CN102911730B - Catalytic conversion method for high sulfur wax oil - Google Patents
Catalytic conversion method for high sulfur wax oil Download PDFInfo
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Abstract
The invention relates to a catalytic conversion method for high sulfur wax oil. The method comprises the following steps: the high sulfur wax oil and a thermal regeneration catalyst are contacted at the lower part of a first catalyst unit reactor and are subjected to a cracking reaction, and the generated oil gas and catalyst containing carbon ascend and are subjected to a secondary cracking reaction and an isomerization reaction under a certain reaction environment; the oil gas is subjected to a separation reaction to obtain a reaction product containing liquefied gas, gasoline and catalytic wax oil; a spent catalyst is subjected to steam stripping and regeneration to be recycled, wherein the catalytic wax oil and optional other secondary processed wax oil are hydrogenated; and the hydrogenated wax oil enters a second catalyst unit to be further cracked. According to the method, low carbon olefins such as propylene are furthest produced, and meanwhile the high-octane gasoline is also produced. The invention provides a new way for the cleanness of an oil refining production process and the cleanness of oil-refined 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 high-sulfur 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 sulfur 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 hydrocarbon 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.
US3775290 discloses and a kind of desalted crude, catalysis heavy-cycle oil and wax tailings etc. mixing carries out hydrotreatment, and hydrogenation tail oil carries out the combined technical method of catalytic cracking again.US4780193 discloses a kind of method adopting high pressure, low temperature hydrogenation treatment technology to improve catalytically cracked material quality, the reaction temperature 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 process conditions being conducive to aromatic saturation, improved the cracking performance of catalytic cracking unit raw material by hydrofinishing, thus improve the conversion ratio 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 at 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, reaction product 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 operating cost.Products scheme is flexible, can produce high-quality low-sulfur gasoline, fine-quality diesel oil and reformer feed simultaneously.
EP0022883A1 discloses a kind of catalytic cracking and hydroprocessing technique combines the method for producing high-knock rating gasoline for the treatment of sulfur-bearing raw material.First it be that sulfur-bearing raw material is obtained catalytic gasoline in the reaction production of first cracking district, then catalytic gasoline enters at least saturated some olefin of the second cracking reaction zone, and the product of cracking again is at least partially hydroprocessed high-knock rating gasoline or the high-knock rating gasoline blend component of producing low sulfur content.
CN1667089A disclose a kind of by first for heavy charge hydrogenation again catalytic cracking carry out to produce to greatest extent the chemical industry type oil refining method of propylene, ethene and aromatic hydrocarbons simultaneously, but the method hydrogen consumption is too high, simultaneously because meeting in the first hydrogenation process of raw material is inevitably due to the raw material of acid cracking loss of reaction part producing propylene.
Therefore be not difficult to find, when adopting above-mentioned catalytic cracking and poor quality or sulfur-bearing raw material are processed in hydroprocessing technique combination, its main purpose produces the high-knock rating gasoline of low-sulfur.This is mainly because faulty wax oil raw material reduces through hydrotreatment after stain thing, aromatic hydrocarbons obtains saturated to some extent, thus can improve its Catalytic Cracking Performance and producing high-octane gasoline.But a problem that can not be ignored is as noted, because cracking reaction and generating portion diesel oil, naphtha and lighter hydrocarbons can occur in the catalytic action of acid in catalyst in the first hydroprocessing processes of raw material, therefore the hydrotreated bottom oil obtained is unfavorable for as fcc raw material the Organic Chemicals that fecund is important, low-carbon alkene, as propylene, ethene, butylene etc.Therefore be necessary to develop a kind of method of producing low-carbon alkene and high-knock rating gasoline for high-sulfur faulty wax oil.
In addition, along with environmental regulation requires increasingly stringent to catalytic cracking production process and product quality, high-sulfur wax oil inferior first through hydrotreatment again catalytic cracking still there is many problems, the SO in regeneration fume from catalytic cracking
xdischarge is also difficult to meet environmental requirement, and still needing increases regenerated flue gas treating apparatus.As the SO of regenerated flue gas treating apparatus process lower content
xduring flue gas, its treatment effeciency 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 sulfur content in gasoline to be reduced to 10 micrograms/gram below, gasoline still needs post processing.When the gasoline adopting S ~ Zorb technical finesse sulfur content lower, S ~ Zorb because of the sulfur 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 the catalytic cracking of a kind of high-sulfur faulty wax oil and hydrotreatment, mainly for the production of low-carbon alkene particularly propylene take into account the method for high-knock rating gasoline simultaneously.
Catalysis conversion method provided by the invention comprises the following steps:
(1) high-sulfur wax oil and hot recycling catalytic cracking catalyst the first catalyst unit reactor lower contacts and there is cracking reaction, the oil gas generated and up containing the catalyst of charcoal, secondary cracking reaction and isomerization reaction is optionally there is further under certain reaction environment, separating reaction oil gas and reclaimable catalyst, separating reaction oil gas obtains the product comprising propylene, propane, butane, light petrol, heavy petrol, diesel oil and catalytic wax oil, and reclaimable catalyst uses through stripping, regeneration Posterior circle;
(2) from catalytic wax oil and other optional secondary operations wax oil mixing of step (1), as the feedstock oil of hydrotreater, enter hydrotreating unit and carry out polycyclic aromatic hydrocarbon selective hydrogenation;
(3) wax oil after hydrogenation enters the second catalyst unit reactor, and with hot recycling catalytic cracking catalyst generation catalytic cracking reaction, separating reaction oil gas and reclaimable catalyst, reclaimable catalyst uses through stripping, regeneration Posterior circle;
(4) reaction oil gas described in separating step (3) obtains the product comprising propylene, propane, butane, light petrol, heavy petrol and diesel oil.
The product of preferred steps of the present invention (1) and (4) comprise propane, butane and light petrol one or more return the second catalyst unit reactor;
The heavy petrol of step (1) and (4) enters gasoline sweetener, and diesel oil enters diesel fuel desulfurization device;
The regenerated flue gas of step (1) and (4) enters flue gas processing device and processes, the fume emission after process.
Catalysis conversion method provided by the invention is so concrete enforcement:
(1), the first catalyst unit
A the high-sulfur feed of (), preheating enters the first catalyst unit reactor first reaction zone and contacts with hot recycling catalytic cracking catalyst and cracking reaction occurs, reaction temperature is 500 DEG C ~ 650 DEG C, be preferably 520 DEG C ~ 620 DEG C, reaction time is 1 second ~ 10 seconds, the weight ratio (hereinafter referred to as oil ratio) of catalyst and described feedstock oil is 5 ~ 30, the weight ratio (hereinafter referred to as water-oil factor) of water vapour and described feedstock oil is 0.05 ~ 0.6, pressure (absolute pressure) 0.15 ~ 0.4MPa;
B (), the oil gas generated and used catalyst are advanced into the first catalyst cracker second reaction zone, secondary cracking reaction and isomerization reaction is there is under certain reaction environment, reaction temperature is lower than the first reaction zone cracking reaction temperature 5 ~ 30 DEG C preferred low 5 ~ 20 DEG C, weight (hourly) space velocity (WHSV) 0.5 ~ 20h
-1, oil ratio is 5 ~ 50, and water-oil factor is 0.05 ~ 0.6, pressure (absolute pressure) 0.15 ~ 0.4MPa;
C (), reaction product isolated obtain propylene, propane, butane, light petrol, heavy petrol, diesel oil, catalytic wax oil and other products, reclaimable catalyst enters regenerator through stripping, use through coke burning regeneration Posterior circle, regenerated flue gas enters flue gas processing device and processes, the fume emission after process.
D (), catalytic wax oil are directly or/and enter hydrotreater after removing a small amount of catalyst granules.Catalytic wax oil can be passed through filter device or/and distilling apparatus removes a small amount of catalyst granules.
First catalyst unit reactor used can be the reducing riser reactor of the double-reaction area including the first and second reaction zones, and the detailed description of this reducing riser reactor is shown in ZL99105903.4; The compound reactor that also can be the compound reactor be made up of riser and fluid bed, the compound reactor be made up of riser and downstriker pipeline, the compound reactor be made up of plural riser, the compound reactor be made up of the fluid beds of two, the compound reactor be made up of plural downstriker pipeline or be made up of plural moving bed.First reactor of compound reactor is called the first reaction zone in the methods of the invention, and the second reactor and subsequent reactor are called second reaction zone.The preferred reactor of the inventive method is reducing riser reactor.
In first catalytic cracking unit, no matter adopt compound reactor or reducing riser reactor, cold shock medium can be injected at the binding site of second reaction zone and the first reaction zone, also can not inject cold shock medium, but preferably inject cold shock medium, to control the reaction temperature of second reaction zone.Cold shock medium is selected from one or more in cold shock agent, reclaimable catalyst, the regenerated catalyst of cooling and the semi regeneration catalyst of cooling.Wherein cold shock agent is selected from one or more in diesel oil, heavy diesel fuel or water; The regenerated catalyst of cooling and the semi regeneration catalyst of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration.
In first catalyst unit, regenerated catalyst carbon content is 0.1 heavy below %, is 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 % ~ 0.5.
In first catalyst unit, the MAT Active pharmaceutical of regenerated catalyst is 30% ~ 80%, preferably 35% ~ 75%.If introduce reclaimable catalyst, semi regeneration catalyst controls second reaction zone temperature, then the MAT Active pharmaceutical of reclaimable catalyst, semi regeneration catalyst is 20% ~ 60%, preferably 40% ~ 55%.
(2) second catalyst units
This catalytic cracking unit reactor used can be the reducing riser reactor of the double-reaction area including the first and second reaction zones, and the detailed description of this reducing riser reactor is shown in ZL99105903.4; The compound reactor that also can be the compound reactor be made up of riser and fluid bed, the compound reactor be made up of riser and downstriker pipeline, the compound reactor be made up of plural riser, the compound reactor be made up of plural fluid bed, the compound reactor be made up of plural downstriker pipeline or be made up of plural moving bed.First reactor of compound reactor is called the first reaction zone in the methods of the invention, and the second reactor is called second reaction zone.The preferred reactor of the inventive method is reducing riser reactor.
When adopting compound reactor to be reactor, in compound reactor, the first reaction zone process conditions are: reaction temperature is 520 ~ 670 DEG C preferably 530 ~ 660 DEG C, pressure (absolute pressure) 0.15 ~ 0.4MPa, 1 ~ 10 second time of staying, oil ratio are 5 ~ 30, water-oil factor is 0.05 ~ 0.6.In compound reactor, the process conditions of second reaction zone are: reaction temperature is higher than the first reaction zone temperature 10 ~ 100 DEG C, preferably 15 ~ 80 DEG C; Pressure (absolute pressure) 0.15 ~ 0.4MPa, weight (hourly) space velocity (WHSV) 0.5 ~ 20h
-1, this reaction zone inner catalyst amount and the first and second reaction zones the weight ratio of combined feed be 5 ~ 50, the weight ratio of water vapour and high-sulfur wax oil is 0.05 ~ 0.6.
When adopting the reducing riser reactor containing the first and second reaction zones to be reactor, the process conditions of reducing riser reactor are: pressure (absolute pressure) 0.15 ~ 0.4MPa of reactor.In first reaction zone: reaction temperature is 500 ~ 650 DEG C preferably 520 ~ 620 DEG C, preferably 2 ~ 8 seconds 1 ~ 10 second time of staying, oil ratio is 5 ~ 30, water-oil factor is 0.05 ~ 0.6.In second reaction zone: reaction temperature is higher than the first reaction zone temperature 10 ~ 100 DEG C, preferably 15 ~ 80 DEG C; Weight (hourly) space velocity (WHSV) 0.5 ~ 30h
-1, the weight ratio of the combined feed of this reaction zone Inner eycle catalytic amount and the first and second reaction zones is 5 ~ 50, and the weight ratio of water vapour and high-sulfur wax oil is 0.05 ~ 0.6.
First reaction zone temperature of the second catalyst unit is higher than the first reaction zone temperature of the first catalyst unit.
In second catalyst unit, no matter adopt compound reactor or reducing riser reactor, need further injected media at the binding site of second reaction zone and the first reaction zone, to realize further propylene enhancing object.Medium comprises thermal medium and various hydrocarbon recycle.Thermal medium is selected from one or more in high-temperature regenerated catalyst and high temperature semi regeneration catalyst, for improving the high selectivity preferred high temperature semi regeneration catalyst of propylene.One or more in the propane that hydrocarbon recycle obtains after being through separation of products, butane and light petrol.
In second catalyst unit, regenerated catalyst carbon content is 0.1 heavy below %, is 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 % ~ 0.5.
In second catalyst unit, the MAT Active pharmaceutical of regenerated catalyst is 30% ~ 70%, preferably 35% ~ 65%.The MAT Active pharmaceutical of semi regeneration catalyst is 20% ~ 60%, preferably 30% ~ 50%.
In second catalyst unit, when the light petrol mentioned refers to and adopts ASTM D86 method, boiling range does the gasoline fraction being less than 120 DEG C, is preferably less than the gasoline fraction of 80 DEG C.
In second catalyst unit, for controlling the reaction temperature of second reaction zone, required temperature can be precooled to as required to supplementing the thermal medium entering second reaction zone.
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 sulfur content and should be greater than 0.5 heavy %, more preferably greater than 1.0 heavy %.
Step (2) other secondary operations wax oil described is selected from CGO, DAO and composition thereof.
Two reaction zones in the method can be suitable for the catalyst of all same types, both can be amorphous silicon aluminium catalyst, also can be zeolite catalyst, the active component of zeolite catalyst is selected from y-type zeolite, HY type zeolite, ultrastable, ZSM ~ 5 series zeolite or has one or more in the silica-rich 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 catalyst, and dissimilar catalyst can be the catalyst that catalyst that granular size is different and/or apparent bulk density are different.The catalyst 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, ZSM ~ 5 series zeolite or has one or more in the silica-rich 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 catalyst and/or height apparent bulk density catalyst can enter different reaction zones respectively, such as, oarse-grained catalyst containing ultrastable enters the first reaction zone, increase cracking reaction, short grained catalyst containing rare earth Y type zeolite enters second reaction zone, increase hydrogen transfer reaction, the catalyst that granular size is different regenerates at same stripper stripping and same regenerator, then isolate bulky grain and catalyst particle, catalyst particle enters second reaction zone through cooling.The catalyst that granular size is different is demarcated between 30 ~ 40 microns, and the catalyst that apparent bulk density is different is with 0.6 ~ 0.7g/cm
3between boundary.
(2) hydrotreating unit
The wax oil mixing of other secondary operations that catalytic wax oil is first and optional, then heat and mix with hydrogen, enter the hydrotreatment reaction zone of filling hydrogenation catalyst, polycyclic aromatic hydrocarbon 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.
The reaction system of described hydrotreater is generally fixed bed reactors, and hydrotreatment reaction condition is: reaction pressure 8.0 ~ 16.0MPa, preferred 11.0MPa ~ 15.0MPa; Reaction temperature 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 reactors loads hydrogenation protecting agent, HDM desulfurizing agent and hydrotreating catalyst successively.With integer catalyzer volume for benchmark, the admission space percentage of hydrogenation protecting agent, HDM desulfurizing agent and hydrotreating catalyst is respectively 2 ~ 20 volume %, 0 ~ 20 volume %, 60 ~ 98 volume %.
Heavily % molybdenum oxides, surplus are alumina support to 0.5 ~ 5.0 heavy % nickel oxide, 2.0 ~ 10.0 that consists of of described hydrogenation protecting agent.
Described HDM desulfurizing agent consists of 2.0 ~ 7.0 heavy % cobalt oxides, 10.0 ~ 30.0, and heavily % molybdenum oxides, surplus are alumina support.
Described hydrotreating catalyst be load at unformed aluminium 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.
Described catalytic wax oil (FGO) is not less than the cut of 260 DEG C for initial boiling point, and hydrogen content 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 content is not less than 10.8 heavy %.The wax oil of described secondary operations is wax tailings (CGO), deasphalted oil (DAO) and mixed material oil thereof.
(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 hydrogen utilization rate in raw material, improve again the utilization rate of the hydrogen of hydrotreatment simultaneously, thus can petroleum resources be saved.
3, directly can produce the low-carbon alkenes such as propylene to greatest extent from high-sulfur faulty wax oil and take into account high-knock rating gasoline production simultaneously.
Accompanying drawing explanation
Accompanying drawing is the catalysis conversion method principle process schematic diagram of high-sulfur wax oil provided by the invention.
Detailed description of the invention
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.
Accompanying drawing is the schematic flow sheet of the preferred embodiment of the present invention, by the catalytic cracking of reducing riser reactor and the hydrotreatment of fixed bed reactors integrated, the shape of equipment and pipeline, size by the restriction of accompanying drawing, but are determined as the case may be.In accompanying drawing, each numbering is described as follows:
1,3,4,6,11,13,17,18,31,32,33,34,36,37,52,53,56 all pipeline is represented; 2 is the pre lift zone of the first catalyst unit riser; 5,7 the first reaction zone, the second reaction zone being respectively the first catalyst unit riser; 8 is the outlet area of the first catalyst unit riser; 9 is the first catalyst unit settler, 10 is the first catalyst unit cyclone separator, 12 is the first catalyst unit stripping section, 14 is the first catalyst unit inclined tube to be generated, and 15 is the first catalyst unit regenerator, and 16 is the first catalyst unit regenerator sloped tube, 20 is fractionating column, 30 is fixed bed hydrogenation device, and 35 is high-pressure separator, 51,50 the first reaction zone, the second reaction zone being respectively the second catalyst unit riser.
At the first catalyst unit, pre-lift steam enters from riser pre lift zone 2 through pipeline 1, and the regenerated catalyst of heat enters riser pre lift zone through regenerator sloped tube 16 and promoted by pre-lift steam.High-sulfur wax oil raw material after preheating enters from riser 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.React logistics and be mixed into second reaction zone 7 from the cold shock agent of pipeline 6 and/or the catalyst (not marking in figure) of cooling, carry out secondary response, reacted logistics enters outlet area 8, this reaction zone improves the linear speed of logistics, make reaction logistics enter settler 9, cyclone separator 10 in gas solid separation system fast, product goes piece-rate system 20 through pipeline 11.After reaction, the reclaimable catalyst of band charcoal enters stripper 12, through entering regenerator 15 from after the water vapour 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 regenerator through pipeline 18, enter flue gas processing device to process, fume emission (not shown) after process, the regenerated catalyst of heat returns riser bottom cycle through regenerator sloped tube 16 and uses.
In piece-rate system 20, isolate dry gas, liquefied gas, light petrol, heavy petrol, diesel oil and catalytic wax oil, catalytic wax oil delivers to hydrotreating unit 30 through pipeline 31.Wherein liquefied gas is separated into one of object product propylene and propane, butane further, propane, butane and light petrol return to the second reaction zone of the second catalyst unit riser reactor, heavy petrol enters gasoline sweetener, and diesel oil enters diesel fuel desulfurization device (not shown).
After the recycle hydrogen of the catalytic wax oil from pipeline 31 and the new hydrogen from pipeline 32 and pipeline 33 mixes, enter hydrotreating unit 30 and carry out polycyclic aromatic hydrocarbon saturated reaction, the reaction generation oil obtained enters high-pressure separator 35 through pipeline 34 and is separated, high-pressure separator 35 top gas phase stream passes via line 36 is extracted out, and bottom liquid phases logistics is hydrogenation wax oil extracts out through pipeline 37, the first reaction zone 51 delivering to the reducing riser reactor of the second catalyst unit carries out catalytic cracking reaction again, in the bottom of the second catalyst unit second reaction zone 50, hydrocarbon recycle is introduced by pipeline 52, thermal medium is introduced by pipeline 53, the reaction oil gas obtained at the second reaction member is sent into separator 20 by pipeline 56 and is carried out separation of products.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.The feedstock oil character used in embodiment, comparative example lists in table 1, in hydrotreatment fixed bed reaction district, the catalyst commercial grades of filling is respectively RG ~ 10A/RG ~ 10B/RMS ~ 1/RN ~ 32V, admission space ratio is 4: 4: 15: 77, and above catalyst is produced by Sinopec catalyst branch company.
In embodiment, the preparation method of catalytic cracking catalyst used is as follows:
1) by 20g NH
4cl is dissolved in 1000g water, and (Sinopec catalyst branch company produces, SiO then to add 100g (butt) crystallization product ZRP-1 zeolite
2/ Al
2o
3=30, RE
2o
3=4.0%), 90 DEG C exchange 0.5h, filter to obtain filter cake.Add 4.0g H
3pO
4(concentration 85%) and 4.5g Fe (NO
3)
3be dissolved in 90g water, dry with filter cake hybrid infusion.Calcination process 2h at 550 DEG C subsequently.
2) with 250kg decationized Y sieve water, by 75.4kg halloysite, (Suzhou china clay company produces, solid content 71.6%) making beating, add 54.8kg boehmite (Shandong Aluminum Plant produces, solid content 63%) again, with hydrochloric acid, its PH is adjusted to 2 ~ 4, stir, leave standstill aging 1h at 60 ~ 70 DEG C, keep PH to 2 ~ 4, cool the temperature to less than 60 DEG C, (Sinopec catalyst branch company produces, Al to add 41.5kg Alumina gel
2o
3content is 21.7%), stir 40 minutes, obtain mixed serum.
3) by step 1) (Sinopec catalyst branch company produces, and lattice constant is 2.445 ~ 2.448nm, RE for the MFI mesopore zeolite (butt 45kg) of phosphorous and iron prepared and DASY zeolite
2o
3be 2.0%, butt 7.5kg) join step 2) in the slurries that obtain, stir, spraying dry.With ammonium dihydrogen phosphate (phosphorus content is 1%) washing, drying obtains catalyst sample.
Embodiment 1
The present embodiment illustrates and adopts method provided by the invention, the product distribution of raw material A after kitty cracker and medium-sized hydrotreater process and the situation of product property.First catalyst unit all adopts mutually isostructural kitty cracker with the second catalyst unit, but the operating condition of two catalyst units is different.
Kitty cracker adopts reducing riser reactor.The pre lift zone of reactor, the first reaction zone, second reaction zone, outlet area total height are 15 meters, and pre lift zone diameter is 0.025 meter, and it is highly 1.5 meters; First reaction zone diameter is 0.025 meter, and it is highly 4 meters; Second reaction zone diameter is 0.1 meter, and it is highly 6.5 meters; The diameter of outlet area is 0.025 meter, and it is highly 3 meters; The drift angle of the vertical section isosceles trapezoid of first and second reaction zone binding site is 45 °; The base angle of the vertical section isosceles trapezoid of second reaction zone and outlet area binding site is 60 °.
The raw material A of preheating is first processed at the kitty cracker of the first catalyst unit, raw material A listed by table 1 enters in this reactor, in the presence of water vapor, contact with the catalyst CGP-1 of heat and react, reaction product isolated obtains sour gas, dry gas, liquefied gas, catalytic light gasoline (doing 80 DEG C), catalysis heavy petrol, catalytic diesel oil, catalytic wax oil and coke also can calculate the distribution of its product, reclaimable catalyst enters regenerator through stripping, and regenerated catalyst uses through burning Posterior circle.In certain test period, obtain the catalytic wax oil of some, 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 catalyst wax oil.In certain test period, obtain the hydrogenation catalyst wax oil of some.
Hydrogenation catalyst wax oil enters the first reaction zone of the kitty cracker of the second catalyst unit as raw material, the catalytic light gasoline that first catalyst unit obtains enters the second reaction zone of the second catalyst unit device, carry out catalytic cracking reaction, reaction obtains dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy oil and coke equally.
The gross product distribution of three tests sums up process in the ratio of regulation to three cover product distributions, 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 sample presentation analyzes gained.
Operating condition and the product slates of test list in table 2, and the character of product lists in table 3.
Comparative example 1
Medium-sized tester is identical with embodiment 1 with catalyst.Just raw material 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, naphtha, hydrogenated diesel oil and hydrogenation catalyst wax oil.In certain test period, obtain the hydrogenation catalyst wax oil of some, the kitty cracker that hydrogenation catalyst wax oil enters the first catalyst unit subsequently reacts.The product distribution of two cover medium-sized testers is summed up calculating in the ratio of regulation, obtains the product distribution that twice test is total, table 2 is listed in its operating condition and product distribution.Catalytic gasoline, catalytic diesel oil and hydrogenated diesel oil character obtained through sample presentation 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 0.28 heavy %, and reduce 74.55 heavy %, productivity of propylene is increased to 30.36% from 20.76%, and content of olefin in gasoline rises to 18.4 body % by 10.3 body %.
Table 1
| Feedstock oil is numbered | A |
| Feedstock oil title | High-sulfur wax oil |
| Density (20 DEG C), kg/m 3 | 907.7 |
| Kinematic viscosity, millimeter 2/ second | |
| 80℃ | 11.53 |
| 100℃ | 7.02 |
| Carbon residue, heavy % | 0.30 |
| Condensation point, DEG C | 37 |
| Nitrogen, heavy % | 0.12 |
| Sulphur, heavy % | 1.80 |
| Carbon, heavy % | 85.49 |
| Hydrogen, heavy % | 12.34 |
| Boiling range, DEG C | |
| Initial boiling point | 242 |
| 5％ | 349 |
| 10％ | 377 |
| 50％ | 446 |
| 70％ | 464 |
| 90％ | 498 |
| The end point of distillation | 511 |
Table 2
| Embodiment 1 | Comparative example 1 | |
| Operating condition | ||
| First catalyst unit | ||
| Reaction temperature, DEG C | ||
| First reaction zone/second reaction zone | 540/530 | 560/580 |
| The first reaction zone time of staying, second | 1.5 | 2.0 |
| Second reaction zone weight (hourly) space velocity (WHSV), h -1 | 10 | 5 |
| Oil ratio | 10.0 | 14.0 |
| Water-oil factor | 0.15 | 0.15 |
| Hydrogenation unit | ||
| Hydrogen dividing potential drop, MPa | 12.0 | 8.0 |
| Reaction temperature, 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 |
| Second catalyst unit | ||
| Reaction temperature, DEG C | ||
| First reaction zone/second reaction zone | 560/580 | / |
| The first reaction zone time of staying, second | 2.0 | / |
| Second reaction zone weight (hourly) space velocity (WHSV), h -1 | 10 | / |
| Oil ratio | 14.0 | / |
| Water-oil factor | 0.15 | / |
| Product slates, heavy % | ||
| Hydrogen sulfide | 1.27 | 1.60 |
| Ammonia | 0.04 | 0.12 |
| H 2+CH 4+C 2H 6 | 5.90 | 3.90 |
| Ethene | 9.27 | 6.0 |
| Liquefied gas | 58.46 | 46.01 |
| Wherein propylene | 30.36 | 20.76 |
| Gasoline | 11.08 | 21.74 |
| Wherein naphtha | 0.00 | 0.77 |
| Catalytic gasoline | 11.08 | 20.97 |
| Light diesel fuel | 4.90 | 12.21 |
| Heavy oil | 1.10 | 1.77 |
| Coke | 8.26 | 7.75 |
| Add up to | 100.28 | 101.10 |
| Chemistry consumption hydrogen, heavy % | 0.28 | 1.10 |
Table 3
| Embodiment 1 | Comparative example 1 | |
| Catalytic gasoline character and composition | ||
| Octane number | ||
| RON | 98.8 | 97.8 |
| MON | 86 | 82.5 |
| Sulfur content, μ g/g | 1910 | 360 |
| Group composition, volume % | ||
| Alkene | 18.4 | 10.3 |
| Aromatic hydrocarbons | 75.1 | 72.2 |
| Wherein benzene | 1.9 | 1.6 |
| Toluene | 9.7 | 7.2 |
| Dimethylbenzene+ethylbenzene | 21.2 | 18.6 |
| Catalytic diesel oil character | ||
| Density (20 DEG C), kg/m 3 | 950.0 | 945.0 |
| Sulfur content, heavy % | 3.2 | 0.20 |
| Boiling range scope, DEG C | 200～360 | 200～360 |
| Cetane number | 19 | 21 |
Claims (22)
1. a catalysis conversion method for high-sulfur wax oil, is characterized in that the method comprises the following steps:
(1) high-sulfur wax oil and hot recycling catalytic cracking catalyst the first catalyst unit reactor lower contacts and there is cracking reaction, the reaction time of cracking reaction is 1.5 ~ 10 seconds, the oil gas generated and up containing the catalyst of charcoal, secondary cracking reaction and isomerization reaction is optionally there is further under certain reaction environment, separating reaction oil gas and reclaimable catalyst, separating reaction oil gas obtains the product comprising propylene, propane, butane, light petrol, heavy petrol, diesel oil and catalytic wax oil, and reclaimable catalyst uses through stripping, regeneration Posterior circle;
(2) from catalytic wax oil and other optional secondary operations wax oil mixing of step (1), as the feedstock oil of hydrotreater, enter hydrotreating unit and carry out polycyclic aromatic hydrocarbon selective hydrogenation;
(3) wax oil after hydrogenation enters the second catalyst unit reactor, and with hot recycling catalytic cracking catalyst generation catalytic cracking reaction, separating reaction oil gas and reclaimable catalyst, reclaimable catalyst uses through stripping, regeneration Posterior circle;
(4) reaction oil gas described in separating step (3) obtains the product comprising propylene, propane, butane, light petrol, heavy petrol and diesel oil;
The sulfur content of described high-sulfur wax oil is greater than 0.5 heavy %.
2., according to the method for claim 1, one or more that it is characterized in that the product of step (1) comprises propane, butane and light petrol return the second catalyst unit reactor.
3., according to the method for claim 1, it is characterized in that the heavy petrol of step (1) and (4) enters gasoline sweetener, diesel oil enters diesel fuel desulfurization device.
4., according to the method for claim 1, it is characterized in that the regenerated flue gas of step (1) and (4) enters flue gas processing device and processes, the fume emission after process.
5., according to the method for claim 1, it is characterized in that the sulfur content of described high-sulfur wax oil is greater than 1.0 heavy %.
6., 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.
7., according to the method for claim 1, it is characterized in that other secondary operations wax oil described is selected from wax tailings, deasphalted oil and composition thereof.
8., according to the method for claim 1, it is characterized in that described first catalyst unit cracking reaction condition is as follows: reaction temperature is 500 DEG C ~ 650 DEG C, and the weight ratio of catalyst and high-sulfur wax oil is 5 ~ 30.
9., according to the method for claim 8, it is characterized in that described first catalyst unit cracking reaction condition is as follows: reaction temperature is 520 DEG C ~ 620 DEG C.
10. according to the method for claim 1, it is characterized in that described first catalyst unit secondary cracking reaction and isomerization reaction temperature lower than cracking reaction temperature 5 ~ 30 DEG C, weight (hourly) space velocity (WHSV) 0.5 ~ 20h
-1.
11. according to the method for claim 1, it is characterized in that described first catalyst unit secondary cracking reaction and isomerization reaction temperature lower than cracking reaction temperature 5 ~ 20 DEG C.
12. according to the method for claim 1, it is characterized in that injecting cold shock medium at the binding site in described first catalytic cracking unit secondary cracking and isomerization reaction zone and cracking reaction district, cold shock medium is selected from one or more in cold shock agent, reclaimable catalyst, the regenerated catalyst of cooling and the semi regeneration catalyst of cooling, and wherein cold shock agent is selected from one or more in diesel oil or water; The regenerated catalyst of cooling and the semi regeneration catalyst of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration.
13. according to the method for claim 1, it is characterized in that the compound reactor that step (1) and (3) reactor used are selected from the reducing riser reactor comprising double-reaction area, the compound reactor be made up of riser and fluid bed, the compound reactor be made up of riser and downstriker pipeline, the compound reactor be made up of plural riser, the compound reactor be made up of the fluid beds of two, the compound reactor be made up of plural downstriker pipeline or are made up of plural moving bed.
14. according to the method for claim 13, and it is characterized in that the first reactor of described compound reactor is the first reaction zone, the second reactor and subsequent reactor are second reaction zone.
15. according to the method for claim 14, and it is characterized in that the second catalyst unit first reaction zone conditions is as follows: reaction temperature is 520 DEG C ~ 670 DEG C, the reaction time is 1 second ~ 10 seconds, and the weight ratio of catalyst and high-sulfur wax oil is 5 ~ 30.
16., according to the method for claim 15, is characterized in that the second catalyst unit first reaction zone conditions is as follows: reaction temperature is 530 DEG C ~ 660 DEG C.
17., according to the method for claim 13, is characterized in that the second catalyst unit second reaction zone condition is as follows: reaction temperature is higher than the first reaction zone reaction temperature 10 ~ 100 DEG C, weight (hourly) space velocity (WHSV) 0.5 ~ 20h
-1.
18., according to the method for claim 17, is characterized in that the second catalyst unit second reaction zone reaction temperature is higher than the first reaction zone reaction temperature 15 ~ 80 DEG C.
19. according to the method for claim 13, it is characterized in that the binding site injected media in the second catalyst unit second reaction zone and the first reaction zone, described medium comprises thermal medium and various hydrocarbon recycle, wherein thermal medium is selected from one or more in high-temperature regenerated catalyst and high temperature semi regeneration catalyst, one or more in the propane that hydrocarbon recycle obtains after being through separation of products, butane and light petrol.
20. according to the method for claim 1, it is characterized in that step (1) and (3) catalyst used are zeolite catalysts, its active component is selected from y-type zeolite, HY type zeolite, ultrastable, ZSM ~ 5 series zeolite or has one or more in the silica-rich zeolite of five-membered ring structure, ferrierite.
21., according to the method for claim 1, is characterized in that the described hydrotreatment reaction condition of step (2) is: reaction pressure 8.0 ~ 16.0MPa, reaction temperature 300 ~ 430 DEG C, volume space velocity 0.2 ~ 5.0h
-1, hydrogen to oil volume ratio 300 ~ 1000Nm
3/ m
3.
22., according to the method for claim 21, is characterized in that the described hydrotreatment reaction condition of step (2) is: reaction pressure 11.0MPa ~ 15.0MPa, reaction temperature 310 ~ 380 DEG C, volume space velocity 0.4 ~ 3.0h
-1.
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| CN101362959A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing propone and high-octane number gasoline |
| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
| 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 |
| CN101987972A (en) * | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for processing inferior crude oil through combined processes |
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| CN101362959A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing propone and high-octane number gasoline |
| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
| 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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