CN106987268A - A kind of processing method of wax tailings - Google Patents
A kind of processing method of wax tailings Download PDFInfo
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- CN106987268A CN106987268A CN201610041906.7A CN201610041906A CN106987268A CN 106987268 A CN106987268 A CN 106987268A CN 201610041906 A CN201610041906 A CN 201610041906A CN 106987268 A CN106987268 A CN 106987268A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a kind of processing method of wax tailings, this method includes：A, wax tailings are subjected to fractionation processing, using cut of the boiling range more than the first cut-point and below the second cut-point as the first cut, the cut and/or boiling range that boiling range is less than to the first cut-point are more than the cut of the second cut-point and are used as the second cut；B, the first feedstock oil including the first cut of gained in step a contact with absorption denitrification catalyst in absorption denitrification reactor and carry out absorption denitrification reaction, obtain absorption denitrogenation product；C, by step b gained absorption denitrogenation product and include in step a gained the second cut the second feedstock oil feeding catalyst cracker carry out catalytic cracking reaction, obtain catalytic cracking production.The method of the present invention, which can mitigate, mixes the adverse effect that refining wax tailings are produced in catalytically cracked material, improve wax tailings and mix refining ratio in catalytically cracked material, and produced high value products are more.
Description
Technical field
The present invention relates to petrochemical industry, in particular it relates to a kind of processing method of wax tailings.
Background technology
As crude oil heaviness, the aggravation of in poor quality degree and light-end products demand increasingly increase, develop
Heavy oil Efficient Conversion technology turns into the urgent task of current petroleum refining industry.Delayed coking is heavy oil lightweight
One of Main Means of change, account for more than the 30 weight % of world's processing of heavy oil ability.In coking
In product distribution, the yield of wax tailings (Coker Gas Oil) is usually 20-30 weight %, this portion
The processing and utilization of fractionation point, directly affects heavy oil transformation efficiency, the key as restriction heavy oil deep processing
Problem.
At present, wax tailings are usually as secondary operation device such as catalytic cracking (Fluid Catalytic
Cracking the raw material), being hydrocracked.Taking the process program being hydrocracked more external the oil refining enterprise；By
Restricted in by conditions such as hydrogenation capability, hydrogen inadequate resources, with reference to each refinery facilities it is supporting the characteristics of, I
Wax tailings are mainly mixed refining raw material by state as catalytic cracking process.Production practices show, wax tailings
Reactivity worth it is poor, cause catalytic cracking process conversion ratio decline, product distribution deteriorate, product quality
How a series of adverse consequences such as variation, therefore, improve adaptability of the catalytic cracking unit to inferior raw material,
Reduction mix refining wax tailings produced by adverse effect, be tackle coking production capacity increase rapidly it is urgent
Demand.In order to solve this problem, production unit and researcher enter in terms of wax tailings processing technology
Substantial amounts of work is gone.
For example, Chinese patent CN1891791 A disclose a kind of method and apparatus of processing coked waxy oil,
The bottom of riser reactor is specifically divided into the separate reaction zones of two vertical parallels, coking wax is allowed
It is oily to enter different reaction zones progress catalytic cracking reactions from other convenient source oil for comparing high-quality, two
Reacted logistics converges on the top of the riser reactor in individual reaction zone, i.e. riser reactor
Bottom is the separate reaction zones that two branch pipes are constituted.But, it is demonstrated experimentally that mixing coking in the above method
Adverse effect produced by wax oil is still larger, there is conversion ratio decline, product distribution and deteriorates and product matter
The defect of quantitative change difference, so as to cause wax tailings to mix refining than still relatively low in catalytic cracking.
The content of the invention
It is an object of the invention to provide a kind of processing method of wax tailings, this method can mitigate catalysis and split
Change the adverse effect mixed and refined produced by wax tailings in raw material, improve wax tailings in catalytically cracked material
Mix refining ratio, and produced high value products are more.
To achieve these goals, the present invention provides a kind of processing method of wax tailings, and this method includes：
A, by wax tailings carry out fractionation processing, by boiling range more than the first cut-point and below the second cut-point
Cut as the first cut, cut and/or boiling range that boiling range is less than the first cut-point are more than the second segmentation
The cut of point is used as the second cut；Wherein, first cut-point is any in the range of 390-410 DEG C
Temperature, second cut-point is the arbitrary temp in the range of 440-460 DEG C；B, will include step a in
First feedstock oil of the cut of gained first is contacted simultaneously in absorption denitrification reactor with absorption denitrification catalyst
Absorption denitrification reaction is carried out, obtains adsorbing denitrogenation product；C, by step b gained absorption denitrogenation product
Catalysis is carried out with the second feedstock oil feeding catalyst cracker including the second cut of gained in step a to split
Change reaction, obtain catalytic cracking production.
Preferably, the first cut-point described in step a is the arbitrary temp in the range of 395-405 DEG C, institute
It is the arbitrary temp in the range of 445-455 DEG C to state the second cut-point.
Preferably, the second cut described in step a is less than cut and the institute of the first cut-point for the boiling range
State the cut that boiling range is more than the second cut-point.
Preferably, the first feedstock oil described in step b is also higher than 0.2 weight % high nitrogen containing nitrogen content
Catalytically cracked material.
Preferably, the high nitrogen catalytically cracked material is shale oil and/or wax tailings, and described first is former
The weight ratio of first cut described in material oil and the high nitrogen catalytically cracked material is (0.01-100)：1.
Preferably, in stepb, first feedstock oil is sent at least two and can regenerated in turn
Adsorb and absorption denitrification reaction is carried out in denitrification reactor, the condition of the absorption denitrification reaction is：Temperature is
20-250 DEG C, pressure is 0-10 MPas, and volume space velocity is 0.3-12 hours-1。
Preferably, by weight, the acid that denitrification catalyst contains 1-25 weight % is adsorbed described in step b
Property agent, 1-25 weight % complexing agent, 50-80 weight % carrier and 1-25 weight % water；Wherein,
The acidizer is mineral acid agent and/or organic acidity agent, and the mineral acid agent is selected from sulfuric acid, Asia
Sulfuric acid, sulfur trioxide, nitric acid, nitrous acid, chloric acid, perchloric acid, hypochlorous acid, hydrochloric acid, phosphoric acid, partially
At least one of phosphoric acid and phosphorous acid；The complexing agent is transition metal salt, the transition metal salt
Class is in copper nitrate, ferric nitrate, silver nitrate, chromic nitrate, titanium sulfate, titanium tetrachloride and ammonium molybdate
At least one；The carrier is selected from least one of boehmite, activated carbon and silica gel.
Preferably, the second feedstock oil described in step c is also less than 0.2 weight % low nitrogen containing nitrogen content
Catalytically cracked material.
Preferably, the low nitrogen catalytically cracked material is selected from straight-run gas oil, solvent-deasphalted oils and decompression
At least one of residual oil, the weight ratio of second feedstock oil and the low nitrogen catalytically cracked material is
(0.01-100)：1.
Preferably, in step c, the weight ratio of absorption the denitrogenation product and second feedstock oil is
(0.01-1)：1.
Preferably, the condition of catalytic cracking reaction is described in step c：Temperature is 480-550 DEG C, agent
Oil is than being 3-8, and the reaction time is 0.6-3.0 seconds, and air speed is 1-20 hours-1, catalyst cracker
Outlet pressure is 0.1-0.4 MPas.
By above-mentioned technical proposal, the inventive method by by boiling range more than the first cut-point and second point
Absorption denitrogenation is carried out after high nitrogen content wax tailings cut fractionation below cutpoint, wax tailings can be mitigated
To the deactivation of catalytic cracking catalyst so that catalytic cracking conversion rise, product distribution more preferably and
Product quality is improved, so that improve wax tailings mixes refining ratio in catalytically cracked material, in addition with Jiao
The method that change wax oil whole progress absorption denitrogenation carries out catalytic cracking again is compared, and handles identical under identical cost
The wax tailings and straight-run gas oil of weight, produced high value products are more.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is that a kind of embodiment of processing method of wax tailings of the present invention uses the structure of device
Schematic diagram, while also including the schematic flow sheet of the inventive method；
Fig. 2 is a kind of schematic flow sheet of embodiment of processing method of wax tailings of the present invention.
Description of reference numerals
The 1 fractionating column 2 first absorption absorption denitrification reactor of denitrification reactor 3 second
4 riser reactors 5 strip the regenerator of sedimentation device 6
Pipeline under the cut of 12 first cut pipeline of pipeline 13 second on 11 second cuts
The mixed material pipeline of 21 first inlet valve, 22 first outlet valve 23
The stripper of 31 second inlet valve, 32 second outlet valve 51
The settler of 52 cyclone separator 53
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that
Embodiment described herein is merely to illustrate and explain the present invention, and is not limited to this hair
It is bright.
The present invention provides a kind of processing method of wax tailings, and this method includes：A, wax tailings are entered
Row fractionation is handled, and cut of the boiling range more than the first cut-point and below the second cut-point is evaporated as first
Point, the cut and/or boiling range that boiling range is less than to the first cut-point are used as second more than the cut of the second cut-point
Cut；Wherein, first cut-point is the arbitrary temp in the range of 390-410 DEG C, is preferably
Arbitrary temp in the range of 395-405 DEG C, the arbitrary temp in the range of more preferably 398-402 DEG C, enters one
Step is preferably 400 DEG C, and second cut-point is the arbitrary temp in the range of 440-460 DEG C, is preferably
Arbitrary temp in the range of 445-455 DEG C, the arbitrary temp in the range of more preferably 448-452 DEG C, enters one
Step is preferably 450 DEG C；B, by including in step a gained the first cut the first feedstock oil absorption denitrogenation
Contacted in reactor with absorption denitrification catalyst and carry out absorption denitrification reaction, obtain adsorbing denitrogenation product；
C, by step b gained absorption denitrogenation product and include in step a gained the second cut the second raw material
Oil carries out catalytic cracking reaction, obtains catalytic cracking production.
According to the present invention, fractionation processing is well-known to those skilled in the art, is mixed using boiling point separation
A kind of method of compound, for example, can be carried out in the fractionating column shown in Fig. 1.Cut-point, is also named segmentation
Temperature, is a temperature limit being manually set during fractionation is handled, so that boiling point is more than cut-point and boils
Component separation of the point below cut-point；The boiling range of cut refers to just start to distill out the temperature of component in cut
The temperature range for the temperature (i.e. the end point of distillation) that degree (i.e. initial boiling point) is distilled out to all components, boiling
Cut of the journey more than the first cut-point and below the second cut-point refers to that initial boiling point is at first point in boiling range
More than cutpoint and cut of the end point of distillation below the second cut-point, the cut that boiling range is less than the first cut-point is
Refer to the cut that the end point of distillation in boiling range is less than the first cut-point, the cut that boiling range is more than the second cut-point refers to boiling
Initial boiling point is more than the cut of the second cut-point in journey.
According to the present invention, wax tailings are the contents of the product of thermal cracking residue, wherein aromatic hydrocarbons, nitrogen and sulphur
It is higher, if directly carrying out catalytic cracking, easily inactivate catalytic cracking catalyst, therefore be typically not suitable for
Direct catalytic cracking is carried out, but refining is mixed with other feedstock oils, and the method for the present invention can make coking wax
Oil more suitably carries out catalytic cracking, so as to lift economic benefit.
According to the present invention, it is nitrogenous more than the cut of the second cut-point that boiling range is less than the first cut-point or boiling range
Amount is relatively low, can directly carry out catalytic cracking, therefore second cut can be small for the boiling range
In the cut of the first cut-point, or the boiling range is more than the cut of the second cut-point, preferably boils
Journey is less than the cut of cut and boiling range more than the second cut-point of the first cut-point.
According to the present invention, if desired increase the treating capacity of device, the first feedstock oil may be used also described in step b
To be higher than 0.2 weight % high nitrogen catalytically cracked material, such as shale oil and/or coking wax containing nitrogen content
Oil, the weight ratio of the first cut described in first feedstock oil and the high nitrogen catalytically cracked material can be with
For (0.01-100)：1, be preferably (0.1-10):1.
According to the present invention, absorption denitrification reactor is well-known to those skilled in the art, and the present invention is no longer
Repeat, in stepb, first feedstock oil can be sent at least two and the suction that can be regenerated in turn
Absorption denitrification reaction is carried out in attached denitrification reactor, for example, one or more in absorption denitrification reactor
In work, and remaining is regenerated, then periodically switching；Adsorbing denitrification reaction is also
Well-known to those skilled in the art, the present invention is repeated no more, and its condition can be：Temperature is
20-250 DEG C, pressure (gauge pressure) is 0-10 MPas, and volume space velocity is 0.3-12 hours-1。
According to the present invention, absorption denitrification catalyst is also well-known to those skilled in the art, for example, with
Weight meter, adsorbing denitrification catalyst described in step b can the acidizer containing 1-25 weight %, 1-25
The water of weight % complexing agent, 50-80 weight % carrier and 1-25 weight %；Wherein, the acidity
Agent can be mineral acid agent and/or organic acidity agent, and the mineral acid agent can be selected from sulfuric acid, Asia
Sulfuric acid, sulfur trioxide, nitric acid, nitrous acid, chloric acid, perchloric acid, hypochlorous acid, hydrochloric acid, phosphoric acid, partially
At least one of phosphoric acid and phosphorous acid；The complexing agent can be transition metal salt class, the transition gold
Belong to salt can be selected from copper nitrate, ferric nitrate, silver nitrate, chromic nitrate, titanium sulfate, titanium tetrachloride and
At least one of ammonium molybdate；The carrier can be in boehmite, activated carbon and silica gel
It is at least one.
According to the present invention, if desired increase the treating capacity of device, the second feedstock oil may be used also described in step c
To be less than 0.2 weight % low nitrogen catalytically cracked material containing nitrogen content, for example, it can contain and be selected from straight run
At least one of wax oil, solvent-deasphalted oils and decompression residuum, second feedstock oil and the low nitrogen
The weight ratio of catalytically cracked material can be (0.01-100)：1, be preferably (0.1-10):1.
According to the present invention, for the convenience that catalytic cracking is handled, in step c, the absorption denitrogenation production
The weight ratio of thing and second feedstock oil for example can be able to be (0.01-1) in interior change in a big way：
1, be preferably (0.01-0.4)：1, more preferably (0.05-0.3)：1.
According to the present invention, catalytic cracking reaction is well-known to those skilled in the art, and the present invention no longer goes to live in the household of one's in-laws on getting married
State, the condition of catalytic cracking reaction can be described in step c：Temperature is 480-550 DEG C, is preferably
490-530 DEG C, oil ratio is 3-8, preferably 5-7, and the reaction time is 0.6-3.0 seconds, preferably 1-2
Second, air speed is 1-20 hours-1, preferably 2-15 hours-1, the outlet pressure of catalyst cracker is
0.1-0.4 MPas, preferably 0.2-0.3 MPas.
According to the present invention, catalyst cracker is well known to those skilled in the art, for example, can be to carry
Riser reactors, dense bed reactor etc., wherein stripper, settler and cyclone separator can be set
Deng gas-solid separating device.Catalytic cracking catalyst in catalyst cracker is also those skilled in the art
Known, the present invention is repeated no more.In addition, the catalytic cracking catalyst after reaction green coke can also be sent
Enter in regenerator and regenerated, the regenerator and regenerative process be also it is well-known to those skilled in the art,
The present invention is repeated no more.
A kind of embodiment of the inventive method is provided below in conjunction with accompanying drawing, but the present invention is not
Therefore it is any way limited.
As shown in figure 1, the device that the inventive method is used is anti-including the absorption denitrogenation of fractionating column 1, first
Device 2, second is answered to adsorb denitrification reactor 3, riser reactor 4, stripping sedimentation device 5 and regenerator
6。
As depicted in figs. 1 and 2, the middle part for wax tailings being sent into fractionating column 1 carries out fractionation processing, obtains
To the first cut can add high nitrogen catalytically cracked material as the first feedstock oil from first fractionation pipeline
12 feedings first, which are adsorbed, carries out absorption denitrification reaction in denitrification reactor 2, obtain adsorbing denitrogenation product, inhale
Attached denitrogenation condition can be：Temperature is 20-250 DEG C, and pressure is 0-10 MPas, and volume space velocity is 0.3-12
Hour-1., can be by first after the absorption denitrification catalyst in the first absorption denitrification reactor 2 is inactivated
Absorption denitrification reactor 2 cuts out reaction system and regenerated, and the second absorption denitrification reactor 3 is cut
Reaction system is used to react, then cyclic switching again.Adsorbing the regeneration condition of denitrification catalyst can be：
Regeneration temperature is 250-600 DEG C, and preferably 300-500 DEG C, the recovery time is 1-10 hours, is preferably
3-6 hours.By fractionation handle obtained by the second cut respectively from the cut of pipeline on the second cut 11 and second
Lower pipeline 13 sends out fractionating column, and obtains the second feedstock oil after adding low nitrogen catalytically cracked stock；Its
In, cut of the boiling range more than the first cut-point and below the second cut-point is as the first cut, and boiling range is small
The cut for being more than the second cut-point in the cut and/or boiling range of the first cut-point is used as the second cut, first point
Cutpoint is the arbitrary temp in the range of 390-410 DEG C, and the second cut-point is any in the range of 440-460 DEG C
Temperature.
Absorption denitrogenation product and the second feedstock oil are sent into riser after mixed material pipeline 23 is mixed anti-
The bottom and the regeneration catalyzing Cracking catalyst from regenerator 6 for answering device 4 are reacted, obtained mixing
Stripped in thing feeding stripping sedimentation device 5 and in stripper 51 wherein, what is obtained to be generated urges
Agent feeding regenerator 6 is regenerated, and obtained oil gas and the mixture of part reclaimable catalyst is in sedimentation
Settled in device 53, settle obtained reclaimable catalyst and regenerated, carry a small amount of reclaimable catalyst secretly
Oil gas go upward to cyclonic separation carried out in secondary cyclone 52, the catalysis that cyclonic separation is obtained is split
Change product and send out the follow-up processing of reaction unit progress, the reclaimable catalyst of cyclonic separation is sent into by dipleg
Regenerator 6 is sent into after being settled in settler 53 to be regenerated.
The present invention will be further illustrated by embodiment below, but therefore the present invention is not taken office
What is limited.
The method of testing of catalytic cracking production of the present invention is as follows：Gaseous product is by the GC of Agilent 6890
(TCD detectors) on-line analysis is constituted；Product liquid carries out simulation distillation and gasoline detailed hydrocarbon point respectively
Analyse (being tested using RIPP 81-90 method of testings), the cut cut point of gasoline and diesel oil is respectively
221 DEG C and 343 DEG C；Green coke catalyst is regenerated by pure oxygen, and coke content is calculated by regenerated flue gas composition.
The present invention RIPP method of testings be selected from《Petrochemical Engineering Analysis method (RIPP test methods)》, poplar
Emerald green fixed wait is compiled, Science Press, 1990.
In following examples, straight-run gas oil and wax tailings come from Chang Ling refinery factory, specific nature such as table 1
It is shown.Absorption denitrification catalyst composition used includes：60 weight % absorbent charcoal carriers, 10 weight % water,
15 weight % nitrous acid and 15 weight % chromic nitrates.Catalytic cracking catalyst used is conventional MLC-500
The catalyst of commercial grades.
Embodiment 1
As depicted in figs. 1 and 2, wax tailings are sent into and fractionation processing is carried out in fractionating column 1, by boiling range
Boiling range is less than first by the cut more than the first cut-point and below the second cut-point as the first cut
The cut of cut-point is incorporated as the second cut with boiling range more than the second cut-point cut, and the first cut-point is
400 DEG C, the second cut-point is 450 DEG C；First cut discharges fractionating column 1 through the first cut pipeline 12,
Second cut discharges fractionating column 1 through pipeline 13 under the cut of pipeline on the second cut 11 and second, and first evaporates
The weight ratio divided with the second cut is 0.4:0.6.
First cut is adsorbed into denitrification reactor 2 with absorption denitrification catalyst as the first feedstock oil first
It is middle to contact and carry out absorption denitrification reaction, obtain adsorbing denitrogenation product.Adsorb the absorption in denitrification reactor
Denitrification reaction condition is：Adsorption temp is 200 DEG C, and pressure is 2 MPas, and volume space velocity is 6 hours-1。
To adsorb denitrogenation product and the second cut as the second feedstock oil mix after from mixed material pipeline
23 bottoms for entering riser reactor 4 are contacted simultaneously with the regeneration catalyzing Cracking catalyst from regenerator 6
Generation catalytic cracking reaction, the condition of catalytic cracking reaction is：Temperature is 500 DEG C, and oil ratio is 6,
Reaction time is 1.5 seconds, and air speed is 10 hours-1, the outlet pressure of catalyst cracker is 0.25 million
Handkerchief, by the gas solid separation of stripping sedimentation device 5, obtains catalyst cracking product S1.
Embodiment 2
The coking petrolatum oil processing method of embodiment 2 is same as Example 1, and difference is, second
Cut, which enters, introduces straight-run gas oil before catalytic cracking unit, together as the second feedstock oil, introduces straight-run gas oil
Amount determined by the total processing capacity of wax tailings, wax tailings is mixed refining amount and reach 40 weight %, at the same with
First feedstock oil enters catalyst cracker and carries out subsequent reactions together, obtains catalytic cracking production S2.
Embodiment 3
The coking petrolatum oil processing method of embodiment 3 is same as Example 2, and difference is, first point
Cutpoint is 395 DEG C, and the second cut-point is 445 DEG C, obtains catalytic cracking production S3.
Embodiment 4
The coking petrolatum oil processing method of embodiment 4 is same as Example 2, and difference is, first point
Cutpoint is 405 DEG C, and the second cut-point is 455 DEG C, obtains catalytic cracking production S4.
Embodiment 5
The coking petrolatum oil processing method of embodiment 5 is same as Example 2, and difference is, first point
Cutpoint is 390 DEG C, and the second cut-point is 440 DEG C, obtains catalytic cracking production S5.
Embodiment 6
The coking petrolatum oil processing method of embodiment 6 is same as Example 2, and difference is, first point
Cutpoint is 410 DEG C, and the second cut-point is 460 DEG C, obtains catalytic cracking production S6.
Embodiment 7
The coking petrolatum oil processing method of embodiment 7 is same as Example 2, and difference is, coking wax
The refining amount of mixing of oil is 20 weight %, that is to say, that the ratio between wax tailings and straight-run gas oil are 2:8, urged
Change crackate S7.
Comparative example 1
The coking petrolatum oil processing method of comparative example 1 is same as Example 1, and difference is, by coking
Wax oil directly carries out absorption denitrogenation processing without fractionation processing, but keeps same amount of suction with embodiment 1
Attached dose and identical absorption denitrogenation condition, obtained absorption denitrogenation product are sent directly into catalyst cracker
Catalytic cracking reaction is carried out, catalytic cracking production D1 is obtained.
Comparative example 2
The coking petrolatum oil processing method of comparative example 2 is identical with comparative example 1, and difference is, is to introduce
A part of the straight-run gas oil as the second feedstock oil so that wax tailings mix refining amount for 40 weight %,
Obtain catalytic cracking production D2.
Comparative example 3
The coking petrolatum oil processing method of comparative example 3 is identical with comparative example 1, and difference is, is to introduce
A part of the straight-run gas oil as the second feedstock oil so that wax tailings mix refining amount for 20 weight %,
Obtain catalytic cracking production D3.
Comparative example 4
Wax tailings are directly carried out catalytic cracking reaction and handle and adsorb without fractionation and be de- by comparative example 4
Nitrogen reacts, and catalytic cracking reaction condition is same as Example 1, obtains catalytic cracking production D4.
Comparative example 5
The coking petrolatum oil processing method of comparative example 5 is identical with comparative example 4, is positioned at difference, will
Wax tailings and straight-run gas oil mix refining, and wherein wax tailings mix refining amount for 20 weight %, obtain catalysis and split
Change product D5.
Method of testing according to foregoing catalytic cracking production determines embodiment 1-7 and comparative example 1-5 and obtained
Catalytic cracking production S1-S7 and D1-D5 in product (including dry gas, liquefied gas, gasoline, diesel oil,
Slurry oil and coke) distribution, and calculate yield of light oil in product (gasoline and diesel oil), embodiment 1-2,
Embodiment 7, comparative example 1-5 catalytic cracking production data are as shown in table 2, embodiment 3-6 catalysis
Crackate data are as shown in table 3.
It can be seen from table 2-3 data, the method for not being fractionated into directly carrying out catalytic cracking with wax tailings
Compared to (i.e. comparative example 4 and 5), the toxic action of method of the invention to catalytic cracking catalyst is small, energy
Enough so that conversion ratio rises, product distribution is more preferably improved with product quality, exist so as to improve wax tailings
Refining ratio is mixed in catalytic cracking；It is not fractionated into directly all carrying out absorption denitrification reaction with wax tailings and urges
The method for changing cracking compares (i.e. comparative example 1-3), and the inventive method is used under identical cost by coking wax
Oil carries out catalytic cracking after carrying out absorption denitrification reaction, not only high conversion rate, and yield of light oil is high,
That is, wax tailings and straight-run gas oil that the present invention handles identical weight under identical cost are obtained
High value products it is many；In addition, as can be seen that using the first cut-point from embodiment 2-6 comparison
For 395-405 DEG C and the second cut-point be 445-455 DEG C wax tailings are cut if, can obtain
More preferable effect, reason is Jiao of the boiling range more than first cut-point and below second cut-point
Change wax oil cut and be more rich in condensed-nuclei aromatics and nitrogen, more there is toxic action to catalytic cracking catalyst,
If being fractionated and carrying out absorption denitrogenation, can just it cause catalytic cracking catalyst is played dynamical
Catalytic action, thus improves the efficiency of catalytic cracking.
The specific nature of the straight-run gas oil of table 1 and wax tailings
The embodiment 1-2 of table 2, embodiment 7, comparative example 1-5 catalytic cracking production data
The embodiment 3-6 of table 3 catalytic cracking production data
Claims (11)
1. a kind of processing method of wax tailings, this method includes：
A, wax tailings are subjected to fractionation processing, by boiling range more than the first cut-point and the second cut-point
Cut and/or boiling range that boiling range is less than the first cut-point are more than second by following cut as the first cut
The cut of cut-point is used as the second cut；Wherein, first cut-point is in the range of 390-410 DEG C
Arbitrary temp, second cut-point is the arbitrary temp in the range of 440-460 DEG C；
B, by including in step a gained the first cut the first feedstock oil absorption denitrification reactor in
Absorption denitrification catalyst contacts and carries out absorption denitrification reaction, obtains adsorbing denitrogenation product；
C, by step b gained absorption denitrogenation product and include in step a gained the second cut second
Feedstock oil feeding catalyst cracker carries out catalytic cracking reaction, obtains catalytic cracking production.
2. according to the method described in claim 1, wherein, the first cut-point is described in step a
Arbitrary temp in the range of 395-405 DEG C, second cut-point is any temperature in the range of 445-455 DEG C
Degree.
3. according to the method described in claim 1, wherein, the second cut is described described in step a
Boiling range is less than the cut of cut and the boiling range more than the second cut-point of the first cut-point.
4. according to the method described in claim 1, wherein, the first feedstock oil also contains described in step b
There is the high nitrogen catalytically cracked material that nitrogen content is higher than 0.2 weight %.
5. method according to claim 4, wherein, the high nitrogen catalytically cracked material is shale
Oil and/or wax tailings, the first cut described in first feedstock oil and the high nitrogen catalytically cracked material
Weight ratio be (0.01-100)：1.
6. according to the method described in claim 1, wherein, in stepb, by first raw material
Absorption denitrification reaction is carried out in oil feeding at least two and the absorption denitrification reactor that can be regenerated in turn, it is described
Absorption denitrification reaction condition be：Temperature is 20-250 DEG C, and pressure is 0-10 MPas, and volume space velocity is
0.3-12 hours-1。
7. according to the method described in claim 1, wherein, by weight, described in step b adsorb
Denitrification catalyst contains 1-25 weight % acidizer, 1-25 weight % complexing agent, 50-80 weight %
Carrier and 1-25 weight % water；
Wherein, the acidizer is mineral acid agent and/or organic acidity agent, and the mineral acid agent is
Selected from sulfuric acid, sulfurous acid, sulfur trioxide, nitric acid, nitrous acid, chloric acid, perchloric acid, hypochlorous acid, salt
At least one of acid, phosphoric acid, metaphosphoric acid and phosphorous acid；The complexing agent is transition metal salt, institute
It is selected from copper nitrate, ferric nitrate, silver nitrate, chromic nitrate, titanium sulfate, four chlorinations to state transition metal salt
At least one of titanium and ammonium molybdate；The carrier is in boehmite, activated carbon and silica gel
It is at least one.
8. according to the method described in claim 1, wherein, the second feedstock oil also contains described in step c
There is the low nitrogen catalytically cracked material that nitrogen content is less than 0.2 weight %.
9. method according to claim 8, wherein, the low nitrogen catalytically cracked material be selected from
At least one of straight-run gas oil, solvent-deasphalted oils and decompression residuum, second feedstock oil with it is described
The weight ratio of low nitrogen catalytically cracked material is (0.01-100)：1.
10. according to the method described in claim 1, wherein, in step c, it is described absorption denitrogenation production
The weight ratio of thing and second feedstock oil is (0.01-1)：1.
11. according to the method described in claim 1, wherein, catalytic cracking reaction described in step c
Condition is：Temperature is 480-550 DEG C, and oil ratio is 3-8, and the reaction time is 0.6-3.0 seconds, and air speed is
1-20 hours-1, the outlet pressure of catalyst cracker is 0.1-0.4 MPas.
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