CN107557063A - A kind of catalysis conversion method of inferior feedstock oil - Google Patents
A kind of catalysis conversion method of inferior feedstock oil Download PDFInfo
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- CN107557063A CN107557063A CN201610509273.8A CN201610509273A CN107557063A CN 107557063 A CN107557063 A CN 107557063A CN 201610509273 A CN201610509273 A CN 201610509273A CN 107557063 A CN107557063 A CN 107557063A
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Abstract
The invention discloses a kind of catalysis conversion method of inferior feedstock oil, this method includes：A, the inferior feedstock oil of preheating is sent into riser reactor (2) from the middle and lower part of the first conversion zone (I) of riser reactor (2) and is contacted with the first regenerated catalyst and carry out the first catalytic conversion reaction, obtain the first reaction product and half reclaimable catalyst；B, the first reaction product of gained in step a and half reclaimable catalyst are subjected to the second catalytic conversion reaction in second conversion zone (II), obtain the second reaction product and reclaimable catalyst；Wherein, take out the reclaimable catalyst of part half from the middle and lower part of extension diameter section and be sent into regenerator (13) and regenerated, the middle and upper part of extension diameter section or the middle and lower part of second conversion zone (II) of riser reactor (2) are sent into using the partial regeneration agent in regenerator (13) as the second regenerated catalyst.The catalysis conversion method of the present invention can improve the conversion ratio of catalyzed conversion.
Description
Technical field
The present invention relates to a kind of catalysis conversion method of inferior feedstock oil.
Background technology
Crude quality with being continuously increased for oil extraction amount and worse and worse, is mainly manifested in oil density and becomes big, glue
Degree uprises, and content of beary metal, sulfur content, nitrogen content, resin and asphalt content and acid number uprise.At present, crude oil with poor quality with it is excellent
The price difference of matter crude oil is also increasing with the shortage of petroleum resources, causes cheap crude oil with poor quality to exploit and process
Method increasingly attracts attention, that is to say, that improves the yield of light oil as much as possible from crude oil with poor quality, this gives traditional original
Oily process technology brings huge challenge.
Catalytic cracking is the important technical of petroleum heavy cut processing, is occupied considerablely in petroleum refining industry
Position.Existing fluidized catalytic cracker so far uses riser reactor mostly.Length of tube is lifted typically 30~36
Between rice.In riser fluid catalytic cracking, feedstock oil and catalyst enter from the bottom of riser, along the up hair of riser
Raw reaction, then leaves from riser top exit.Catalyst constantly has coke generation simultaneously during rising along riser
It is deposited on catalyst surface active center, is gradually reduced catalyst activity.Activity has been at the half of riser height
More than half is lost, the activity at leg outlet only reaches 1/3rd of initial activity or so.Therefore, in lifting tube reaction
Second half section catalytic action be deteriorated.Because riser second half section temperature is still higher, exacerbate to product selectivity and product property
The effect of unfavorable heat cracking reaction, cause dry gas and coke yield height, yield of light oil is low, catalytic gasoline olefin(e) centent mistake
Height, requirement of the new gasoline standard to its olefin(e) centent can not be met.
Chinese patent CN1302843A is disclosed a kind of " catalytic cracking process with two-segment lift pipe ", and the technology is by riser
It is divided into two sections, the first reacting section catalyst comes from regenerator, and reaction terminates rear catalyst with oil gas at the first conversion zone end
End separation, oil gas react into second segment.The catalyst of second conversion zone is to take heat by external warmer from regenerator
Regenerated catalyst, with the higher regenerative agent of the activity catalyst that all the first conversion zone of displacement is inactivated due to coke part.Pass through
The riser reactor of two-part realizes oil gas series connection, catalyst relay, segmentation reaction, shortening reaction time and improves catalyst
The purpose of average behavior, but the mode of patent whole displacement catalyst reduces the utilization ratio of catalyst, and riser
Centre must increase separation equipment, complicate technological process, add operation difficulty.Meanwhile in process residual oils, there is also
Settler coking is serious, and coke and dry gas yied are high, and whole product distribution also tends to deteriorate.
Chinese patent CN1226388A discloses a kind of riser catalytic cracking method and apparatus, device disclosed in the patent
Including riser reactor, the first regenerator and Second reactivator.Riser reactor is divided into two sections, in riser reactor
Portion is provided with middle part catalyst inlet, and two sections of catalyst transports are provided between middle part catalyst inlet and Second reactivator, lifting
One section of catalyst transport is provided between pipe reactor bottom catalyst inlet and the first regenerator, under the catalyst inlet of middle part
Riser reactor form the first conversion zone, the riser reactor on the catalyst inlet of middle part forms the second conversion zone.
Compared to patent CN1302843A, although the patent improves the utilization ratio of catalyst, eliminated among riser reactor
Separation equipment, but the investment of regenerator is added, energy consumption is added, and the second conversion zone can not flexible modulation control.
Chinese patent CN102925207A discloses a kind of catalytic cracking unit of processing heavy oil, is to carry the characteristics of the device
Riser device is divided into main riser and secondary riser two parts, and secondary riser top is connected with the middle and upper part of main riser, and two
Person axis is not at grade.Main riser is the riser of reducing, and middle part is extension diameter section, and top is radially main riser
Lower lift pipe etc. is big or the outlet section that reduces.Inferior raw material and quality raw materials are separated cracking by the device, are advantageous to drop
Low coke and dry gas yied, improve light oil yield.But set two risers to add operating cost, and to riser
Linear speed has higher control requirement.
Chinese patent CN1237477A discloses a kind of riser reactor for fluidized catalytic conversion, and the patent will carry
Riser reactors are vertically divided into pre lift zone coaxial each other successively, the first reaction zone, enlarged-diameter from bottom to up
Second reaction zone, the outlet area that reduces of diameter.The reactor can control former in the first and second reaction zone flexible modulations
Different reaction types occurs for material, and structure of reactor is simple, without excessively being changed to original device.But the patent without
Method solves the problems, such as riser reaction zone second half section catalyst activity variation, is difficult to when processing inferior feedstock oil higher
Light oil yield and preferable gasoline quality.
In addition, being the high nitrogen of few sulphur compared with the crude oil of foreign countries, the characteristics of crude oil in China, the mass fraction of nitrogen is general in crude oil
More than 0.3%, and more than 80% is distributed in inside heavy oil.In recent years in order to expand the raw material sources of FCC apparatus, more and more
Mix refining heavy charge in refinery so that the nitrogen content in raw material is continuously increased.Nitrogen-containing compound in oil gives PETROLEUM PROCESSING technique
Many detrimental effects are brought with the performance of product：Basic nitrogen compound in FCC feedstock can with the acidity of catalyst
Hearty cord closes, and reduces catalyst activity, causes conversion ratio to reduce, green coke increase, and influences product liquid distribution；Fuel oil and lubrication
Even if containing micro nitrogen-containing compound in oil, also easily form colloid, make oil product discoloration rotten, so as to influence the quality of product and
Stability in storage；Nitrogen-containing compound can etching apparatus in oil product storage or transport；The nitrogen oxides row that nitrogenous fuel combustion is formed
It is put into air and pollutes the environment；Caused NOx causes environmental pollution in catalyst regeneration process.So in environmental requirement and
Under the increasingly strict situation of petroleum product-quality standard, research adapts to catalytic cracking or the catalytic conversion technique day of high-nitrogen raw oil
Benefit is taken seriously.
United States Patent (USP) US4090948 discloses a kind of catalyst cracking method for processing high-nitrogen stock, by high-nitrogen stock first
Contacted with the reclaimable catalyst drawn from stripping section, so that the accumulation of pollutants such as nitride, metal in feedstock oil is to be generated
Catalyst surface, the hydro carbons not reacted completely and reclaimable catalyst mixture again with from regenerator come regenerated catalyst contact into
Single step reaction, the inactivation of regenerated catalyst can be mitigated in this way.
United States Patent (USP) US4436613 discloses a kind of method that high-nitrogen stock is handled using two-stage catalytic cracking process,
First order catalyst cracker is by high-nitrogen stock and low activity catalyst (reclaimable catalyst and the mixture of regenerated catalyst)
Contact, so as to remove the pollutants such as the nitrogen compound of catalyst, heavy metal；Enter knockout drum after obtained reaction oil gas cooling,
The second stage reactor is refilled with pump after mink cell focus is heated, with high activated catalyst (regenerated catalyst and fresh catalyst
Mixture) contact carry out high severity cracking reaction.
United States Patent (USP) US5051163 discloses a kind of catalytic cracking process of resistance to high-nitrogen stock, the regeneration from regenerator
Catalyst is partly into pre-contact area, is reacted with high-nitrogen stock pre-contact, and then oil gas and reclaimable catalyst together enter anti-
Area is answered, with another part regenerated catalyst haptoreaction.After reaction oil gas separates with reclaimable catalyst, reclaimable catalyst goes to regenerate
Device regeneration Posterior circle uses, and reaction oil gas enters following process process.This method can be lowered into the nitrogen of the raw material of reaction zone
Content, so as to reduce product nitrogen content, but the activity of a part of regenerated catalyst is sacrificed, drop the oil ratio of reaction zone
It is low, it is unfavorable for cracking reaction.
United States Patent (USP) US5660716 discloses a kind of catalytic cracking process and equipment for processing high alkalinity nitrogen raw material, the work
Skill is using downstriker lifting Manifold technology, raw material and the regenerated catalyst contact for coming autoreactor top, under gravity along anti-
Device is answered to flow downward and react, in reactor bottom Oil-gas Separation, the reclaimable catalyst after stripping is in the presence of gas is lifted
Regenerator regeneration Posterior circle is moved upwardly into use.Using the technology, can add under the conditions of suitable Hydrocarbon Content by Catalytic Cracking Operation
FCC feedstock of the work basic n content between 0.035%~0.13wt%.
United States Patent (USP) US6149875 discloses the catalytic cracking process and equipment of a kind of high-nitrogen stock, first high-nitrogen stock
With adsorbent haptoreaction, the pollutant such as nitrogenous, sulphur in high-nitrogen stock is removed, it is anti-then with regenerated catalyst to carry out cracking again
Should, reacted adsorbent and reclaimable catalyst are latter with separator is delivered to through stripping, and adsorbent and catalysis are utilized in separator
The density difference of agent is delivered to independent regenerator regeneration Posterior circle and used respectively after both are separated.United States Patent (USP) US7008595
Also disclose that similar catalytic cracking process and equipment, itself main difference is that the separation of reclaimable catalyst and adsorbent be
Completed in stripper, separate in stripper and followed after delivering to independent regenerator regeneration respectively after reclaimable catalyst and adsorbent
Ring uses.
United States Patent (USP) US7744745B2 discloses a kind of technique using double lift pipe catalytic cracking high-nitrogen stock and set
Standby, the technique has a duo-lift tube reactor system of shared catalyst stripping equipment and regenerator, and regenerated catalyst is from regeneration
Device respectively enters two riser reactors after coming out, using main reactor processing high grade raw material, with the high nitrogen of auxiliary reactor cracking
Raw material, both nitrogen content difference are at least above 0.02wt%.
Chinese patent CN1088246A discloses a kind of catalyst cracking method for processing high-nitrogen stock, is by two kinds of feedstock oils
The not blended different parts for being injected separately into same reactor, quality raw materials are entered into reactor bottom and from regenerator
Regenerated catalyst contact, reaction, up, high-nitrogen stock a certain position injection among reactor, after cracking quality raw materials
Band Pd/carbon catalyst contacts, so as to mitigate murder by poisoning of the nitride to catalyst in high-nitrogen stock.
Chinese patent CN103031147A applications disclose a kind of catalysis that high-nitrogen stock is processed on reducing riser and turned
Change method, high-nitrogen stock are contacted in the first reaction zone with the regenerated catalyst of relatively lower temp, reacted, up, institute's shape first
Into oil agent mixture enter second reaction zone (expanding) and contact continuation with the regenerated catalyst of higher temperature from regenerator
Cracking reaction, gas solid separation behind the reacted device outlet of oil agent mixture come out from second reaction zone, the band charcoal catalysis isolated
Agent uses through stripping, coke burning regeneration Posterior circle, and the reaction oil gas isolated delivers to subsequent product piece-rate system.
The content of the invention
It is an object of the invention to provide a kind of catalysis conversion method of inferior feedstock oil, the catalysis conversion method can improve
The conversion ratio of catalyzed conversion.
To achieve these goals, the present invention provides a kind of catalysis conversion method of inferior feedstock oil, and this method includes：a、
By the inferior feedstock oil of preheating from the lifting for including pre lift zone, the first conversion zone, extension diameter section and the second conversion zone from the bottom to top
The middle and lower part of first conversion zone of pipe reactor is sent into riser reactor with being transported to the first of pre lift zone from regenerator
Regenerated catalyst contacts and carries out the first catalytic conversion reaction in first conversion zone, obtains the first reaction product and partly treats
Raw catalyst；B, the first reaction product of gained and half reclaimable catalyst in step a are continued into up, warp in riser reactor
The second catalytic conversion reaction is carried out in second conversion zone after crossing the extension diameter section, the second reaction is obtained after gas solid separation
Product and reclaimable catalyst, the second reaction product is sent into subsequent separation system, reclaimable catalyst is sent into the regenerator and entered
Row regeneration；Wherein, take out the reclaimable catalyst of part half from the middle and lower part of the extension diameter section and be sent into the regenerator and regenerated,
It is sent into using the partial regeneration agent in the regenerator as the second regenerated catalyst in the extension diameter section of riser reactor
Top or the middle and lower part of second conversion zone.
Preferably, the extension diameter section includes the first extension diameter section and close to the second extension diameter section above the first extension diameter section, from institute
The middle and lower part taking-up reclaimable catalyst of the part half feeding regenerator for stating the first extension diameter section is regenerated, by the regenerator
Partial regeneration agent be sent into as the second regenerated catalyst in second extension diameter section.
Preferably, this method also includes：Under lightweight material oil and/or cold shock medium are sent into second conversion zone
Portion and first reaction product, remaining half reclaimable catalyst and the second regenerated catalyst mix after in second conversion zone
Second catalytic conversion reaction described in middle progress step b；Wherein, the lightweight material oil is selected from liquefied gas, gasoline and diesel oil
At least one of, the cold shock medium be in liquefied gas, raw gasoline, stable gasoline, diesel oil, heavy diesel fuel and water at least
It is a kind of.
Preferably, the condition of the first catalytic conversion reaction includes described in step a：Temperature is 500-600 DEG C, and the time is
0.05-1.5 seconds, oil ratio are (3-15)：1, water-oil factor is (0.03-0.3)：1, pressure is 130-450 kPas；Institute in step b
Stating the condition of the second catalytic conversion reaction includes：Temperature is 420-550 DEG C, and the time is the 1.5-20 seconds.
Preferably, by weight, the described of 1-20 weight % for accounting for catalyst internal circulating load in riser reactor is partly treated
Raw catalyst takes out from the extension diameter section, will account for described the second of the 1-20 weight % of catalyst internal circulating load in riser reactor
Regenerated catalyst is sent into the riser reactor.
Preferably, the inferior feedstock oil is selected from decompression residuum, reduced crude, hydrogenated residue, coker gas oil, de- drip
At least one of blue or green oily, high carbon residue crude oil, viscous crude, super-viscous oil, liquefied coal coil, tar sand oil and shale oil.
Preferably, carrying out the catalyst of first catalytic conversion reaction and the second catalytic conversion reaction includes zeolite, nothing
Machine oxide and optional clay；Counted by butt and on the basis of the weight of the catalyst, the content of the zeolite is 1-50
Weight %, the content of inorganic oxide is 5-99 weight %, and the content of clay is 0-70 weights %；The zeolite is selected from ZSM-5, ZSM-
11st, in ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZRP, Rare Earth Y, rare earth hydrogen Y, super steady Y and high silicon Y at least
One kind, the inorganic oxide are silica and/or aluminum oxide, and the clay is kaolin and/or halloysite.
Preferably, this method also includes：By the inferior feedstock oil be sent into the middle and lower part of second conversion zone with it is described
Walked after first reaction product, remaining half reclaimable catalyst and the mixing of the second regenerated catalyst in second conversion zone
Second catalytic conversion reaction described in rapid b；Wherein, it is sent into from the middle and lower part of second conversion zone in the riser reactor
The weight for carrying out the inferior feedstock oil of second catalytic conversion reaction accounts for the inferior raw material being sent into the riser reactor
Oily gross weight is more than zero to 50 heavy %.
Preferably, the condition of first catalytic conversion reaction and the second catalytic conversion reaction includes independently of one another：Temperature
Spend for 460-580 DEG C, the time is the 0.1-8.0 seconds, and oil ratio is (2-25)：1, water-oil factor is (0.05-1.0)：1, pressure is
0.2-1.0 MPas.
Preferably, the inferior feedstock oil includes total nitrogen content higher than 0.15 weight % or basic n content is higher than 0.05 heavy %
High-nitrogen raw oil, the high-nitrogen raw oil be selected from decompressed wax oil, extract oil, recycle oil inferior, wax tailings, depitching
At least one of oil, crude oil, tar sand oil and shale oil.
Preferably, it is molecular sieve to carry out first catalytic conversion reaction and the catalyst of second catalytic conversion reaction
Catalyst and/or amorphous silicon Al catalysts, the molecular sieve in the molecular sieve catalyst include selected from Y, REY, HY, USY,
At least one of REUSY, ZSM-5 and five-membered ring silica-rich zeolite.
Compared with prior art, advantages of the present invention is as follows：
1st, the present invention takes out the reclaimable catalyst of part half by extension diameter section, then supplements the regenerated catalyst of part second, carries
The high catalyst activity of riser reactor second half section, the ratio of catalytic conversion reaction and heat cracking reaction is improved, simultaneously
The activity of catalyst is taken full advantage of again, can improve the conversion ratio of inferior feedstock oil, reduces the yield of coke and dry gas.
2nd, it can control and take reactor reaction condition before and after agent and tonic, realize and strengthen different reaction types, realize
Reduce content of olefin in gasoline and improve the purpose of yield of gasoline and octane number.
3rd, the feedstock oil of identical or different property can be made to carry out segmentation cracking, reaction depth is controlled, realize purpose product
High yield and high quality.
4th, the present invention reduces the linear speed of catalyst in extension diameter section, extends the reaction time, while facilitate catalyst to take out.
5th, inferior feedstock oil used in the present invention can be high-nitrogen raw oil, and high-nitrogen raw oil is first in the first conversion zone
Contacted with the first regenerated catalyst of high activity and carry out the first catalytic conversion reaction, make the nitrogen in high-nitrogen raw oil
A large amount of acid centre haptoreactions on compound and the first regenerated catalyst, so that most of nitrogen in high-nitrogen raw oil
Compound is removed substantially in the first conversion zone.The first reaction product formed is up to extension diameter section taking-up with half reclaimable catalyst
The reclaimable catalyst of part half, the regenerated catalyst of part second is then supplemented, under conditions of reaction severity is not changed, high activity
The supplement of second regenerated catalyst can significantly improve the reaction conversion level of high-nitrogen raw oil, improve the choosing of catalytic conversion reaction
Selecting property, undesirable thermal cracking is reduced, so as to be produced the purpose of improving the conversion ratio of high-nitrogen stock and product selectivity, improve gasoline
The yield of product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a 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 includes a kind of structural representation of embodiment of used riser reactor of the present invention, also wraps
Include a kind of schematic flow sheet of embodiment of the inventive method.
Fig. 2 includes the structural representation of the used riser reactor another kind embodiment of the present invention,
The schematic flow sheet of another embodiment including the inventive method.
Description of reference numerals
The pipeline of 1 pipeline, 2 riser reactor 3
The pipeline of 4 pipeline, 5 pipeline 6
The collection chamber of 7 outlet section, 8 settling section 9
The inclined tube of 10 stripping section, 11 pipeline 12
The pipeline of 13 regenerator, 14 pipeline 15
The pipeline of 16 inclined tube, 17 pipeline 18
19 pipelines
I the first conversion zone II the second conversion zone the first extension diameter sections of III
The extension diameter sections of III' second
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As shown in Figure 1-2, the present invention provides a kind of catalysis conversion method of inferior feedstock oil, and this method includes：A, will be pre-
The inferior feedstock oil of heat is from the riser for including pre lift zone, the first conversion zone I, extension diameter section and the second conversion zone II from the bottom to top
First conversion zone I of reactor 2 middle and lower part is sent into riser reactor 2 with being transported to the of pre lift zone from regenerator 13
One regenerated catalyst contact simultaneously carry out the first catalytic conversion reaction in the first conversion zone I, obtain the first reaction product and
Half reclaimable catalyst；B, by the first reaction product of gained in step a and on half reclaimable catalyst continues in riser reactor 2
OK, the second catalytic conversion reaction is carried out in the second conversion zone II after the extension diameter section, is obtained after gas solid separation
Second reaction product and reclaimable catalyst, the second reaction product is sent into subsequent separation system, reclaimable catalyst is sent into described in
Regenerator 13 is regenerated；Wherein, take out the reclaimable catalyst of part half from the middle and lower part of the extension diameter section and be sent into the regenerator
Regenerated in 13, send the partial regeneration agent in the regenerator 13 as the second regenerated catalyst into riser reactor 2
The middle and upper part of the extension diameter section or the middle and lower part of the second conversion zone II.
According to the present invention, as shown in Fig. 2 the extension diameter section can include the first extension diameter section III and close to the first extension diameter section
The second extension diameter section III' above III, the reclaimable catalyst of part half can be taken out from the middle and lower part of the first extension diameter section III and sent
Enter the regenerator 13 to be regenerated, the partial regeneration agent in the regenerator 13 can be sent into as the second regenerated catalyst
In the second extension diameter section III'.Close to the first extension diameter section III and the second extension diameter section III' between can be provided with one section of contracting
Footpath section, the effect of the undergauge section are to separate the first extension diameter section III and the second extension diameter section III', prevent from coming from the second extension diameter section III'
The second regenerated catalyst leave riser reactor from the first extension diameter section III, lived beneficial to each section of oil ratio and catalyst is maintained
Property, ensure response intensity.The ratio between the internal diameter of the undergauge section and the first extension diameter section III internal diameter can be 1：(1.2-5.0), the contracting
The length of footpath section can be that (0% refers to and is not provided with undergauge section, the first extension diameter section and the second expansion by the 0-5% of the height of riser reactor 2
Footpath section can be joined directly together by the linkage section of truncated cone-shaped).
According to the present invention, in order to which more efficient processes raw material and controlled temperature, this method can also include：Lightweight is former
Material oil and/or cold shock medium are sent into the middle and lower part of the second conversion zone II and first reaction product, remaining half to be generated urged
It is anti-that the second catalyzed conversion described in step b is carried out in the second conversion zone II after agent and the mixing of the second regenerated catalyst
Should；Wherein, the lightweight material oil can be that the cold shock medium can selected from least one of liquefied gas, gasoline and diesel oil
Think selected from least one of liquefied gas, raw gasoline, stable gasoline, diesel oil, heavy diesel fuel and water.Lightweight material oil and cold shock are situated between
The composition of matter be able to can also be differed with identical, and the effect of cold shock medium is the temperature for controlling outlet section and subsequent reactions,
Such as can be normal temperature, lightweight material oil can be re-fed into after preheating in the outlet section 7.Lightweight material oil and/or
In cold shock medium, liquefied gas can be the liquefied gas obtained by the inventive method and/or the liquefied gas obtained by other methods, can also
It is a certain component in liquefied gas, for example, propane and C4Hydrocarbon；Gasoline can be gasoline and/or other sides obtained by the inventive method
Gasoline obtained by method；Diesel oil can be diesel oil obtained by the inventive method and/or the diesel oil obtained by other methods；Gasoline and diesel oil
Boiling range can be adjusted according to actual needs, be not limited only to full range gasoline or diesel oil.
According to the present invention, catalyzed conversion is well-known to those skilled in the art, and the present invention repeats no more.Institute in step a
It is mainly macromolecular cracking reaction to state the first catalytic conversion reaction, to remove in metal in inferior feedstock oil, sulphur, nitrogen and aphthenic acids
At least one impurity, its condition can include：Temperature be 500-600 DEG C, preferably 520-580 DEG C, time 0.05-1.0
Second, preferably 0.1-0.5 seconds, oil ratio are (3-15)：1, be preferably (4-12):1, water-oil factor is (0.03-0.3)：1, preferably
For (0.05-0.2):1, pressure is 130-450 kPas；First conversion zone I gas velocity can be that the meter per second of 2 meter per second -30 (is disregarded and urged
Agent).Second catalytic conversion reaction described in step b is mainly cracking reaction, hydrogen transfer reaction and isomerization reaction, its condition
It can include：Temperature is 420-550 DEG C, and preferably 460-530 DEG C, the time is the 1.5-20 seconds, and preferably 2-10 seconds, oil ratio is
(3-20)：1, water-oil factor 0.03-0.8：1.According to the difference of reaction raw materials, first catalytic conversion reaction and the second catalysis
The condition of conversion reaction can also include independently of one another：Temperature be 460-580 DEG C, preferably 480-540 DEG C, time 0.1-
8.0 seconds, preferably 1-4 seconds, oil ratio are (2-25)：1, be preferably (4-15)：1, water-oil factor is (0.05-1.0)：1, be preferably
(0.1-0.5):1, pressure is 0.2-1.0 MPas, preferably 0.2-0.5 MPas.
According to the present invention, taking out the reclaimable catalyst of part half in extension diameter section, (carbon content of half reclaimable catalyst can be
0.1-0.9 weight %, preferably 0.15-0.7 weights %), it is supplemented part second in extension diameter section middle and upper part or the second conversion zone and regenerates
Catalyst, on the premise of reaction severity is not increased, the raising of catalyst activity can significantly improve turning for inferior feedstock oil
Change depth；Meanwhile the second regenerated catalyst of supplement is advantageous to strengthen the second catalytic conversion reaction, and it is anti-to improve the second catalyzed conversion
The selectivity answered, the product yield such as liquefied gas and gasoline is improved, reduces undesirable thermal cracking.In stepb, by weight,
The 1-50 weight % of catalyst internal circulating load in riser reactor can will be accounted for, 1-20 weight % is preferably accounted for, more preferably accounts for 5-10
Weight % half reclaimable catalyst takes out from the extension diameter section, can will account for the 1-50 of catalyst internal circulating load in riser reactor
Weight %, 1-20 weight % are preferably accounted for, second regenerated catalyst for more preferably accounting for 5-10 weight % is sent into the riser
In reactor.For the ease of taking out half reclaimable catalyst, half reclaimable catalyst can be 0.05-0.5 in the extension diameter section residence time
Second, preferably 0.1-0.3 seconds.The catalyst internal circulating load be it is well-known to those skilled in the art, can use thermal balance and
The method of carbon (material) balance is measured.
According to the present invention, inferior feedstock oil is known to those skilled in the art, for example, being distinguished from source, can be attached most importance to
Matter petroleum hydrocarbon and/or other mineral oil, wherein heavy petroleum hydrocarbon can be selected from decompression residuum (VR), reduced crude (AR), add
At least one of hydrogen residual oil, coker gas oil, deasphalted oil, high carbon residue crude oil, viscous crude and super-viscous oil；Other mineral oil can be with
For selected from least one of liquefied coal coil, tar sand oil and shale oil.Distinguished from performance indications, the inferior feedstock oil it is close
Degree can be 900-1000 kgs/m3, preferably 930-960 kgs/m3, carbon residue can be 4-15 weights %, preferably 6-12
Weight %, tenor can be 15-600ppm, preferably 15-100ppm, and acid number can be 0.5-20.0mgKOH/g, be preferably
0.5-10.0mgKOH/g.The inferior feedstock oil can also include total nitrogen content higher than 0.15 weight % or basic n content is higher than
0.05 weight % high-nitrogen raw oil, the high-nitrogen raw oil can be selected from decompressed wax oil, extract oil, recycle oil inferior, coking
At least one of wax oil, deasphalted oil, crude oil, tar sand oil and shale oil.The basic n content refers to basic nitrogen compound
Content, the nitrogen-containing compound in oil can be divided into basic nitrogen compound and non basic nitrogen compound, alkali nitride by its acid-base property
Thing refers to the nitride that can be extracted in petroleum refining process by 10% sulfuric acid, and these nitride have certain alkalescence,
Can with strong acid forming salt and be dissolved in acid, therefore can be extracted from oil reservoir to acid layer.Another division methods are：In glacial acetic acid and benzene
Sample solution in the nitrogen-containing compound that can be titrated by homo amino acid glacial acetic acid, referred to as basic nitrogen compound, it is impossible to titrated title
For non basic nitrogen compound, the present invention uses second of division methods.
According to the present invention, the catalyst for carrying out first catalytic conversion reaction and/or the second catalytic conversion reaction can be with
Including zeolite, inorganic oxide and optional clay；Counted by butt and on the basis of the weight of the catalyst, the zeolite contains
Amount can be 1-50 weight %, and the content of inorganic oxide can be 5-99 weight %, and the content of clay can be 0-70 weights %.Wherein
Described zeolite can be mesopore zeolite and/or optional large pore zeolite, it is total that mesopore zeolite can account for zeolite as active component
The 0-50 weight % of weight, preferably account for 0-20 weight %, and large pore zeolite can account for the 0-100 weight % of zeolite gross weight, preferably account for 20-80
Weight %.Mesopore zeolite can be ZSM series zeolites and/or ZRP zeolites, and can be to nonmetalloids such as above-mentioned mesopore zeolite phosphorus
And/or the transition metal such as iron, cobalt, nickel is modified, more description may refer to United States Patent (USP) to relevant ZRP zeolites in detail
US5,232,675, ZSM series zeolites can be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38,
One or more kinds of mixtures among the zeolite of ZSM-48 and other similar structures, relevant ZSM-5 are more retouched in detail
State and may refer to United States Patent (USP) US3,702,886.Large pore zeolite can be selected from by Rare Earth Y (REY), rare earth hydrogen Y (REHY), no
One or more kinds of mixtures in the zeolite that super steady Y, the high silicon Y obtained with method is formed.Preferably, the zeolite can
Think selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZRP, Rare Earth Y, rare earth hydrogen Y, super
Steady at least one of Y and high silicon Y.Inorganic oxide can be selected from silica (SiO as bonding agent2) and/or aluminum oxide
(Al2O3), clay can be kaolin and/or halloysite as matrix (i.e. carrier).In addition, in order to adapt to different material
The catalyzed conversion of oil, such as high-nitrogen raw oil, progress first catalytic conversion reaction and second catalytic conversion reaction
Catalyst can also be molecular sieve catalyst and/or amorphous silicon Al catalysts, and the molecular sieve in the molecular sieve catalyst can
With including selected from least one of Y, REY, HY, USY, REUSY, ZSM-5 and five-membered ring silica-rich zeolite.
According to the present invention, the catalyst for carrying out first catalytic conversion reaction and/or the second catalytic conversion reaction also may be used
Be used in Conventional catalytic reforming unit give up equilibrium catalyst.
According to the present invention, the first catalytic conversion reaction and the second catalytic conversion reaction of the invention can be applicable same type of
Catalyst, can also be applied different type catalyst, different type catalyst can be the different catalyst of granular size and/or
The different catalyst of apparent bulk density.On the different catalyst of granular size and/or the different catalyst of apparent bulk density
Active component can also select different type zeolite respectively.The catalyst and/or height apparent bulk density of particle of different sizes
Catalyst can respectively enter different conversion zones, for example, the catalyst of the bulky grain containing ultrastable enter first
Conversion zone, increase cracking reaction, the short grained catalyst containing rare earth Y type zeolite enters the second conversion zone, increases hydrogen migration
Reaction, the different catalyst of granular size same stripping section stripping and same regenerator regeneration, be then demultiplex out bulky grain and
Catalyst particle, catalyst particle enter the second conversion zone through cooling.The different catalyst of granular size can be in 30-40
A certain particle diameter boundary in micron, the different catalyst of apparent bulk density can be in 0.6-0.7g/cm3In a certain density point
Boundary.
According to the present invention, in order to more efficiently process inferior feedstock oil, this method can also include：By the inferior raw material
Oil is sent into middle and lower part and first reaction product, remaining half reclaimable catalyst and the second regeneration of the second conversion zone II
The second catalytic conversion reaction described in step b is carried out in the second conversion zone II after catalyst mixing；Wherein, from described
The inferior feedstock oil for carrying out second catalytic conversion reaction is sent into the riser reactor 2 in two conversion zone II middle and lower part
Weight account for the inferior feedstock oil gross weight be sent into the riser reactor 2 be more than zero to 50 heavy %, preferably account for and be more than
Zero to 30 heavy %.
The occupation mode of catalytic conversion reactor provided by the invention is illustrated below in conjunction with the accompanying drawings, but not because
This and limit the present invention.
As shown in figure 1, pre-lift medium is entered through pipeline 1 by the bottom of riser reactor 2, first from pipeline 16 is again
Raw catalyst moves upwards under the castering action of pre-lift medium along riser reactor, and inferior feedstock oil is through pipeline 3 with coming
It is existing with riser reactor from the bottom of the atomizing steam of the pipeline 4 together conversion zone I of injecting lift pipe reactor 2 first
Logistics mixes, and in the first regenerated catalyst of heat the first catalytic conversion reaction occurs for inferior feedstock oil, and moves upwards.
The first extension diameter section III, half catalysis to be generated of part are advanced on first reaction product of generation and half reclaimable catalyst
Agent is sent into regenerator 13 through pipeline 18 and regenerated；First reaction product and remaining half reclaimable catalyst are in the first extension diameter section III
Exit the second conversion zone II middle and lower part mixes and up with the second regenerated catalyst from pipeline 19.Lightweight material oil
And/or cold shock medium through pipeline 5 the conversion zone II of injecting lift pipe reactor 2 second together with the atomizing steam from pipeline 6
Bottom, mixed with the existing logistics of riser reactor, lightweight material oil and/or cold shock medium and the first reaction product are in product
The second catalytic conversion reaction occurs in the second relatively low regenerated catalyst of charcoal amount, and moves upwards, the second reaction product of generation
The cyclone separator entered with reclaimable catalyst through outlet section 7 in settling section 8, realize reclaimable catalyst and the second reaction product
Separation, the second reaction product enter collection chamber 9, and reclaimable catalyst returns to settling section by dipleg.Reclaimable catalyst stream in settling section
To stripping section 10, contacted with the steam from pipeline 11.The oil gas being stripped off from reclaimable catalyst is laggard through cyclone separator
Enter collection chamber 9, the oil gas in collection chamber 9 enters follow-up product separation system by main oil gas piping 17.It is to be generated after stripping
Catalyst enters regenerator 13 through inclined tube 12, and main wind enters regenerator through pipeline 14, the coke on burning-off reclaimable catalyst, makes mistake
Reclaimable catalyst regeneration living, flue gas enter cigarette machine through pipeline 15, and regenerative agent enters riser reactor 2 through inclined tube 16.
As shown in Fig. 2 pre-lift medium is entered through pipeline 1 by the bottom of riser reactor 2, first from inclined tube 16 is again
Raw catalyst accelerates upwards under the castering action of pre-lift medium along riser reactor 2, part high-nitrogen raw oil warp
Pipeline 3 injects the first conversion zone I together with the atomizing steam from pipeline 4, is mixed with 2 existing logistics of riser reactor,
First catalytic conversion reaction occurs in the first regenerated catalyst for high-nitrogen raw oil, and moves upwards.First reaction production of generation
The first extension diameter section III is advanced on thing and half reclaimable catalyst, the reclaimable catalyst of which part half leaves riser through pipeline 18
Reactor 2 is regenerated into regenerator 13, the first reaction product and remaining half reclaimable catalyst continue on be advanced into the second extension diameter section
III', mixed with the second regenerated catalyst (coming to regenerator 13, conveyed by pipeline 19) of supplement.Another part high-nitrogen stock
Oil through pipeline 5 together with the atomizing steam from pipeline 6 from above the second extension diameter section III' the second conversion zone II bottoms it is a certain
Position enters the second conversion zone II, is mixed with 2 existing logistics of riser reactor, high-nitrogen raw oil it is relatively low containing charcoal second
The second catalytic conversion reaction occurs in regenerated catalyst, the second reaction product of generation and the reclaimable catalyst of inactivation are anti-through second
The gas-solid separator for answering section II top exit to enter in settling section 8, realizes the separation of reclaimable catalyst and the second reaction product,
Second reaction product enters collection chamber 9, and reclaimable catalyst returns to settling section 8 by dipleg.Reclaimable catalyst flows to vapour in settling section 8
Section 10 is put forward, is contacted with the steam from pipeline 11.The oil gas being stripped off from reclaimable catalyst enters collection after gas-solid separator
Air chamber 9.Reclaimable catalyst after stripping regenerates through inclined tube 12 into regenerator 13, the coke on burning-off reclaimable catalyst, makes mistake
Reclaimable catalyst regeneration living, regenerative agent enter riser reactor 2 through inclined tube 16.
In above embodiment, pre-lift medium can be selected from least one of water vapour, dry gas and nitrogen.
150 DEG C -400 DEG C will be preheating to, be preferably preheating to 180 DEG C -380 DEG C inferior feedstock oil or high-nitrogen raw oil in pre-lift medium
In the presence of flow up and the first regenerated catalyst haptoreaction.The temperature for the first regenerated catalyst being sent into from pre lift zone
It can be 600 DEG C -800 DEG C, the temperature of the second regenerated catalyst of riser reactor is entered from extension diameter section or the second conversion zone
For 600 DEG C -800 DEG C, the first regenerated catalyst and the second regenerated catalyst can come from regenerator 13.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction.
The embodiment of the present invention and comparative example octane number are determined using RIPP 85-90 methods, and gasoline PIONA compositions use vapour
Oily detailed hydrocarbon analysis measure.
Reaction product obtained by the embodiment of the present invention and comparative example is dry gas, liquefied gas, gasoline, slurry oil, coke and diesel oil, instead
Answer product distribution plus and for 100%, conversion ratio is the yield sum of dry gas, liquefied gas, gasoline and coke.
RIPP standard methods of the present invention for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, and 1990
Year version.
Raw material used is decompression residuum A and decompression residuum B in 1-2 of the embodiment of the present invention and comparative example 1-2, and its property is such as
Shown in table 1.
The embodiment of the present invention 3 and comparative example 3 it is raw materials used be wax tailings and decompressed wax oil, specific nature is as shown in table 5.
Catalytic converting catalyst GZ-1 preparation methods used are following (property is listed in table 2) in embodiment 1-2：
1), by 20gNH4Cl is dissolved in 1000g water, is boiled to addition 100g (butt) crystallization product ZRP-1 in solution is obtained
Stone (Qilu Petrochemical Company's catalyst plant production, SiO2/Al2O3=30, content of rare earth RE2O3=2.0 heavy %), in 90 DEG C of exchanges
After 0.5h, filter cake is filtered to obtain；Add 4.0g H3PO4(concentration 85%) and 4.5g Fe (NO3)3It is dissolved in 90g water, is mixed with filter cake
Close dipping drying；Then handled in 550 DEG C of roasting temperatures and obtain within 2 hours phosphorous and iron MFI structure mesopore zeolite, its element
Analytical chemistry composition is 0.1Na2O·5.1Al2O3·2.4P2O5·1.5Fe2O3·3.8RE2O3·88.1SiO2。
2), with 250 kilograms of decationized Y sieve water by 75.4 kilograms of halloysites (Suzhou china clay company industrial products, admittedly contain
Measure 71.6 heavy %) mashing, 54.8 kilograms of boehmites (Shandong Aluminum Plant's industrial products, 63 heavy % of solid content) are added, use salt
Its pH is adjusted to 2-4 by acid, is stirred, and aging 1 hour is stood at 60-70 DEG C, holding pH is 2-4, cools the temperature to 60 DEG C
Hereinafter, 41.5 kilograms of Alumina gels (Qilu Petrochemical Company's catalyst plant product, Al are added2O3Content is 21.7 heavy %), stir 40 points
Clock, obtain mixed serum.
3) the phosphorous and MFI structure mesopore zeolite of iron (butt is 2 kilograms) and DASY zeolites for, preparing step 1)
(Qilu Petrochemical Company's catalyst plant industrial products, lattice constant 2.445-2.448nm, butt are 22.5 kilograms) is added to step
In the rapid mixed serum 2) obtained, stir, spray drying forming, washed with ammonium dihydrogen phosphate (phosphorus content is 1 heavy %)
Wash, wash away free Na+, it is drying to obtain catalytic converting catalyst GZ-1, the composition of the catalyst is 2 weight % are phosphorous and the MFI of iron
Structure mesoporous zeolite, 18 weight %DASY zeolites, 32 weight % boehmites, 7 heavy % Alumina gels and balance kaolin.
MLC-500 catalyst used in comparative example 1-2 of the present invention is by China PetroChemical Corporation's Shandong catalyst plant life
Production, property are listed in table 2.
Catalyst used in the embodiment of the present invention 3 and comparative example 3 is RHZ-200, and specific nature is listed in table 4.
Embodiment 1
The embodiment is tested according to Fig. 1 flow, and decompression residuum A is as inferior feedstock oil, in riser reactor
Middle- scale device (height of riser reactor 2 is 30 meters, and the internal diameter of pre lift zone is 0.8 meter, the height 1.5 of pre lift zone
Rice, the first conversion zone I internal diameters are 1 meter, and the first conversion zone I height is 6 meters, and the first extension diameter section III internal diameter is 3 meters, expanding
Section III height is 1 meter, and the second conversion zone II internal diameters are 1 meter, and the second conversion zone II height is 19 meters, the internal diameter of outlet section 7
For 0.8 meter, the height of outlet section 7 is 2.5 meters, similarly hereinafter) on tested, used catalyst is catalyst GZ-1.Decompression residuum A
Into the first conversion zone I bottoms, contacted with the first regenerated catalyst from pre lift zone and the first catalytic conversion reaction occurs.
In the first conversion zone I, decompression residuum A is in 550 DEG C of reaction temperature, 0.4 second reaction time, oil ratio 6, the bar that water-oil factor is 0.10
The first catalytic conversion reaction, the reaction product of gained first and half reclaimable catalyst is carried out under part to take out into the first extension diameter section III
The reclaimable catalyst of part half, the first reaction product is in the first extension diameter section III 0.1 second residence time, wherein accounting for lifting tube reaction
Half reclaimable catalyst of device internal circulating load 8% sends out the first extension diameter section III and enters regenerator regeneration, the first reaction product, remaining
The second regenerated catalyst for accounting for riser reactor internal circulating load 8% of half reclaimable catalyst and high temperature is mixed into the second conversion zone
II, (external gasoline and decompression residuum A weight ratio are 1 with external gasoline：4) after mixing, in 500 DEG C of reaction temperature, reaction
Between 5 seconds, water-oil factor carry out the second catalytic conversion reaction under the conditions of being 0.05, obtain the second reaction product and reclaimable catalyst heavy
Drop section separation, the second reaction product be sent into piece-rate system cut by boiling range, so as to obtain dry gas, liquefied gas (including propylene,
Propane and C4 hydrocarbon, similarly hereinafter), gasoline, diesel oil and slurry oil.Operating condition and product distribution are listed in table 3.
From table 3 it can be seen that gasoline yield is up to 49.37 heavy %, wherein olefin(e) centent is that 23.26%, RON reaches
93.2, dry gas yied is only 2.26 heavy %, and coke yield is 6.43 heavy %, and slurry oil yield significantly declines.
Comparative example 1
The comparative example is the raw material directly as catalyzed conversion with vacuum residuum feed A, is filled in middle scale riser reactor
Tested on putting and (being not provided with extension diameter section compared with Example 1, do not take agent and tonic), in 500 DEG C of reaction temperature, reaction time
For 2.5 seconds, oil ratio 6, water-oil factor be 0.10 under the conditions of carry out catalytic conversion reaction, reaction product and the reclaimable catalyst with charcoal
Separated in settling section, reaction product is sent into piece-rate system and cut by boiling range, so as to obtain dry gas, liquefied gas, gasoline, bavin
Oil, slurry oil.Operating condition and product distribution are listed in table 3.
From table 3 it can be seen that gasoline yield is 41.40 heavy %, wherein olefin(e) centent is 50.81%, RON 91.0, but
MON is only 75.1, and dry gas yied is up to 4.46 heavy %, and slurry oil yield is up to 9.85 heavy %, coke yield 9.27%.With reality
Apply example 1 to compare, gasoline yield is relatively low, and olefin(e) centent is too high, and the by-product yields of low value are higher, cause petroleum resources to utilize
The reduction of efficiency.
Embodiment 2
The embodiment is tested according to Fig. 1 flow, and decompression residuum B is as inferior feedstock oil, used in embodiment 1
Tested on the middle- scale device of riser reactor, used catalyst is catalyst GZ-1.Decompression residuum A enters the first reaction
Section I bottoms, contact with the first regenerated catalyst from pre lift zone and the first catalytic conversion reaction occur.In the first conversion zone
I, decompression residuum A carry out first under conditions of being 0.12 in 560 DEG C of reaction temperature, 0.4 second reaction time, oil ratio 7, water-oil factor
Catalytic conversion reaction, the reaction product of gained first and half reclaimable catalyst enter the first extension diameter section III and take out that part half is to be generated urges
Agent, the first reaction product is in the first extension diameter section III 0.15 second residence time, wherein accounting for riser reactor internal circulating load 12%
Half reclaimable catalyst send out the first extension diameter section III enter regenerator regeneration, the first reaction product, remaining half reclaimable catalyst
The second conversion zone II is mixed into the second regenerated catalyst for accounting for riser reactor internal circulating load 12% of high temperature, in reaction temperature
Degree 510 DEG C, 5 seconds reaction time, water-oil factor be 0.12 under the conditions of carry out the second catalytic conversion reaction, obtain the second reaction product and
Reclaimable catalyst separates in settling section, and the second reaction product is sent into piece-rate system and cut by boiling range, so as to obtain dry air-liquid
Change gas, gasoline, diesel oil and slurry oil.Operating condition and product distribution are listed in table 3.
From table 3 it can be seen that gasoline yield is up to 48.68 heavy %, wherein olefin(e) centent is that 27.26%, RON reaches
92.0, dry gas yied is only 2.75 heavy %, and coke yield is 6.83 heavy %, and slurry oil yield significantly declines.
Comparative example 2
The comparative example is the raw material directly as catalyzed conversion with decompression residuum B, middle scale riser reactor assembly (with
The device of comparative example 1 is identical) on tested, in 510 DEG C of reaction temperature, reaction time be 2.5 seconds, oil ratio 7, water-oil factor be
Catalytic conversion reaction is carried out under the conditions of 0.12, reaction product and the reclaimable catalyst with charcoal are separated in settling section, and reaction product is sent
Enter piece-rate system to be cut by boiling range, so as to obtain dry gas, liquefied gas, gasoline, diesel oil, slurry oil.Operating condition and product point
Cloth is listed in table 3.
From table 3 it can be seen that gasoline yield is 38.20 heavy %, wherein olefin(e) centent is 55.01%, RON 91, but MON
Only 70.2, and dry gas yied is up to 5.54 heavy %, slurry oil yield is up to 10.46 heavy %, coke yield 10.97%.With reality
Apply example 2 to compare, gasoline yield is relatively low, and olefin(e) centent is too high, and the by-product yields of low value are higher, cause petroleum resources to utilize
The reduction of efficiency.
Embodiment 3
The embodiment is tested according to Fig. 2 flow, middle- scale device (riser of the present embodiment in riser reactor
The height of reactor 2 is 30 meters, and the internal diameter of pre lift zone is 0.8 meter, 1.5 meters of the height of pre lift zone, the first conversion zone I internal diameters
For 1 meter, the first conversion zone I height is 6 meters, and the first extension diameter section III internal diameter is 3 meters, and the first extension diameter section III height is
1.5 meters, the internal diameter of undergauge section is 1 meter, is highly 1 meter, and the second extension diameter section III' internal diameter is 3 meters, the second extension diameter section III''s
Highly be 1.5 meters, the second conversion zone II internal diameter is 0.8 meter, and the second conversion zone II height is 17.5 meters) on tested,
Used catalyst is catalyst RHZ-200.It is preheated to 350 DEG C of wax tailings and enters the first conversion zone I bottoms, and from carries in advance
The first regenerated catalyst for rising section contacts and the first catalytic conversion reaction occurs.In the first conversion zone I, wax tailings are in reaction temperature
520 DEG C of degree, 2.0 seconds reaction time, oil ratio 8, water-oil factor carry out the first catalytic conversion reaction under conditions of being 0.13, gained the
One reaction product and half reclaimable catalyst enter the first extension diameter section III and take out the reclaimable catalyst of part half, account for riser reactor
Half reclaimable catalyst of internal circulating load 20% is sent out the first extension diameter section III and regenerated into regenerator, the first reaction product, remaining half
Reclaimable catalyst mixes with the second regenerated catalyst for accounting for riser reactor internal circulating load 25% from the second extension diameter section III'
Into the second conversion zone II, carry out the second catalysis under the conditions of being 0.13 in 520 DEG C of reaction temperature, 5 seconds reaction time, water-oil factor and turn
Change reaction, obtain the second reaction product and reclaimable catalyst and separated in settling section, the second reaction product is sent into piece-rate system by evaporating
Cheng Jinhang is cut, so as to obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil.Operating condition and product distribution are listed in table 6.
Comparative example 3
The comparative example according to Conventional catalytic conversion reaction process operation, using with embodiment 3 similar in Conventional riser it is anti-
Device is answered, the difference with embodiment 3 is to be not provided with the first extension diameter section and the second extension diameter section, and its raw material processed is also relatively low with nitrogen content
Decompressed wax oil replace wax tailings, operating condition and product distribution are listed in table 6.
As can be seen from Table 6, the feedstock property of embodiment 3 provided by the invention will substantially be inferior to the feedstock oil of comparative example 3,
The former total nitrogen content of raw material is the latter more than 6 times, but conversion ratio but improves 16.5%, and liquefied gas yield improves
1.8%, gasoline yield improves 16.0%, and unconverted heavy oil yield reduces 4.3%, and coke yield reduces 1.0%, and does
Gas yield reduces 0.3%, and diesel yield reduces 12.2%.As shown in Table 6, method provided by the invention is adapted to high-nitrogen stock
The catalyzed conversion of oil, at the same the purpose of liquefied gas, gasoline can be significantly improved product yield.
Table 1 is raw material used in 1-2 of the embodiment of the present invention and comparative example 1-2
| Feedstock oil title | Decompression residuum | Decompression residuum |
| Feedstock oil code name | A | B |
| Density (20 DEG C), kg/m3 | 920.9 | 932.1 |
| Kinematic viscosity (100 DEG C), mm2/s | 114.4 | 116.3 |
| Carbon residue, weight % | 11.2 | 15.3 |
| Condensation point, DEG C | 25 | 23 |
| Elementary analysis, weight % | / | |
| N | 0.33 | 0.45 |
| S | 0.21 | 0.20 |
| C | 86.91 | 88.23 |
| H | 12.55 | 11.23 |
| Tenor, ppm | ||
| Ni | 8.8 | 7.9 |
| V | 0.1 | 0.1 |
| Fe | 1.8 | 1.9 |
| Cu | <0.1 | <0.1 |
| Na | 3.0 | 41 |
| Boiling range, DEG C | ||
| Initial boiling point | 415 | 425 |
| 10% | 545 | 556 |
Table 2 is catalyst used in 1-2 of the embodiment of the present invention and comparative example 1-2
| Catalyst is numbered | MLC-500 | GZ-1 |
| Zeolite type | Large pore zeolite | Mesopore and large pore zeolite |
| Chemical composition, weight % | ||
| Aluminum oxide | 50.2 | 40.0 |
| Sodium oxide molybdena | 0.321 | 0.29 |
| Iron oxide | / | 1.1 |
| Rare earth | / | 2.5 |
| Apparent density, kg/m3 | 700 | 750 |
| Pore volume, mL/g | 0.38 | 0.40 |
| Specific surface area, m2/g | 229 | 196 |
| Abrasion index, weight % | 1.9 | 1.5 |
| Screening composition, weight % | ||
| 0~40 micron | 17.3 | 20.2 |
| 40~80 microns | 49.3 | 50.1 |
| >80 microns | 33.4 | 29.7 |
The embodiment 1-2 of table 3 and comparative example 1-2 operating condition and product distribution
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 | |
| Feedstock oil is numbered | A | A | B | B |
| Reactor | Expanding riser | Riser | Expanding riser | Riser |
| Catalytic conversion unit | ||||
| Catalyst | GZ-1 | MLC-500 | GZ-1 | MLC-500 |
| Outlet temperature of riser, DEG C | 500 | 500 | 510 | 510 |
| Conversion zone I/II temperature, DEG C | 550/500 | / | 560/510 | / |
| Conversion zone I/II reaction time, second | 0.4/5 | 2.5 the second | 0.4/5 | 2.5 the second |
| Oil ratio | 6 | 6 | 7 | 7 |
| Water-oil factor | 0.10 | 0.10 | 0.12 | 0.12 |
| Product is distributed, weight % | ||||
| Dry gas | 2.26 | 4.46 | 2.75 | 5.54 |
| Liquefied gas | 16.61 | 13.64 | 15.98 | 12.77 |
| Gasoline | 49.37 | 41.40 | 48.68 | 38.20 |
| Diesel oil | 19.46 | 21.38 | 18.76 | 22.38 |
| Slurry oil | 5.87 | 9.85 | 7.0 | 10.14 |
| Coke | 6.43 | 9.27 | 6.83 | 10.97 |
| It is total | 100 | 100 | 100 | 100 |
| Conversion ratio | 74.67 | 68.77 | 74.24 | 67.48 |
| Gasoline family forms, weight % | ||||
| N-alkane | 4.39 | 8.38 | 6.32 | 10.41 |
| Isoparaffin | 35.73 | 18.23 | 33.23 | 12.20 |
| Alkene | 23.26 | 50.81 | 27.26 | 55.01 |
| Cycloalkane | 10.38 | 11.32 | 11.38 | 12.12 |
| Aromatic hydrocarbons | 26.24 | 11.26 | 21.81 | 10.26 |
| Octane number | ||||
| RON | 93.2 | 91.0 | 92.0 | 91.2 |
| MON | 81.7 | 75.1 | 80.5 | 72.2 |
Catalyst used in the embodiment of the present invention 3 of table 4 and comparative example 3
| Catalyst | RHZ-200 |
| Chemical composition, wt% | |
| Aluminum oxide | 45.1 |
| Sodium oxide molybdena | 0.20 |
| Apparent density, kg/m3 | 861 |
| Total pore volume, mL/g | 0.20 |
| Specific surface area, m2/g | 117 |
| Abrasion index, wt%h-1 | 1.6 |
| Screening composition, wt% | |
| 0-40μm | 15.6 |
| 40-80μm | 66.2 |
| 80 μm of ＞ | 18.2 |
Feedstock oil used in the embodiment of the present invention 3 of table 5 and comparative example 3
| Feedstock oil title | Wax tailings | Decompressed wax oil |
| Density, kg/m3(20℃) | 913.1 | 887.9 |
| Viscosity, mm2/s(100℃) | 4.2 | 4.1 |
| Carbon residue, wt% | 0.26 | 0.01 |
| Condensation point, DEG C | 28.0 | 27.6 |
| Total nitrogen, wt% | 0.68 | 0.11 |
| Alkali nitrogen, wt% | 0.22 | 0.04 |
| Sulphur, wt% | 0.21 | 0.56 |
| Carbon, wt% | 86.91 | 85.69 |
| Hydrogen, wt% | 12.55 | 13.21 |
| Boiling range, DEG C | ||
| 10% | 366 | 293 |
| 50% | 403 | 346 |
| 90% | 465 | 425 |
The operating condition and product of the embodiment 3 of table 6 and comparative example 3 are distributed
| Project | Embodiment 3 | Comparative example 3 |
| Feedstock oil | Wax tailings | Decompressed wax oil |
| Raw material preheating temperature, DEG C | 350 | 350 |
| Outlet temperature of riser, DEG C | 520 | 520 |
| Conversion zone I/II temperature, DEG C | 520/520 | / |
| Water-oil factor | 0.13 | 0.13 |
| Oil ratio | 8.0(I) | 8.0 |
| Reaction time, s | 2.0(I)/5.0(II) | 2.0 |
| Reaction pressure, MPa | 0.2 | 0.2 |
| Product is distributed, wt% | ||
| Dry gas | 1.6 | 1.9 |
| Liquefied gas | 15.2 | 13.4 |
| Gasoline | 52.1 | 36.1 |
| Diesel oil | 20.4 | 32.6 |
| Heavy oil | 5.9 | 10.2 |
| Coke | 4.8 | 5.8 |
| Conversion ratio, % | 73.7 | 57.2 |
Claims (11)
1. a kind of catalysis conversion method of inferior feedstock oil, this method include：
A, the inferior feedstock oil of preheating is reacted from pre lift zone, the first conversion zone (I), extension diameter section and second is included from the bottom to top
The middle and lower part of the first conversion zone (I) of the riser reactor (2) of section (II) be sent into riser reactor (2) with from regenerator
(13) it is transported to the first regenerated catalyst contact of pre lift zone and the first catalyzed conversion is carried out in first conversion zone (I)
Reaction, obtains the first reaction product and half reclaimable catalyst；
B, the first reaction product of gained in step a and half reclaimable catalyst are continued into up, process in riser reactor (2)
The second catalytic conversion reaction is carried out after the extension diameter section in second conversion zone (II), it is anti-that second is obtained after gas solid separation
Product and reclaimable catalyst are answered, the second reaction product is sent into subsequent separation system, reclaimable catalyst is sent into the regenerator
(13) regenerated；
Wherein, take out the reclaimable catalyst of part half from the middle and lower part of the extension diameter section and be sent into the middle progress of the regenerator (13) again
It is raw, it send the partial regeneration agent in the regenerator (13) as the second regenerated catalyst into the described of riser reactor (2)
The middle and upper part of extension diameter section or the middle and lower part of second conversion zone (II).
2. catalysis conversion method according to claim 1, wherein, the extension diameter section is including the first extension diameter section (III) and tightly
The second extension diameter section (III') above adjacent first extension diameter section (III), part is taken out from the middle and lower part of first extension diameter section (III)
Half reclaimable catalyst is sent into the regenerator (13) and regenerated, using the partial regeneration agent in the regenerator (13) as second
Regenerated catalyst is sent into second extension diameter section (III').
3. catalysis conversion method according to claim 1, this method also include：By lightweight material oil and/or cold shock medium
It is sent into middle and lower part and first reaction product, remaining half reclaimable catalyst and the second regeneration of second conversion zone (II)
The second catalytic conversion reaction described in step b is carried out in second conversion zone (II) after catalyst mixing；Wherein, it is described light
Matter feedstock oil be selected from least one of liquefied gas, gasoline and diesel oil, the cold shock medium be selected from liquefied gas, raw gasoline,
At least one of stable gasoline, diesel oil, heavy diesel fuel and water.
4. catalysis conversion method according to claim 1, wherein, the condition of the first catalytic conversion reaction described in step a
Including：Temperature is 500-600 DEG C, and the time is the 0.05-1.5 seconds, and oil ratio is (3-15)：1, water-oil factor is (0.03-0.3)：1,
Pressure is 130-450 kPas；The condition of the second catalytic conversion reaction includes described in step b：Temperature is 420-550 DEG C, the time
For the 1.5-20 seconds.
5. catalysis conversion method according to claim 1, wherein, by weight, catalyst in riser reactor will be accounted for
The 1-20 weight % of internal circulating load half reclaimable catalyst takes out from the extension diameter section, will account for catalyst in riser reactor
The 1-20 weight % of internal circulating load second regenerated catalyst is sent into the riser reactor.
6. catalysis conversion method according to claim 1, wherein, the inferior feedstock oil is selected from decompression residuum, normal pressure
Residual oil, hydrogenated residue, coker gas oil, deasphalted oil, high carbon residue crude oil, viscous crude, super-viscous oil, liquefied coal coil, tar sand oil and page
At least one of shale oil.
7. catalysis conversion method according to claim 1, wherein, carry out first catalytic conversion reaction and the second catalysis
The catalyst of conversion reaction includes zeolite, inorganic oxide and optional clay；In terms of butt and using the weight of the catalyst as
Benchmark, the content of the zeolite is 1-50 weight %, and the content of inorganic oxide is 5-99 weight %, and the content of clay is 0-70
Weight %；The zeolite be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZRP, Rare Earth Y,
At least one of rare earth hydrogen Y, super steady Y and high silicon Y, the inorganic oxide are silica and/or aluminum oxide, the clay
For kaolin and/or halloysite.
8. catalysis conversion method according to claim 1, this method also include：The inferior feedstock oil is sent into described the
The middle and lower part of two conversion zones (II) mixes with first reaction product, remaining half reclaimable catalyst and the second regenerated catalyst
The second catalytic conversion reaction described in step b is carried out in second conversion zone (II) afterwards；Wherein, from second conversion zone
(II) weight for the inferior feedstock oil for carrying out second catalytic conversion reaction is sent into the riser reactor (2) in middle and lower part
The inferior feedstock oil gross weight that amount is accounted in the feeding riser reactor (2) is more than zero to 50 heavy %.
9. catalysis conversion method according to claim 1, wherein, first catalytic conversion reaction and the second catalyzed conversion
The condition of reaction includes independently of one another：Temperature is 460-580 DEG C, and the time is the 0.1-8.0 seconds, and oil ratio is (2-25)：1, water
Oily ratio is (0.05-1.0)：1, pressure is 0.2-1.0 MPas.
10. catalysis conversion method according to claim 1, wherein, the inferior feedstock oil is higher than including total nitrogen content
The high-nitrogen raw oil of 0.15 weight % or basic n content higher than 0.05 weight %, the high-nitrogen raw oil are selected from decompressed wax oil, taken out
Carry at least one of recycle oil, wax tailings, deasphalted oil, crude oil, tar sand oil and shale oil oily, inferior.
11. catalysis conversion method according to claim 1, wherein, carry out first catalytic conversion reaction and described the
The catalyst of two catalytic conversion reactions is molecular sieve catalyst and/or amorphous silicon Al catalysts, in the molecular sieve catalyst
Molecular sieve include be selected from least one of Y, REY, HY, USY, REUSY, ZSM-5 and five-membered ring silica-rich zeolite.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109370644A (en) * | 2018-10-12 | 2019-02-22 | 中国石油大学(华东) | A kind of method of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons |
| CN110819385A (en) * | 2018-08-10 | 2020-02-21 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN114105724A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and aromatic hydrocarbon from waste plastic oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
| CN102021031A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing superior fuel oil from inferior crude oil |
| WO2016054879A1 (en) * | 2014-10-09 | 2016-04-14 | 石宝珍 | Regeneration method for catalytic cracking reaction |
-
2016
- 2016-06-30 CN CN201610509273.8A patent/CN107557063B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
| CN102021031A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing superior fuel oil from inferior crude oil |
| WO2016054879A1 (en) * | 2014-10-09 | 2016-04-14 | 石宝珍 | Regeneration method for catalytic cracking reaction |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819385A (en) * | 2018-08-10 | 2020-02-21 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN110819385B (en) * | 2018-08-10 | 2021-10-08 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN109370644A (en) * | 2018-10-12 | 2019-02-22 | 中国石油大学(华东) | A kind of method of crude oil preparing low-carbon olefin by catalytically cracking and aromatic hydrocarbons |
| CN114105724A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and aromatic hydrocarbon from waste plastic oil |
| CN114105724B (en) * | 2020-09-01 | 2024-06-11 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and aromatic hydrocarbon from waste plastic oil |
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