chang Ling refinery company catalyst plant produces,
Butt 71 weight %) and 1039 grams of Ludox (Haiyang Chemical Plant, Qingdao's product, dioxide-containing silicas
It is 30 weight %) mix homogeneously.The mixture banded extruder obtained is extruded into circumscribed circle diameter is 1.4
The butterfly bar of millimeter, and the wet bar of extrusion is dried 4 hours at 120 DEG C, then 600 DEG C of roastings 3
Hour, preparing carrier Z1, in carrier Z1, silica content is 18.0 weight %, and alumina content is
82.0 weight %.The water absorption rate of Z1 is 0.85.
(3) S1 solution is settled to 85mL, 100 grams of carriers of saturated dipping Z12 hour, then
Being dried 2 hours at 120 DEG C successively, 250 DEG C are dried 3 hours, obtain catalyst D1, and its composition is shown in
Table 2.
Table 2
| MoO3(weight %) | CoO (weight %) | P2O5(weight %) | C (weight %) | |
| D1 | 20.5 | 4.0 | 2.2 | 1.7 |
Embodiment 1
Raw oil A and hydrogen together enter in the reactor equipped with hydrogenation catalyst C, hydrogen to oil volume ratio
For 300Nm3/m3, under the effect of hydrogenation catalyst C, carry out deep hydrodesulfurizationof reaction, react bar
Part is: reaction temperature 380 DEG C, volume space velocity 4.0h during raw material fluid-1, reacting system pressure is
6.0MPa, in gained reactor effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.
Loading hydrogenation catalyst D1 in the middle part of high pressure hot separator, reactor effluent is high by heat through heat exchange
Pressure separator middle and upper part enters in high pressure hot separator, from top to down by being seated in high pressure hot separator
In beds, the temperature of high pressure hot separator is 320 DEG C, and pressure is 6.0MPa, body during liquid
Long-pending air speed 12.0h-1.Another burst of hydrogen gas stream enters from high pressure hot separator bottom, to lower and on pass through
The bed of novel cobalt-molybdenum hydrogenation catalyst, inversely contacts with liquid phase stream, and described hydrogen gas stream is in standard
Volume flow under state is 20 times of liquid phase stream.The liquid phase stream of high pressure hot separator isolated
Hydrogasoline and hydrogenated diesel oil is obtained after cooled, fractional distillation.
Reaction condition and the hydrogenated diesel oil product property of the present embodiment are as shown in table 2.
Embodiment 2
Raw oil B and hydrogen together enter in the reactor equipped with hydrogenation catalyst C, hydrogen to oil volume ratio
For 500Nm3/m3, under the effect of hydrogenation catalyst C, carry out deep hydrodesulfurizationof reaction, react bar
Part is: reaction temperature 390 DEG C, volume space velocity 2.8h during raw material fluid-1, reacting system pressure is
8.0MPa, in gained reactor effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.
Loading hydrogenation catalyst D1 in the middle part of high pressure hot separator, reactor effluent is high by heat through heat exchange
Pressure separator middle and upper part enters in high pressure hot separator, from top to down by being seated in high pressure hot separator
In beds, the temperature of high pressure hot separator is 330 DEG C, and pressure is 8.0MPa, body during liquid
Long-pending air speed 12.0h-1.Another burst of hydrogen gas stream enters from high pressure hot separator bottom, to lower and on pass through
The bed of novel cobalt-molybdenum hydrogenation catalyst, inversely contacts with liquid phase stream, and described hydrogen gas stream is in standard
Volume flow under state is 50 times of liquid phase stream.The liquid phase stream of high pressure hot separator isolated
Hydrogasoline and hydrogenated diesel oil is obtained after cooled, fractional distillation.
Reaction condition and the hydrogenated diesel oil product property of the present embodiment are as shown in table 3.
Comparative example 1a
Raw oil A and hydrogen together enter in the reactor equipped with hydrogenation catalyst C, hydrogen to oil volume ratio
For 300Nm3/m3, under the effect of hydrogenation catalyst C, carry out deep hydrodesulfurizationof reaction, react bar
Part is: reaction temperature 380 DEG C, volume space velocity 4.0h during raw material fluid-1, reacting system pressure is
6.0MPa, in gained reactor effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.
Loading hydrogenation catalyst D in the middle part of high pressure hot separator, reactor effluent is high by heat through heat exchange
Pressure separator middle and upper part enters in high pressure hot separator, from top to down by being seated in high pressure hot separator
In beds, the temperature of high pressure hot separator is 320 DEG C, and pressure is 6.0MPa, body during liquid
Long-pending air speed 12.0h-1.Another burst of hydrogen gas stream enters from high pressure hot separator bottom, to lower and on pass through
The bed of hydrogenation catalyst D, inversely contacts with liquid phase stream, and described hydrogen gas stream is in normal conditions
Volume flow is liquid phase stream 30 times.The liquid phase stream of high pressure hot separator isolated is through cold
But, hydrogasoline and hydrogenated diesel oil are obtained after fractional distillation.
Reaction condition and the hydrogenated diesel oil product property of the present embodiment are as shown in table 2.
Comparative example 1b
Raw oil A and hydrogen together enter in the reactor equipped with hydrogenation catalyst C, hydrogen to oil volume ratio
For 300Nm3/m3, under the effect of hydrogenation catalyst C, carry out deep hydrodesulfurizationof reaction, react bar
Part is: reaction temperature 380 DEG C, volume space velocity 2.8h during raw material fluid-1, reacting system pressure is 6.0MPa
In gained reactor effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.
Reactor effluent enters fractionation apparatus after high-pressure separator, low pressure separator and is hydrogenated with
Gasoline and hydrogenated diesel oil.Reaction condition and hydrogenated diesel oil product main character are as shown in table 2.
Comparative example 2a
Raw oil B and hydrogen together enter in the reactor equipped with hydrogenation catalyst C, hydrogen to oil volume ratio
For 500Nm3/m3, under the effect of hydrogenation catalyst C, carry out deep hydrodesulfurizationof reaction, react bar
Part is: reaction temperature 390 DEG C, volume space velocity 2.8h during raw material fluid-1, reacting system pressure is
8.0MPa, in gained reactor effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.
Loading hydrogenation catalyst C in the middle part of high pressure hot separator, reactor effluent is high by heat through heat exchange
Pressure separator middle and upper part enters in high pressure hot separator, from top to down by being seated in high pressure hot separator
In beds, the temperature of high pressure hot separator is 330 DEG C, and pressure is 8.0MPa, body during liquid
Long-pending air speed 10.0h-1.Another burst of hydrogen gas stream enters from high pressure hot separator bottom, to lower and on pass through
The bed of hydrogenation catalyst C, inversely contacts with liquid phase stream, and described hydrogen gas stream is in normal conditions
Volume flow is liquid phase stream 60 times.The liquid phase stream of high pressure hot separator isolated is through cold
But hydrogasoline and hydrogenated diesel oil are obtained after, separating.
Reaction condition and the hydrogenated diesel oil product property of the present embodiment are as shown in table 3.
Comparative example 2b
Raw oil B and hydrogen together enter in the reactor equipped with hydrogenation catalyst C, hydrogen to oil volume ratio
For 500Nm3/m3, under the effect of hydrogenation catalyst C, carry out deep hydrodesulfurizationof reaction, react bar
Part is: reaction temperature 390 DEG C, volume space velocity 2.0h during raw material fluid-1, reacting system pressure is
8.0MPa.In gained reactor effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.
Reactor effluent enters fractionation apparatus after high-pressure separator, low pressure separator and is hydrogenated with
Gasoline and hydrogenated diesel oil.Reaction condition and hydrogenated diesel oil product main character are as shown in table 3.
Table 1 raw oil character
| Embodiment 1 | Embodiment 2 | |
| Raw oil | A | B |
| Density (20 DEG C), g/cm3 | 0.8498 | 0.8591 |
| Sulfur content, μ g/g | 10200 | 10400 |
| Nitrogen content, μ g/g | 251 | 1200 |
| Boiling range ASTM D-86, DEG C | ||
| IBP | 211 | 219 |
| 10% | 223 | 256 |
| 50% | 285 | 294 |
| 90% | 352 | 342 |
| FBP | 367 | 362 |
Table 2
| Process conditions | Embodiment 1 | Comparative example 1a | Comparative example 1b |
| Reacting system pressure, MPa | 6.0 | 6.0 | 6.0 |
| Hydrogen dividing potential drop, MPa | 4.8 | 4.8 | 4.8 |
| Reactor reaction temperature, DEG C | 380 | 380 | 380 |
| High pressure hot separator temperature, DEG C | 320 | 320 | 320 |
| Volume space velocity during reactor liquid, h-1 | 4.0 | 4.0 | 2.8 |
| Volume space velocity during high pressure hot separator liquid, h-1 | 12.0 | 12.0 | Nothing |
| Hydrogen to oil volume ratio in high pressure hot separator | 20 | 30 | Nothing |
| Cumulative volume air speed, h-1 | 3.0 | 3.0 | 2.8 |
| Hydrogenated diesel oil product property | |||
| Reactor outlet sulfur content, μ g/g | 32 | 32 | 8 |
| Product sulfur content, μ g/g | 6 | 7 | 8 |
| Product nitrogen content, μ g/g | <0.2 | <0.2 | <0.2 |
| Colourity (ASTM D1500) | 0.3 | 0.3 | 1.6 |
| Colourity (ASTM D1500) after placing 10 days | 0.4 | 0.4 | 2.4 |
As it can be seen from table 1 the raw oil A of embodiment 1 is a kind of high-sulfur straight(-run) diesel distillate, sulfur
Content is 10200 μ g/g, and nitrogen content is 251 μ g/g.From table 2 it can be seen that use embodiment 1
Method of hydrotreating, reactor outlet sulfur content is 32 μ g/g, the hydrodesulfurization in high pressure hot separator
And decoloring reaction, the sulfur content of product is reduced to 6 μ g/g, and colourity is only 0.3, and cumulative volume air speed is up to
3.0h-1.Using the method that comparative example 1a provides, total air speed, product colourity are consistent with embodiment 1,
But hydrogen to oil volume ratio is higher in product sulfur content and high pressure hot separator, respectively 7 μ g/g and 30.Adopt
The method provided by comparative example 1b, total air speed is 2.8h-1, owing to through process improvement colourity,
To the sulfur content of product be 8 μ g/g, but colourity is up to 1.6.And the product after changing colour and processing
Product have more preferable stability, and after placing 10 days, the product colourity of embodiment 1 and comparative example 1a is
0.4, increase only 0.1, and the product colourity of comparative example 1b is 2.4, add 0.8.
The method that the present invention provides employs the hydrogenation catalyst II that active metal is cobalt-molybdenum, uses this
The method of bright offer, be possible not only to realize under lower hydrogen to oil volume ratio the more degree of depth hydrodesulfurization and
Product colourity greatly improves, and can strengthen the colour stability of product.
Table 3
| Process conditions | Embodiment 2 | Comparative example 2a | Comparative example 2b |
| Reacting system pressure, MPa | 8.0 | 8.0 | 8.0 |
| Hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 6.4 |
| Reactor reaction temperature, DEG C | 390 | 390 | 390 |
| High pressure hot separator temperature, DEG C | 330 | 330 | 330 |
| Volume space velocity during reactor liquid, h-1 | 2.8 | 2.8 | 2.0 |
| Volume space velocity during high pressure hot separator liquid, h-1 | 12.0 | 10.0 | Nothing |
| Hydrogen to oil volume ratio in high pressure hot separator | 50 | 60 | Nothing |
| Cumulative volume air speed, h-1 | 2.3 | 2.2 | 2.0 |
| Hydrogenated diesel oil product property | |||
| Reactor outlet sulfur content, μ g/g | 28 | 28 | 7 |
| Product sulfur content, μ g/g | 7 | 7 | 7 |
| Product nitrogen content, μ g/g | 5 | 5 | 6 |
| Colourity (ASTM D1500) | 0.7 | 0.7 | 2.3 |
| Colourity (ASTM D1500) after placing 10 days | 0.9 | 0.9 | 3.5 |
As it can be seen from table 1 the raw oil B of embodiment 2 is a kind of high sulfur-containing diesel fraction, sulfur content
Being 10400 μ g/g, nitrogen content is 1200 μ g/g.From table 2 it can be seen that use the hydrogenation of embodiment 2
Method, reactor outlet sulfur content is 28 μ g/g, and the hydrodesulfurization in high pressure hot separator is with de-
Colour response, the sulfur content of product is reduced to 7 μ g/g, and colourity is only 0.7, and cumulative volume air speed is up to 2.3h-1。
Using the method that comparative example 2a provides, product sulfur content is consistent with embodiment 1 with colourity, but total air speed
It is only 2.2h-1, in high pressure hot separator, hydrogen to oil volume ratio is 60.Use the method that comparative example 2b provides,
Owing to not through improving the process of colourity, the sulfur content of the product obtained is 7 μ g/g, but colourity is high
Reach 2.3.And the product after changing colour and processing has more preferable stability, after placing 10 days, real
The product colourity executing example 2 and comparative example 2a is 0.9, increase only 0.2, and the product of comparative example 2b
Colourity is 3.5, adds 1.2.
The method that the present invention provides employs the hydrogenation catalyst II that active metal is cobalt-molybdenum, uses this
The method of bright offer, is possible not only to realize hydrodesulfurization under lower hydrogen to oil volume ratio and more high-speed
Greatly improve with product colourity, and the colour stability of product can be strengthened.
Claims (13)
1. diesel hydrogenation for removal sulphur and a method for decolouring, including:
(1) diesel raw material oil enters reactor together with hydrogen, and hydrogen to oil volume ratio is
100～1000Nm3/m3, under the effect of hydrogenation catalyst I, carry out hydrogenation reaction,
(2) reactor effluent enters high pressure hot separator, the behaviour of high pressure hot separator after heat exchange
As condition it is: temperature 240～360 DEG C, pressure 3.0～15.0MPa, reactor effluent isolated liquid
Phase logistics and gaseous stream, gained liquid phase stream is urged by the hydrogenation that active metal is cobalt-molybdenum from top to down
The bed of agent II, during liquid, volume space velocity is 5.0～20.0h-1, one is introduced from high pressure hot separator bottom
Stock hydrogen gas stream, described hydrogen gas stream to lower and on be the hydrogenation catalyst of cobalt-molybdenum by active metal
The bed of II,
(3) liquid phase stream of high pressure hot separator isolated is extracted out by bottom high pressure hot separator, warp
Hydrogasoline and hydrogenated diesel oil, the gas gas-phase objects of high pressure hot separator isolated is obtained after cooling, fractional distillation
Flow through high pressure hot separator top to extract out, recycle after treatment；
Described hydrogenation catalyst II contains carrier and loads cobalt on the carrier and molybdenum, described load
Body is aluminium oxide and/or silica-alumina, and described hydrogenation catalyst II employing comprises the following steps
Method prepares: with a kind of impregnation liquid dipping carrier, dipping is obtained solid matter and is dried, described
Impregnation liquid contains at least one cobalt compound, at least one molybdate compound, at least one is containing phosphatization
Compound and citric acid, in described impregnation liquid, the concentration of cobalt compound in terms of cobalt element is
0.01-0.1g/mL, the concentration of the molybdate compound counted with molybdenum element is as 0.05-0.4g/mL, with P elements
The concentration of the phosphorus-containing compound of meter is 0.005-0.1g/mL, and the concentration of citric acid is 0.05-0.5g/mL,
With ultraviolet-visible spectrum analysis and characterization, λ≤1 of described impregnation liquid, λ is in ultraviolet-visible spectrum 517
The ratio of spectral peak peak height at spectral peak peak height and 772 ± 10nm at ± 10nm.
Method the most according to claim 1, it is characterised in that described hydrogenation catalyst II carrier
For silica-alumina, the silica content in described silica-alumina is 2-45 weight %, oxygen
The content changing aluminum is 55-98 weight %.
Method the most according to claim 1, it is characterised in that with cobalt element in described impregnation liquid
The concentration of the cobalt compound of meter is 0.02-0.09g/mL, the concentration of the molybdate compound in terms of molybdenum element
For 0.08-0.35g/mL, the concentration of the phosphorus-containing compound counted with P elements as 0.007-0.08g/mL, lemon
The concentration of lemon acid is 0.05-0.4g/mL, with ultraviolet-visible spectrum analysis and characterization, described impregnation liquid
λ=0-0.95.
4. according to the arbitrary described method of claim 1-3, it is characterised in that urge with described hydrogenation
On the basis of the total amount of agent II, in terms of oxide, the content of cobalt is 1-10 weight %, the content of molybdenum
For 5-50 weight %.
The most in accordance with the method for claim 1, it is characterised in that in step (1) reactor
Hydrogen to oil volume ratio is 200～600Nm3/m3。
The most in accordance with the method for claim 1, it is characterised in that step (1) reactor anti-
The condition is answered to be: average reaction temperature is 320～420 DEG C, system pressure 3.0～15.0MPa, volume during liquid
Air speed 0.5～6.0h-1。
The most in accordance with the method for claim 1, it is characterised in that step (1) reactor anti-
The condition is answered to be: average reaction temperature is 340～410 DEG C, system pressure 5.0～12.0MPa, volume during liquid
Air speed 1.0～4.0h-1。
The most in accordance with the method for claim 1, it is characterised in that step (1) gained reactor
In effluent, the sulfur content of liquid phase stream is less than 50 μ g/g.
The most in accordance with the method for claim 1, it is characterised in that step (2) thermal high separates
The operating condition of device is: temperature 280～340 DEG C, pressure 5.0～12.0MPa.
The most in accordance with the method for claim 1, it is characterised in that under described high pressure hot separator
Portion arranges the bed of the hydrogenation catalyst II that filling active metal is cobalt-molybdenum, at hydrogenation catalyst II bed
Layer be provided above vapor-liquid separation tower tray, the entrance of reactor effluent is arranged on gas-liquid separation tower tray
Top, after reactor effluent enters high pressure hot separator, by vapor-liquid separation tower tray isolated liquid
Phase logistics and gaseous stream, the liquid phase stream of gained passes through the bed of hydrogenation catalyst II from top to down,
During its liquid, volume space velocity is 6.0～15.0h-1。
11. in accordance with the method for claim 1, it is characterised in that step (2) is divided by thermal high
The hydrogen gas stream injected from device bottom, the volume flow under its standard state is liquid in high pressure hot separator
5～200 times of phase logistics.
12. in accordance with the method for claim 1, it is characterised in that step (2) is divided by thermal high
The hydrogen gas stream injected from device bottom, the volume flow under its standard state is liquid in high pressure hot separator
10～100 times of phase logistics.
13. in accordance with the method for claim 1, the described hydrogenation catalyst loaded in the reactor
Agent I is the group vib base metal and/or VIII being supported in unformed aluminium oxide and/or silica-alumina supports
The non-noble metal catalyst of race, wherein group vib base metal is Mo and/or W, VIII non-noble gold
Belong to for Ni and/or Co.
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| CN1940028A (en) * | 2005-09-28 | 2007-04-04 | 中国石油化工股份有限公司 | Diesel fraction deep desulfurization and decoloring hydrogenation |
| CN102950003A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof |
| CN103509598A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工集团公司 | Hydrogenation system for producing ultralow-sulfur diesel oil, and method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1940028A (en) * | 2005-09-28 | 2007-04-04 | 中国石油化工股份有限公司 | Diesel fraction deep desulfurization and decoloring hydrogenation |
| CN102950003A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof |
| CN103509598A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工集团公司 | Hydrogenation system for producing ultralow-sulfur diesel oil, and method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707474A (en) * | 2018-07-09 | 2018-10-26 | 孙志良 | A kind of process for refining of diesel oil |
| CN108707474B (en) * | 2018-07-09 | 2020-10-09 | 宁夏宁鲁石化有限公司 | Refining process of diesel oil |
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