CN106590742B - A kind of heavy charge oil treatment process - Google Patents
A kind of heavy charge oil treatment process Download PDFInfo
- Publication number
- CN106590742B CN106590742B CN201510671952.0A CN201510671952A CN106590742B CN 106590742 B CN106590742 B CN 106590742B CN 201510671952 A CN201510671952 A CN 201510671952A CN 106590742 B CN106590742 B CN 106590742B
- Authority
- CN
- China
- Prior art keywords
- oil
- reaction
- catalytic cracking
- hydrogenation
- wax
- 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 kind of heavy charge oil treatment process, this method includes：A, heavy raw oil is subjected to either shallow hydrogenation reaction, obtains hydrogenation gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue；Wherein, on the basis of the heavy raw oil, the yield for controlling the hydrogenated residue is 85-95 weights %；B, gained hydrogenated residue in step a is contacted with catalytic cracking catalyst and is carried out the first catalytic cracking reaction, obtain the first dry gas, the first liquefied gas, the first gasoline, the first light cycle oil, the first wax oil and externally extracting oil；C, wax oil hydrogenation reaction will be carried out after the filtering of the first wax oil of gained in step b, and will obtain adding hydrogen wax oil；D, gained in step c plus hydrogen wax oil are subjected to the first catalytic cracking reaction or the second catalytic cracking reaction.The method of the present invention significantly extends the heavy oil hydroprocessing units cycle of operation while significantly improving dry gas and coke selectivity and increasing production lightweight transport fuel.
Description
Technical field
The present invention relates to a kind of heavy charge oil treatment process.
Background technology
With the Continued of world's crude oil demand, heaviness and the in poor quality of crude resources are more and more obvious.It is same with this
When, global oil product demand structure is also changing, and the consumption figure of boiler and heavy fuel oil peculiar to vessel is being reduced year by year, and chemical industry is used
The demand of light oil and high-quality vehicle fuel oil is increasing year by year.Therefore it is good light-end products by more heavy oil conversions
Have become the important directions of the World Refining technology development.Although the exploitation of Residue Catalytic Cracking technology can to heavy raw oil into
The effective working process of row, but it is inclined due to containing a large amount of sulphur, nitrogen, metal impurities and hydrogen-carbon ratio in heavy raw oil
It is low, carbon residue is high, not only increase the difficulty of processing and operating cost of catalytic cracking unit, and that there are yield of light oil is low,
The outstanding problems such as dry gas and coke yield height.
Residual hydrogenation technology has more and more been paid attention to as the effective means of light materialization of heavy oil, high quality.
By adding hydrogen sulphur, nitrogen, metal impurities and carbon residue in feedstock oil can be greatly lowered, and can improve in low grade oils
Raw material hydrogen-carbon ratio, while to reduce difficulty of processing that heavy raw oil is brought to catalytic cracking unit, additionally it is possible to which improvement is urged
Change the product distribution and product quality of cracking, increases high value light-end products yield.Residual hydrogenation and catalytic cracking combined technique
As a kind of high efficient technology scheme of low grade oils lighting.
Major issue existing for current heavy-oil hydrogenation-catalytic cracking combined technique is heavy oil hydrogenation process because of a large amount of product
Carbon green coke, metal deposit cause bed to block, catalyst inactivation, and bed pressure drop increases, and hot spot occurs etc., cause the fortune of device
The row period is restricted.Therefore how to improve the cycle of operation of technique becomes an important research direction.
CN1382776A discloses a kind of residual hydrocracking and catalytically cracking heavy oil method.This method by residual oil,
Slurry oil steaming thing, heavy catalytic cycle oil, optional distillate enter hydrotreater together, in hydrogen and hydrogenation catalyst
Hydrogenation reaction is carried out in the presence of agent；After the generation oil of reaction gained steams petrol and diesel oil, hydrogenated residue and optional pressure reduction gas
Oil enters catalytic cracking unit together, and cracking reaction is carried out in the presence of Cracking catalyst；Reaction gained heavy-cycle oil enters slag
Oily hydrogenation plant.
A kind of residual hydrocrackings of CN102344829B, catalytic cracking heavy oil add the combined method of hydrogen and catalytic cracking.Slag
The residual hydrogenation tail oil that liquid phase stream obtained by oily hydrogenation reactor is fractionated enters catalysis as the raw material of catalytic cracking and splits
Makeup is set, and the catalytic cracking heavy oil in catalytic cracking production is mixed into catalysis with the gaseous stream obtained by residual hydrogenation reactor
Cracked fuel oil hydrogenation reactor adds the catalytic cracking heavy oil after hydrogen to be recycled back to catalytic cracking unit.The present invention takes full advantage of slag
The hydrogen source of oily hydrogenation plant, catalytic cracking heavy oil add hydrogen to be not necessarily to individual hydrogen source and circulating hydrogen compressor, investment are greatly saved
Expense and operating cost.
CN1144860 discloses a kind of method of residual hydrocracking.First in weight, residual hydrogenation reaction system
Reactor adds one or more feed inlets, changes simultaneously original catalyst grade and matches, when an anticatalyst bed pressure drop is dress
When installing meter 0.4~0.8 times of maximum pressure drop, use next feed inlet instead successively, at the same original feed inlet can into recycle oil or
The mixture of recycle oil and feedstock oil.The technique can prevent bed pressure drop and extend the service life of residual oil hydrocatalyst, and
And the processing capacity of device can be increased.
Optimizing catalyst grading distribution scheme also becomes the scheme for improving the device cycle of operation.Existing commercial plant is using complicated
Catalyst system, including guard catalyst (GUARD), Hydrodemetalation catalyst (HDM), Hydrobon catalyst (HDS)
With hydrodenitrogenation catalyst (HDN), filling principle it is all descending in line with catalyst particle size and aperture, activity by it is weak to
Strong order can play good effect.
CN101928593B discloses a kind of grading method extending heavy-oil hydrogenation catalyst service life.This method passes through
Reactor loads Hydrodemetalation catalyst 5~55%, hydrodesulfurization 5~55% and hydrodenitrogenation catalyst respectively from top to bottom
5~55%；Along logistics direction, catalyst activity gradually increases, and aperture is gradually reduced, and granularity is gradually reduced, and porosity gradually subtracts
It is small；The distribution of the active metal component and acidic assistant concentration of catalyst for demetalation and desulphurization catalyst is in uneven distribution, with urging
Catalyst particles are reduced by center to outer surface, the active metal component and acidic assistant concentration gradient of catalyst for demetalation, denitrogenation
The active metal component and acidic assistant concentration gradient of catalyst increase；The active metal and acidic assistant concentration of desulphurization catalyst
It is evenly distributed；Catalyst for demetalation, desulphurization catalyst and denitrification catalyst are made of one or more catalyst respectively；Catalysis
The demetalization of agent grading composition system, de- carbon residue, desulfurization, denitrification activity and high stability, service life are long.
In the optimization of residual oil hydrocatalyst, similarly studied.CN101376106B discloses one kind can
Improve the catalyst and preparation method thereof for holding metal ability and service life.Carrier and a effective amount of at least one are selected from VIII group
With at least one metal component selected from group vib, which is characterized in that the concentration of the group VIII metal component is along catalyst diameter
It is in non-uniform Distribution to section.Wherein, the ratio between concentration of the concentration of outer surface metal component and central metal component for 0.1~
0.85；The concentration of the vib metals component is evenly distributed along catalyst radial section.Wherein, outer surface metal component
The ratio between the concentration of concentration and central metal component be 0.90-1.5.Compared with the catalyst that the prior art provides, sent out by this
When bright offer catalyst is for heavy-oil hydrogenation processing reaction, which not only shows preferable hydrodemetallization activity, together
When the Center shift to catalyst granules tended to by the metal of the catalyst removal, the metal-accepting propertie to improving catalyst simultaneously carries
The service life of high catalyst is advantageous.
All it is above the considerations of individually angle from residual hydrogenation equipment carries out and exploitation to the optimization in process operation period,
Contain process route, catalyst grade is matched, catalyst etc..The optimization of these techniques needs that residual hydrogenation dress is significantly transformed
It installs standby or reconfigures catalyst, cause not returning to work in a short time or the problems such as cost of investment is larger.
In summary, residual hydrocracking device is suitble to the preferable residual oil of working properties, even so, residual hydrocracking
About 12 months or so the operation cycle of device, and the hydrogenated residue of more difficult cracking is provided for catalytic cracking unit, cause catalysis to split
Purpose product selectivity variation is set in makeup, and two covering devices fail to give full play to respective strong point.
Invention content
The object of the present invention is to provide a kind of heavy charge oil treatment process, this method is significantly improving dry gas and coke
Selectivity and increase production lightweight transport fuel while, significantly extend the heavy oil hydroprocessing units cycle of operation.
To achieve the goals above, the present invention provides a kind of heavy charge oil treatment process, and this method includes：A, it will weigh
Matter feedstock oil carries out either shallow hydrogenation reaction, obtains hydrogenation gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue；Wherein, with institute
On the basis of stating heavy raw oil, the yield for controlling the hydrogenated residue is 85-95 weights %；B, by gained hydrogenated residue in step a
The first catalytic cracking reaction is contacted and carried out with catalytic cracking catalyst, obtain the first dry gas, the first liquefied gas, the first gasoline,
First light cycle oil, the first wax oil and externally extracting oil；Wherein, the micro anti-evaluation activity of the catalytic cracking catalyst is 40-55；
C, wax oil hydrogenation reaction will be carried out after the filtering of the first wax oil of gained in step b, and will obtain adding hydrogen wax oil；It will be got rid of outside gained in step b
Slurry oil carries out the first catalytic cracking reaction described in step b；D, gained in step c plus hydrogen wax oil are subjected to the second Catalytic Cracking Unit of Measure
It answers or first catalytic cracking reaction.
Preferably, this method further includes step e：By the second wax oil obtained by the second catalytic cracking reaction described in step d into
Wax oil hydrogenation described in row step c reacts.
Preferably, in step a, on the basis of the heavy raw oil, the yield for controlling the hydrogenated residue is 87-93
Weight %.
Preferably, in step a, the desulfurization degree for controlling the heavy raw oil is 50-95 weights %, denitrification percent 20-70
Weight %, it is 20-70 weight % to take off carbon yield, and demetallization per is 50-90 weights %.
Preferably, the condition of the either shallow hydrogenation reaction is：Hydrogen partial pressure is 10-20 megapascal, reaction temperature 320-420
DEG C, volume space velocity is 0.2-1.0 hours when liquid-1, total hydrogen to oil volume ratio is 300-1500 standard cubic meters/cubic meter.
Preferably, the heavy raw oil is petroleum hydrocarbon and/or other mineral oil, and wherein petroleum hydrocarbon is selected from normal pressure gas
At least one of oil, vacuum gas oil (VGO), reduced crude, decompression residuum, hydrogenated residue, coker gas oil and deasphalted oil,
His mineral oil is selected from least one of liquid oil, tar sand oil, fine and close oil and shale oil of coal and natural gas derivatives.
Preferably, the heavy raw oil meets：Density at 20 DEG C is for 910-1000 kilograms per cubic meter and/or residual
Charcoal proportion is 4-15 weight % and/or tenor is 12-600ppm.
Preferably, the reaction condition of the first catalytic cracking described in step b is：Reaction temperature is 450-670 DEG C, weighs space-time
Speed is 10-100 hours-1, regenerated catalyst and feedstock oil weight ratio are 1-30, and the weight ratio of vapor and raw material is 0.03-
1.0。
Preferably, the hydrogen content for controlling first wax oil is 9.0-13.0 weights %；It is with hydrogenated residue described in step b
Benchmark, the yield for controlling first wax oil are 15-50 weights %.
Preferably, the solid content of gained externally extracting oil is less than 6 grams per liters in step b, and the density at 20 DEG C is 920-1150
Kilograms per cubic meter.
Preferably, the solid content of filtered first wax oil is less than 10ppm in step c.
Preferably, the reaction of wax oil hydrogenation described in step c will be carried out together with secondary operation wax oil and the first wax oil；Described two
Secondary processing wax oil is is produced at least one of catalytic cracking wax oil selected from wax tailings, deasphalted oil and other devices.
Preferably, the reaction of wax oil hydrogenation described in step c carries out in fixed bed reactors；By reaction stream in institute
It states and loads hydrogenation protecting agent, hydrodemetallization desulfurizing agent and hydrotreating catalyst in fixed bed reactors successively.
Preferably, the condition of the reaction of wax oil hydrogenation described in step c is：Reaction pressure is 6.0-18.0 megapascal, reaction temperature
Degree is 270-420 DEG C, and volume space velocity is 0.2-1.0 hours-1, hydrogen to oil volume ratio is 200-1800 standard cubic meters/cubic meter.
Preferably, the condition of the second catalytic cracking reaction described in step d is：Reaction temperature is 450 DEG C -620 DEG C, when heavy
Air speed is 1-100 hours-1, oil ratio 1-25, water-oil factor 0.03-0.3.
Compared with the prior art, the advantages of the present invention are as follows：
1, heavy-oil hydrogenation processing load reasonable distribution is creatively given more covering devices of entire technique by the present invention, specially
It reduces the severity of heavy oil hydroprocessing units and controls conversion level of the catalytic cracking unit to hydrogenated residue, can slow down significantly
The rate of the coking of residual hydrogenation equipment catalyst and metal deposit can significantly extend the cycle of operation of heavy oil hydrogenation equipment；
2, the present invention need not change residual hydrogenation and catalytic cracking unit the two most important devices on a large scale
It makes, downtime can be shortened and saves cost；
3, the present invention carries out individual hydrotreating to the catalytic wax oil rich in polycyclic aromatic hydrocarbon and colloid, also can be heavy oil
Hydrogenation plant shares part machining load, and generates polycyoalkane in large quantities, can more fully convert low grade oils
For light-end products, optimized product is distributed and improves lightweight oily yield, and dry gas and coke yield can be greatly lowered, not output
Slurry oil increases economic benefit.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of flow diagram of specific implementation mode of the method for the present invention.
Reference sign
1 either shallow hydrogenation reactor, 2 either shallow hydrogenation products separative element 3 recycles gas processing system
4 circulating hydrogen compressor, 5 hydrogenation fractionating unit, 6 first catalyst cracker
7 wax oil hydrogenation reactor, 8 wax oil hydrogenation product separative element, 9 pipeline
10 pipeline, 11 pipeline, 12 pipeline, 13 pipeline, 14 pipeline, 15 pipeline, 16 pipeline, 17 pipeline
18 pipeline, 19 pipeline, 20 pipeline, 21 pipeline, 22 pipeline, 23 pipeline, 24 pipeline, 25 pipeline
26 pipeline, 27 pipeline, 28 pipeline, 29 pipeline, 30 pipeline
Specific implementation mode
The specific implementation mode of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific implementation mode stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of heavy charge oil treatment process, and this method includes：A, heavy raw oil is subjected to either shallow
Hydrogenation reaction obtains hydrogenation gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue；Wherein, using the heavy raw oil as base
Standard, the yield for controlling the hydrogenated residue are 85-95 weight %, preferably 87-93 weights %；B, by gained hydrogenated residue in step a
The first catalytic cracking reaction is contacted and carried out with catalytic cracking catalyst, obtain the first dry gas, the first liquefied gas, the first gasoline,
First light cycle oil, the first wax oil and externally extracting oil；Wherein, the micro anti-evaluation activity of the catalytic cracking catalyst is 40-55；
C, the wax oil hydrogenation reaction (solid content of filtered first wax oil will be carried out after the filtering of the first wax oil of gained in step b
10ppm can be less than, wax oil sedimentation and/or Centrifugal treatment device and/or any form of filter may be used, it is preferably golden
Belong to powder sintered purpose ceramic-film filter and be filtered the first wax oil), it obtains adding hydrogen wax oil；By in step b gained externally extracting oil into
First catalytic cracking reaction described in row step b；D, gained in step c plus hydrogen wax oil are subjected to the second catalytic cracking reaction or institute
State the first catalytic cracking reaction.
According to the present invention, the micro anti-evaluation activity is well-known to those skilled in the art, and the present invention repeats no more, can
To be measured using RIPP 92-90 test methods.
The method of the present invention further includes step e：Second wax oil obtained by second catalytic cracking reaction described in step d is carried out
Wax oil hydrogenation described in step c reacts.
Present inventors discovered unexpectedly that when heavy raw oil is carried out hydrogenation reaction, when hydrogenated residue yield control
System is between 85-95 weights %, and metal deposition capability increases slowly with the increase of the device duration of runs on catalyst, residual hydrogenation
The operation cycle of reaction unit significantly improves, and such hydrogenation reaction is known as either shallow hydrogenation reaction by the present invention.Specifically, of the invention
Heavy raw oil is subjected to Modulatory character either shallow hydrogenation reaction in either shallow hydrotreating unit, by dynamic modulation reaction condition,
Hydrogenated residue yield that product obtains after detaching, being fractionated and impurity removal percentage is set to stablize relatively, when specially being operated with device
Between increase, when hydrogenated residue yield increase and/or impurity removal percentage reduce when, improve reaction temperature and/or reduce volume space velocity.
Generally, the condition of the either shallow hydrogenation reaction can be：Hydrogen partial pressure is 10-20 megapascal, and reaction temperature is 320-420 DEG C,
Volume space velocity is 0.2-1.0 hours when liquid-1, total hydrogen to oil volume ratio is 300-1500 standard cubic meters/cubic meter.In addition, using
Compared with the hydrogenation conditions of low severity, main purpose is the desulfurization degree of heavy raw oil, denitrification percent, de- carbon yield and takes off
Metal rate is controlled in reduced levels.Specifically, the desulfurization degree that can control the heavy raw oil is 50-95 weight %, denitrification percent
For 20-70 weight %, it is 20-70 weight % to take off carbon yield, and demetallization per is 50-90 weights %.Gold in demetallization per of the present invention
Category refers in particular to nickel and vanadium.
According to the present invention, the heavy raw oil is that this field institute is conventional use of, for example, the heavy raw oil is stone
Petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon are selected from AGO (atmospheric gas oil), vacuum gas oil (VGO), reduced crude, decompression residuum, add
At least one of hydrogen residual oil, coker gas oil and deasphalted oil, other mineral oils are selected from the liquid of coal and natural gas derivatives
At least one of oil, tar sand oil, fine and close oil and shale oil.In addition, in terms of properties, the heavy raw oil can expire
Foot：Density at 20 DEG C is 910-1000 kilograms per cubic meter and/or carbon residue proportion is 4-15 weight % and/or tenor is
12-600ppm。
According to the present invention, highly selective catalytic cracking process may be used in first catalytic cracking reaction, and the technique is not
Feedstock oil conversion per pass highest is pursued, and by conversion ratio control in proper level, so as to effectively improve dry gas, coke choosing
Selecting property, while larger amount of catalytic cracking wax oil is generated, it is used for further hydrotreating.The use of the technique can effectively make up
Either shallow residual hydrogenation to inferior raw material working depth deficiency problem, and can optimized product distribution.First catalysis described in step b
The reaction condition of cracking is：Reaction temperature is 450-670 DEG C, and preferably 490-570 DEG C, weight (hourly) space velocity (WHSV) is 10-100 hours-1, excellent
It is selected as 30-80 hours-1, regenerated catalyst is 1-30, preferably 5-12, the weight ratio of vapor and raw material with feedstock oil weight ratio
For 0.03-1.0, preferably 0.03-0.1.Furthermore it is possible to which the hydrogen content for controlling first wax oil is 9.0-13.0 weights %；With
On the basis of hydrogenated residue described in step b, the yield that can control first wax oil is 15-50 weights %, preferably 30-45
Weight %；The solid content of gained externally extracting oil can be less than 6 grams per liters in step b, and the density at 20 DEG C can be 920-1150 thousand
Gram/cubic metre.
Secondary operation wax oil can be carried out step by a kind of specific implementation mode according to the present invention together with the first wax oil
Wax oil hydrogenation described in c reacts, to increase the raw material sources of the second catalytic cracking；The secondary operation wax oil can be selected from coke
Change at least one of wax oil, deasphalted oil and the produced catalytic cracking wax oil of other devices, other produced catalytic cracking of device
Wax oil is not limited to the first wax oil and the second wax oil of the present invention, can come from other catalytic cracking units.
According to the present invention, the condition of the reaction of wax oil hydrogenation described in step c can be：Reaction pressure is 6.0-18.0 million
Pa, preferably 8.0-15.0 megapascal, reaction temperature are 270-420 DEG C, and preferably 280-390 DEG C, volume space velocity is that 0.2-1.0 is small
When-1, preferably 0.4-0.8 hours-1, hydrogen to oil volume ratio is 200-1800 standard cubic meters/cubic meter, preferably 500-1100
Standard cubic meter/cubic meter.In addition, the reaction of wax oil hydrogenation described in step c can carry out in fixed bed reactors；By reaction
Logistics to can load hydrogenation protecting agent, hydrodemetallization desulfurizing agent and hydrotreating successively in the fixed bed reactors
Catalyst.
According to the present invention, the second catalytic cracking reaction described in step d can carry out under the normal condition of this field, example
Such as, reaction temperature is 450 DEG C -620 DEG C, and weight (hourly) space velocity (WHSV) is 1-100 hours-1, oil ratio 1-25, water-oil factor 0.03-0.3.
It should be noted that such as without special requirement, hydrogenation catalyst, catalytic cracking catalyst plus hydrogen used by method of the invention
Device and catalytic cracking unit can use the conventional use of catalyst of this field institute and device as needed.For example, described
Catalyst used by first catalytic cracking reaction can using zeolite as active component, preferably be selected from mesopore zeolite and/or optionally
Large pore zeolite, mesopore zeolite therein can be selected from ZSM series and/or ZRP series；The device of second catalytic cracking can
To be conventional catalytic cracking unit and its improve device, Chinese patent CN1232069A and CN1232070A specifically may refer to
Equal documents.The catalyst cracker can be selected from equal diameter riser, etc. linear speeds riser, reducing riser, dense-phase flow
Change one of bed or/and two of which combined reactor or/and wherein several reactors it is single or multiple arranged side by side anti-
Answer device.The hydrogenation reactor can be a set of or a set of above fixed bed, suspension bed, ebullated bed or moving bed, preferably
For fixed bed.
The specific implementation mode of the present invention is provided below in conjunction with attached drawing.
Heavy raw oil from pipeline 9 with from pipeline 11 new hydrogen and after cycle hydrogen mixed gas mixes, entrance is shallow
Hydrogenation reactor 1 is spent, under appropriate either shallow hydrogenation process conditions, it is de- to carry out removing impurities matter, hydrodemetallization, hydrodesulfurization plus hydrogen
Nitrogen is reacted with removal of ccr by hydrotreating.Obtained product is through pipeline 13, into either shallow hydrogenation products separative element 2, hydrogen-rich gaseous stream
Enter cycle gas processing system 3 through pipeline 14, through pipeline 16 and from pipeline 10 after pipeline 15 is sent into circulating hydrogen compressor 4
New hydrogen mixing.Enter hydrogenation fractionating unit 5 through pipeline 17 by the liquid phase stream that 2 bottom of piece-rate system comes out, respectively obtains and add hydrogen
Gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue pass sequentially through the submitting of pipeline 18,19,20,21.Hydrogenated residue is through pipeline
21 enter the first catalyst cracker 6, are reacted under the conditions of highly selective catalytic cracking process, and by detaching, dividing
The first dry gas, the first liquefied gas, the first gasoline, the first light cycle oil, the first wax oil and externally extracting oil are obtained after evaporating successively, respectively
It is sent out through pipeline 25,26,27,28,29, externally extracting oil does not go out device but is pumped to the first catalysis by slurry oil by pipeline 30 and splits
The riser slurry oil nozzle for changing reactor 6 is further contacted and is reacted with catalyst.
It is anti-that wherein the first wax oil is recycled back to another set of wax oil hydrogenation after pipeline 29 and the mixing hydrogen mixing from pipeline 12
Answer device 7.Wax oil hydrogenation product separative element 8, obtained hydrogen-rich gaseous stream are passed through by the logistics that wax oil hydrogenation reactor 7 comes out
Enter recycle hydrogen processing system 3 after pipeline 23 is mixed with the hydrogen-rich gaseous stream from pipeline 14, liquid phase stream adds hydrogen wax oil
Enter the first catalyst cracker 6 after pipeline 24 is mixed with the hydrogenated residue from pipeline 21.
In conjunction with invention content, the invention mainly relates to the comprehensive utilizations of three sets of process units.It is understood that in appropriateness
Under the conditions of heavy oil hydrogenation process, heavy oil hydroprocessing units volume space velocity improves, and reaction temperature reduces, so as to reduce to original
Expect the working depth of oil so that device reduces the removal efficiency of raw material well cuts, and obtained hydrogenated residue proportion improves.For
The feedstock oil of phase homogenous quantities is handled, under the conditions of appropriate heavy oil hydrogenation process, the deposition of various impurity will be apparent on catalyst
It reduces, so as to significantly improve the cycle of operation of device.But the working depth of simple reduction Residue Hydrotreating Technology, it can make
It is low at product yield, product irrational distribution；Sulphur, nitrogen, metal impurities content are high in product；Catalytic cracking process is caused
The various aspects problems such as operation difficulty increase.The related process for thus needing while adjusting catalytic cracking, makes up heavy oil hydrogenation equipment
The adverse effect that the reduction of feedstock oil working depth is brought.
Used catalytic cracking process creatively abandons the maximization for pursuing heavy raw oil conversion per pass, and
The relatively large first wax oil warp emphasized conversion ratio in the reasonable scope, while dry gas and coke selectivity can be reduced, and generate
It crosses individually plus carries out catalytic cracking reaction again after hydrogen.
The polycyclic aromatic hydrocarbon and colloid being rich in first wax oil can add hydrogen in wax oil hydrogenation processing unit by selectivity
Saturation generates polycyclic ring alkane, to be used as good catalytically cracked material, is conducive to generate light-end products, reduces dry gas and coke
Charcoal yield.In addition, wax oil hydrogenation processing unit can equally remove the partial impurities in oil product.From entire technological angle,
The presence of wax oil hydrogenation processing unit is not only distributed and is improved in lightweight oily yield in optimize technique product and played an important role,
The sub-load of heavy oil hydrogenation process imurity-removal and hydrotreating can be more shared, is that the extension of process cycle generates positive shadow
It rings.
It is further illustrated the present invention by embodiment below in conjunction with attached drawing, but therefore the present invention is not taken office
What is limited.The used instrument of the embodiment of the present invention and reagent are unless otherwise instructed instrument and reagent commonly used in the art.
The raw material oil nature such as table 1 that embodiment is used with comparative example.Either shallow hydropyrolysis experiment is in two sets of continuous high pressure fixed beds
It is carried out in pilot-plant, reactor is 3 reactor series process flows, is respectively provided with hydrogenation protecting agent, hydrodemetallization is urged
Agent, Hydrobon catalyst, trade names are respectively RG-10A, RDM-2B, RMS-1B, and admission space ratio is 5:45:50.
When experiment carries out, two covering devices are in start of run, and the duration of runs was less than 100 hours.FCC tests are connected at two sets
It is tested on the middle- scale device of riser reactor, used catalytic cracking fresh catalyst trade names are ASC-4.It urges
Change wax oil hydrogenation processing experiment to carry out on fixed bed hydrogenation reactor, the catalyst commercial grades loaded in reaction zone are respectively
RG-10A, RG-10B, RMS-1, RN-32V, admission space ratio are 10:10:30:50, the above catalyst is urged by Sinopec
Agent branch company produces.
The present invention measures the micro anti-evaluation activity of catalyst using RIPP 92-90 test methods.
The embodiment of the present invention is measured using inductive coupling plasma emission spectrograph (ICP-AES) and generates nickel and vanadium in oil
Content (instrument is U.S.'s PE companies PE-5300 type plasma quantometers, and specific method is shown in petrochemical analysis method
RIPP124-90).The content of sulphur is measured using coulometry (specific method is shown in petrochemical analysis method RIPP62-90).It uses
Coulometry measures the content of nitrogen (specific method is shown in petrochemical analysis method RIPP63-90).Contained using microdetermination carbon residue
It measures (specific method is shown in petrochemical analysis method RIPP148-90).
The removal efficiency of sulphur, carbon residue, nitrogen and metal is calculated separately according to the following formula：
RIPP test methods of the present invention are selected from《Petrochemical egineering analysis method (RIPP test methods)》, Yang Cui is fixed etc.
It compiles, Science Press, 1990.
Embodiment 1
Embodiment 1 carries out Modulatory character appropriateness either shallow hydrogenation reaction, and wherein reaction temperature and volume space velocity is with the reaction time
Interim adjusting is carried out, and hydrogen to oil volume ratio is respectively maintained at 800 standard cubic meters/cubic meter and 12 megapascal with hydrogen partial pressure, has
Body mode of operation is shown in Table 2.In residual hydrogenation product, the cut point of hydrogenated residue is 350 DEG C.With the deposition of metal on catalyst
(MOC, per 100kg fresh catalysts on nickel and vanadium metal deposition) be associated with the service life of residual oil hydrocatalyst, wherein MOC
It is inversely proportional with catalyst life.The comparisons such as device impurity removal percentage and MOC such as table 2.
Comparative example 1
Comparative example 1 is conventional residual oil hydropyrolysis experiment, and experimental provision, experimental raw are same as Example 1.The difference is that
Residual hydrogenation reaction temperature and volume space velocity are constant in 390 DEG C and 0.25h respectively-1.1 process conditions of comparative example, experimental product are miscellaneous
Matter removal efficiency and MOC comparison such as table 2.
As can be found from Table 2, during whole device is run, stage carries embodiment 1 by increasing with the duration of runs
High device reaction temperature and reduction volume space velocity, can make the yield of hydrogenated residue and impurity removal percentage maintain relatively stable water
It is flat.And the yield and impurity removal percentage of the hydrogenated residue of comparative example 1 then show the extension with the duration of runs and significantly
Variation.Secondly, MOC values under comparative unit time, volume space velocity, embodiment 1 and respectively 6.66 (Kg/100Kg) of comparative example 1/
(1000h·h-1) and 7.90 (Kg/100Kg)/(1000hh-1).For theoretically, in identical feed rate and charging
Between under, the service life of catalyst is than comparative example 1 high 18% (i.e. (7.90-6.66)/6.66) under 1 technique of embodiment.
Embodiment 2
As shown in Figure 1, after the reaction in 1 residual hydrogenation equipment of selection example operating 5000-5500h generates product conduct
The experimental subjects of continuous technique (product characteristics are shown in Table 3 after specific residual hydrogenation reaction).Catalytic cracking used in the present invention program
Equilibrium catalyst activity is 50 or so.Feedstock oil of the hydrogenated residue as highly selective first catalytic cracking, by catalyzed conversion,
The first dry gas, the first liquefied gas, the first gasoline, the first light cycle oil, the first wax oil and externally extracting oil are obtained after separation and fractionation.
First wax oil initial boiling point is about 330 DEG C, accounts for the 29.20% of inlet amount, and the first wax oil is handled using individual wax oil hydrogenation,
Middle wax oil hydrogenation reaction pressure is 11.5MPa, and average reaction temperature is 350 DEG C, and catalytic wax oil volume space velocity is 0.5h-1, hydrogen oil
Volume ratio is 800 standard cubic meters/cubic meter, and hydrogen wax oil is added to return to above-mentioned first catalyst cracker.Externally extracting oil is by oil
The reaction was continued back to above-mentioned catalytic cracking processing unit riser slurry oil nozzle for stock pump, resulting device not output slurry oil.Technique
Operating condition is shown in Table 4, and product distribution is shown in Table 5.
Comparative example 2
The technological process of comparative example 2 is existing residual hydrogenation-heavy oil catalytic cracking group technology flow.Comparative selection example
1 residual hydrogenation equipment operates the reaction in 5000-5500h and generates product (specific residual oil adds as the experimental subjects of subsequent technique
After hydrogen reaction 3) product characteristics are shown in Table.Catalytic cracking equilibrium catalyst activity used in the present invention program is 66 or so.Add hydrogen
Residual oil obtains dry gas, liquefied gas, gasoline, light cycle oil, slurry oil and coke after catalyzed conversion, separation and fractionation.Technique is grasped
4 are shown in Table as condition, product distribution is shown in Table 5.
Comparative example 3
The technological process of comparative example 3 is identical with embodiment 2, the difference is that 1 residual hydrogenation of comparative selection example fills
Set the experimental subjects (product after specific residual hydrogenation reacts that the reaction in operating 5000-5500h generates product as subsequent technique
3) property is shown in Table.Catalytic cracking equilibrium catalyst property used in the present invention program is same as Example 2.Process condition
4 are shown in Table, product distribution is shown in Table 5.
By table 3 and table 5, comparative example 2 and comparative example 2, the dry gas of embodiment 2, coke yield are distinguished than comparative example 2
Low 1.40 and 1.58 percentage points, total liquid yield is about 8.5 percentage points high.Urged in contrast to existing residual hydrogenation-heavy oil
Change process, the present invention not only has a clear superiority on dry gas, coke selectivity, additionally it is possible to the lightweight of the more high values of output
Oil.Comparative example 2 and comparative example 3, it can be found that embodiment 2 and the catalytic cracking product distribution of comparative example 3 reach unanimity, but
Embodiment is less than comparative example to the consumption of hydrogen.Therefore, embodiment technique can be proved in processing by appropriate Residue Hydrotreating Technology
Good adaptability is shown when the hydrogenated residue of output, has reached invention effect.
Table 1
| Raw material | Decompression residuum+reduced crude |
| Density (20 DEG C), g/cm3 | 0.984 |
| Kinematic viscosity (100 DEG C), mm2/s | 160.12 |
| Carbon, weight % | 85.02 |
| Hydrogen, weight % | 11.01 |
| Sulphur, weight % | 3.04 |
| Nitrogen, weight % | 0.36 |
| Carbon residue, weight % | 13.15 |
| Metal (Ni+V), ppm | 77.4 |
| Saturated hydrocarbons, weight % | 24.6 |
| Aromatic hydrocarbons, weight % | 46.7 |
| Colloid, weight % | 24.5 |
| Asphalitine (C7Insoluble matter), weight % | 4.2 |
Table 2
Table 3
Table 4
Table 5
Claims (15)
1. a kind of heavy charge oil treatment process, this method include：
A, heavy raw oil is subjected to either shallow hydrogenation reaction, obtains hydrogenation gas, hydrotreated naphtha, hydrogenated diesel oil and adds hydrogen slag
Oil；Wherein, on the basis of the heavy raw oil, during entire hydrogenation plant is run, pass through dynamic modulation reaction condition control
The yield stable for making the hydrogenated residue is 85-95 weights %；
B, gained hydrogenated residue in step a is contacted with catalytic cracking catalyst and is carried out the first catalytic cracking reaction, obtain the
One dry gas, the first liquefied gas, the first gasoline, the first light cycle oil, the first wax oil and externally extracting oil；Wherein, the catalytic cracking
The micro anti-evaluation activity of catalyst is 40-55；
C, wax oil hydrogenation reaction will be carried out after the filtering of the first wax oil of gained in step b, and will obtain adding hydrogen wax oil；By gained in step b
Externally extracting oil carries out the first catalytic cracking reaction described in step b；
D, gained in step c plus hydrogen wax oil are subjected to the second catalytic cracking reaction or first catalytic cracking reaction.
2. the method according to claim 1, this method further includes step e：Obtained by the second catalytic cracking reaction described in step d
Second wax oil carries out wax oil hydrogenation reaction described in step c.
3. the method according to claim 1, wherein in step a, on the basis of the heavy raw oil, in entire hydrogenation plant
During operation, the yield stable that the hydrogenated residue is controlled by dynamic modulation reaction condition is 87-93 weights %.
4. the method according to claim 1, wherein anti-by dynamic modulation during entire hydrogenation plant is run in step a
The desulfurization degree that condition controls the heavy raw oil is answered to stabilize to 50-95 weight %, denitrification percent stabilizes to 20-70 weight %, takes off carbon residue
Rate stabilizes to 20-70 weight %, and demetallization per stabilizes to 50-90 weights %.
5. the method according to claim 1, wherein the condition of the either shallow hydrogenation reaction is：Hydrogen partial pressure is 10-20 megapascal, instead
It is 320-420 DEG C to answer temperature, and volume space velocity is 0.2-1.0 hours when liquid-1, total hydrogen to oil volume ratio is 300-1500 standard cubes
Rice/cubic meter.
6. the method according to claim 1, wherein the heavy raw oil is petroleum hydrocarbon and/or other mineral oil, petrochina
Hydrocarbon is in AGO (atmospheric gas oil), vacuum gas oil (VGO), reduced crude, decompression residuum, hydrogenated residue, coker gas oil and deasphalted oil
At least one, in liquid oil of other mineral oils selected from coal and natural gas derivatives, tar sand oil, fine and close oil and shale oil extremely
Few one kind.
7. the method according to claim 1, wherein the heavy raw oil meets：Density at 20 DEG C is 910-1000 thousand
Gram/cubic metre and/or carbon residue proportion are 4-15 weight % and/or tenor is 12-600ppm.
8. the method according to claim 1, wherein the reaction condition of the first catalytic cracking described in step b is：Reaction temperature is
450-670 DEG C, weight (hourly) space velocity (WHSV) is 10-100 hours-1, regenerated catalyst and feedstock oil weight ratio are 1-30, vapor and raw material
Weight ratio is 0.03-1.0.
9. the method according to claim 1, wherein the hydrogen content of control first wax oil is 9.0-13.0 weights %；With step b
Described on the basis of hydrogenated residue, the yield for controlling first wax oil is 15-50 weights %.
10. the method according to claim 1, wherein the solid content of gained externally extracting oil is less than 6 grams per liters in step b, at 20 DEG C
When density be 920-1150 kilograms per cubic meter.
11. the method according to claim 1, wherein the solid content of filtered first wax oil is less than in step c
10ppm。
12. the method according to claim 1, wherein wax described in step c will be carried out together with secondary operation wax oil and the first wax oil
Oily hydrogenation reaction；The secondary operation wax oil is is produced catalytic cracking wax oil selected from wax tailings, deasphalted oil and other devices
At least one of.
13. the method according to claim 1, wherein the reaction of wax oil hydrogenation described in step c carries out in fixed bed reactors；
By reaction stream to, loaded successively in the fixed bed reactors hydrogenation protecting agent, hydrodemetallization desulfurizing agent and add hydrogen at
Manage catalyst.
14. the method according to claim 1, wherein wax oil hydrogenation described in step c reaction condition be：Reaction pressure is
6.0-18.0 megapascal, reaction temperature are 270-420 DEG C, and volume space velocity is 0.2-1.0 hours-1, hydrogen to oil volume ratio 200-1800
Standard cubic meter/cubic meter.
15. the method according to claim 1, wherein the condition of the second catalytic cracking reaction described in step d is：Reaction temperature
It it is 450 DEG C -620 DEG C, weight (hourly) space velocity (WHSV) is 1-100 hours-1, oil ratio 1-25, water-oil factor 0.03-0.3.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671952.0A CN106590742B (en) | 2015-10-15 | 2015-10-15 | A kind of heavy charge oil treatment process |
| KR1020187013817A KR102648572B1 (en) | 2015-10-15 | 2016-10-17 | Low-grade feedstock oil conversion method |
| SG11201803154QA SG11201803154QA (en) | 2015-10-15 | 2016-10-17 | A process for converting inferior feedstock oil |
| PCT/CN2016/000577 WO2017063309A1 (en) | 2015-10-15 | 2016-10-17 | Method for processing inferior feedstock oil |
| TW105133457A TWI716471B (en) | 2015-10-15 | 2016-10-17 | Method for processing poor quality raw oil |
| SG10201911151WA SG10201911151WA (en) | 2015-10-15 | 2016-10-17 | A process for converting inferior feedstock oil |
| US15/768,437 US11365360B2 (en) | 2015-10-15 | 2016-10-17 | Process for converting inferior feedstock oil |
| RU2018117582A RU2720990C2 (en) | 2015-10-15 | 2016-10-17 | Conversion method of low-quality oil stock |
| GB1807649.7A GB2558157B (en) | 2015-10-15 | 2016-10-17 | A process for converting inferior feedstock oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510671952.0A CN106590742B (en) | 2015-10-15 | 2015-10-15 | A kind of heavy charge oil treatment process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106590742A CN106590742A (en) | 2017-04-26 |
| CN106590742B true CN106590742B (en) | 2018-11-02 |
Family
ID=58553770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510671952.0A Active CN106590742B (en) | 2015-10-15 | 2015-10-15 | A kind of heavy charge oil treatment process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106590742B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109423334B (en) * | 2017-08-30 | 2020-11-13 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN112745946B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Method and system for processing heavy raw oil |
| CN112745947B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Method and system for processing heavy raw oil |
| CN113122333B (en) * | 2019-12-31 | 2022-06-07 | 中国石油化工股份有限公司 | Production method and system of low-sulfur petroleum coke |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332783A (en) * | 1998-12-30 | 2002-01-23 | 埃克森研究工程公司 | Integrated staged catalytic cracking and staged hydroprocessing process |
| CN1903994A (en) * | 2006-08-03 | 2007-01-31 | 湖南长岭石化科技开发有限公司 | Method of producing fuel oil by coal tar hydrogenation modifying |
| CN101987972A (en) * | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for processing inferior crude oil through combined processes |
| CN102719274A (en) * | 2011-03-31 | 2012-10-10 | 中国石油化工股份有限公司 | High efficiency catalytic conversion method of petroleum hydrocarbon |
| CN102796556A (en) * | 2011-05-26 | 2012-11-28 | 中国石油化工股份有限公司 | Method for catalytic conversion of petroleum hydrocarbons |
| CN102911730A (en) * | 2011-08-04 | 2013-02-06 | 中国石油化工股份有限公司 | Catalytic conversion method for high sulfur wax oil |
-
2015
- 2015-10-15 CN CN201510671952.0A patent/CN106590742B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332783A (en) * | 1998-12-30 | 2002-01-23 | 埃克森研究工程公司 | Integrated staged catalytic cracking and staged hydroprocessing process |
| CN1903994A (en) * | 2006-08-03 | 2007-01-31 | 湖南长岭石化科技开发有限公司 | Method of producing fuel oil by coal tar hydrogenation modifying |
| CN101987972A (en) * | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for processing inferior crude oil through combined processes |
| CN102719274A (en) * | 2011-03-31 | 2012-10-10 | 中国石油化工股份有限公司 | High efficiency catalytic conversion method of petroleum hydrocarbon |
| CN102796556A (en) * | 2011-05-26 | 2012-11-28 | 中国石油化工股份有限公司 | Method for catalytic conversion of petroleum hydrocarbons |
| CN102911730A (en) * | 2011-08-04 | 2013-02-06 | 中国石油化工股份有限公司 | Catalytic conversion method for high sulfur wax oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106590742A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101875855B (en) | Method for hydrogenation and catalytic cracking of residual oil | |
| CN101684415B (en) | Hydrocracking method for producing chemical materials to maximum with low cost | |
| CN106590742B (en) | A kind of heavy charge oil treatment process | |
| CN102453535B (en) | Hydrocracking method for reforming material yield increase | |
| CN103059986B (en) | Hydrocracking method for producing chemical materials | |
| CN102041095A (en) | Resid hydrotreating and catalytic cracking combined processing method | |
| JPWO2016194686A1 (en) | Method for producing hydrotreated oil and method for producing catalytic cracking oil | |
| CN102732315A (en) | Hydrotreatment and catalytic cracking deeply-combined method for residuum | |
| CN106590740B (en) | A kind of inferior raw material oil treatment process | |
| CN101376841B (en) | Heavy fraction oil hydrotreating method | |
| CN101376840B (en) | Heavy fraction oil hydrotreating method | |
| CN102732313A (en) | Hydrotreatment and catalytic cracking deeply-combined method for residuum | |
| CN106590744B (en) | A kind of inferior raw material oil treatment process | |
| CN102453544B (en) | Residual oil hydrogenation treatment and catalytic cracking combination method | |
| CN102732312A (en) | Hydrotreatment and catalytic cracking deeply-combined method for residuum | |
| CN102311798A (en) | Residual oil hydrogenation treatment and catalytic cracking combined processing method | |
| CN102311801A (en) | Residual oil hydrogenation treatment and catalytic cracking combined method | |
| CN114437786B (en) | Hydrocracking method of inferior raw oil | |
| CN101434866B (en) | Heavy distillate hydrogenation and catalytic cracking combined method | |
| CN112745952B (en) | Method and system for processing aromatic-rich distillate oil | |
| CN102732311A (en) | Hydrotreatment and catalytic cracking combined method for residuum | |
| WO2021045884A1 (en) | Synthetic crude composition | |
| CN110408431A (en) | A kind of method of group technology processing low grade oils | |
| CN106350110A (en) | Method for producing middle distillate oil from Fischer-Tropsch synthetic oil | |
| CN101434865B (en) | Heavy distillate hydrogenation and catalytic cracking combined method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |