CN102453519B - Catalytic conversion method for improving product distribution - Google Patents
Catalytic conversion method for improving product distribution Download PDFInfo
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- CN102453519B CN102453519B CN201010514128.1A CN201010514128A CN102453519B CN 102453519 B CN102453519 B CN 102453519B CN 201010514128 A CN201010514128 A CN 201010514128A CN 102453519 B CN102453519 B CN 102453519B
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Abstract
The invention discloses a catalytic conversion method for improving product distribution. The method comprises the following steps of: allowing high-quality raw oil and a thermally regenerative catalyst with lower activity and coarse size distribution to contact on the lower part of a reactor to undergo cracking reaction, performing selective hydrogen transfer reaction and isomerization reaction on the generated oil gas and a carbon-containing catalyst in upstream under a certain reaction environment, separating reaction products, and stripping and regenerating spent catalysts for recycle. By the method, under the condition that the isobutene content in the liquefied gas and the olefin content in gasoline group composition are increased, the dry gas yield and coke are obviously reduced; and the particles of the catalysts are more uniform, so the local temperature distribution is more uniform in the regenerating process, and the breaking tendency of the catalysts is correspondingly reduced.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon in the absence of hydrogen, more particularly, is belong to the catalysis conversion method improving product slates.
Background technology
Conventional catalytic cracking process is mainly for the production of gasoline, and gasoline yield is up to 50 heavy more than %.Early eighties, unleaded gasoline forces catalytic cracking technology to the future development producing stop bracket gasoline, and for this reason, processing condition and the catalyst type of catalytic cracking there occurs wide variation.At process aspect, mainly improve temperature of reaction, Reaction time shorten, raising reaction severity, suppress hydrogen transfer reactions and cross cracking reaction and improve the contact efficiency of oil gas and catalyzer bottom riser tube; In catalyzer, develop USY type zeolite in conjunction with inert base or the catalyzer of active matrix and the catalyzer of dissimilar zeolite compound.
Though catalytic cracking technology has obtained above-mentioned progress, meet the requirement of unleaded gasoline, improve the octane value of gasoline, but no matter be by changing processing condition, still use novel zeolite catalyst to improve gasoline octane rating, be all improve olefin(e) centent in gasoline component to increase the octane value of gasoline, in current gasoline component, olefin(e) centent is 35 ~ 65 heavy %, and this and the requirement of reformulated gasoline to olefin(e) centent differ greatly.In liquefied gas composition, olefin(e) centent is higher, and greatly about 70 heavy about %, wherein butylene is the several times of Trimethylmethane, is difficult to as raw material for alkylation.
ZL99105904.2 discloses a kind of catalysis conversion method produced Trimethylmethane and be rich in isoparaffin gasoline, be by preheating after stock oil enter one and comprise in the reactor of two reaction zones, contact with the cracking catalyst of heat, the temperature of the first reaction zone is 530 ~ 620 DEG C, the reaction times is 0.5 ~ 2.0 second; The temperature of second reaction zone is 460 ~ 530 DEG C, the reaction times is 2 ~ 30 seconds, reaction product isolated, and reclaimable catalyst enters revivifier through stripping and burns Posterior circle and use.In the liquefied gas adopting method provided by the invention to produce, Trimethylmethane content is 20 ~ 40 heavy %, isoparaffin content in gasoline family's composition is 30 ~ 45 heavy %, olefin(e) centent is reduced to 30 heavy below %, and its research octane number (RON) is 90 ~ 93, and motor-method octane number is 80 ~ 84.
ZL99105905.0 discloses a kind of preparing propone, Trimethylmethane and is rich in the catalysis conversion method of isoparaffin gasoline, be by preheating after stock oil enter one and comprise in the reactor of two reaction zones, contact with the cracking catalyst of heat, the temperature of the first reaction zone is 550 ~ 650 DEG C, the reaction times is 0.5 ~ 2.5 second; The temperature of second reaction zone is 480 ~ 550 DEG C, the reaction times is 2 ~ 30 seconds, reaction product isolated, and reclaimable catalyst enters revivifier through stripping and burns Posterior circle and use.The liquefied gas yield adopting method provided by the invention to produce can reach 25 ~ 40 heavy %, and wherein propylene content is 30 heavy about %, and Trimethylmethane content is 20 ~ 40 heavy %, and the productive rate of gasoline can reach 35 ~ 50 heavy %, and the isoparaffin in gasoline composition is 30 ~ 45 heavy %.
ZL99105903.4 discloses a kind of riser reactor for fluidized catalytic conversion, vertically to be followed successively by the outlet area of pre lift zone coaxial each other, the first reaction zone, the second reaction zone of enlarged-diameter, reduced from bottom to up, to have a level pipe at outlet area end.It is different with the processing condition of second reaction zone that this reactor both can control the first reaction zone, the stock oil of different performance can be made again to carry out segmentation cracking, obtain required object product.
These patents just, constitute the basic patent of the catalytic cracking process (MIP) of maximizing iso-paraffins, and are widely used, and have been applied to nearly 50 cover catalytic cracking unit at present, have obtained huge economic benefit and social benefit.Although prior art can obtain being rich in the liquefied gas of Trimethylmethane and be rich in isoparaffin gasoline, but to the catalytically cracked stock of process high-quality, especially hydrogenation wax oil, cause content of olefin in gasoline on the low side, iso-butylene content in liquefied gas is on the low side, products distribution is optimized not, and petroleum resources are underused.
The fine particle being less than 40 μm in the size composition of conventional catalytic cracking catalyst is about 20% (volume).Find after deliberation, although these fine grain catalyzer have higher cracking capability, but it is poor to the selectivity of dry gas and coke, and in regenerative process, catalyzer is easy to broken more, therefore the size composition of optimization of catalysts can improve the selectivity of dry gas and coke, and improves the work-ing life of catalyzer.
Summary of the invention
The object of this invention is to provide a kind of catalysis conversion method improving product slates.
Method provided by the invention is: high quality raw material oil and the lower contacts generation cracking reaction of the active lower and hot regenerated catalyst of thick size distribution at reactor, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, reaction product isolated, reclaimable catalyst uses through stripping, regeneration Posterior circle.
Method provided by the invention be one comprise realize two class differential responses reactor in carry out, this reactor be selected from equal diameter riser tube, etc. the one in linear speed riser tube, reducing riser tube, fluidized-bed, also can be the compound reactor be made up of equal diameter riser tube and fluidized-bed.
Method provided by the invention is so concrete enforcement:
(1), the high quality raw material oil of preheating enter reactor and activity be 35 ~ 55 preferably 40 ~ 50 and slightly the hot regenerated catalyst of size distribution contact, temperature of reaction 490 DEG C ~ 620 DEG C preferably 500 DEG C ~ 600 DEG C, 0.5 second ~ 2.0 seconds preferably 0.8 second ~ 1.5 seconds reaction times, the weight ratio (hereinafter referred to as agent-oil ratio) 3 ~ 15: 1 of catalyzer and stock oil preferably 3 ~ 12: 1 condition under there is cracking reaction;
(2), generate oil gas and used catalyst up, temperature of reaction 420 DEG C ~ 550 DEG C preferably 460 DEG C ~ 500 DEG C, the reaction times is, under the condition of 2 seconds ~ 30 seconds preferably 3 seconds ~ 15 seconds, optionally hydrogen transfer reactions and isomerization reaction occur;
(3), reaction product isolated obtains being rich in the liquefied gas of iso-butylene and the moderate gasoline of olefin(e) centent and other products, and reclaimable catalyst enters revivifier coke burning regeneration Posterior circle through stripping and uses.
The pressure of step (1) described cracking reaction, step (2) described hydrogen transfer reactions and isomerization reaction is 130kPa ~ 450kPa, the weight ratio (hereinafter referred to as water-oil ratio) of water vapor and stock oil is 0.03 ~ 0.3: 1, is preferably 0.05 ~ 0.3: 1.
The reactor that the method is suitable for can be selected from equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or reducing riser tube, also can be the compound reactor be made up of equal diameter riser tube and fluidized-bed.
Method provided by the invention can equal diameter riser tube, etc. carry out in linear speed riser tube or fluidized-bed reactor, its intermediate diameters riser tube is identical with the catalyst cracker of refinery's routine, waits the linear speed of fluid in linear speed riser tube substantially identical.Equal diameter riser tube, etc. linear speed riser reactor be followed successively by pre lift zone, the first reaction zone, second reaction zone from bottom to up, fluidized-bed reactor is followed successively by the first reaction zone, second reaction zone from bottom to up, and the ratio of the height of the first reaction zone, second reaction zone is 10 ~ 40: 90 ~ 60.When use equal diameter riser tube, etc. linear speed riser tube or fluidized-bed reactor time, one or more cold shock medium inlet is established bottom second reaction zone, and/or heat collector is set in second reaction zone, the height of heat collector accounts for 50% ~ 90% of second reaction zone height.Control temperature and the reaction times of each reaction zone respectively.Cold shock medium is the mixture of one or more the arbitrary proportion be selected from cold shock agent, the regenerated catalyst of cooling and the semi regeneration catalyzer of cooling.Wherein cold shock agent is the mixture of one or more the arbitrary proportion be selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or water; The regenerated catalyst of cooling and the semi regeneration catalyzer of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration, regenerated catalyst carbon content is 0.1 heavy below %, be preferably 0.05 heavy below %, semi regeneration coke on regenerated catalyst is the 0.1 heavy % in heavy % ~ 0.9, and best carbon content is the 0.15 heavy % in heavy % ~ 0.7.
Method provided by the invention also can be carried out in the compound reactor be made up of equal diameter riser tube and fluidized-bed, the equal diameter riser tube of bottom is the first reaction zone, the fluidized-bed on top is second reaction zone, controls temperature and the reaction times of each reaction zone respectively.Establish one or more cold shock medium inlet in the bottom of fluidized-bed, and/or arrange heat collector in second reaction zone, the height of heat collector accounts for 50% ~ 90% of second reaction zone height.Control temperature and the reaction times of each reaction zone respectively.Cold shock medium is the mixture of one or more the arbitrary proportion be selected from cold shock agent, the regenerated catalyst of cooling and the semi regeneration catalyzer of cooling.Wherein cold shock agent is the mixture of one or more the arbitrary proportion be selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or water; The regenerated catalyst of cooling and the semi regeneration catalyzer of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration, regenerated catalyst carbon content is 0.1 heavy below %, be preferably 0.05 heavy below %, semi regeneration coke on regenerated catalyst is the 0.1 heavy % in heavy % ~ 0.9, and best carbon content is the 0.15 heavy % in heavy % ~ 0.7.
Method provided by the invention can also be carried out in reducing riser reactor (see ZL99105903.4), the constitutional features of this reactor is as shown in Figure 1: riser reactor is vertically followed successively by the outlet area d of pre lift zone a coaxial each other, the first reaction zone b, the second reaction zone c of enlarged-diameter, reduced from bottom to up, is connected with one section of level pipe e at outlet area end.The combining site of first and second reaction zone is truncated cone-shaped, and the apex angle α of its longitudinal section isosceles trapezoid is 30 ° ~ 80 °; The combining site of second reaction zone and outlet area is truncated cone-shaped, and the base angle β of its longitudinal section isosceles trapezoid is 45 ° ~ 85 °.
The height sum of the pre lift zone of this reactor, the first reaction zone, second reaction zone, outlet area is the total height of reactor, is generally 10 meters ~ 60 meters.
The diameter of pre lift zone is identical with conventional equal diameter riser reactor, and be generally 0.02 meter ~ 5 meters, it highly accounts for 5% ~ 10% of total reactor height.The effect of pre lift zone is under the existence of pre-lift medium, make regenerated catalyst move upward and accelerate, and used identical of pre-lift medium used and conventional equal diameter riser reactor, is selected from water vapor or dry gas.
The similar of the first reaction zone is in the equal diameter riser reactor of routine, its diameter can be identical with pre lift zone, also can comparatively pre lift zone be slightly large, the diameter of the first reaction zone and the diameter ratio of pre lift zone are 1.0 ~ 2.0: 1, and it highly accounts for 10% ~ 30% of total reactor height.After the mixing of this district, at higher temperature of reaction and agent-oil ratio, under the shorter residence time (being generally 0.5 second ~ 2.5 seconds), mainly there is cracking reaction in stock oil and catalyzer.
Second reaction zone is thicker than the first reaction zone, and the diameter ratio of its diameter and the first reaction zone is 1.5 ~ 5.0: 1, and it highly accounts for 30% ~ 60% of total reactor height.Its effect is the flow velocity and the temperature of reaction that reduce oil gas and catalyzer.Reduce the method for this district's temperature of reaction, cold shock medium can be injected from the combining site of this district and the first reaction zone, and/or by arranging heat collector in this district, take partial heat away to reduce this district's temperature of reaction, thus reach the object suppressing secondary cracking reaction, increase isomerization reaction and hydrogen transfer reactions.Cold shock medium is the mixture of one or more the arbitrary proportion be selected from cold shock agent, the regenerated catalyst of cooling and the semi regeneration catalyzer of cooling.Wherein cold shock agent is the mixture of one or more the arbitrary proportion be selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or water; The regenerated catalyst of cooling and the semi regeneration catalyzer of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration, regenerated catalyst carbon content is 0.1 heavy below %, be preferably 0.05 heavy below %, semi regeneration coke on regenerated catalyst is the 0.1 heavy % in heavy % ~ 0.9, and best carbon content is the 0.15 heavy % in heavy % ~ 0.7.If arrange heat collector, then it highly accounts for 50% ~ 90% of second reaction zone height.Logistics can be longer in this reaction zone residence time, is 2 seconds ~ 30 seconds.
The similar of outlet area is in the equal diameter riser reactor top exit part of routine, and the diameter ratio of its diameter and the first reaction zone is 0.8 ~ 1.5: 1, and it highly accounts for 0 ~ 20% of total reactor height.Logistics Ke Gai district stops certain hour, to suppress cracking reaction and heat cracking reaction, improves rate of flow of fluid.
One end of level pipe is connected with outlet area, and the other end is connected with settling vessel; When the height of outlet area be 0 that is riser reactor does not have an outlet area time, one end of level pipe is connected with second reaction zone, and the other end is connected with settling vessel.The effect of level pipe the product of reaction generation and reclaimable catalyst is delivered to separation system carry out gas solid separation.Its diameter is determined as the case may be by those skilled in the art.The effect of pre lift zone is under the existence of pre-lift medium, is promoted by the catalyzer after regeneration, enters the first reaction zone.
The high quality raw material oil that the method is suitable for can be the petroleum cuts of different boiling ranges.Specifically, one or more in atmospheric overhead, gasoline, catalytic gasoline, diesel oil, straight-run gas oil, hydrogenation wax oil of high quality raw material grease separation.
Two reaction zones in the method can be suitable for the catalyzer of all same types, both can be amorphous silicon aluminium catalyzer, also can be zeolite catalyst, the active ingredient of zeolite catalyst is selected from y-type zeolite, HY type zeolite, ultrastable Y－type zeolite, ZSM-5 series zeolite or has the mixture of one or more the arbitrary proportion in the supersiliceous zeolite of five-membered ring structure, ferrierite, this zeolite can contain rare earth and/or phosphorus, also can not contain rare earth and phosphorus.
Two reaction zones in the method also can be suitable for dissimilar catalyzer, and dissimilar catalyzer can be the catalyzer that catalyzer that granular size is different and/or apparent bulk density are different.The catalyzer that granular size is different and/or the different activity over catalysts component of apparent bulk density select dissimilar zeolite respectively, zeolite is selected from y-type zeolite, HY type zeolite, ultrastable Y－type zeolite, ZSM-5 series zeolite or has the mixture of one or more the arbitrary proportion in the supersiliceous zeolite of five-membered ring structure, ferrierite, this zeolite can contain rare earth and/or phosphorus, also can not contain rare earth and phosphorus.Vary in size particle catalyzer and/or height apparent bulk density catalyzer can enter different reaction zones respectively, such as, oarse-grained catalyzer containing ultrastable Y－type zeolite enters the first reaction zone, increase cracking reaction, short grained catalyzer containing rare earth Y type zeolite enters second reaction zone, increase hydrogen transfer reactions, the catalyzer that granular size is different regenerates at same stripper stripping and same revivifier, then isolate macrobead and catalyst particle, catalyst particle enters second reaction zone through cooling.The catalyzer that granular size is different is demarcated between 30 ~ 40 microns, and the catalyzer that apparent bulk density is different is with 0.6 ~ 0.7g/cm
3between boundary.
The size distribution of described catalyzer is thick size distribution.The size composition of the catalyzer of described thick size distribution is: the particle being less than 40 microns accounts for the volume ratio of all particles lower than 10%, is preferably lower than 5%; The particle being greater than 80 microns accounts for the volume ratio of all particles lower than 15%, and be preferably lower than 10%, all the other are the particle of 40 ~ 80 microns.
The catalyzer that the activity that the method is suitable for is lower refers to that catalyst activity is 35 ~ 55, preferably 40 ~ 50.It is measured by measuring method of the prior art: the mat activity test method " Petrochemical Engineering Analysis method (RIPP test method) " of company standard RIPP 92-90--catalytic cracking, Yang Cui waits people surely, 1990, hereinafter referred to as RIPP 92-90.Described catalyst activity is represented by light oil microactivity (MA), and its calculation formula is the gasoline yield+gas yield+coke yield lower than 204 DEG C in MA=(lower than the gasoline production+gas yield+coke output of 204 DEG C in product)/charging total amount * 100%=product.The appreciation condition of light oil micro-reactor device (with reference to RIPP 92-90) is: become by catalyst breakage diameter to be the particle of 420 ~ 841 microns, loading amount is 5 grams, reaction raw materials to be boiling range the be straight distillation light diesel oil of 235 ~ 337 DEG C, temperature of reaction is 460 DEG C, and weight space velocity is 16 hours
-1, agent-oil ratio is 3.2.
The invention has the advantages that:
If 1 adopts conventional equal diameter riser tube or fluidized-bed reactor to implement the present invention, only need reduce treatment capacity, the prolongation reaction times just can implement.
If 2 adopt reducing riser reactor, the advantage of this reactor had both retained the higher temperature of reaction of Conventional riser reactor bottom and agent-oil ratio increases a cracking reaction, that suppresses top crosses cracking and heat cracking reaction simultaneously, top extends the reaction times under lower temperature of reaction in the reactor again, increases the isomerization reaction of alkene, hydrogen transfer reactions.
3, in the liquefied gas produced by method provided by the invention, iso-butylene content increases by 30 heavy more than %, and it is 30 heavy more than % that the olefin(e) centent in gasoline family's composition rises to.
4, in liquefied gas iso-butylene content and gasoline family composition in olefin(e) centent increase, dry gas yied and coke reduce significantly.
5, catalyzer because of particle more even, thus the temperature distribution of local is also more even in regenerative process, and catalyst breakage tendency also correspondingly reduces.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of Novel hoisting pipe reactor, and a, b, c, d, e in figure represent pre lift zone, the first reaction zone, second reaction zone, outlet area, level pipe respectively.
Fig. 2 is the schematic flow sheet of preferred forms of the present invention.In accompanying drawing, each numbering is described as follows:
1,3,4,6,11,13,17,18 all pipeline is represented; 2 is the pre lift zone of riser tube; 5,7 the first reaction zone, the second reaction zone being respectively riser tube; 8 is the outlet area of riser tube; 9 is settling vessel, and 10 is cyclonic separator, and 12 is stripper, and 14 is inclined tube to be generated, and 15 is revivifier, and 16 is regenerator sloped tube.
Embodiment
The present invention has different embodiments.
One of embodiment:
In the bottom of conventional equal diameter riser reactor, the stock oil of preheating and hot regenerated catalyst of thick size distribution lower with activity contacts and cracking reaction occurs, the oil gas generated contacts with the up regenerated catalyst cooled with injection of used catalyst, isomerization reaction and hydrogen transfer reactions occur, after reaction, effluent enters settling vessel thereupon; Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part enters this reactor bottom, and another part enters this reactor middle and lower part after cooling.
Embodiment two:
In the bottom of conventional equal diameter riser reactor, the stock oil of preheating and hot regenerated catalyst of thick size distribution lower with activity contacts and cracking reaction occurs, the oil gas generated and the up semi regeneration catalyst exposure with injecting cold shock agent and cooling of used catalyst, isomerization reaction and hydrogen transfer reactions occur, after reaction, effluent enters settling vessel thereupon; Reaction product isolated, reclaimable catalyst is after stripping, enter in two-stage regeneration device and burn, from first paragraph revivifier, semi regeneration catalyzer out enters this reactor middle and lower part after cooling, and from second segment revivifier, regenerated catalyst out directly returns this reactor bottom without cooling.
Embodiment three:
For the catalytic cracking unit with Conventional riser-fluidized-bed reactor, traditional cracking raw material after preheating enters lower with activity and thick size distribution hot regenerated catalyst from the bottom of riser tube contacts, the oil gas generated after reaction goes upward to the top of riser tube, proceed to react with the catalyst exposure after cooling, after reaction, effluent enters settling vessel; Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part enters the bottom of riser tube, and another part enters the top of riser tube after cooling.
Embodiment four:
This embodiment is preferred forms of the present invention.
For the catalytic cracking unit with Novel diameter reducing riser reactor, traditional cracking raw material after preheating enters lower with activity and thick size distribution hot regenerated catalyst from the first bottom, reaction zone of reactor contacts, there is cracking reaction, the oil gas generated after reaction goes upward to the bottom, second reaction zone of reactor and the catalyst exposure after lowering the temperature carries out hydrogen transfer reactions and isomerization reaction, and after reaction, effluent enters settling vessel; Reaction product isolated, then reclaimable catalyst enters bottom, second reaction zone through stripping, regeneration.
Method provided by the invention is not limited thereto.
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Fig. 2 adopts reducing riser reactor, improves the flow process of the catalysis conversion method of product slates, and shape, the size of equipment and pipeline not by the restriction of accompanying drawing, but are determined as the case may be.
Pre-lift steam enters from riser tube pre lift zone 2 through pipeline 1, active lower and hot regenerated catalyst that is thick size distribution enters riser tube pre lift zone through regenerator sloped tube 16 is promoted by pre-lift steam.Stock oil after preheating enters from riser tube pre lift zone by a certain percentage through pipeline 4 and the atomizing steam from pipeline 3, enters in the first reaction zone 5, carry out cracking reaction under certain conditions with the thermocatalyst of thick size distribution after mixing.Reactant flow is mixed into second reaction zone 7 with the catalyzer (not marking in figure) from the cold shock agent of pipeline 6 and/or the thick size distribution of cooling, carry out secondary reaction, reacted logistics enters outlet area 8, the linear speed of logistics is improved in this reaction zone, make reactant flow enter settling vessel 9, cyclonic separator 10 in gas solid separation system fast, reaction product goes separation system through pipeline 11.After reaction, the reclaimable catalyst of band charcoal enters stripper 12, through entering revivifier 15 from after the water vapor stripping of pipeline 13 by inclined tube 14 to be generated, reclaimable catalyst is coke burning regeneration in the air from pipeline 17, flue gas goes out revivifier through pipeline 18, and the hot regenerated catalyst of thick size distribution returns riser tube bottom cycle through regenerator sloped tube 16 and uses.
The following examples will be further described the present invention, but not thereby limiting the invention.The stock oil used in embodiment, comparative example and the character of catalyzer list in table 1 and table 2 respectively.Catalyzer in table 2 is produced by China PetroChemical Corporation's Shandong catalyst plant.ZCM-7 catalyzer in table 2 is through 800 DEG C, and 100% water vapor aging 12 hours and 30 hours respectively, obtain ZCM-7L and ZCM-7H of two kinds of different activities levels, namely activity is respectively 45 and 67.Carry out elutriation by aging for part ZCM-7L dose again, removing fine particle and the particle being greater than 100 μm, obtain the catalyzer of thick size distribution, ZCM-7LA, its character lists in table 2.
Embodiment 1
The present embodiment illustrates and adopts method provided by the invention, uses the catalyzer of thick size distribution, medium-sized reducing riser reactor improves the situation of iso-butylene content and content of olefin in gasoline in liquefied gas.
The pre lift zone of reactor, the first reaction zone, second reaction zone, outlet area total height are 15 meters, and pre lift zone diameter is 0.025 meter, and it is highly 1.5 meters; First reaction zone diameter is 0.025 meter, and it is highly 4 meters; Second reaction zone diameter is 0.1 meter, and it is highly 6.5 meters; The diameter of outlet area is 0.025 meter, and it is highly 3 meters; The drift angle of the longitudinal section isosceles trapezoid of first and second reaction zone combining site is 45 °; The base angle of the longitudinal section isosceles trapezoid of second reaction zone and outlet area combining site is 60 °.
Stock oil listed by the table 1 of preheating enters in this reactor, in the presence of water vapor, with the catalyst Z CM-7LA contact reacts listed by the table 2 of heat, ZCM-7LA catalyst activity is 45, reaction product isolated obtains liquefied gas and gasoline and other products, reclaimable catalyst enters revivifier through stripping, and regenerated catalyst uses through burning Posterior circle.
The operational condition tested, product slates and vapour oil properties list in table 3.
Comparative example 1
Adopt type of reactor identical with embodiment 1 with operational condition, raw material used is also the stock oil listed by table 1, and catalyzer is also the catalyst Z CM-7L of the conventional particle size distribution listed by table 2, and just now ZCM-7L catalyst activity is 45.The operational condition tested, product slates and vapour oil properties list in table 3.
Comparative example 2
Adopt type of reactor identical with embodiment 1 with operational condition, raw material used is also the stock oil listed by table 1, and catalyzer is also the catalyst Z CM-7H of the conventional particle size distribution listed by table 2, and now ZCM-7H catalyst activity is 67.The operational condition tested, product slates and vapour oil properties list in table 3.
As can be seen from Table 3, relative to embodiment 1, dry gas yied and the coke yield of comparative example 1 increase significantly.Relative to the comparative example 2 adopting high reactivity ZCM-7H (namely activity is 67), adopt low activity ZCM-7L (namely activity is 45), iso-butylene productive rate rises to 2 heavy % by 1.4 heavy %, adds 42.86 heavy %, and content of olefin in gasoline rises to 29.3 heavy % by 16.3 heavy %; In addition, liquid yield still increases by 1.2 percentage points.
Table 1
| Stock oil is numbered | A |
| Stock oil title | Hydrogenation wax oil |
| Density (20 DEG C), kg/m 3 | 899.3 |
| Kinematic viscosity, millimeter 2/ second | |
| 80℃ | 16.22 |
| 100℃ | 9.29 |
| Carbon residue, heavy % | 0.30 |
| Condensation point, DEG C | 44 |
| Basic nitrogen, ppm | 293 |
| Total nitrogen, heavy % | 0.08 |
| Sulphur, heavy % | 0.12 |
| Carbon, heavy % | 87.01 |
| Hydrogen, heavy % | 12.85 |
| Boiling range, DEG C | |
| Initial boiling point | 284 |
| 10％ | 394 |
| 30％ | 433 |
| 50％ | 463 |
| 70％ | 495 |
| 90％ | / |
| Final boiling point | / |
Table 2
| Catalyzer is numbered | A | B | C |
| Trade names | ZCM-7L | ZCM-7H | ZCM-7LA |
| Particle diameter type | Conventional particle size | Conventional particle size | Coarse grain footpath |
| Zeolite type | USY | USY | USY |
| Chemical constitution, heavy % | |||
| Aluminum oxide | 46.4 | 46.4 | 46.1 |
| Sodium oxide | 0.22 | 0.22 | 0.22 |
| Ferric oxide | 0.32 | 0.32 | 0.30 |
| Apparent density, kg/m 3 | 600 | 600 | 600 |
| Pore volume, ml/g | 0.32 | 0.32 | 0.30 |
| Specific surface area, rice 2/ gram | 217 | 217 | 209 |
| Size composition, heavy % | |||
| 0 ~ 40 micron | 16.1 | 16.1 | 7.2 |
| 40 ~ 80 microns | 54.1 | 54.1 | 78.4 |
| > 80 microns | 29.8 | 29.8 | 14.4 |
Table 3
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Catalyst activity | 45 | 45 | 67 |
| Temperature of reaction, DEG C | |||
| First reaction zone | 550 | 550 | 550 |
| Second reaction zone | 500 | 500 | 500 |
| The residence time, second | 5.5 | 5.5 | 5.5 |
| First reaction zone | 2.0 | 2.0 | 2.0 |
| Second reaction zone | 3.5 | 3.5 | 3.5 |
| Agent-oil ratio | 5.0 | 5.0 | 5.0 |
| Water-oil ratio | 0.1 | 0.1 | 0.1 |
| Product slates, heavy % | |||
| Dry gas | 1.3 | 1.4 | 1.8 |
| Liquefied gas | 17.1 | 17.3 | 17.5 |
| Wherein iso-butylene | 2.1 | 2.0 | 1.4 |
| Gasoline | 55.0 | 55.0 | 56.0 |
| Diesel oil | 18.2 | 17.8 | 15.4 |
| Heavy oil | 6.2 | 6.0 | 5.6 |
| Coke | 2.3 | 2.5 | 3.7 |
| Add up to | 90.3 | 90.1 | 88.9 |
| Liquid yield, heavy % | |||
| Octane value | 91.2 | 91.0 | 90.6 |
| RON | 80.8 | 80.7 | 80.5 |
| MON | |||
| Boiling range, DEG C | 38～200 | 38～200 | 37～200 |
| Initial boiling point ~ do | |||
| Group composition, heavy % | |||
| Alkane | 40.3 | 40.5 | 50.6 |
| Naphthenic hydrocarbon | 7.2 | 7.3 | 8.2 |
| Alkene | 29.8 | 29.3 | 16.3 |
| Aromatic hydrocarbons | 22.7 | 22.9 | 24.9 |
Claims (10)
1. improve the catalysis conversion method of product slates, it is characterized in that high quality raw material oil and the lower contacts generation cracking reaction of the active lower and hot regenerated catalyst of thick size distribution at reactor, cracking reaction temperature 490 DEG C ~ 620 DEG C, 0.5 second ~ 2.0 seconds reaction times, the weight ratio 3 ~ 15: 1 of catalyzer and stock oil, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, hydrogen transfer reactions and isomerization reaction temperature 420 DEG C ~ 550 DEG C, reaction times is 2 seconds ~ 30 seconds, reaction product isolated, reclaimable catalyst is through stripping, regeneration Posterior circle uses, the hot regenerated catalyst activity that described activity is lower is 35 ~ 55, and described activity is measured according to company standard RIPP 92-90, the size composition of the catalyzer of described thick size distribution is: the particle being less than 40 microns accounts for the volume ratio of all particles lower than 10%, and the particle being greater than 80 microns accounts for the volume ratio of all particles lower than 15%, and all the other are the particle of 40 ~ 80 microns.
2., according to the method for claim 1, it is characterized in that one or more in atmospheric overhead, gasoline, diesel oil, straight-run gas oil, hydrogenation wax oil of described high quality raw material grease separation.
3., according to the method for claim 1, it is characterized in that the hot regenerated catalyst activity that described activity is lower is 40 ~ 50.
4. according to the method for claim 1, it is characterized in that the size composition of the catalyzer of described thick size distribution is: the particle being less than 40 microns accounts for the volume ratio of all particles lower than 5%, the particle being greater than 80 microns accounts for the volume ratio of all particles lower than 10%, and all the other are the particle of 40 ~ 80 microns.
5., according to the method for claim 1, it is characterized in that described cracking reaction condition is: temperature of reaction 500 DEG C ~ 600 DEG C, 0.8 second ~ 1.5 seconds reaction times, the weight ratio 3 ~ 12: 1 of catalyzer and stock oil.
6., according to the method for claim 1, it is characterized in that described hydrogen transfer reactions and isomerization reaction condition are: temperature of reaction 460 DEG C ~ 500 DEG C, the reaction times is 3 seconds ~ 15 seconds.
7., according to the method for claim 1, it is characterized in that described cracking reaction, the pressure of hydrogen transfer reactions and isomerization reaction is 130kPa ~ 450kPa, the weight ratio of water vapor and stock oil is 0.03 ~ 0.3: 1.
8. according to the method for claim 1, it is characterized in that described reactor be selected from equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or reducing riser tube, or the compound reactor be made up of equal diameter riser tube and fluidized-bed.
9. according to the method for claim 8, it is characterized in that described reducing riser tube to be vertically followed successively by the outlet area of pre lift zone coaxial each other, the first reaction zone, the second reaction zone of enlarged-diameter, reduced from bottom to up, be connected with one section of level pipe at outlet area end, wherein the diameter of second reaction zone and the diameter ratio of the first reaction zone are 1.5 ~ 5.0: 1.
10., according to the method for claim 2, it is characterized in that described gasoline is catalytic gasoline.
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| CN115161060B (en) * | 2021-04-02 | 2024-02-27 | 上海河图工程股份有限公司 | Catalytic cracking method and device for high-yield low-carbon olefin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1232069A (en) * | 1999-04-23 | 1999-10-20 | 中国石油化工集团公司 | Method for catalytic conversion to prepare isobutane and isoalkane-enriched gasoline |
| CN101469274A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for producing high-octane petrol |
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| KR101546466B1 (en) * | 2007-08-09 | 2015-08-24 | 차이나 페트로리움 앤드 케미컬 코포레이션 | A catalytic conversion process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1232069A (en) * | 1999-04-23 | 1999-10-20 | 中国石油化工集团公司 | Method for catalytic conversion to prepare isobutane and isoalkane-enriched gasoline |
| CN101469274A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for producing high-octane petrol |
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