CN106987268B - A kind of processing method of wax tailings - Google Patents
A kind of processing method of wax tailings Download PDFInfo
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- CN106987268B CN106987268B CN201610041906.7A CN201610041906A CN106987268B CN 106987268 B CN106987268 B CN 106987268B CN 201610041906 A CN201610041906 A CN 201610041906A CN 106987268 B CN106987268 B CN 106987268B
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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
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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
- C10G2300/70—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 fraction of the boiling range more than the first cut-point and below the second cut-point as the first fraction, boiling range are less than the fraction of the first cut-point and/or boiling range is more than the fraction of the second cut-point as the second fraction；B, the first feedstock oil including the first fraction of gained in step a in denitrification reactor is adsorbed with absorption denitrification catalyst is contacted and carries out absorption denitrification reaction, obtain absorption denitrogenation product；C, gained absorption denitrogenation product in step b and the second feedstock oil including the second fraction of gained in step a are sent into catalyst cracker and 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 generate in catalytically cracked material, improve wax tailings and mix refining ratio in catalytically cracked material, and generated high value products are more.
Description
Technical field
The present invention relates to petrochemical industries, and in particular, 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, development heavy oil is efficient
Conversing technology becomes the urgent task of current petroleum refining industry.Delayed coking is one of main means of heavy oil lighting, is accounted for
More than the 30 weight % of world's processing of heavy oil ability.In the product distribution of coking, wax tailings (Coker Gas Oil)
Yield be usually 20-30 weight %, the processing and utilization of this part fraction directly affects heavy oil transformation efficiency, becomes restriction
The key issue of heavy oil deep processing.
At present, wax tailings are usually as secondary operation device such as catalytic cracking (Fluid Catalytic
Cracking the raw material), being hydrocracked.Take the process program being hydrocracked in external oil refining enterprise more；Due to by hydrogenation capability,
The restriction of the conditions such as hydrogen inadequate resource, with reference to each refinery facilities it is mating the characteristics of, China mainly using wax tailings as catalysis split
Change process mixes refining raw material.Production practices show that the reactivity worth of wax tailings is poor, cause under catalytic cracking process conversion ratio
How a series of adverse consequences such as drop, product distribution deteriorate, product quality is deteriorated, therefore, improve catalytic cracking unit to poor quality
The adaptability of raw material, reduction mix refining wax tailings caused by adverse effect, be tackle coking production capacity increase rapidly compel
It is essential and asks.In order to solve the problems, such as this, production unit and researcher have carried out largely in terms of wax tailings processing technology
Work.
For example, Chinese patent CN1891791 A disclose a kind of method and apparatus of processing coked waxy oil, specifically will
The lower part of riser reactor is divided into the separate reaction zones of two vertical parallels, allows wax tailings and other more good routines
Feedstock oil enters different reaction zones and carries out catalytic cracking reaction, and the logistics after being reacted in two reaction zones is in the riser
The top of reactor is converged, i.e., the separate reaction zones that riser reactor lower part is formed for two branch pipes.But it is demonstrated experimentally that
Mixed in the above method refining wax tailings caused by adverse effect it is still larger, there are conversion ratio decline, product distribution deteriorate and
It is still relatively low to refine ratio so as to cause wax tailings mixing in catalytic cracking for the defects of product quality is deteriorated.
The content of the invention
The object of the present invention is to provide a kind of processing method of wax tailings, this method can mitigate in catalytically cracked material
Adverse effect caused by mixing refining wax tailings improves wax tailings and mixes refining ratio in catalytically cracked material, and produced
High value products it is more.
To achieve these goals, the present invention provides a kind of processing method of wax tailings, and this method includes：A, by coking
Wax oil carries out fractionation processing, will using fraction of the boiling range more than the first cut-point and below the second cut-point as the first fraction
Boiling range is less than the fraction of the first cut-point and/or boiling range is more than the fraction of the second cut-point as the second fraction；Wherein, described
One cut-point is the arbitrary temp in the range of 390-410 DEG C, and second cut-point is the arbitrary temperature in the range of 440-460 DEG C
Degree；B, by including in step a gained the first fraction the first feedstock oil in denitrification reactor adsorb with absorption denitrification catalyst
It contacts and carries out absorption denitrification reaction, obtain absorption denitrogenation product；C, by gained absorption denitrogenation product in step b and including step
The second feedstock oil of the second fraction of gained is sent into catalyst cracker and carries out catalytic cracking reaction in a, obtains catalytic cracking production
Object.
Preferably, the first cut-point described in step a is the arbitrary temp in the range of 395-405 DEG C, second segmentation
Point is the arbitrary temp in the range of 445-455 DEG C.
Preferably, the second fraction described in step a is big less than the fraction of the first cut-point and the boiling range for the boiling range
In the fraction of the second cut-point.
Preferably, the first feedstock oil described in step b is also former containing high nitrogen catalytic cracking of the nitrogen content higher than 0.2 weight %
Material.
Preferably, the high nitrogen catalytically cracked material is shale oil and/or wax tailings, described in first feedstock oil
The weight ratio of first fraction and the high nitrogen catalytically cracked material is (0.01-100)：1.
Preferably, in stepb, by first feedstock oil be sent at least two and can in turn it is regenerated absorption denitrogenation it is anti-
It answers and absorption denitrification reaction is carried out in device, the condition of the absorption denitrification reaction is：Temperature is 20-250 DEG C, and pressure is 0-10 million
Pa, when volume space velocity is 0.3-12 small-1。
Preferably, by weight, denitrification catalyst is adsorbed described in step b and contains the acidizer of 1-25 weight %, 1-25
The water of the complexing agent of weight %, the carrier of 50-80 weight % and 1-25 weight %；Wherein, the acidizer is mineral acid agent
And/or organic acidity agent, the mineral acid agent are selected from sulfuric acid, sulfurous acid, sulfur trioxide, nitric acid, nitrous acid, chloric acid, height
At least one of chloric acid, hypochlorous acid, hydrochloric acid, phosphoric acid, metaphosphoric acid and phosphorous acid；The complexing agent be transition metal salt, institute
State transition metal salt be in copper nitrate, ferric nitrate, silver nitrate, chromic nitrate, titanium sulfate, titanium tetrachloride and ammonium molybdate extremely
Few one kind；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 former containing low nitrogen catalytic cracking of the nitrogen content less than 0.2 weight %
Material.
Preferably, the low nitrogen catalytically cracked material is in straight-run gas oil, solvent-deasphalted oils and decompression residuum
The weight ratio of at least one, second feedstock oil and the low nitrogen catalytically cracked material is (0.01-100)：1.
Preferably, in step c, the weight ratio of the absorption 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, oil ratio 3-8, instead
It it is 0.6-3.0 seconds between seasonable, when air speed is 1-20 small-1, the outlet pressure of catalyst cracker is 0.1-0.4 megapascal.
Through the above technical solutions, the method for the present invention is by by boiling range more than the first cut-point and below the second cut-point
High nitrogen content wax tailings fraction fractionation after carry out absorption denitrogenation, mistake of the wax tailings to catalytic cracking catalyst can be mitigated
Effect living so that catalytic cracking conversion rises, product distribution is more preferable and product quality improves, and exists so as to improve wax tailings
Refining ratio is mixed in catalytically cracked material, the method phase that absorption denitrogenation carries out catalytic cracking again is in addition all carried out with wax tailings
Than the wax tailings and straight-run gas oil of processing identical weight, generated high value products are more under identical cost.
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 for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is together for explaining the present invention, but be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is that a kind of specific embodiment of processing method of wax tailings of the present invention uses the structure diagram of device,
Also include the flow diagram of the method for the present invention simultaneously；
Fig. 2 is a kind of flow diagram of specific embodiment of processing method of wax tailings of the present invention.
Reference sign
1 fractionating column 2 first absorption denitrification reactor 3 second adsorbs denitrification reactor
4 riser reactors 5 strip 6 regenerator of sedimentation device
Pipeline under 12 first fraction pipeline of pipeline, 13 second fraction on 11 second fractions
21 first inlet valve, 22 first outlet valve, 23 mixed raw material pipeline
31 second inlet valve, 32 second outlet valve, 51 stripper
52 cyclone separator, 53 settler
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of processing method of wax tailings, and this method includes：A, wax tailings are subjected to fractionation processing,
Using fraction of the boiling range more than the first cut-point and below the second cut-point as the first fraction, boiling range is less than the first cut-point
Fraction and/or boiling range be more than the second cut-point fraction as the second fraction；Wherein, first cut-point is 390-410
Arbitrary temp in the range of DEG C is preferably the arbitrary temp in the range of 395-405 DEG C, in the range of more preferably 398-402 DEG C
Arbitrary temp, further preferably 400 DEG C, second cut-point are the arbitrary temp in the range of 440-460 DEG C, are preferably
Arbitrary temp in the range of 445-455 DEG C, the arbitrary temp being more preferably in the range of 448-452 DEG C, further preferably 450
℃；B, by including in step a gained the first fraction the first feedstock oil in denitrification reactor adsorb with absorption denitrification catalyst
It contacts and carries out absorption denitrification reaction, obtain absorption denitrogenation product；C, by gained absorption denitrogenation product in step b and including step
The second feedstock oil of the second fraction of gained carries out catalytic cracking reaction in a, obtains catalytic cracking production.
According to the present invention, fractionation processing is well-known to those skilled in the art, is one using boiling point separating mixture
Kind of method, for example, can be shown in Fig. 1 fractionating column in carry out.Cut-point is also segmentation temperature, is artificially set in fractionation processing
A fixed temperature limit, so that component of the boiling point more than cut-point with boiling point below cut-point separates；The boiling range of fraction
Refer to that just start the temperature that the temperature (i.e. initial boiling point) for distilling out component is distilled out to all components in fraction (evaporates eventually
Point) temperature range, fraction of the boiling range more than the first cut-point and below the second cut-point refer to that initial boiling point is in boiling range
More than one cut-point and fraction of the end point of distillation below the second cut-point, the fraction that boiling range is less than the first cut-point refer in boiling range
The end point of distillation is less than the fraction of the first cut-point, and the fraction that boiling range is more than the second cut-point refers to that initial boiling point is more than second point in boiling range
The fraction of cutpoint.
According to the present invention, wax tailings are the products of thermal cracking residue, and the content of wherein aromatic hydrocarbons, nitrogen and sulphur is higher, if directly
Tap into row catalytic cracking, easily inactivate catalytic cracking catalyst, thus it is general be not suitable for carrying out direct catalytic cracking, but with
Other feedstock oils mix refining, and the method for the present invention can make wax tailings more suitable for carrying out catalytic cracking, so as to promote economy
Benefit.
According to the present invention, boiling range is more than the nitrogen content of the fraction of the second cut-point less than the first cut-point or boiling range relatively
It is low, catalytic cracking can be directly carried out, therefore second fraction can be the fraction that the boiling range is less than the first cut-point,
It can be the fraction that the boiling range is more than the second cut-point, be preferably that boiling range is less than the fraction of the first cut-point and boiling range is more than the
The fraction of two cut-points.
According to the present invention, the treating capacity of device is if desired increased, the first feedstock oil described in step b can also contain nitrogenous
High nitrogen catalytically cracked material of the amount higher than 0.2 weight %, such as shale oil and/or wax tailings, institute in first feedstock oil
The weight ratio for stating the first fraction and the high nitrogen catalytically cracked material can be (0.01-100)：1, be preferably (0.1-10):1.
According to the present invention, it is well-known to those skilled in the art to adsorb denitrification reactor, and the present invention repeats no more, in step
In rapid b, first feedstock oil can be sent at least two and regenerated adsorb in denitrification reactor can be adsorbed in turn
Denitrification reaction, for example, one or more in absorption denitrification reactor is working, and remaining is regenerated,
Then periodically switching；It is also well-known to those skilled in the art to adsorb denitrification reaction, and the present invention repeats no more, and condition can be with
For：Temperature is 20-250 DEG C, and pressure (gauge pressure) is 0-10 megapascal, when volume space velocity is 0.3-12 small-1。
According to the present invention, it is also well-known to those skilled in the art to adsorb denitrification catalyst, for example, by weight, step
Denitrification catalyst is adsorbed described in rapid b can the acidizer containing 1-25 weight %, the complexing agent of 1-25 weight %, 50-80 weights
Measure the carrier of % and the water of 1-25 weight %；Wherein, the acidizer can be mineral acid agent and/or organic acidity agent, institute
It can be selected from sulfuric acid, sulfurous acid, sulfur trioxide, nitric acid, nitrous acid, chloric acid, perchloric acid, hypochlorous acid, salt to state mineral acid agent
At least one of acid, phosphoric acid, metaphosphoric acid and phosphorous acid；The complexing agent can be transition metal salt class, the transition metal
Salt can be at least one in copper nitrate, ferric nitrate, silver nitrate, chromic nitrate, titanium sulfate, titanium tetrachloride and ammonium molybdate
Kind；The carrier can be selected from least one of boehmite, activated carbon and silica gel.
According to the present invention, the treating capacity of device is if desired increased, the second feedstock oil can also contain containing nitrogen described in step c
Low nitrogen catalytically cracked material of the amount less than 0.2 weight %, such as can contain 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 can be (0.01-
100)：1, be preferably (0.1-10):1.
According to the present invention, for the convenience of catalytic cracking processing, in step c, the absorption denitrogenation product and described the
The weight ratio of two feedstock oils can be in interior variation in a big way, such as can be (0.01-1)：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 that the present invention repeats no more, step c
Described in the condition of catalytic cracking reaction can be：Temperature is 480-550 DEG C, is preferably 490-530 DEG C, oil ratio 3-8, excellent
Elect 5-7 as, the reaction time is 0.6-3.0 seconds, is preferably 1-2 seconds, when air speed is 1-20 small-1, when being preferably 2-15 small-1, catalysis
The outlet pressure of cracker is 0.1-0.4 megapascal, is preferably 0.2-0.3 megapascal.
According to the present invention, catalyst cracker is well known to those skilled in the art, such as can be that riser reacts
Device, dense bed reactor etc., wherein the gas-solid separating devices such as stripper, settler and cyclone separator can be set.Catalysis is split
The catalytic cracking catalyst changed in reactor is also well-known to those skilled in the art, and the present invention repeats no more.In addition, reaction
Catalytic cracking catalyst after green coke, which can also be sent into regenerator, to be regenerated, and the regenerator and regenerative process are also this field
Known to technical staff, the present invention repeats no more.
A kind of specific embodiment of the method for the present invention is provided below in conjunction with attached drawing, but the present invention not therefore and by
To any restrictions.
As shown in Figure 1, device includes the absorption denitrification reactor 2, second of fractionating column 1, first used by the method for the present invention
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, the first obtained fraction
High nitrogen catalytically cracked material can be added in and be sent into the first absorption denitrification reactor 2 from the first fractionation pipeline 12 as the first feedstock oil
In carry out absorption denitrification reaction, obtain absorption denitrogenation product, absorption denitrogenation condition can be：Temperature is 20-250 DEG C, and pressure is
0-10 megapascal, when volume space velocity is 0.3-12 small-1.After the absorption denitrification catalyst in the first absorption denitrification reactor 2 inactivates,
First absorption denitrification reactor 2 can be cut out reaction system and regenerated, the second absorption denitrification reactor 3 is cut into reaction
System is for reacting, then cyclic switching again.Adsorbing the regeneration condition of denitrification catalyst can be：Regeneration temperature is 250-
600 DEG C, be preferably 300-500 DEG C, when the recovery time is 1-10 small, when being preferably 3-6 small.The second of processing gained will be fractionated to evaporate
Divide and send out fractionating column from pipeline 13 under 11 and second fraction of pipeline on the second fraction respectively, and add in low nitrogen catalytically cracked stock
After obtain the second feedstock oil；Wherein, fraction of the boiling range more than the first cut-point and below the second cut-point be as the first fraction,
Boiling range is less than the fraction of the first cut-point and/or boiling range is more than the fraction of the second cut-point as the second fraction, the first cut-point
For the arbitrary temp in the range of 390-410 DEG C, the second cut-point is the arbitrary temp in the range of 440-460 DEG C.
Absorption denitrogenation product and the second feedstock oil are sent into after mixed raw material pipeline 23 mixes under riser reactor 4
Portion is reacted with the regeneration catalyzing Cracking catalyst from regenerator 6, and obtained mixture is sent into stripping sedimentation device 5 simultaneously
It is stripped in stripper 51 wherein, obtained reclaimable catalyst is sent into regenerator 6 and is regenerated, obtained oil gas and portion
The mixture of reclaimable catalyst is divided to be settled in settler 53, the reclaimable catalyst settled is regenerated, and entrainment is few
The oil gas of amount reclaimable catalyst, which is gone upward to, carries out cyclonic separation in secondary cyclone 52, the catalytic cracking that cyclonic separation obtains
Product sends out reaction unit and carries out subsequent processing, and the reclaimable catalyst of cyclonic separation, which is sent by dipleg in settler 53, to carry out
Regenerator 6 is sent into after sedimentation to be regenerated.
It will be further illustrated the present invention below by embodiment, but the present invention is not therefore subject to any restriction.
The test method of catalytic cracking production of the present invention is as follows：Gaseous product is by 6890 GC of Agilent (TCD detectors)
On-line analysis forms；Product liquid carries out simulation distillation and gasoline detailed hydrocarbon analysis (using RIPP 81-90 test methods respectively
Tested), the fraction cut point of gasoline and diesel oil is respectively 221 DEG C and 343 DEG C；Green coke catalyst is regenerated by pure oxygen, is led to
It crosses regenerated flue gas composition and calculates coke content.The present invention RIPP test methods be selected from《(RIPP is tried Petrochemical Engineering Analysis method
Proved recipe method)》, Yang Cui surely compile by grade, Science Press, and 1990.
In following embodiment, straight-run gas oil and wax tailings come from Chang Ling refinery factory, and specific nature is as shown in table 1.It is used
Absorption denitrification catalyst composition includes：60 weight % absorbent charcoal carriers, 10 weight % water, 15 weight % nitrous acid and 15 weight %
Chromic nitrate.Catalytic cracking catalyst used is the catalyst of common MLC-500 commercial grades.
Embodiment 1
As depicted in figs. 1 and 2, wax tailings are sent into fractionating column 1 and carry out fractionation processing, by boiling range in the first cut-point
Above and the fraction below the second cut-point is as the first fraction, and boiling range is less than the fraction of the first cut-point and boiling range is more than the
Two cut-point fractions are incorporated as the second fraction, and the first cut-point is 400 DEG C, and the second cut-point is 450 DEG C；First fraction is through
One fraction pipeline 12 discharges fractionating column 1, and the second fraction is through the discharge of pipeline 13 fractionation under 11 and second fraction of pipeline on the second fraction
The weight ratio of tower 1, the first fraction and the second fraction is 0.4:0.6.
Using the first fraction as the first feedstock oil with absorption denitrification catalyst first absorption denitrification reactor 2 in contact simultaneously
Absorption denitrification reaction is carried out, obtains absorption denitrogenation product.Absorption denitrification reactor in absorption denitrification reaction condition be：Absorption temperature
It spends for 200 DEG C, pressure is 2 megapascal, when volume space velocity is 6 small-1。
Denitrogenation product will be adsorbed and carried as entering after the second fraction mixing of the second feedstock oil from mixed raw material pipeline 23
The bottom of riser reactors 4 contacts with the regeneration catalyzing Cracking catalyst from regenerator 6 and catalytic cracking reaction occurs, catalysis
The condition of cracking reaction is：Temperature is 500 DEG C, oil ratio 6, and the reaction time is 1.5 seconds, when air speed is 10 small-1, catalytic cracking
The outlet pressure of reactor is 0.25 megapascal, 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, the difference is that, in the second fraction into catalysis
Straight-run gas oil is introduced before cracking unit, together as the second feedstock oil, introduces the amount of straight-run gas oil by the total processing capacity of wax tailings
It determines, wax tailings is made to mix refining amount and reach 40 weight %, while are carried out together with the first feedstock oil into catalyst cracker
Subsequent reactions obtain catalytic cracking production S2.
Embodiment 3
The coking petrolatum oil processing method of embodiment 3 is same as Example 2, the difference is that, the first cut-point is 395
DEG C, 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, the difference is that, the first cut-point is 405
DEG C, 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, the difference is that, the first cut-point is 390
DEG C, 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, the difference is that, the first cut-point is 410
DEG C, 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, the difference is that, wax tailings mix refining amount
For 20 weight %, that is to say, that the ratio between wax tailings and straight-run gas oil are 2:8, obtain catalytic cracking production S7.
Comparative example 1
The coking petrolatum oil processing method of comparative example 1 is same as Example 1, the difference is that, by wax tailings without
Fractionation processing directly carries out absorption denitrogenation processing, but keeps same amount of adsorbent and identical absorption denitrogenation item with embodiment 1
Part, obtained absorption denitrogenation product are sent directly into catalyst cracker and carry out catalytic cracking reaction, obtain catalytic cracking production
D1。
Comparative example 2
The coking petrolatum oil processing method of comparative example 2 is identical with comparative example 1, the difference is that, it is the introduction of straight-run gas oil
A part 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, the difference is that, it is the introduction of straight-run gas oil
A part 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 denitrification reaction are handled and adsorbed without fractionation by comparative example 4,
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, positioned at the difference is that, by wax tailings and
Straight-run gas oil mixes refining, and wherein wax tailings mix refining amount for 20 weight %, obtain catalytic cracking production D5.
Test method according to foregoing catalytic cracking production measures the catalysis that embodiment 1-7 and comparative example 1-5 is obtained and splits
Change product (including dry gas, liquefied gas, gasoline, diesel oil, the slurry oil and coke) distribution in product S1-S7 and D1-D5, and calculate production
Yield of light oil (gasoline and diesel oil) in object, embodiment 1-2, embodiment 7, the catalytic cracking production data of comparative example 1-5 such as table 2
Shown, the catalytic cracking production data of embodiment 3-6 are as shown in table 3.
According to the data of table 2-3, compared with wax tailings are not fractionated into directly carrying out the method for catalytic cracking (i.e. pair
Ratio 4 and 5), method of the invention is small to the toxic action of catalytic cracking catalyst, conversion ratio is enabled to rise, product point
Cloth is more preferable and product quality improves, and mixes refining ratio in catalytic cracking so as to improve wax tailings；With wax tailings without dividing
It evaporates directly whole absorption denitrification reactions that carry out and (i.e. comparative example 1-3) is compared with the method for catalytic cracking, used under identical cost
The method of the present invention carries out catalytic cracking after wax tailings are carried out absorption denitrification reaction, not only high conversion rate, but also light oil is received
Rate is high, that is to say, that the present invention handles the high price that the wax tailings of identical weight and straight-run gas oil are obtained under identical cost
It is more to be worth product；In addition, as can be seen that the first cut-point is used to split for 395-405 DEG C and second from the comparison of embodiment 2-6
If point cuts wax tailings for 445-455 DEG C, better effect can be obtained, reason is boiling range at this first point
Wax tailings fraction more than cutpoint and below second cut-point is catalyzed catalytic cracking more rich in condensed-nuclei aromatics and nitrogen
Agent more has toxic action, just can be so that catalytic cracking catalyst plays if being fractionated and carrying out absorption denitrogenation
Thus dynamical catalytic action improves the efficiency of catalytic cracking.
The specific nature of 1 straight-run gas oil of table and wax tailings
2 embodiment 1-2 of table, embodiment 7, the catalytic cracking production data of comparative example 1-5
The catalytic cracking production data of 3 embodiment 3-6 of table
Claims (11)
1. a kind of processing method of wax tailings, this method include：
A, wax tailings are subjected to fractionation processing, using fraction of the boiling range more than the first cut-point and below the second cut-point as
Boiling range is less than the fraction of the first cut-point and/or boiling range is more than the fraction of the second cut-point as the second fraction by the first fraction；
Wherein, first cut-point is the arbitrary temp in the range of 390-410 DEG C, and second cut-point is 440-460 DEG C of scope
Interior arbitrary temp；
B, by including in step a gained the first fraction the first feedstock oil in denitrification reactor adsorb with absorption denitrification catalyst
It contacts and carries out absorption denitrification reaction, obtain absorption denitrogenation product；
C, gained absorption denitrogenation product in step b and the second feedstock oil including the second fraction of gained in step a are sent into catalysis
Cracker carries out catalytic cracking reaction, obtains catalytic cracking production.
2. according to the method described in claim 1, wherein, the first cut-point described in step a is times in the range of 395-405 DEG C
Meaning temperature, second cut-point are the arbitrary temp in the range of 445-455 DEG C.
3. according to the method described in claim 1, wherein, the second fraction described in step a is less than the first segmentation for the boiling range
The fraction of point and the boiling range are more than the fraction of the second cut-point.
4. according to the method described in claim 1, wherein, the first feedstock oil described in step b is also higher than 0.2 weight containing nitrogen content
Measure the high nitrogen catalytically cracked material of %.
5. according to the method described in claim 4, wherein, the high nitrogen catalytically cracked material is shale oil and/or wax tailings,
The weight ratio of first fraction described in first feedstock oil and the high nitrogen catalytically cracked material is (0.01-100)：1.
6. according to the method described in claim 1, wherein, in stepb, first feedstock oil is sent at least two and can
Absorption denitrification reaction is carried out in regenerated absorption denitrification reactor in turn, the condition of the absorption denitrification reaction is：Temperature is 20-
250 DEG C, pressure is 0-10 megapascal, when volume space velocity is 0.3-12 small-1。
7. it according to the method described in claim 1, wherein, adsorbs denitrification catalyst by weight, described in step b and contains 1-25
The acidizer of weight %, the complexing agent of 1-25 weight %, the water of the carrier of 50-80 weight % and 1-25 weight %；
Wherein, the acidizer is mineral acid agent and/or organic acidity agent, and the mineral acid agent is selected from sulfuric acid, sulfurous
At least one in acid, sulfur trioxide, nitric acid, nitrous acid, chloric acid, perchloric acid, hypochlorous acid, hydrochloric acid, phosphoric acid, metaphosphoric acid and phosphorous acid
Kind；The complexing agent is transition metal salt, and the transition metal salt is selected from copper nitrate, ferric nitrate, silver nitrate, nitric acid
At least one of chromium, titanium sulfate, titanium tetrachloride and ammonium molybdate；The carrier is selected from boehmite, activated carbon and silica gel
At least one of.
8. according to the method described in claim 1, wherein, the second feedstock oil described in step c is also less than 0.2 weight containing nitrogen content
Measure the low nitrogen catalytically cracked material of %.
9. according to the method described in claim 8, wherein, the low nitrogen catalytically cracked material is to be taken off selected from straight-run gas oil, solvent
At least one of coal tar and decompression residuum, the weight ratio of second feedstock oil and the low nitrogen catalytically cracked material are
(0.01-100)：1.
10. according to the method described in claim 1, wherein, in step c, the absorption denitrogenation product and second raw material
The weight ratio of oil is (0.01-1)：1.
11. according to the method described in claim 1, wherein, the condition of catalytic cracking reaction is described in step c：Temperature is
480-550 DEG C, oil ratio 3-8, the reaction time is 0.6-3.0 seconds, when air speed is 1-20 small-1, catalyst cracker goes out
Mouth pressure is 0.1-0.4 megapascal.
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