CN102719272B - A kind of catalysis conversion method of petroleum hydrocarbon - Google Patents
A kind of catalysis conversion method of petroleum hydrocarbon Download PDFInfo
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- CN102719272B CN102719272B CN201110079684.5A CN201110079684A CN102719272B CN 102719272 B CN102719272 B CN 102719272B CN 201110079684 A CN201110079684 A CN 201110079684A CN 102719272 B CN102719272 B CN 102719272B
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Abstract
A kind of catalysis conversion method of petroleum hydrocarbon, high-sulfur wax oil and hot regenerated catalyst catalytic cracking unit reactor lower contacts and there is cracking reaction, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, separating reaction oil gas obtains comprising liquefied gas, the reaction product of gasoline and catalytic wax oil, reclaimable catalyst is through stripping, regeneration Posterior circle uses, wherein catalytic wax oil and other optional secondary processing wax oil enter hydrotreating unit and carry out polycyclic aromatic hydrocarbons selective hydrogenation, preferred hydrogenation wax oil turns back to catalytic cracking unit.The method improves gasoline yield and productivity of propylene, improve the hydrogen utilization ratio in raw material, improve again the utilization ratio of the hydrogen of hydrotreatment simultaneously, thus can petroleum resources be saved, provide a new approach for oil refining production process cleans to clean with refined oil product.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon, more particularly, relate to the catalysis conversion method of the integrated technique of a kind of faulty wax oil catalytic cracking and hydrotreatment.
Background technology
Conventional catalytic cracking process processing high-sulfur faulty wax oil raw material not only makes the SO in regeneration fume from catalytic cracking
xdischarge does not meet environmental requirement, and the sulphur content in gasoline and diesel product all can not meet product specification requirement.Therefore, these high-sulfur faulty wax oil raw materials are first through hydrotreatment usually, and except desulfuration, nitrogen and metal impurities, the polycyclic aromatic hydrocarbons in saturated raw material, improves its catalytic cracking reaction performance, and then as the raw material of catalytic cracking, produce low-sulphur oil and diesel oil.
US4780193 discloses a kind of method adopting Hydrofining Technology to improve catalytically cracked material quality, the temperature of reaction of this hydro-refining unit lower than 390 DEG C, reaction pressure at least at more than 10.0MPa, preferably at more than 12.0MPa.Under the processing condition being conducive to aromatic saturation, improved the cracking performance of catalytic cracking unit raw material by hydrofining, thus improve the transformation efficiency of catalytic cracking unit, produce high-octane gasoline blending component.CN101684417A discloses a kind of hydrogenation-catalytic cracking combination process of optimization, wax oil raw material reacts in hydrotreatment reaction zone, the hydrogenation wax oil obtained is as catalytically cracked stock, directly catalytic cracking unit is entered without fractionation, catalysis heavy cycle oil loops back hydrotreatment reaction zone, the logistics of high pressure hot separator top gas phase and catalysis gently circulate and enter hydro-upgrading reaction zone with optional gas oil, carry out hydro-upgrading reaction, resultant of reaction obtains hydrotreated naphtha and hydrogenated diesel oil after fractionation.Hydrotreating unit and the public hydrogen gas system of hydro-upgrading unit, reduce appliance arrangement investment and process cost.Products scheme is flexible, can produce high-quality low-sulfur gasoline, fine-quality diesel oil and reformer feed simultaneously.
Usually, faulty wax oil raw material can improve its Catalytic Cracking Performance after hydrotreatment, but understands because boiling range lightens generating portion diesel oil, petroleum naphtha and lighter hydrocarbons in hydroprocessing processes, is unfavorable for voluminous gasoline and propylene.In addition, the catalytic cracking process (MIP) of maximizing iso-paraffins 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, and products distribution is optimized not, and petroleum resources are underused.
MIP technique is widely used, has been applied to nearly 50 cover catalytic cracking unit at present, has obtained huge economic benefit and social benefit.ZL99105904.2, ZL99105905.0 and ZL99105903.4 is seen with the MIP technology detailed description being rich in isoparaffin gasoline about the liquefied gas being rich in Trimethylmethane.
Along with environmental regulation requires increasingly stringent to catalytic cracking production process and quality product, even if catalytic cracking process hydrogenation wax oil, the SO in regeneration fume from catalytic cracking
xdischarge is also difficult to meet environmental requirement, and still needing increases regenerated flue gas treatment unit.As the SO of regenerated flue gas treatment unit process lower aq
xduring flue gas, its processing efficiency will decrease.In addition, though the cracking of hydrogenation wax catalysis to produce content of sulfur in gasoline lower, but still be difficult to the sulphur content in gasoline to be reduced to 10 micrograms/gram below, gasoline still needs aftertreatment.When the gasoline adopting S-Zorb technical finesse sulphur content lower, S-Zorb because of the sulphur content in gasoline too low, be difficult to maintain its balancing run, other sulfide need be supplemented from the external world, cause S-Zorb device utilization benefit to reduce.
Summary of the invention
The object of this invention is to provide the catalysis conversion method of the integrated technique of a kind of faulty wax oil catalytic cracking and hydrotreatment.The first embodiment of the present invention is as follows:
Catalysis conversion method provided by the invention comprises the following steps:
(1) high-sulfur wax oil and hot regenerated catalyst catalytic cracking unit reactor lower contacts and there is cracking reaction, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, separating reaction oil gas obtains the reaction product comprising liquefied gas, gasoline, diesel oil and catalytic wax oil, and reclaimable catalyst uses through stripping, regeneration Posterior circle;
(2) from the catalytic wax oil of step (1) and the wax oil of other optional secondary processing as the stock oil of hydrotreater, enter hydrotreating unit and carry out polycyclic aromatic hydrocarbons selective hydrogenation.
Step (2) gained hydrogenation wax oil turns back to catalytic cracking unit or other catalytic cracking unit of step (1).
The gasoline of step (1) enters gasoline sweetener, and diesel oil enters diesel fuel desulfurization device;
The regenerated flue gas of step (1) enters flue gas processing device and processes, the fume emission after process.
Catalysis conversion method provided by the invention is so concrete enforcement:
(1), catalytic cracking unit
A the high-sulfur inferior feedstock oil of (), preheating enters reactor and contacts with hot regenerated catalyst and cracking reaction occurs, temperature of reaction is 490 DEG C ~ 620 DEG C, be preferably 500 DEG C ~ 600 DEG C, reaction times is 0.5 second ~ 2.0 seconds, be preferably 0.8 second ~ 1.5 seconds, the weight ratio (hereinafter referred to as agent-oil ratio) of catalyzer and stock oil is 3 ~ 15: 1, is preferably 3 ~ 12: 1;
B oil gas and the used catalyst of (), generation are up, optionally hydrogen transfer reactions and isomerization reaction is there is under certain reaction environment, temperature of reaction is 420 DEG C ~ 550 DEG C, be preferably 460 DEG C ~ 500 DEG C, reaction times is 2 seconds ~ 30 seconds, be preferably 3 seconds ~ 15 seconds, the weight ratio of catalyzer and stock oil is 3 ~ 18: 1, be preferably 3 ~ 15: 1, the water vapor of cracking reaction and hydrogen transfer reactions and the weight ratio (hereinafter referred to as water-oil ratio) of stock oil are 0.03 ~ 0.3: 1, be preferably 0.05 ~ 0.3: 1, pressure is 130kPa ~ 450kPa;
C (), reaction product isolated obtain being rich in the liquefied gas of propylene, olefin(e) centent moderate gasoline, diesel oil, catalytic wax oil and other products, reclaimable catalyst enters revivifier through stripping, uses through coke burning regeneration Posterior circle.
D (), catalytic wax oil after filtration device or water distilling apparatus enter hydrotreater after removing a small amount of granules of catalyst.
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 a kind of Novel diameter reducing riser reactor, describes in detail and sees ZL99105903.4.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.
The high-sulfur wax oil that the method is suitable for is selected from atmospheric overhead, atmospheric tower is extracted out distillate, straight run decompressed wax oil, either shallow hydrogenation wax oil, wax tailings (CGO), deasphalted oil (DAO) and composition thereof, it is characterized by sulphur content and should be greater than 0.5 heavy %, more preferably greater than 1.0 heavy %.
Step (2) other secondary processing wax oil described is selected from CGO, DAO and composition thereof.
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.
(2) hydrotreating unit
Catalytic wax oil wax oil that is first and/or other secondary processing mixes, then heat and mix with hydrogen, enter the hydrotreatment reaction zone of filling hydrogenation catalyst, polycyclic aromatic hydrocarbons selective hydrogenation is carried out saturated under 8.0 ~ 16.0MPa pressure, reaction generates the hot high score that oil enters band separation function, the gaseous stream that high pressure hot separator top reserves is the lighter hydrocarbons that hydrogen-rich gas and hydrotreatment reaction generate, and the liquid phase stream reserved bottom high pressure hot separator is hydrogenation wax oil.The logistics of high pressure hot separator bottom liquid phases to be isolated after dissolved gases without fractionation directly as the raw material of catalytic cracking unit or the raw material of other unit further through thermal low-pressure separators.
Described catalytic wax oil (i.e. FGO) is not less than the cut of 260 DEG C for initial boiling point, and hydrogen richness is not less than 10.5 heavy %.In a more preferred embodiment, described catalytic wax oil is the cut that initial boiling point is not less than 330 DEG C, and hydrogen richness is not less than 10.8 heavy %.The wax oil of described secondary processing is wax tailings (CGO), deasphalted oil (DAO) and mixing raw material oil thereof.
The reactive system of described hydrotreater is generally fixed-bed reactor, and hydrotreatment reaction conditions is: reaction pressure 8.0 ~ 16.0MPa, preferred 11.0MPa ~ 15.0MPa; Temperature of reaction 300 ~ 430 DEG C, preferably 310 ~ 380 DEG C; Volume space velocity 0.2 ~ 5.0h
-1, preferably 0.4 ~ 3.0h
-1; Hydrogen to oil volume ratio 300 ~ 1000Nm
3/ m
3.
Catalyst loading pattern in described hydrotreatment fixed-bed reactor loads hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst successively.With integer catalyzer volume for benchmark, the admission space percentage ratio of hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst is respectively 2 ~ 20 volume %, 0 ~ 20 volume %, 60 ~ 98 volume %.
Heavily % molybdenum oxides, surplus are alumina supporter to 0.5 ~ 5.0 heavy % nickel oxide, 2.0 ~ 10.0 that consists of of described hydrogenation protecting agent.
Described hydrodemetallation (HDM) sweetening agent consists of 2.0 ~ 7.0 heavy % cobalt oxides, 10.0 ~ 30.0, and heavily % molybdenum oxides, surplus are alumina supporter.
Described hydrotreating catalyst be load at unformed aluminum oxide or/and the group vib in silica-alumina supports is or/and VIII non-precious metal catalyst, wherein said group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.
(3) other auxiliary units
Gasoline hydrodesulfurizationmethod delivered to by the gasoline of catalytic cracking unit or gasoline absorbing desulfurization device carries out gasoline desulfur, refers to patent CN101314734A or CN1658965A respectively, and the diesel oil of catalytic cracking unit enters diesel fuel desulfurization device and carries out diesel fuel desulfurization; The regenerated flue gas of catalytic cracking unit enters flue gas processing device, carries out fume treatment, the fume emission after process.
The invention has the advantages that:
1, improve different oil Refining Technologies utilization benefit, strengthening oil Refining Technologies is more reasonably integrated, provides a new approach for oil refining production process cleans to clean with refined oil product.
2, improve the utilization ratio of hydrogen in raw material, improve again the utilization ratio of the hydrogen of hydrotreatment simultaneously, thus can petroleum resources be saved.
3, gasoline yield and productivity of propylene is improved.
Accompanying drawing explanation
Fig. 1 is catalytic cracking provided by the invention and hydrotreatment integrated technology process principle process schematic diagram.
Fig. 2 is the schematic flow sheet of the preferred embodiment of the present invention.
Embodiment
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. 1 is catalytic cracking provided by the invention and hydrotreatment integrated technology process principle process schematic diagram.
High-sulfur wax oil raw material enters catalytic cracking reaction unit and carries out catalytic cracking reaction, catalytic cracking reaction unit is separated the catalytic wax oil cut obtained to be transported to hydrotreating unit and to carry out selective hydrogenation, obtain hydrogenation wax oil, this hydrogenation wax oil can turn back to former catalytic cracking unit, also can be transported to other reaction member.
Fig. 2 is the schematic flow sheet of the preferred embodiment of the present invention.Fig. 2 is the catalytic cracking of reducing riser reactor and the hydrotreatment integrated process flow schematic diagram of fixed-bed reactor, and shape, the size of equipment and pipeline not by the restriction of accompanying drawing, but are determined as the case may be.
In Fig. 2, each numbering is described as follows:
1,3,4,6,11,13,17,18,21,22,23 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, and 19 is separation system, and 20 is hydrotreater.
Pre-lift steam enters from riser tube pre lift zone 2 through pipeline 1, and the regenerated catalyst of heat enters riser tube pre lift zone through regenerator sloped tube 16 and 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 thermocatalyst after mixing.Reactant flow be mixed into second reaction zone 7 from the cold shock agent of pipeline 6 and/or the catalyzer (not marking in figure) 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 19 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 regenerated catalyst of heat returns riser tube bottom cycle through regenerator sloped tube 16 and uses.
In separation system 19, isolate dry gas, liquefied gas, gasoline, diesel oil (not marking in figure) and catalytic wax oil, wherein catalytic wax oil delivers to hydrotreater 20 through pipeline 21.
After mixing with new hydrogen and/or recycle hydrogen (not marking in figure) from the catalytic wax oil of pipeline 21, enter hydrotreater 20 and carry out polycyclic aromatic hydrocarbons saturated reaction, be isolated to lighting end and hydrogenation wax oil to extract out through pipeline 22,23 respectively, wherein hydrogenation wax oil is mixed into riser reactor or other catalytic cracking unit through pipeline 23 and high-sulfur wax oil.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.The stock oil character used in embodiment, comparative example lists in table 1, the trade mark of catalytic cracking catalyst is CGP-1, in hydrotreatment fixed bed reaction district, the catalyzer commercial grades of filling is respectively RG-10A/RG-10B/RMS-1/RN-32V, admission space ratio is 4: 4: 15: 77, and above catalyzer is produced by Sinopec catalyzer branch office.
Embodiment 1
The present embodiment illustrates and adopts method provided by the invention, the products distribution of raw material A after kitty cracker and medium-sized hydrotreater process and the situation of product property.
The raw material A of preheating is first processed at kitty cracker, and the pre lift zone of the reactor of kitty cracker, 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 °.Raw material A listed by table 1 enters in this reactor, in the presence of water vapor, contact with the catalyzer CGP-1 of heat and react, reaction product isolated obtains sour gas, dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic wax oil and coke and can calculate its products distribution, reclaimable catalyst enters revivifier through stripping, and regenerated catalyst uses through burning Posterior circle.In certain test period, obtain the catalytic wax oil of some amount, for medium-sized hydrotreater is supplied raw materials.
Catalytic wax oil carries out hydrotreatment on medium-sized hydrotreater, and after process, reaction product isolated obtains sour gas, a small amount of dry gas and liquefied gas and hydrogenation wax oil.In certain test period, obtain the hydrogenation wax oil of some amount, for kitty cracker is supplied raw materials.The operational condition that hydrogenation wax oil is processed on kitty cracker is completely identical with raw material A with catalyzer.The gross product distribution of three tests sums up process in the ratio of regulation to three cover products distribution, and the gasoline that catalytic gasoline character and catalytic diesel oil character obtain medium-sized twice catalytic cracking in the ratio of regulation and diesel oil carry out mixed converting, and then analyze gained.The character of the operational condition tested, product slates and product lists in table 2 and table 3.
Comparative example 1
Adopt medium-sized tester identical with embodiment 1 with catalyzer, stock oil used is also the raw material A listed by table 1.Just raw material A first carries out hydrotreatment on medium-sized hydrotreater, and after process, reaction product isolated obtains sour gas, a small amount of dry gas, a small amount of liquefied gas, petroleum naphtha, hydrogenated diesel oil and hydrogenation wax oil.In certain test period, obtain the hydrogenation wax oil of some amount, for kitty cracker is supplied raw materials.The operational condition that hydrogenation wax oil is processed on kitty cracker is completely identical with raw material A with catalyzer.The products distribution of two cover medium-sized testers is summed up calculating in the ratio of regulation, and obtain the products distribution that twice test is total, its products distribution lists in table 2.Catalytic gasoline, catalytic diesel oil and hydrogenated diesel oil character obtained by analysis.Its character lists in table 3.
As can be seen from table 2 and 3, relative to comparative example, the hydrogen consumption of the present invention's processing is 0.34 heavy %, reduce 69.09%, and both liquid yields are substantially identical, but iso-butylene productive rate rises to 3.65 heavy % by 1.31 heavy %, and add 178.63%, content of olefin in gasoline rises to 29.8 body % by 12.3 body %.
Embodiment 2
The present embodiment illustrates and adopts method provided by the invention, the products distribution of raw material B after kitty cracker and medium-sized hydrotreater process and the situation of product property.
The raw material B of preheating first processes at kitty cracker, and the pre lift zone of the reactor of kitty cracker, 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 °.Raw material B listed by table 1 enters in this reactor, in the presence of water vapor, contact with the catalyzer CGP-1 of heat and react, reaction product isolated obtains sour gas, dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic wax oil and coke and can calculate its products distribution, reclaimable catalyst enters revivifier through stripping, and regenerated catalyst uses through burning Posterior circle.In certain test period, obtain the catalytic wax oil of some amount, for medium-sized hydrotreater is supplied raw materials.
Catalytic wax oil carries out hydrotreatment on medium-sized hydrotreater, and after process, reaction product isolated obtains sour gas, a small amount of dry gas and liquefied gas and hydrogenation wax oil.In certain test period, obtain the hydrogenation wax oil of some amount, for kitty cracker is supplied raw materials.The operational condition that hydrogenation wax oil is processed on kitty cracker is completely identical with raw material B with catalyzer.The gross product distribution of three tests sums up process in the ratio of regulation to three cover products distribution, and the gasoline that catalytic gasoline character and catalytic diesel oil character obtain medium-sized twice catalytic cracking in the ratio of regulation and diesel oil carry out mixed converting, and then analyze gained.The character of the operational condition tested, product slates and product lists in table 2 and table 3.
Comparative example 2
Adopt medium-sized tester identical with embodiment 1 with catalyzer, stock oil used is also the raw material B listed by table 1.Just raw material B first carries out hydrotreatment on medium-sized hydrotreater, and after process, reaction product isolated obtains sour gas, a small amount of dry gas, a small amount of liquefied gas, petroleum naphtha, hydrogenated diesel oil and hydrogenation wax oil.In certain test period, obtain the hydrogenation wax oil of some amount, for kitty cracker is supplied raw materials.The operational condition that hydrogenation wax oil is processed on kitty cracker is completely identical with raw material B with catalyzer.The products distribution of two cover medium-sized testers is summed up calculating in the ratio of regulation, and obtain the products distribution that twice test is total, its products distribution lists in table 4.Catalytic gasoline, catalytic diesel oil and hydrogenated diesel oil character obtained by analysis.Its character lists in table 5.
As can be seen from table 4 and 5, relative to comparative example, the hydrogen consumption of the present invention's processing is 0.44 heavy %, reduce 60.00%, liquid yield is 88.02 heavy %, adds 0.93 percentage point, and iso-butylene productive rate rises to 3.19 heavy % by 1.37 heavy %, add 132.85%, content of olefin in gasoline rises to 33.8 body % by 16.6 body %.
Table 1
| Stock oil is numbered | A | B |
| Stock oil title | High-sulfur wax oil | High-sulfur wax oil |
| Density (20 DEG C), kg/m 3 | 907.7 | 933.7 |
| Kinematic viscosity, millimeter 2/ second | ||
| 80℃ | 11.53 | 10.67 |
| 100℃ | 7.02 | 6.47 |
| Carbon residue, heavy % | 0.30 | 0.67 |
| Condensation point, DEG C | 37 | 34 |
| Nitrogen, heavy % | 0.12 | 0.21 |
| Sulphur, heavy % | 1.80 | 3.26 |
| Carbon, heavy % | 85.49 | 85.24 |
| Hydrogen, heavy % | 12.34 | 11.53 |
| Boiling range, DEG C | ||
| Initial boiling point | 242 | 249 |
| 5％ | 349 | 342 |
| 10％ | 377 | 356 |
| 50％ | 446 | 427 |
| 70％ | 464 | 466 |
| 90％ | 498 | 530 |
| Final boiling point | 511 | / |
Table 2
| Embodiment 1 | Comparative example 1 | |
| Operational condition | ||
| Catalytic unit | ||
| Temperature of reaction, DEG C | ||
| First reaction zone/second reaction zone | 550/500 | 550/500 |
| The residence time, second | 5.5 | 5.5 |
| First reaction zone/second reaction zone | 2.0/3.5 | 2.0/3.5 |
| Agent-oil ratio | 5.0 | 5.0 |
| Water-oil ratio | 0.1 | 0.1 |
| Hydrogenation unit | ||
| Hydrogen dividing potential drop, MPa | 12.0 | 8.0 |
| Temperature of reaction, DEG C | 360 | 370 |
| Cumulative volume air speed, h -1 | 1.0 | 1.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 650 | 500 |
| Product slates, heavy % | ||
| Hydrogen sulfide | 1.27 | 1.60 |
| Ammonia | 0.06 | 0.12 |
| Dry gas | 2.02 | 1.90 |
| Liquefied gas | 24.54 | 22.01 |
| Wherein propylene | 8.34 | 6.76 |
| Iso-butylene | 3.65 | 1.31 |
| Gasoline | 45.87 | 39.74 |
| Wherein petroleum naphtha | 0.00 | 0.77 |
| Catalytic gasoline | 45.87 | 38.97 |
| Solar oil | 19.80 | 28.21 |
| Wherein hydrogenated diesel oil | 0.00 | 9.93 |
| Catalytic diesel oil | 19.80 | 18.28 |
| Heavy oil | 1.20 | 1.77 |
| Coke | 5.58 | 5.75 |
| Add up to | 100.34 | 101.10 |
| Liquid yield, heavy % | 90.21 | 89.96 |
| Chemistry consumption hydrogen, heavy % | 0.34 | 1.10 |
Table 3
| Embodiment 1 | Comparative example 1 | |
| Catalytic gasoline character and composition | ||
| Octane value | ||
| RON | 94.0 | 93.6 |
| MON | 81.0 | 81.0 |
| Boiling range, DEG C | ||
| Initial boiling point ~ do | 38～200 | 37～200 |
| Sulphur content, μ g/g | 1100 | 100 |
| Group composition, volume % | ||
| Alkene | 29.8 | 12.3 |
| Aromatic hydrocarbons | 21.3 | 25.7 |
| Catalytic diesel oil character | ||
| Density (20 DEG C), kg/m 3 | 910.0 | 905.0 |
| Sulphur content, heavy % | 2.0 | 0.20 |
| Boiling range scope, DEG C | 200～350 | 200～350 |
| Cetane value | 27 | 28 |
| Hydrogenated diesel oil character | ||
| Density (20 DEG C), kg/m 3 | / | 856.4 |
| Sulphur content, μ g/g | / | 240 |
| Boiling range scope, DEG C | / | 175～350 |
Table 4
| Embodiment 2 | Comparative example 2 | |
| Operational condition | ||
| Catalytic unit | ||
| Temperature of reaction, DEG C | ||
| First reaction zone/second reaction zone | 550/500 | 550/500 |
| The residence time, second | 5.5 | 5.5 |
| First reaction zone/second reaction zone | 2.0/3.5 | 2.0/3.5 |
| Agent-oil ratio | 5.0 | 5.0 |
| Water-oil ratio | 0.1 | 0.1 |
| Hydrogenation unit | ||
| Hydrogen dividing potential drop, MPa | 13.0 | 10.0 |
| Temperature of reaction, DEG C | 360 | 370 |
| Cumulative volume air speed, h -1 | 1.0 | 1.2 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 700 | 550 |
| Product slates, heavy % | ||
| Hydrogen sulfide | 2.57 | 3.35 |
| Ammonia | 0.18 | 0.21 |
| Dry gas | 2.32 | 2.15 |
| Liquefied gas | 22.50 | 21.12 |
| Wherein propylene | 7.44 | 6.54 |
| Iso-butylene | 3.19 | 1.37 |
| Gasoline | 43.18 | 39.27 |
| Wherein petroleum naphtha | 0.00 | 0.80 |
| Catalytic gasoline | 43.18 | 38.47 |
| Solar oil | 22.34 | 26.70 |
| Wherein hydrogenated diesel oil | 0.00 | 6.42 |
| Catalytic diesel oil | 22.34 | 20.28 |
| Heavy oil | 1.50 | 2.22 |
| Coke | 5.85 | 6.08 |
| Add up to | 100.44 | 101.10 |
| Liquid yield, heavy % | 88.02 | 87.09 |
| Chemistry consumption hydrogen, heavy % | 0.44 | 1.10 |
Table 5
| Embodiment 2 | Comparative example 2 | |
| Catalytic gasoline character and composition | ||
| Octane value | ||
| RON | 95.0 | 94.5 |
| MON | 81.5 | 81.5 |
| Boiling range, DEG C | ||
| Initial boiling point ~ do | 38～200 | 37～200 |
| Sulphur content, μ g/g | 2000 | 200 |
| Group composition, volume % | ||
| Alkene | 33.8 | 16.6 |
| Aromatic hydrocarbons | 22.1 | 26.7 |
| Catalytic diesel oil character | ||
| Density (20 DEG C), kg/m 3 | 935.0 | 920.0 |
| Sulphur content, heavy % | 3.3 | 0.60 |
| Boiling range scope, DEG C | 200～350 | 200～350 |
| Cetane value | 22 | 26 |
| Hydrogenated diesel oil character | ||
| Density (20 DEG C), kg/m 3 | / | 868.7 |
| Sulphur content, μ g/g | / | 568 |
| Boiling range scope, DEG C | / | 176～352 |
Claims (18)
1. a catalysis conversion method for petroleum hydrocarbon, is characterized in that the method comprises the following steps:
(1) high-sulfur wax oil and hot regenerated catalyst catalytic cracking unit reactor lower contacts and there is cracking reaction, 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 are 420C ~ 550 DEG C, reaction times is 2 seconds ~ 30 seconds, separating reaction oil gas obtains comprising liquefied gas, gasoline, the reaction product of diesel oil and catalytic wax oil, gained gasoline enters gasoline sweetener, diesel oil enters diesel fuel desulfurization device, reclaimable catalyst is through stripping, regeneration Posterior circle uses, regenerated flue gas enters flue gas processing device and processes, fume emission after process,
(2) enter hydrotreating unit from the catalytic wax oil of step (1) and other optional secondary processing wax oil and carry out polycyclic aromatic hydrocarbons selective hydrogenation;
The sulphur content of described high-sulfur wax oil is greater than 0.5 heavy %.
2., according to the method for claim 1, it is characterized in that step (2) gained hydrogenation wax oil turns back to catalytic cracking unit, as the stock oil of catalytic cracking.
3., according to the method for claim 1, it is characterized in that the sulphur content of described high-sulfur wax oil is greater than 1.0 heavy %.
4., according to the method for claim 1, it is characterized in that described high-sulfur wax oil is selected from atmospheric overhead, atmospheric tower is extracted out distillate, straight run decompressed wax oil, either shallow hydrogenation wax oil, wax tailings, deasphalted oil and composition thereof.
5., according to the method for claim 1, it is characterized in that other secondary processing wax oil described is selected from wax tailings, deasphalted oil and composition thereof.
6. according to the method for claim 1, it is characterized in that described cracking reaction condition is as follows: temperature of reaction is 490 DEG C ~ 620 DEG C, the reaction times is 0.5 second ~ 2.0 seconds, and the weight ratio of catalyzer and stock oil is 3 ~ 15: 1.
7. according to the method for claim 6, it is characterized in that described cracking reaction condition is as follows: temperature of reaction is 500 DEG C ~ 600 DEG C, the reaction times is 0.8 second ~ 1.5 seconds, and the weight ratio of catalyzer and stock oil is 3 ~ 12: 1.
8. according to the method for claim 1, it is characterized in that described hydrogen transfer reactions and isomerization reaction condition as follows: temperature of reaction is 460 DEG C ~ 500 DEG C, and the reaction times is 3 seconds ~ 15 seconds.
9. according to the method for claim 1, it is characterized in that step (1) reactor used 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.
10. according to the method for claim 9, it is characterized in that reducing riser tube, the diameter ratio of second reaction zone and the first reaction zone is 1.5 ~ 5.0: 1.
11. according to the method for claim 1, it is characterized in that step (1) used be zeolite catalyst, its active ingredient is selected from 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.
12., according to the method for claim 11, is characterized in that described y-type zeolite is selected from HY type zeolite, ultrastable Y－type zeolite or its mixture.
13., according to the method for claim 1, is characterized in that the described hydrotreatment reaction conditions of step (2) is: reaction pressure 8.0 ~ 16.0MPa, temperature of reaction 300 ~ 430 DEG C, volume space velocity 0.2 ~ 5.0h
-1, hydrogen to oil volume ratio 300 ~ 1000Nm
3/ m
3.
14., according to the method for claim 13, is characterized in that the described hydrotreatment reaction conditions of step (2) is: reaction pressure 11.0MPa ~ 15.0MPa, temperature of reaction 310 ~ 380 DEG C, volume space velocity 0.4 ~ 3.0h
-1.
15. according to the method for claim 1; it is characterized in that step (2) described hydrotreating reactor is fixed bed; hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst is loaded successively in fixed-bed reactor; with integer catalyzer volume for benchmark; the admission space percentage ratio of hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst is respectively 2 ~ 20 volume %, 0 ~ 20 volume % and 60 ~ 98 volume %.
16. according to the method for claim 15, it is characterized in that described hydrogenation protecting agent consist of 0.5 ~ 5.0 heavy % nickel oxide, 2.0 ~ 10.0 heavy % molybdenum oxides, surplus be alumina supporter.
17. according to the method for claim 15, it is characterized in that described hydrodemetallation (HDM) sweetening agent consists of 2.0 ~ 7.0 heavy % cobalt oxides, 10.0 ~ 30.0 heavy % molybdenum oxides, surplus are alumina supporter.
18. according to the method for claim 15, it is characterized in that described hydrotreating catalyst be load at unformed aluminum oxide or/and the group vib in silica-alumina supports is or/and VIII non-precious metal catalyst, wherein said group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.
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| CN109395731B (en) * | 2017-08-18 | 2021-09-03 | 中国石油化工股份有限公司 | Polycyclic aromatic hydrocarbon selective hydrogenation catalyst |
Citations (3)
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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 |
| CN1313379A (en) * | 2000-03-10 | 2001-09-19 | 中国石油化工集团公司 | Process for hydrogenating poor-quality raw material for catalytic cracking |
| CN101942340A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from inferior raw material oil |
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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 |
| CN1313379A (en) * | 2000-03-10 | 2001-09-19 | 中国石油化工集团公司 | Process for hydrogenating poor-quality raw material for catalytic cracking |
| CN101942340A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from inferior raw material oil |
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