CN102719272A - Catalytic conversion method of petroleum hydrocarbon - Google Patents
Catalytic conversion method of petroleum hydrocarbon Download PDFInfo
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Abstract
The invention discloses a catalytic conversion method of petroleum hydrocarbon, characterized by contacting high-sulfur wax oil with a heat regeneration catalyst at the lower portion of a catalytic cracking unit reactor and conducting cracking reaction, letting the generated oil gas and carbon-containing catalyst upstream be subject to selective hydrogen transfer reaction and isomerization reaction under certain reaction environment, separating the reaction oil gas to obtain a reaction product containing liquefied gas, gasoline and catalytic wax oil, and letting the spent catalyst be recycled after stripping and regeneration, wherein the catalytic wax oil and optional other secondary processing wax oil enters into the hydrotreatment unit to conduct polycyclic aromatic hydrocarbons selective hydrogenation, preferably the hydrogenation wax oil returns to the catalytic cracking unit. According to the invention, the gasoline yield and propylene yield are raised, the utilization rate of hydrogen in the raw materials is raised, and simultaneously the utilization rate of hydrogen in hydrotreatment is raised, thus the petroleum resource can be saved, and the invention provides a new approach for cleaning the refining process and refined oil products.
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 the regeneration fume from catalytic cracking
XDischarging does not meet environmental requirement, and the sulphur content in gasoline and the diesel product all can not meet the product specification requirement.Therefore, these high-sulfur faulty wax oil raw materials remove desulfuration, nitrogen and metal impurities earlier through hydrotreatment usually, and the polycyclic aromatic hydrocarbons in the 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 employing unifining technology and has improved the catalytically cracked material method for quality, and the temperature of reaction of this hydro-refining unit is lower than 390 ℃, and reaction pressure more than 10.0MPa, is preferably in more than the 12.0MPa at least.Helping under the saturated processing condition of aromatic hydrocarbons, improving the cracking performance of CCU raw material, thereby improving the transformation efficiency of CCU, producing high-octane gasoline blend component through unifining.CN101684417A discloses a kind of hydrogenation-catalytic cracking combination process of optimization; The wax oil raw material reacts at the hydrotreatment reaction zone; The hydrogenation wax oil that obtains is as catalytically cracked stock; Directly get into catalytic cracking unit without fractionation, catalysis heavy cycle oil loops back the hydrotreatment reaction zone, and the light circulation of high pressure hot separator top gaseous stream and catalysis gets into the hydro-upgrading reaction zone with optional gas oil; Carry out the hydro-upgrading reaction, resultant of reaction obtains hydrotreated naphtha and hydrogenated diesel oil after fractionation.The public hydrogen gas system in hydrotreatment unit and hydro-upgrading unit reduces 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, the faulty wax oil raw material can improve its catalytic cracking performance after hydrotreatment, but in the hydrotreatment process, can produce part diesel oil, petroleum naphtha and lighter hydrocarbons because boiling range lightens, and is unfavorable for voluminous gasoline and propylene.In addition, the catalytic cracking process of voluminous isoparaffin (MIP) is to handling fine catalytically cracked stock, especially hydrogenation wax oil; Cause content of olefin in gasoline on the low side; Iso-butylene content in the liquefied gas is on the low side, and products distribution is optimized inadequately, and petroleum resources are underused.
MIP technology is widely used, has been applied to nearly 50 cover CCUs at present, obtains huge economic benefit and social benefit.See ZL99105904.2, ZL99105905.0 and ZL99105903.4 about liquefied gas that is rich in Trimethylmethane and the MIP technology detailed description that is rich in isoparaffin gasoline.
Along with environmental regulation requires increasingly stringent to catalytic cracking production process and quality product, even hydrogenation wax oil, the SO in the regeneration fume from catalytic cracking are handled in catalytic cracking
XDischarging also is difficult to compliance with environmental protection requirements, still need increase the regenerated flue gas treatment unit.Handle the SO of lower aq when the regenerated flue gas treatment unit
XDuring flue gas, its processing efficiency will decrease.In addition, lower even content of sulfur in gasoline is produced in the cracking of hydrogenation wax catalysis, but still be difficult to the sulphur content in the gasoline is reduced to that 10 micrograms/below the gram, gasoline still needs aftertreatment.When adopting the lower gasoline of S-Zorb technical finesse sulphur content, S-Zorb is difficult to keep its balancing run because of the sulphur content in the gasoline is low excessively, needs to replenish from the external world other sulfide, causes S-Zorb device utilization benefit to reduce.
Summary of the invention
The catalysis conversion method that the purpose of this invention is to provide the integrated technique of a kind of faulty wax oil catalytic cracking and hydrotreatment.First kind of embodiment of the present invention is following:
Catalysis conversion method provided by the invention may further comprise the steps:
(1) the high-sulfur wax oil contacts in the bottom of catalytic cracking unit reactor drum with hot regenerated catalyst and cracking reaction takes place; The oil gas that generates and the catalyzer that contains charcoal be up, and optionally hydrogen transfer reactions and isomerization reaction take place under the certain reaction environment; Separating reaction oil gas obtains comprising the reaction product of liquefied gas, gasoline, diesel oil and catalytic wax oil, and reclaimable catalyst recycles after stripping, regeneration;
(2) from the wax oil of the catalytic wax oil of step (1) and optional other secondary processing raw oil, get into the hydrotreatment unit and carry out the polycyclic aromatic hydrocarbons selective hydrogenation as hydrotreater.
Step (2) gained hydrogenation wax oil turns back to catalytic cracking unit or other CCU of step (1).
The gasoline of step (1) gets into gasoline sweetener, and diesel oil gets into the diesel fuel desulfurization device;
The regenerated flue gas of step (1) gets into flue gas processing device and handles the fume emission after the processing.
Catalysis conversion method provided by the invention is such practical implementation:
(1), catalytic cracking unit
(a), the high-sulfur inferior feedstock oil of preheating gets into reactor drum and contacts with hot regenerated catalyst and cracking reaction takes place; Temperature of reaction is 490 ℃～620 ℃; Be preferably 500 ℃～600 ℃, the reaction times is 0.5 second～2.0 seconds, is preferably 0.8 second～1.5 seconds; The weight ratio of catalyzer and raw oil (hereinafter to be referred as agent-oil ratio) is 3～15: 1, is preferably 3～12: 1;
(b), the oil gas and the used catalyst that generate be up, and optionally hydrogen transfer reactions and isomerization reaction take place under the certain reaction environment, temperature of reaction is 420 ℃～550 ℃; Be preferably 460 ℃～500 ℃; Reaction times is 2 seconds～30 seconds, is preferably 3 seconds～15 seconds, and the weight ratio of catalyzer and raw oil is 3～18: 1; Be preferably 3～15: 1; The water vapor of cracking reaction and hydrogen transfer reactions and the weight ratio of raw oil (hereinafter to be referred as WOR) they are 0.03～0.3: 1, are preferably 0.05～0.3: 1, and pressure is 130kPa～450kPa;
(c), reaction product isolated obtains being rich in moderate gasoline, diesel oil, catalytic wax oil and other product of liquefied gas, olefin(e) centent of propylene, reclaimable catalyst gets into revivifier through stripping, behind coke burning regeneration, recycles.
(d), catalytic wax oil gets into hydrotreater after filtration unit or water distilling apparatus are removed a spot of granules of catalyst.
The reactor drum that this method is suitable for can be selected from the equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or the reducing riser tube, also can be the compound reactor that constitutes by equal diameter riser tube and fluidized-bed.
Method provided by the invention can the equal diameter riser tube, etc. carry out in linear speed riser tube or the fluidized-bed reactor, the conventional catalyst cracker in its intermediate diameters riser tube and refinery is identical, waits in the linear speed riser tube fluidic linear speed basic identical.The equal diameter riser tube, etc. the linear speed riser reactor be followed successively by pre lift zone, first reaction zone, second reaction zone from bottom to up; Fluidized-bed reactor is followed successively by first reaction zone, second reaction zone from bottom to up, and the ratio of the height of first reaction zone, second reaction zone is 10～40: 90～60.When use the equal diameter riser tube, etc. when linear speed riser tube or fluidized-bed reactor; Establish one or more cold shocks medium inlet in second reaction zone bottom; And/or in second reaction zone, heat collector being set, the height of heat collector accounts for 50%～90% of the second reaction zone height.Control the temperature and the reaction times of each reaction zone respectively.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from cold shock agent, refrigerative regenerated catalyst and refrigerative half regenerated catalyst.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively; The regenerated catalyst carbon content is below the 0.1 heavy %; Be preferably below the 0.05 heavy %; Half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.
Method provided by the invention also can be carried out in the compound reactor that is made up of equal diameter riser tube and fluidized-bed; The equal diameter riser tube of bottom is first reaction zone; The fluidized-bed on top is second reaction zone, controls the temperature and the reaction times of each reaction zone respectively.Establish one or more cold shocks medium inlet in the bottom of fluidized-bed, and/or in second reaction zone, heat collector is set, the height of heat collector accounts for 50%～90% of the second reaction zone height.Control the temperature and the reaction times of each reaction zone respectively.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from cold shock agent, refrigerative regenerated catalyst and refrigerative half regenerated catalyst.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively; The regenerated catalyst carbon content is below the 0.1 heavy %; Be preferably below the 0.05 heavy %; Half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.
Method provided by the invention can also be carried out in a kind of novel reducing riser reactor, describes in detail and sees ZL99105903.4.The diameter of pre lift zone is identical with conventional equal diameter riser reactor, is generally 0.02 meter～5 meters, and it highly accounts for 5%～10% of total reactor height.The effect of pre lift zone be promote in advance medium in the presence of regenerated catalyst moved upward and quicken, used identical of used preparatory lifting medium and the equal diameter riser reactor of routine is selected from water vapor or dry gas.
The similar of first reaction zone is in the equal diameter riser reactor of routine; Its diameter can be identical with pre lift zone; Also can be big slightly than pre lift zone, the diameter of first reaction zone and the diameter ratio of pre lift zone are 1.0～2.0: 1, it highly accounts for 10%～30% of total reactor height.Cracking reaction under higher temperature of reaction and agent-oil ratio, residence time (being generally 0.5 second～2.5 seconds) of lacking, mainly takes place in raw oil and catalyzer after this district is mixed.
Second reaction zone is thicker than first reaction zone, and the diameter ratio of its diameter and first reaction zone is 1.5～5.0: 1, and it highly accounts for 30%～60% of total reactor height.Its effect is flow velocity and the temperature of reaction that reduces oil gas and catalyzer.Reduce the method for this district's temperature of reaction; Can inject the cold shock medium from the combining site of this district and first reaction zone; And/or through heat collector being set in this district; Take the part heat away to reduce this district's temperature of reaction, suppress the purpose that secondary cracking reacts, increases isomerization reaction and hydrogen transfer reactions thereby reach.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from cold shock agent, refrigerative regenerated catalyst and refrigerative half regenerated catalyst.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively; The regenerated catalyst carbon content is below the 0.1 heavy %; Be preferably below the 0.05 heavy %; Half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.If heat collector is set, then it highly accounts for 50%～90% of the 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 first reaction zone is 0.8～1.5: 1, and it highly accounts for 0～20% of total reactor height.Logistics can stop certain hour in this district, to suppress cracking reaction and heat cracking reaction, improves rate of flow of fluid.
The high-sulfur wax oil that this method is suitable for is selected from distillate that atmospheric overhead, atmospheric tower extract out, straight run decompressed wax oil, shallow degree hydrogenation wax oil, wax tailings (CGO), deasphalted oil (DAO) and composition thereof; It is characterized by sulphur content should be greater than 0.5 heavy %, more preferably greater than 1.0 heavy %.
Said other secondary processing wax oil of step (2) is selected from CGO, DAO and composition thereof.
Two reaction zones in this method can be suitable for the catalyzer of all same types; It both can be the amorphous silicon aluminium catalyzer; It also can be zeolite catalyst; The active ingredient of zeolite catalyst is selected from y-type zeolite, HY type zeolite, ultrastable Y, ZSM-5 series zeolite or has the supersiliceous zeolite of five-membered ring structure, one or more the mixture of arbitrary proportion in the ferrierite, and this zeolite can contain rare earth and/or phosphorus, also can not contain rare earth and phosphorus.
Two reaction zones in this method also can be suitable for dissimilar catalyzer, and dissimilar catalyzer can be particle size different catalyst and/or apparent bulk density different catalyst.Active ingredient is selected dissimilar zeolites respectively for use on particle size different catalyst and/or the apparent bulk density different catalyst; Zeolite is selected from y-type zeolite, HY type zeolite, ultrastable Y, ZSM-5 series zeolite or has the supersiliceous zeolite of five-membered ring structure, one or more the mixture of arbitrary proportion in the ferrierite; This zeolite can contain rare earth and/or phosphorus, also can not contain rare earth and phosphorus.The catalyzer of particulate catalyzer and/or the height apparent bulk density of varying in size can get into different reaction zones respectively; For example; The oarse-grained catalyzer that contains ultrastable Y gets into first reaction zone, increases cracking reaction, and the short grained catalyzer that contains rare earth Y type zeolite gets into second reaction zone; Increase hydrogen transfer reactions; The particle size different catalyst is isolated macrobead and catalyst particle then in same stripper stripping and the regeneration of same revivifier, and catalyst particle gets into second reaction zone through cooling.The particle size different catalyst is between 30～40 microns, to demarcate, and the apparent bulk density different catalyst is with 0.6～0.7g/cm
3Between the boundary.
(2) hydrotreatment unit
The wax oil of catalytic wax oil elder generation and/or other secondary processing mixes; Heating and mix then with hydrogen; Get into the hydrotreatment reaction zone of filling hydrogenation catalyst, it is saturated under 8.0～16.0MPa pressure, to carry out the polycyclic aromatic hydrocarbons selective hydrogenation, and reaction generates the hot high score that oil gets into the band separation function; The gaseous stream that the high pressure hot separator top is reserved is the lighter hydrocarbons that hydrogen-rich gas and hydrotreatment reaction generate, and the liquid phase stream that the high pressure hot separator bottom is reserved is the hydrogenation wax oil.The logistics of high pressure hot separator bottom liquid phases after thermal low-pressure separators is further isolated dissolved gases without fractionation directly as raw material or other unitary raw materials of catalytic cracking unit.
Described catalytic wax oil (being FGO) is for over point is not less than 260 ℃ cut, and hydrogen richness is not less than 10.5 heavy %.In a more preferred embodiment, said catalytic wax oil is that over point is not less than 330 ℃ cut, 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 the hydrotreatment reaction conditions is: reaction pressure 8.0～16.0MPa, preferred 11.0MPa～15.0MPa; 300～430 ℃ of temperature of reaction, preferred 310～380 ℃; Volume space velocity 0.2～5.0h
-1, preferred 0.4～3.0h
-1Hydrogen to oil volume ratio 300～1000Nm
3/ m
3
Catalyst loading pattern in the described hydrotreatment fixed-bed reactor loads hydrogenation protecting agent, HDM sweetening agent and hydrotreating catalyst successively.With the integer catalyzer volume is benchmark, and the admission space percentage ratio of hydrogenation protecting agent, 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 HDM sweetening agent consists of 2.0～7.0 heavy % powder blues, 10.0～30.0, and heavily % molybdenum oxides, surplus are alumina supporter.
Described hydrotreating catalyst be load on unformed aluminum oxide or/and the group vib on the silica-alumina supports or/and VIII family non-precious metal catalyst; Wherein said group vib base metal is a molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, the iron.
(3) other auxiliary units
Gasoline hydrodesulfurizationmethod delivered to by the gasoline of catalytic cracking unit or the gasoline absorbing desulfurization device carries out gasoline desulfur, sees patent CN101314734A or CN1658965A respectively for details, and the diesel oil of catalytic cracking unit gets into the diesel fuel desulfurization device and carries out diesel fuel desulfurization; The regenerated flue gas of catalytic cracking unit gets into flue gas processing device, carries out flue gas and handles the fume emission after the processing.
The invention has the advantages that:
1, improve different oil Refining Technologies utilization benefits, it is more reasonably integrated to strengthen oil Refining Technologies, cleans the new approach that provides for the oil refining production process cleans with refined oil product.
2, improved the utilization ratio of hydrogen in the raw material, improved the utilization ratio of the hydrogen of hydrotreatment again simultaneously, thereby can practice thrift petroleum resources.
3, improve gasoline yield and productivity of propylene.
Description of drawings
Fig. 1 is catalytic cracking provided by the invention and hydrotreatment integrated technology process principle process synoptic diagram.
Fig. 2 is the schematic flow sheet of preferred implementation of the present invention.
Embodiment
Further specify method provided by the present invention below in conjunction with accompanying drawing, but therefore the present invention does not receive any restriction.
Fig. 1 is catalytic cracking provided by the invention and hydrotreatment integrated technology process principle process synoptic diagram.
High-sulfur wax oil raw material gets into the catalytic cracking reaction unit and carries out catalytic cracking reaction; The catalytic cracking reaction unit is separated the catalytic wax oil cut obtain to be transported to the hydrotreatment unit and to carry out selective hydrogenation; Obtain the 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 preferred implementation of the present invention.Fig. 2 is the catalytic cracking of reducing riser reactor and the hydrotreatment integrated technique schematic flow sheet of fixed-bed reactor, and the shape of equipment and pipeline, size do not receive the restriction of accompanying drawing, but confirms as the case may be.
Each numbering explanation is as follows among Fig. 2:
1,3,4,6,11,13,17,18,21,22,23 all represents pipeline; 2 is the pre lift zone of riser tube; 5,7 be respectively riser tube first reaction zone, second reaction zone; 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.
Promote steam in advance and get into from riser tube pre lift zone 2 through pipeline 1, the regenerated catalyst of heat gets into the riser tube pre lift zone through regenerator sloped tube 16 and is promoted by preparatory lifting steam.Raw oil after the preheating gets into from the riser tube pre lift zone through pipeline 4 and atomizing steam from pipeline 3 by a certain percentage, mixes with thermocatalyst in back entering first reaction zone 5, carries out cracking reaction under certain conditions.Reactant flow be mixed into second reaction zone 7 from the cold shock agent and/or the refrigerative catalyzer (not marking among the figure) of pipeline 6; Carry out secondary reaction; Reacted logistics gets into outlet area 8; This reaction zone improves the linear speed of logistics, makes reactant flow get into settling vessel 9, cyclonic separator 10 in the gas solid separation system fast, and reaction product is gone separation system 19 through pipeline 11.The reclaimable catalyst of reaction back band charcoal gets into stripper 12; After from the water vapor stripping of pipeline 13, get into revivifier 15 by inclined tube 14 to be generated; Reclaimable catalyst is coke burning regeneration in from the air of pipeline 17; Flue gas goes out revivifier through pipeline 18, and the regenerated catalyst of heat returns the 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 among the figure) and catalytic wax oil, wherein catalytic wax oil is delivered to hydrotreater 20 through pipeline 21.
From the catalytic wax oil of pipeline 21 with after new hydrogen and/or recycle hydrogen (not marking among the figure) mix; Get into hydrotreater 20 and carry out the polycyclic aromatic hydrocarbons saturated reaction; The warp separation obtains lighting end and the hydrogenation wax oil is extracted out through pipeline 22,23 respectively, and wherein the hydrogenation wax oil is mixed into riser reactor or other CCU through pipeline 23 and high-sulfur wax oil.
Embodiment
Following embodiment will further specify the present invention, but therefore not limit the present invention.Employed raw oil character is listed in table 1 in embodiment, the Comparative Examples; The trade mark of catalytic cracking catalyst is CGP-1; The commercial trade mark of the catalyzer of filling is respectively RG-10A/RG-10B/RMS-1/RN-32V in the hydrotreatment fixed bed reaction district; The admission space ratio is 4: 4: 15: 77, and above catalyzer is produced by Sinopec catalyzer branch office.
Method provided by the invention is adopted in present embodiment explanation, products distribution and the situation of product property of raw material A after kitty cracker and medium-sized hydrotreater are handled.
The raw material A of preheating is processed at kitty cracker earlier, and the pre lift zone of the reactor drum of kitty cracker, first reaction zone, second reaction zone, outlet area total height are 15 meters, and the pre lift zone diameter is 0.025 meter, and it highly is 1.5 meters; First reaction zone diameter is 0.025 meter, and it highly is 4 meters; Second reaction zone diameter is 0.1 meter, and it highly is 6.5 meters; The diameter of outlet area is 0.025 meter, and it highly is 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 °.The listed raw material A of table 1 gets in this reactor drum; 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, and reclaimable catalyst gets into revivifier through stripping, and regenerated catalyst recycles after burning.In certain test period, obtain the catalytic wax oil of some amount, for medium-sized hydrotreater is supplied raw materials.
Catalytic wax oil is carried out hydrotreatment on medium-sized hydrotreater, handle the back reaction product isolated and obtain 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 the hydrogenation wax oil is processed on kitty cracker is fully identical with raw material A with catalyzer.The gross product of three tests the ratio in regulation of distributing adds three cover products distribution and handles, and catalytic gasoline character and catalytic diesel oil character are mixed the medium-sized twice resulting gasoline of catalytic cracking and diesel oil in the ratio of stipulating and converted, and analyze gained then.The operational condition of test, product distribute and the character of product is listed in table 2 and table 3.
Comparative Examples 1
Adopt medium-sized tester and catalyzer and embodiment 1 identical, used raw oil also is the listed raw material A of table 1.Just raw material A is carried out earlier hydrotreatment on medium-sized hydrotreater, handles the back reaction product isolated and obtains sour gas, a small amount of dry gas, a spot 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 the hydrogenation wax oil is processed on kitty cracker is fully identical with raw material A with catalyzer.The products distribution of the two cover medium-sized testers ratio in regulation is added and calculates, obtain the total products distribution of twice test, its products distribution is listed in table 2.Catalytic gasoline, catalytic diesel oil and hydrogenated diesel oil character are resulting through analyzing.Its character is listed in table 3.
Can find out from table 2 and 3; With respect to Comparative Examples, the hydrogen consumption of the present invention's processing is 0.34 heavy %, has reduced by 69.09%; And liquid yield both are basic identical; But the iso-butylene productive rate rises to 3.65 heavy % by 1.31 heavy %, has increased by 178.63%, and content of olefin in gasoline rises to 29.8 body % by 12.3 body %.
Method provided by the invention is adopted in present embodiment explanation, products distribution and the situation of product property of raw material B after kitty cracker and medium-sized hydrotreater are handled.
The raw material B of preheating processes at kitty cracker earlier, and the pre lift zone of the reactor drum of kitty cracker, first reaction zone, second reaction zone, outlet area total height are 15 meters, and the pre lift zone diameter is 0.025 meter, and it highly is 1.5 meters; First reaction zone diameter is 0.025 meter, and it highly is 4 meters; Second reaction zone diameter is 0.1 meter, and it highly is 6.5 meters; The diameter of outlet area is 0.025 meter, and it highly is 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 °.The listed raw material B of table 1 gets in this reactor drum; 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, and reclaimable catalyst gets into revivifier through stripping, and regenerated catalyst recycles after burning.In certain test period, obtain the catalytic wax oil of some amount, for medium-sized hydrotreater is supplied raw materials.
Catalytic wax oil is carried out hydrotreatment on medium-sized hydrotreater, handle the back reaction product isolated and obtain 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 the hydrogenation wax oil is processed on kitty cracker is fully identical with raw material B with catalyzer.The gross product of three tests the ratio in regulation of distributing adds three cover products distribution and handles, and catalytic gasoline character and catalytic diesel oil character are mixed the medium-sized twice resulting gasoline of catalytic cracking and diesel oil in the ratio of stipulating and converted, and analyze gained then.The operational condition of test, product distribute and the character of product is listed in table 2 and table 3.
Comparative Examples 2
Adopt medium-sized tester and catalyzer and embodiment 1 identical, used raw oil also is the listed raw material B of table 1.Just raw material B carries out earlier hydrotreatment on medium-sized hydrotreater, handles the back reaction product isolated and obtains sour gas, a small amount of dry gas, a spot 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 the hydrogenation wax oil is processed on kitty cracker is fully identical with raw material B with catalyzer.The products distribution of the two cover medium-sized testers ratio in regulation is added and calculates, obtain the total products distribution of twice test, its products distribution is listed in table 4.Catalytic gasoline, catalytic diesel oil and hydrogenated diesel oil character are resulting through analyzing.Its character is listed in table 5.
Can find out that from table 4 and 5 with respect to Comparative Examples, the hydrogen consumption of the present invention's processing is 0.44 heavy %; Reduced by 60.00%; Liquid yield is 88.02 heavy %, has increased by 0.93 percentage point, and the iso-butylene productive rate rises to 3.19 heavy % by 1.37 heavy %; Increased by 132.85%, content of olefin in gasoline rises to 33.8 body % by 16.6 body %.
Table 1
| The raw oil numbering | A | B |
| The raw oil title | The high-sulfur wax oil | The high-sulfur wax oil |
| Density (20 ℃), kilogram/rice 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, ℃ | 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, ℃ | ||
| Over point | 242 | 249 |
| 5％ | 349 | 342 |
| 10％ | 377 | 356 |
| 50％ | 446 | 427 |
| 70％ | 464 | 466 |
| 90％ | 498 | 530 |
| Final boiling point | 511 | / |
Table 2
| |
Comparative Examples 1 | |
| Operational condition | ||
| Catalytic unit | ||
| Temperature of reaction, ℃ | ||
| 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 |
| WOR | 0.1 | 0.1 |
| Hydrogenation unit | ||
| The hydrogen dividing potential drop, MPa | 12.0 | 8.0 |
| Temperature of reaction, ℃ | 360 | 370 |
| The TV air speed, h -1 | 1.0 | 1.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 650 | 500 |
| Product distributes, heavy % | ||
| Hydrogen sulfide | 1.27 | 1.60 |
| Ammonia | 0.06 | 0.12 |
| Dry gas | 2.02 | 1.90 |
| Liquefied gas | 24.54 | 22.01 |
| Propylene wherein | 8.34 | 6.76 |
| Iso-butylene | 3.65 | 1.31 |
| Gasoline | 45.87 | 39.74 |
| Petroleum naphtha wherein | 0.00 | 0.77 |
| Catalytic gasoline | 45.87 | 38.97 |
| Solar oil | 19.80 | 28.21 |
| Hydrogenated diesel oil wherein | 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
| |
Comparative Examples 1 | |
| Catalytic gasoline character and composition | ||
| Octane value | ||
| RON | 94.0 | 93.6 |
| MON | 81.0 | 81.0 |
| Boiling range, ℃ | ||
| Over 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 ℃), kilogram/rice 3 | 910.0 | 905.0 |
| Sulphur content, heavy % | 2.0 | 0.20 |
| The boiling range scope, ℃ | 200～350 | 200～350 |
| Cetane value | 27 | 28 |
| Hydrogenated diesel oil character | ||
| Density (20 ℃), kilogram/rice 3 | / | 856.4 |
| Sulphur content, μ g/g | / | 240 |
| The boiling range scope, ℃ | / | 175～350 |
Table 4
| |
Comparative Examples 2 | |
| Operational condition | ||
| Catalytic unit | ||
| Temperature of reaction, ℃ | ||
| 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 |
| WOR | 0.1 | 0.1 |
| Hydrogenation unit | ||
| The hydrogen dividing potential drop, MPa | 13.0 | 10.0 |
| Temperature of reaction, ℃ | 360 | 370 |
| The TV air speed, h -1 | 1.0 | 1.2 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 700 | 550 |
| Product distributes, heavy % | ||
| Hydrogen sulfide | 2.57 | 3.35 |
| Ammonia | 0.18 | 0.21 |
| Dry gas | 2.32 | 2.15 |
| Liquefied gas | 22.50 | 21.12 |
| Propylene wherein | 7.44 | 6.54 |
| Iso-butylene | 3.19 | 1.37 |
| Gasoline | 43.18 | 39.27 |
| Petroleum naphtha wherein | 0.00 | 0.80 |
| Catalytic gasoline | 43.18 | 38.47 |
| Solar oil | 22.34 | 26.70 |
| Hydrogenated diesel oil wherein | 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
| |
Comparative Examples 2 | |
| Catalytic gasoline character and composition | ||
| Octane value | ||
| RON | 95.0 | 94.5 |
| MON | 81.5 | 81.5 |
| Boiling range, ℃ | ||
| Over 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 ℃), kilogram/rice 3 | 935.0 | 920.0 |
| Sulphur content, heavy % | 3.3 | 0.60 |
| The boiling range scope, ℃ | 200～350 | 200～350 |
| |
22 | 26 |
| Hydrogenated diesel oil character | ||
| Density (20 ℃), kilogram/rice 3 | / | 868.7 |
| Sulphur content, μ g/g | / | 568 |
| The boiling range scope, ℃ | / | 176～352 |
Claims (21)
1. the catalysis conversion method of a petroleum hydrocarbon is characterized in that this method may further comprise the steps:
(1) the high-sulfur wax oil contacts in the bottom of catalytic cracking unit reactor drum with hot regenerated catalyst and cracking reaction takes place; The oil gas that generates and the catalyzer that contains charcoal be up, and optionally hydrogen transfer reactions and isomerization reaction take place under the certain reaction environment; Separating reaction oil gas obtains comprising the reaction product of liquefied gas, gasoline, diesel oil and catalytic wax oil, and reclaimable catalyst recycles after stripping, regeneration;
(2) carry out the polycyclic aromatic hydrocarbons selective hydrogenation from the catalytic wax oil of step (1) with other optional secondary processing wax oil entering hydrotreatment unit.
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 raw oil of catalytic cracking.
3. according to the method for claim 1, it is characterized in that the gasoline of step (1) gets into gasoline sweetener, diesel oil gets into the diesel fuel desulfurization device.
4. according to the method for claim 1, it is characterized in that the regenerated flue gas entering flue gas processing device of step (1) is handled the fume emission after the processing.
5. according to the method for claim 1, the sulphur content that it is characterized in that said high-sulfur wax oil is greater than 0.5 heavy %.
6. according to the method for claim 5, the sulphur content that it is characterized in that said high-sulfur wax oil is greater than 1.0 heavy %.
7. according to the method for claim 1, it is characterized in that said high-sulfur wax oil is selected from the distillate of atmospheric overhead, atmospheric tower extraction, straight run decompressed wax oil, shallow degree hydrogenation wax oil, wax tailings, deasphalted oil and composition thereof.
8. according to the method for claim 1, it is characterized in that said other secondary processing wax oil is selected from wax tailings, deasphalted oil and composition thereof.
9. according to the method for claim 1, it is characterized in that said cracking reaction condition is following: temperature of reaction is 490 ℃～620 ℃, and the reaction times is 0.5 second～2.0 seconds, and the weight ratio of catalyzer and raw oil is 3～15: 1.
10. according to the method for claim 9, it is characterized in that said cracking reaction condition is following: temperature of reaction is 500 ℃～600 ℃, and the reaction times is 0.8 second～1.5 seconds, and the weight ratio of catalyzer and raw oil is 3～12: 1.
11. according to the method for claim 1, it is characterized in that said hydrogen transfer reactions and isomerization reaction condition are following: temperature of reaction is 420 ℃～550 ℃, the reaction times is 2 seconds～30 seconds.
12. according to the method for claim 11, it is characterized in that said hydrogen transfer reactions and isomerization reaction condition are following: temperature of reaction is 460 ℃～500 ℃, the reaction times is 3 seconds～15 seconds.
13. according to the method for claim 1, it is characterized in that the used reactor drum of step (1) be selected from the equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or the reducing riser tube, or the compound reactor that constitutes by equal diameter riser tube and fluidized-bed.
14. according to the method for claim 13, it is characterized in that the reducing riser tube, the diameter ratio of second reaction zone and first reaction zone is 1.5～5.0: 1.
15. method according to claim 1; It is characterized in that step (1) used be zeolite catalyst, its active ingredient is selected from y-type zeolite, HY type zeolite, ultrastable Y, ZSM-5 series zeolite or has the supersiliceous zeolite of five-membered ring structure, one or more the mixture of arbitrary proportion in the ferrierite.
16., it is characterized in that the said hydrotreatment reaction conditions of step (2) is: reaction pressure 8.0～16.0MPa, 300～430 ℃ of temperature of reaction, volume space velocity 0.2～5.0h according to the method for claim 1
-1, hydrogen to oil volume ratio 300～1000Nm
3/ m
3
17., it is characterized in that the said hydrotreatment reaction conditions of step (2) is: reaction pressure 11.0MPa～15.0MPa, 310～380 ℃ of temperature of reaction, volume space velocity 0.4～3.0h according to the method for claim 16
-1
18. method according to claim 1; It is characterized in that the said hydrotreating reactor of step (2) is a fixed bed; In fixed-bed reactor, load hydrogenation protecting agent, HDM sweetening agent and hydrotreating catalyst successively; With the integer catalyzer volume is benchmark, and the admission space percentage ratio of hydrogenation protecting agent, HDM sweetening agent and hydrotreating catalyst is respectively 2～20 volume %, 0～20 volume % and 60～98 volume %.
19., it is characterized in that consist of 0.5～5.0 heavy % nickel oxide, 2.0～10.0 heavy % molybdenum oxides, surplus of said hydrogenation protecting agent is alumina supporter according to the method for claim 18.
20. according to the method for claim 18, heavily % molybdenum oxides, surplus are alumina supporter to it is characterized in that consisting of 2.0～7.0 heavy % powder blues, 10.0～30.0 by said HDM sweetening agent.
21. method according to claim 18; It is characterized in that said hydrotreating catalyst be load on unformed aluminum oxide or/and the group vib on the silica-alumina supports or/and VIII family non-precious metal catalyst; Wherein said group vib base metal is a molybdenum or/and tungsten, and VIII family base metal is one or more in nickel, cobalt, the iron.
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| WO2017063309A1 (en) * | 2015-10-15 | 2017-04-20 | 中国石油化工股份有限公司 | Method for processing inferior feedstock oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017063309A1 (en) * | 2015-10-15 | 2017-04-20 | 中国石油化工股份有限公司 | Method for processing inferior feedstock oil |
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| US11365360B2 (en) | 2015-10-15 | 2022-06-21 | China Petroleum & Chemical Corporation | Process for converting inferior feedstock oil |
| GB2558157B (en) * | 2015-10-15 | 2022-07-13 | China Petroleum & Chem Corp | A process for converting inferior feedstock oil |
| CN109395731A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics selective hydrocatalyst |
| 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 |
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