CN1142255C - Process for catalytic cracking of heavy petroleum hydrocarbon - Google Patents
Process for catalytic cracking of heavy petroleum hydrocarbon Download PDFInfo
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- CN1142255C CN1142255C CNB001093762A CN00109376A CN1142255C CN 1142255 C CN1142255 C CN 1142255C CN B001093762 A CNB001093762 A CN B001093762A CN 00109376 A CN00109376 A CN 00109376A CN 1142255 C CN1142255 C CN 1142255C
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Abstract
The present invention relates to a catalytic cracking method of heavy petroleum hydrocarbons, which comprises: a regenerated cracking catalyst after being lowered in the temperature by a thermal balance adjustor is supplied into a four-section serial reactor, contacts preheated heavy hydrocarbons as raw materials and react with the preheated heavy hydrocarbons under the conditions that the temperature is from 500 to 550DEG C, the pressure is from 130 to 350 Kpa, the catalyst-oil ratio is from 5 to 20, and the reaction time is from 1 to 4 seconds; the catalyst to be regenerated after the reaction is supplied into the thermal balance adjustor to be lowered in the temperature after being stripped and regenerated, and the cracking catalyst lowered in the temperature is returned to the reactor and circularly used. The light oil yield of the heavy hydrocarbons as the raw materials processed with the method provided by the present invention can reach 65 to 68 wt%, and the total yield of light hydrocarbon liquid can reach 80 to 84 wt% or even higher.
Description
Technical field
The invention belongs to the catalyst cracking method of petroleum hydrocarbon, more particularly, is the catalyst cracking method that belongs to processing heavy petroleum hydrocarbon in the presence of molecular sieve catalyst.
Background technology
Along with the heaviness of crude oil in the world wide, need process more long residuum, vacuum residuum, wax tailings and diasphaltene wet goods heavy, inferior raw material as the catalytic cracking process of one of main means of oil refining industry ＂ heavy oil lighting ＂.Over past ten years, the refining ratio of mixing of above-mentioned heavy feed stock improves year by year, has brought considerable economic to oil refining enterprise.Vacuum residuum particularly, according to statistics, one ton of vacuum residuum of catalyzed cracking processing, economic benefit can improve 300～500 yuan.
Along with the development of heavy oil fluid catalytic cracking technology, at present, the catalytic cracking that with the long residuum of some crude oil is raw material is in industrial successful operation more than ten years, and obtained favorable economic benefit.But with full vacuum residuum is that the catalytic cracking of raw material remains in certain difficulty.These difficulties are mainly reflected in the following aspects: (1) vacuum residuum density is big, carbon residue is high, is difficult to fully cracking under the catalytic cracking reaction condition of routine, and the coke yield height.(2) vacuum residuum heavy metal content height has almost concentrated heavy metals whole in the crude oil, and is to the murder by poisoning of cracking catalyst very serious.(3) the content height of impurity such as vacuum residuum sulphur, nitrogen influences product property, and causes the environmental pollution of various ways.(4) on-stream time is short, and the equipment coking is serious.(5) plant energy consumption height, agent consumption height.
In order to address the above problem, the heavy oil fluid catalytic cracking technology is further advanced, the worker that refines oil is both at home and abroad carrying out studying untiringly and exploring always.
In " the 5th annual meeting report of the catalytic cracking cooperative groups collection of thesis " of nineteen ninety-five publication, " research and development of the direct catalytic cracking of Jilin vacuum residuum " and " simple analysis of Jilin vacuum residue catalytic Technology " two pieces of articles have been introduced with Jilin vacuum residuum as the medium-sized test of catalytically cracked material and the situation of commerical test, and proposed following several major technique measures: (1) stock oil contact with abundant high-temperature regenerated catalyst by the high-efficient atomizing nozzle, and regenerated catalyst is the uniform and stable perpendicular flow state that makes progress when passing through the nozzle position.Also particularly point out in this article, in processing during vacuum residuum, the dense phase temperature of second revivifier is controlled at 720～725 ℃, agent-oil ratio about 6.5～7.0, and effect is relatively good.How to realize " uniform and stable upwards perpendicular flow " for regenerated catalyst, do not introduce in the literary composition.(2) in order to prevent the equipment coking, should improve raw material oil throwing, evaporation conditions, make it to vaporize fully.But do not introduce the actual conditions that improves stock oil atomizing, evaporation in the literary composition.(3) screening is applicable to the USY type molecular sieve catalyst of slag oil cracking.(4) utilize gas energy to reclaim the energy consumption that equipment such as coaxial four units, catalyzer external warmer, smoke and waste steam boiler, oil slurry steam generator reclaim heat, reduce device.
In " refining of petroleum and chemical industry " the 1st phase in 1999 " new development of China's residual oil deep process technology " literary composition, introduced 10 technical characterstics of vacuum residue catalytic, comprised the operation of short contacting time, high agent-oil ratio, high atomizing steam amount and mixing temperature control techniques " or the like.But, only be the design of having mentioned above-mentioned technology in this article, and predicted that the product of the full vacuum residue catalytic of grand celebration distributes, and does not introduce the concrete measure of its realization.
CN1217366A discloses a kind of riser tube reactive system that can prevent catalyzer landing and back-mixing effectively, and this reactive system comprises pre lift zone and three reaction zones dividing along the riser tube height.Compare with the riser reactor of routine, the characteristics of this reactive system are: 1. pre lift zone is provided with along gaseous media nozzle and a feed nozzle of axle tangential distribution.2. the pre lift zone top is first reaction zone of diameter contraction.3. first reaction zone top is second reaction zone of expanded in diameter, and this reaction zone is provided with gaseous media nozzle, the secondary feeds nozzle of regenerator inlet inclined tube and edge axle tangential distribution.4. the 3rd reaction zone of second reaction zone top is the horizontal section of riser tube, and the initial portion of this horizontal section is provided with the liquid medium inlet, and its outlet links to each other with the fast sub-system of finish.
USP RE33,728 disclose a kind of method of residual oil catalyzed conversion,, adopt the higher regeneration temperature more than 732 ℃, 0.5～3.0 second short reaction times that is, carry out the catalytic conversion reaction of residual oil under the effect of the USY of high silica alumina ratio type catalyzer.This method has only emphasized that the pyritous regenerated catalyst helps the macromolecular cracking of residual oil, and not to be noted too high regeneration temperature can make the speed of heat cracking reaction increase significantly, the selectivity of influence reaction.Simultaneously, too high regeneration temperature also can be accelerated the hydrothermal deactivation speed of catalyzer, and the agent consumption is increased.
Summary of the invention
The objective of the invention is on the basis of above-mentioned prior art, to provide a kind of novel method of processing heavy petroleum hydrocarbon, so that make heavy such as vacuum residuum, petroleum hydrocarbon inferior can be directly as the stock oil of catalytic cracking unit, and can access comparatively that the ideal product distributes.
Method provided by the invention is: the cracking catalyst after the regeneration enters in four sections placed in-line reactors that are made of the close phase finish of no back-mixing contact segment, the up conversion zone of short contact, short contact horizontal section and gas-solid quickly separating section after the cooling of thermal equilibrium setter, contact with the heavier hydrocarbon feeds after the preheating, under 500～550 ℃, 130～350Kpa, agent-oil ratio 5～20, the condition in 1～4 second reaction times, react, reacted spent agent enters in the thermal equilibrium setter after stripping, regeneration and reduces temperature, and the cracking catalyst Returning reactor after the cooling recycles.
Description of drawings
Fig. 1 is the schematic flow sheet of heavy crude hydrocarbon catalytic cracking process provided by the invention.
Embodiment
Particular content of the present invention is as follows: the catalyzer that (1) the present invention uses
The cracking catalyst that the present invention uses contains faujusite 10～60 heavy %, in phosphorus 0.01～1.5 heavy % of Vanadium Pentoxide in FLAKES, in rare earth 0.1～5 heavy % of rare earth oxide, al binder 10～60 heavy %, clay 0～75 heavy % in aluminum oxide, above-mentioned weight percent number average is benchmark with the total catalyst weight.
Described faujusite is the mixture of zeolite a and zeolite b, and the weight ratio of zeolite a and zeolite b is 0.1～10.Wherein, zeolite a is the persilicic rare earth exchanged Y zeolite, and its relative crystallinity is 65～85%, and its second hole volume accounts for 20～80% of total pore volume, and it is with RE
2O
3The content of rare earth of meter is 1～17 heavy %, and described rare earth element is La or Ce or based on the mixed rare-earth elements of La and/or Ce; Zeolite b is that the unit empirical formula is (RE
wAl
xR
y) O
2Contain the rare earth zeolite, in the formula, RE represents one or more in the rare earth element, and at least a portion of rare earth element exists with the form of skeleton rare earth, R represents silicon, boron or phosphorus atom, w, x and y represent the molar fraction of the RE, aluminium and the R that exist with the tetrahedronal oxide of skeleton unit respectively, and w gets 0.001～0.5, and preferred 0.001～0.06; X gets 0.001～0.5, and preferred 0.01～0.3; Y gets 0.001～0.998, and preferred 0.65～0.95.
The double aluminium binder that described al binder is made up of pseudo-boehmite and aluminium colloidal sol, in aluminum oxide, the weight ratio of pseudo-boehmite and aluminium colloidal sol is 0.1～10.
Described rare earth in rare earth oxide is La or Ce or based on the mixed rare-earth elements of La and/or Ce.
Described phosphorus is introduced mixture uniform mixing, drying, 450～600 ℃ of roastings of P contained compound and above-mentioned zeolite a and zeolite b; And described P contained compound is the phosphorated water-soluble cpds, it is selected from ortho-phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, the ammonium phosphite one or more, more preferably phosphoric acid ammonium, Secondary ammonium phosphate or primary ammonium phosphate.The described P contained compound aqueous solution is in phosphorus content, and its concentration can be 0.1～30 heavy %, preferred 0.5～2.5 heavy %, and P contained compound solution and zeolite weight ratio can change in a big way, and preferred 0.5～5.0.
The preparation method of the cracking catalyst that the present invention uses comprises the steps: 1. prepare zeolite
Zeolite a is to be 99110996.1 according to application number, and denomination of invention is method preparation disclosed in the patent application of " a kind of improved rare earth Y type zeolite and preparation thereof ".Its preparation method comprises: with Na
2O content be the rare earth exchanged Y zeolites of 2.5～8 heavy % with siliceous solution impregnation after drying, make said rare earth exchanged Y zeolite contain the silicon of 1～15 weight % (with SiO
2Meter), then with the siliceous rare earth exchanged Y zeolite of gained in steam atmosphere in 500～850 ℃ of roastings 0.5～30 hour; Wherein said siliceous solution is selected from a kind of in silicon sol, water glass, silicofluoric acid or the organic silicon solution.
Zeolite b is to be 99105792.9 according to application number, and denomination of invention is for the preparation of the method disclosed in the patent application of " a kind of molecular sieve that contains rare earth and preparation method thereof ".Its preparation method comprises: under 25～120 ℃ temperature, with a kind of in oxide compound, the solution of at least a material among the rare-earth type zeolite that contains the heavy % of rare earth 0.1～40 and a kind of at least a material and (II) that contains in (I) as follows contacts at least 0.1 hour, isolate the product that obtains, drying; Wherein (I) comprises mineral acid, mineral alkali, organic acid or can form the reagent of complex compound with aluminium; (II) comprise solubility ammonium salt, organic acid salt and amine, alcohol, aldehyde, ketone; Wherein, the pH value of solution is 3～12, and (II) mol ratio of contained rare earth element is 0.01～20 in the material in and the rare-earth type zeolite; Described rare-earth type zeolite refers to the zeolite of the natural or synthetic that partial cation position at least occupied by rare earth element.
Above-mentioned zeolite a and zeolite b can obtain the zeolite of catalyst system therefor of the present invention according to the mixed of weight ratio 0.1～10.2. the preparation of matrix
The matrix of catalyst system therefor of the present invention is to be CN1195014A according to publication number, and denomination of invention is the modified kaolin of the method that discloses in the patent application of " improvement of kaolin " after handling.Described kaolin method of modifying comprises: with the kaolin high-temperature roasting, then with kaolin after this roasting and acid-respons, filter, use the deionized water wash product, product after the dry washing, wherein, described kaolinic high-temperature roasting temperature is 850～920 ℃, roasting time 10 minutes to 5 hours; Described acid refers to the mixing acid of inorganic monoprotic acid and diprotic acid, the mol ratio of monoprotic acid and diprotic acid is 1.0～5.0 in the mixing acid, acid strength is 0.4～4N, the consumption of acid is wanted to flood described kaolin solid at least, the temperature of kaolin and acid-respons is 90～150 ℃ after the roasting, and the time is 4～40 hours.3. Preparation of catalysts
The catalyzer that the present invention uses is to be CN1217231A with reference to publication number, and denomination of invention is method preparation disclosed in the patent application of " phosphorous faujusite cracking catalyst and preparation method thereof ".Its preparation method comprises: the aqueous solution of above-mentioned mixed zeolite of being made up of zeolite a and zeolite b and P contained compound is even, left standstill 0～8 hour, and drying more than 0.5 hour, obtains the phosphorated zeolite in 450～600 ℃ of roastings; Double aluminium binder of forming with P-contained zeolite, by pseudo-boehmite and aluminium colloidal sol and modified kaolin mix, behind the homogeneous in 400～600 ℃ of roastings or spraying drying, wash resulting product according to a conventional method, promptly obtain catalyzer used in the present invention.(2) hydrocarbon raw material that is suitable for of the present invention
Used hydrocarbon raw material can be any heavy petroleum hydrocarbon that is applicable to catalytic cracking process among the present invention, and for example, density is 0.89～0.94g/cm
3, carbon residue is 2～8 heavy %, the content sum of heavy metal Ni and V is less than the hydrocarbon raw material of 18ppm.Specifically, the hydrocarbon raw material that the present invention is suitable for can be: the time processing distillate comprises decompressed wax oil, long residuum, vacuum residuum etc.; The mixture of the arbitrary proportion of two or more above-mentioned time processing distillate; Be mixed with the time processing distillate of part wax tailings, deasphalted oil or other secondary processing distillate or its mixture; Be mixed with the time processing distillate of recycle stock and/or reprocessed oil slurry or the mixture of time processing distillate and secondary processing distillate.
In above-mentioned hydrocarbon raw material, vacuum residuum and the petroleum fractions suitable with vacuum residuum character more are applicable to the present invention.(3) method provided by the invention
The catalyst cracking method of heavy petroleum hydrocarbon provided by the invention mainly may further comprise the steps: 1. heavy petroleum hydrocarbon contacts, reacts with catalyzer provided by the invention in four sections tandem reactors provided by the invention.2. reaction oil gas enters follow-up separation and absorption-stable system is carried out product separation.3. reacted reclaimable catalyst falls into stripping stage by settling vessel, the oil gas that the stripping reclaimable catalyst is adsorbed.4. enter in the revivifier through steam stripped reclaimable catalyst and burn, regenerate.5. the catalyzer after the regeneration enters in the thermal equilibrium setter, and the temperature by the heat-obtaining facility is regulated regenerated catalyst makes it to satisfy the desired reaction conditions of heavy crude hydrocarbon cracking.
To above-mentioned 5 steps that the invention provides method be elaborated below.Step is 1.: the present invention adopts four sections placed in-line reactor patterns, with the atomizing effect that improves stock oil, strengthen the macromolecular cracking of residual oil.First section of this reactor is the close phase finish of no back-mixing contact segment, and second section is the up conversion zone of short contact, and the 3rd section is the short contact horizontal section, and the 4th section is the gas-solid quickly separating section.
600～700 ℃ high-temperature regenerated catalyst at first enters first section of this reactor through regenerator sloped tube, does not promptly have the bottom of the close phase finish of back-mixing contact segment, transfers upwards motion equably to by downward landing under the effect of fluidizing medium.With dry gas, steam or their the mixture fluidizing medium as this conversion zone, fluidizing medium is 1.0～1.5m/s at the gas superficial linear speed of this conversion zone.The beds density of this conversion zone is 250～600kg/m
3, preferred 350～450kg/m
3The sparger of above-mentioned fluidizing medium is positioned at the bottom of this conversion zone, above the fluidizing medium sparger, be provided with along 4～6 at the gas jet of the tangential equally distributed anti-limit wall particle landing of perisporium axle, nozzle opening up, axial angle is 20～40 °.With dry gas, steam or their mixture gaseous media, inject by the above-mentioned gas nozzle as the wall particle landing of anti-limit.The stock oil nozzle is positioned at the top of above-mentioned anti-limit wall particle landing gas jet, and the position of stock oil nozzle should be controlled at the transition point place of emulsion zone and freeboard of fluidized bed.The stock oil nozzle can adopt various high-efficient atomizing nozzles, for example, and the nozzle of models such as KH type, LPC type, BWJ type.The stock oil nozzle should be 4～8, and evenly is provided with along the perisporium of this conversion zone.The droplet diameter of stock oil after above-mentioned feed nozzle atomizing should be less than 100 μ m.The length of the close phase finish of no back-mixing contact segment should be 3～6 meters, and diameter should be 1～2 meter, and aspect ratio is 3～6.Main operating parameters in the close phase finish of the no back-mixing contact segment is as follows: the finish mixing temperature is 530～600 ℃, and agent-oil ratio is 5～20, and finish duration of contact is 0.1～0.4 second.
Reaction oil gas in the close phase finish of the no back-mixing contact segment and catalyzer be along being advanced into second section of this reactor on the reactor, i.e. the up conversion zone of short contact.Between no back-mixing close phase finish contact segment and the up conversion zone of short contact is the radial shrinkage transition portion, and the angle of throat at this position is 15～60 °, and contracted length is 0.2～0.5 meter.The main operating parameters of the up conversion zone of short contact is as follows: the residence time of reactant flow is 0.2～2.0 second, and preferred 0.3～1.5 second, the best was 0.5～1.2 second.The diameter of the up conversion zone of short contact should be less than the close phase finish of no back-mixing contact segment, and the two diameter ratio is 1: 2～3: 4.The length of the up conversion zone of short contact should be 20～50 meters.
Reactant flow enters the 3rd section of this reactor, i.e. short contact horizontal section through the up conversion zone of short contact.The diameter of this level pipe should be greater than the diameter of up reaction tubes, and both diameter ratios are 4: 3～2: 1.The residence time of mixed oil and gas in the short contact horizontal section should be less than 1 second, preferred 0.1～0.5 second.Inject scorch retarder from the junction of short contact horizontal section and the up conversion zone of short contact.Scorch retarder can be selected from one or more in water, steam, raw gasline, the recycle stock, preferred acidic water or raw gasline.The ratio that scorch retarder accounts for combined feed total feed is 0～20 heavy %, preferred 5～15 heavy %.
The outlet of the up conversion zone of short contact and this reactor the 4th section, promptly the gas-solid quickly separating section links to each other, and this system is called for short gas-solid quickly separating system.This system can select any device type that is applicable to reaction oil gas and catalyzer sharp separation for use, for example, revolves slightly that fast branch, three leaves divide soon, vortex quick separation, the airtight pattern of grading of revolving.Reactant flow is as follows in the intrasystem main operational condition of gas-solid quickly separating: the temperature of reactant flow is 490～530 ℃, and its residence time is 0.1～0.5 second.
In a word, the reaction conditions of heavy petroleum hydrocarbon in above-mentioned four sections tandem reactors may be summarized to be: temperature of reaction, and promptly short contact horizontal section temperature out should be controlled at 500～550 ℃, reaction pressure 130～350Kpa, agent-oil ratio 5～20, total reaction time 1～4 second; Preferred reaction conditions is: 500～530 ℃ of temperature of reaction, reaction pressure 130～300Kpa, agent-oil ratio 5～15, total reaction time 1.5～3.5 seconds.Step is 2.: drawn by the gas pipeline at settling vessel top through the reaction oil gas that above-mentioned reaction process generates, enter follow-up fractionating system and absorption-stable system, carry out product separation according to the method for routine.Step is 3.: isolated reclaimable catalyst is fallen in the stripping stage by settling vessel from reactant flow, by the adsorbed reaction oil gas of stripping medium displacement catalyzer.This stripping process can be the single hop stripping, also can be the multistage stripping.Step is 4.: the reclaimable catalyst behind the stripping enters coke burning regeneration in the revivifier through inclined tube to be generated.Used revivifier can be the revivifier that is applicable to any pattern of catalytic cracking process, for example, and single hop regeneration, two-stage regeneration, cyclic regeneration etc.Regeneration condition provided by the present invention is: regeneration pressure 150～400kPa, 650～750 ℃ of regeneration dense phase temperatures, 1～6 minute catalyst regeneration time.This revivifier can be regulated the regeneration dense phase temperature by interior heat collector and/or external warmer.Step is 5.: after above-mentioned regenerative process was finished, regenerated catalyst entered in the thermal equilibrium setter through pipeline.This thermal equilibrium setter is one to be positioned at revivifier downstream, container that material is identical with revivifier.One of characteristics of this thermal equilibrium setter are: the regenerated catalyst in this thermal equilibrium setter is that the form with dense bed exists, and with oxygen-containing gas as fluidizing medium.Fluidizing medium is introduced by the sparger that is positioned at thermal equilibrium setter bottom, the regenerated catalyst in this setter is carried out fluidisation, and reduce the temperature of regenerated catalyst to a certain extent.Two of the characteristics of this thermal equilibrium setter are: this setter has the heat-obtaining facility, heat collector and/or external warmer in being provided with, wherein preferred external warmer.By the heat-obtaining amount of heat collector in regulating and/or external warmer, reach the purpose of control regenerated catalyst temperature, thereby the thermal balance state of whole catalytic cracking unit is improved, for the cracking of heavy petroleum hydrocarbons such as residual oil creates conditions.The effect of thermal equilibrium setter is exactly in order to improve the thermal balance state of catalytic cracking unit, make catalyzer under suitable higher temperature, finish regenerative process, so that reach regeneration effect preferably, for example, regeneration temperature is controlled at 650～750 ℃, and the carbon content of regenerated catalyst is controlled at 0.01～0.20 heavy %.And the catalyzer after the regeneration enters the thermal equilibrium setter and suitably lowers the temperature, and for example, regenerated catalyst temperature can be reduced to 600～680 ℃, so that adopt bigger agent-oil ratio in reactive moieties, strengthens the macromolecular cracking of heavy oil.In method provided by the invention, the layout of thermal equilibrium setter can be more flexibly, for example, can arrange with revivifier is coaxial, also can arrange side by side with revivifier, or adopt other more reasonably to install decoration form.Behind the above-mentioned fluidizing medium process thermal equilibrium setter, draw, incorporate into as a part of burning medium in the main air of revivifier by the top of this setter.
Below in conjunction with accompanying drawing method provided by the invention is illustrated further, but not thereby limiting the invention.
As shown in Figure 1, fluidizing medium enters first section of four sections tandem reactors 3 equably through pipeline 1 and sparger 2, does not promptly have the bottom of the close phase finish of back-mixing contact segment 4, and fluidizing medium evenly up flows the regenerated catalyst that is entered in this section by regenerator sloped tube 12.In exit, keep away particle landing gas jet 5 by anti-limit and spray into gaseous medias such as dry gas and/or steam near the close phase finish of no back-mixing contact segment 4.Stock oil after the preheating injects from the close phase finish of the no back-mixing contact segment 4 that the is positioned at anti-limit wall particle landing gas jet 5 tops stock oil nozzle 7 with the up conversion zone of short contact 6 junctions; fully atomizing under the effect of high temperature regeneration agent, and enter the up conversion zone 6 of short contact immediately and react.Reactant flow is up along this reaction tubes, enter expanded in diameter short contact horizontal section 8, scorch retarder such as raw gasline or water injects reactant flow by the scorch retarder nozzle 13 of the starting position that is arranged in this level pipe, plays termination reaction and prevents the effect of heavy constituent condensation green coke.The outlet of short contact horizontal section links to each other with the fast sub-system 9 of finish, with the sharp separation of realization response oil gas and catalyzer.Reaction oil gas is sent into subsequent separation system through the gas pipeline 11 that is positioned at settling vessel 10 tops and is carried out product separation.Long-pending have the catalyzer of coke to fall into stripping stage 14 by settling vessel 10, and the stripping medium is introduced in the stripping stage 14 by pipeline 15, and the reclaimable catalyst of finishing stripping process enters coke burning regeneration in the revivifier through inclined tube 16 to be generated.High temperature catalyst after the regeneration enters in the thermal equilibrium setter 19 through pipeline 18.Oxygen-containing gas after the compression plays fluidisation, loosening and heat exchange through pipeline 20, by the sparger 21 introducing thermal equilibrium setters that are arranged in thermal equilibrium setter 19 bottoms.Part catalyzer in the thermal equilibrium setter enters in the heat collector 23 by pipeline 22, after heat transferring medium such as deaerated water heat exchange, returns in the thermal equilibrium setter through pipeline 24, plays the effect that reduces thermal equilibrium setter inner catalyst temperature.Catalyzer after the appropriateness cooling enters the bottom cycle of the close phase finish of the no back-mixing contact segment of four sections tandem reactors and uses through regenerator sloped tube 12.
The present invention compared with prior art has following outstanding feature:
(1) except conventional catalytically cracked material, the heavy that density is big, carbon residue is high, heavy metal content is high, inferior raw material, for example, long residuum, vacuum residuum etc. can be as stock oils of the present invention.Therefore, raw material range of the present invention is more more extensive than prior art.
(2) catalyzer provided by the invention has characteristics such as heavy oil cracking ability is strong, preventing from heavy metal pollution, good hydrothermal stability, high-value product yield height, for favourable condition has been created in the catalytic cracking of heavy petroleum hydrocarbon.
(3) the present invention is according to the characteristics of heavy petroleum hydrocarbon catalytic cracking reaction, a kind of four sections novel placed in-line reactor patterns are provided, and the duration of contact of the interior finish mixture of strict each conversion zone of control, thereby improve raw material atomizing effect, strengthen cracking to heavy oil, and suppress the generation of coke effectively.
(4) thermal equilibrium setter of the present invention is to regulate the thermally equilibrated effective means of catalytic cracking unit.Can make " reaction of stock oil " and " regeneration of catalyzer " become two relatively independent processes by this setter, both can satisfy the needed bigger agent-oil ratio of pressure fuel, the catalyzer of band charcoal is regenerated under suitable higher temperature, obtain the good effect of burning.
(5) method yield of light oil height provided by the invention, coke yield are low, and the gasoline octane rating height, and RON can reach more than No. 90.With processing paraffinic base vacuum residuum is example, adopt method provided by the invention, its gasoline yield and diesel yield sum can reach 65～68 heavy %, the productive rate sum of gasoline, diesel oil and liquefied gas can reach 80～84 heavy % even higher, and coke yield has only 9.5～11 heavy %, dry gas yied to be lower than 5 heavy %.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Relevant test among the embodiment is to carry out on the catalytic cracking middle-scale device by real-time computer control, and the processing power of this device is 0.36t/d.For method provided by the invention is implemented, before the test the reaction-regeneration system to this middle-scale device carried out corresponding transformation.
Testing used stock oil is grand celebration vacuum residuum, and its property analysis data are listed in table 1.As can be seen from Table 1, it is big to test raw materials used viscosity, and carbon residue, heavy metal, aromatic hydrocarbons and gum level height are a kind of catalytically cracked materials of poor quality.
Test catalyst system therefor A prepares according to following steps:
(1) preparation of zeolite a: with double centner (dry basis) lattice constant is NaY type zeolite (sodium oxide content 14 heavy %, Qilu Petrochemical Zhou village catalyst plant is produced) and 2000 liters of (NH that concentration are 5 heavy % of 2.473 nanometers
4)
2SO
4The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, obtained NH with deionized water wash after the drying
4NaY type zeolite.NH with 90 kilograms of (dry basis) above-mentioned preparations
4NaY type zeolite 90 ℃ of following ion-exchanges 0.5 hour, filters in the lanthanum chloride solution of 2000 liters of 0.2M, to there not being acid group, obtains containing the NH of lanthanum with the deionized water wash filter cake after the drying
4NaY type zeolite records its Na
2O content is 4.0 heavy %.80 kilograms of (dry basis) above-mentioned preparations are contained lanthanum NH
4(Changhong chemical plant, Beijing commerical prod contains 12%SiO to NaY type zeolite at the double centner silicon sol
2) in soaked 30 minutes, 120 ℃ of dryings 2 hours, make molecular sieve contain the SiO of 10 heavy % by butt then
2, obtain containing lanthanum NH with silicon dipping
4NaY type zeolite.70 kilograms of (dry basis) above-mentioned preparations are contained lanthanum NH with silicon dipping
4The roasting 16 hours in 650 ℃ of steam atmospheres of NaY type zeolite, the product that obtains with 20 times deionized water wash promptly obtains zeolite-1 after the drying again.
(2) preparation of zeolite b: with double centner (dry basis) NH
4Y zeolite (sodium oxide content is 0.8 heavy %, and lattice constant is 24.73 dusts, and lattice avalanche temperature is 930 ℃, and the Zhou village catalyst plant is produced) adds the NH of 2000 liter of 0.5 mol
4In the Cl solution, stir into slurries, the rare earth chloride that to add 500 liters of rare earth oxide content again be 24 grams per liters is (wherein, with La
2O
3And CeO
2Meter, the weight ratio of lanthanum and cerium is 4.08, Baotou rare earth factory produces) solution, fully stir evenly, regulating its PH with hydrochloric acid is 3.5, is warmed up to 95 ℃ then, stirs 2 hours, filter, earlier with 30 times deionized water wash, be that 4.0 hydrochloric acid soln and pH value are that 10.0 ammonia soln washs with 30 times pH value respectively again, use 20 times of deionized water wash at last, drying obtains the rare-earth type zeolite.The N of 5000 liter of 0.09 mol of configuration, N-two inferior salicylic acid solutions, to wherein slowly adding quadrol and ammoniacal liquor, the pH value that makes solution is 4.0.Above-mentioned rare-earth type molecular sieve is added in this solution, it is 3.0 that the quadrol add-on makes the mol ratio of contained rare earth element in quadrol and the rare-earth type zeolite, being warming up to 90 ℃ stirred 2 hours, filtering, earlier with 30 times deionized water wash, is that 4.0 hydrochloric acid soln washs with 30 times pH value again, use 20 times of deionized water wash at last, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 2 hours obtain zeolite-2.
(3) preparation of matrix: select kaolin (Suzhou kaolin company product) 920 ℃ of roastings 1 hour in 500 kilograms of Suzhou machines, the kaolin that takes by weighing after the roasting contains 80.0 liter of 37% hydrochloric acid (chemical pure for 240 kilograms and 720 liters, Beijing Inst. of Chemical Reagent produces) and 13.6 liter of 98% vitriol oil (chemical pure, Beijing Inst. of Chemical Reagent's product) mixed acid solution mixes, 100 ℃ of reactions 26 hours, filter, with deionized water wash to there not being acid group, dry, 550 ℃ of roastings 4 hours obtain modified kaolin.
(4) preparation of catalyst A is carried out according to following steps:
With 10.0 kilograms of zeolite a and 10.0 kilograms of zeolite b and 30.0 kilograms of primary ammonium phosphate (chemical pure that concentration is 4.5 heavy %, the Beijing Chemical Plant produces) and 10.0 kg aluminium colloidal sols (Zhou village, Shandong catalyst plant product, its alumina content is 21 heavy %) mix, left standstill 2 hours, drying was in 500 ℃ of roastings 1 hour.
(Shandong Aluminum Plant produces with 30.0 kilograms of pseudo-boehmites, its alumina content is 35.0 heavy %) and 80.0 kilograms of deionized waters mix, (Baotou rare earth factory in the Inner Mongol produces, and after 1 hour, measure rare earth oxide content is RE to described REClx through 800 ℃ of roastings to add 5.0 kilograms of REClx
2O
3Be 46 heavy %, La
2O
324.5 heavy %, CeO
26.0 heavy %, Pr
5O
3Heavy %, Nd
2O
39.5 heavy %), mix, under agitation slowly add 8.0 kilograms of concentrated hydrochloric acids (chemical pure contains the heavy % in HCl36～38, and the Beijing Chemical Plant produces), be warming up to 60 ℃, aging 2.5 hours, get the aged pseudo-boehmite.Above-mentioned mixed zeolite, 15.0 kilograms of aforementioned modified kaolins, aged pseudo-boehmite and 40.0 kg aluminium colloidal sols are mixed, in 500 ℃ of roastings 2 hours.
Above-mentioned resulting product is pulverized, weighed % and NH with 20 times of weight in hydrochloric 0.84 of sample butt down at 60 ℃ respectively
3H
2The acid solution of the heavy % of O 0.62, contain NH
3H
2The alkali lye of the heavy % of O 0.17 and deionized water mix making beating, washing, wash after-filtration at every turn, obtain filter cake at last in 120 ℃ of dryings 2 hours, promptly get the catalyst A of using among the present invention.
The catalyst sample A that makes according to the method described above needs to handle through 790 ℃, 100% water vapour, 33 hours medium-sized hydrothermal aging before testing, so that simulate the activity level of industrial poiser preferably.
The aged samples of catalyst A is carried out the cyclic polluting of heavy metal nickel, promptly at first nickel naphthenate is dissolved in the solar oil, on kitty cracker, repeat 48 hours reaction, regenerative process, make that the activity of heavy metal nickel reaches balance on the catalyzer.The catalyst sample of finishing this cyclic polluting process promptly can be used for test, and its physicochemical property see Table 2.Catalyst sample A is behind above-mentioned burin-in process and heavy metal nickel cyclic polluting, and its micro-activity is 64.
Example 1
This example explanation: can realize flexible to regenerated catalyst temperature by thermal equilibrium setter provided by the invention, guarantee the abundant vaporization and the cracking of vacuum residuum with lower regenerator temperature and bigger agent-oil ratio, thereby avoid the generation of too much heat cracking reaction.
The step of catalytic cracking medium-sized test is summarized as follows: grand celebration vacuum residuum at first mixes with the low condensation point component of freshening wet goods, is preheated to 200 ℃ through process furnace then, and the viscosity of vacuum residuum is dropped in the desired scope of high-efficient atomizing nozzle; Above-mentioned raw materials injects the bottom of the close phase finish of no back-mixing contact bed by the high-efficient atomizing nozzle, contacts with high-temperature regenerated catalyst from regenerator sloped tube, enters the up conversion zone of short contact immediately and carries out cracking reaction; The moment that enters the short contact horizontal section in reactant flow is injected scorch retarder, crosses cracking and heavy oil condensation green coke to prevent intermediate oil; Reactant flow is after the separating of the fast sub-system realization response of finish oil gas and catalyzer, and the gas pipeline of reaction oil gas through the settling vessel top enters follow-up fractionating system and absorbing-stabilizing system, carries out product separation and metering according to ordinary method.Reclaimable catalyst enters revivifier and burns behind the water vapour stripping, regenerative process is by the needs of electric heater simulate thermal equilibrium, but flexible regenerator temperature.Volume and compositional analysis data computation coke yield according to regenerated flue gas.Calculate the resulting material balance of test at last, and analyze the character of main productss such as vapour, diesel oil.
The main operational condition of each conversion zone and material balance see Table the numbering 1 and 2 in 3 in the test.The data of numbering 1 and 2 are compared, as can be seen, under the situation identical in the riser tube temperature out, that the fuel oil preheating temperature is identical, regeneration temperature and agent-oil ratio that numbering 2 adopts are favourable to the cracking of vacuum residuum, its heavy oil conversion rate improves 5.56 heavy %, and total lighter hydrocarbons liquid is received and improved 3.86 heavy %.
Example 2
The explanation of this example: four sections cascade reaction systems of the present invention both can create good initial finish contact condition, vacuum residuum feed is vaporized and cracking fully, can control short finish duration of contact again, thereby realize effective control reaction depth.
Test raw materials used oil, catalyzer, device and main testing sequence with example 1, the main operational condition of test and material balance see Table the numbering 3 and 4 in 4.The data of numbering 3 and 4 are compared, as can be seen, under the situation identical in the riser tube temperature out, that the fuel oil preheating temperature is identical, numbering 4 has adopted the short reaction times, the about 2.4 heavy % though its heavy oil conversion rate descends, but coke yield descends significantly, and it is about 15% to descend relatively, and total lighter hydrocarbons liquid is received and increased by 1.4 heavy %.As seen, adopting the short reaction time is favourable to vacuum residue catalytic.
Example 3
The explanation of this example: scorch retarder is injected at the short contact horizontal section place at four sections tandem reactors provided by the invention, both can improve the stability of operation, slows down the equipment coking, and prolong operation cycle can play the chilling effect again, improve product distribution and product property.
Test raw materials used oil, catalyzer, device and main testing sequence with example 1, the main operational condition of test and material balance see Table the numbering 5 and 6 in 5.Numbering 5 and 6 data are compared, as can be seen, with water as the scorch retarder injecting reactor after, transformation efficiency improves, product distributes and improves, and has prolonged 3.5 times runtime.
Example 4
This example explanation: adopt method processing grand celebration vacuum residuum provided by the invention, not only can obtain comparatively ideal product and distribute, and the character of vapour, diesel product meets the demands.
Test raw materials used oil, catalyzer, device and main testing sequence with example 1, the main operational condition and the material balance of test see Table 6, and the character of vapour, diesel product sees Table 7.By the material balance data in the table 6 as can be seen, liquefied gas, gasoline and diesel oil three's yield sum, promptly total lighter hydrocarbons liquid is received and is reached 84.20 heavy %, and coke yield only is 11.48 heavy %.By the product property data in the table 7 as can be seen, the RON of gasoline is 91.5, MON is 78.5, and inductive phase greater than 485, therefore, can be used as the blend component of No. 90 commercial gasolines; The character of diesel oil is suitable with the character of conventional catalytic cracking diesel oil.Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
| The stock oil title | Grand celebration vacuum residuum |
| Density (20 ℃), g/cm 3Refractive index n D 70Kinematic viscosity, mm 2/s(80℃) mm 2/ s (100 ℃) condensation point, ℃ Conradson carbon residue, m% bromine valency gBr/100g ratio of carbon-hydrogen, m% | 0.9193 1.5019 254.3 117.6 33 7.3 5.7 6.92 |
| Hydrocarbon system forms, m% stable hydrocarbon aromatic hydrocarbons gum asphalt | 38.9 35.8 24.6 0.9 |
| Metal content, ppm Fe Ni V Na | 3.9 8.4 0.2 6.1 |
| Boiling range, 5% 10% 500 ℃ of quantity of distillate of ℃ initial boiling point, v% | 429 519 545 4.0 |
| Live catalyst character: chemical constitution, heavy % Al 2O 3 Na 2O RE 2O 3 P 2O 5The physical properties specific surface area, m 2/ g pore volume, ml/g tap density, g/cm 3Abrasion index, %h -1 | 47.3 0.12 2.1 0.8 304 0.43 0.66 2.5 |
| The aging medium-sized aging condition nickel contamination of the catalyzer amount of polluting, ppm pollutes the back micro-activity | 790 ℃/33h, 100% water vapour 4,000 64 |
| Example | Example 1 | |
| Investigate object | Agent-oil ratio, regeneration temperature | |
| Numbering | 1 | 2 |
| Temperature of reaction, ℃ agent-oil ratio total reaction time, s first conversion zone, s second conversion zone, s the 3rd conversion zone, s the 4th conversion zone, the s regeneration temperature, ℃ operating method | 510 5.5 2.4 0.2 1.7 0.3 0.2 710 one way | 510 7.1 2.3 0.2 1.6 0.3 0.2 685 one way |
| Material balance, heavy % dry gas (H 2～C 2) liquefied gas (C 3～C 4) gasoline, diesel heavy oil coke loss total | 3.03 10.22 39.66 22.56 14.48 10.05 0.50 100.00 | 3.60 13.80 44.02 18.48 8.92 10.78 0.40 100.00 |
| Transformation efficiency, heavy % heavy oil conversion rate, heavy % yield of light oil, the total lighter hydrocarbons liquid of heavy % is received, heavy % | 62.96 85.52 62.22 72.44 | 72.60 91.08 62.50 76.30 |
| Example | Example 2 | |
| Investigate object | The short contact reaction times | |
| Numbering | 3 | 4 |
| Temperature of reaction, ℃ agent-oil ratio total reaction time, s first conversion zone, s second conversion zone, s the 3rd conversion zone, s the 4th conversion zone, the s regeneration temperature, ℃ operating method | 510 9.7 2.3 0.2 1.6 0.3 0.2 650 one way | 510 9.6 1.4 0.2 0.8 0.2 0.2 650 one way |
| Material balance, heavy % dry gas (H 2～C 2) liquefied gas (C 3～C 4) gasoline, diesel heavy oil coke loss total | 4.59 21.11 45.05 12.76 3.59 12.15 0.75 100.00 | 2.93 16.42 49.74 14.19 5.98 10.31 0.43 100.00 |
| Transformation efficiency, heavy % heavy oil conversion rate, heavy % yield of light oil, the total lighter hydrocarbons liquid of heavy % is received, heavy % | 83.65 96.41 57.81 78.92 | 79.83 94.02 63.93 80.35 |
| Numbering | 5 | 6 |
| Agent oil contact fluidized-bed reaction temperature, ℃ anti-scorch dosage (accounting for charging), heavy % agent-oil ratio total reaction time, s operating method Average Operation Time, h | No back-mixing bed 510 0 5.9 2.1 one way 7 | No back-mixing bed 515 5 6.8 1.9 one way 26 |
| Material balance, heavy % dry gas (H 2～C 2) liquefied gas (C 3～C 4) gasoline, diesel heavy oil coke loss total | 2.81 13.17 42.44 20.63 10.38 9.92 0.65 100.00 | 3.34 13.81 43.83 18.93 9.44 9.95 0.70 100.00 |
| Transformation efficiency, heavy % | 68.99 | 71.63 |
| Numbering agent oil contact fluidized-bed reaction temperature, ℃ anti-scorch dosage (accounting for charging), heavy % agent-oil ratio total reaction time, s first conversion zone, s second conversion zone, s the 3rd conversion zone, s the 4th conversion zone, s recycle ratio operating method | 7 no back-mixing bed 510 9.8 6.2 1.9 0.2 1.3 0.2 0.2 0.11 full freshenings |
| Material balance, heavy % dry gas (H 2～C 2) liquefied gas (C 3～C 4) gasoline, diesel heavy oil coke loss total | 3.82 16.51 44.19 23.50 0.00 11.48 0.50 100.00 |
| Transformation efficiency, heavy % yield of light oil, the total lighter hydrocarbons liquid of heavy % rate, heavy % | 76.50 67.69 84.20 |
| The oil product title | Gasoline | Diesel oil |
| Density (20 ℃), g/cm 3Existent gum, mg/100ml acidity, mgKOH/100ml copper corrosion refractive index, n D 20Inductive phase, the min maleic value, gI/100g bromine valency, gBr/100g kinematic viscosity, mm 2/ s (20 ℃) condensation point, ℃ aniline point, ℃ 10% carbon residue, heavy % cetane value | 0.7471 6 0.88 qualified 1.4269 607 1.14 107 // /// | 0.8715 50 2.91 qualified 1.4994 // 26 3.3-33 39.5 0.09 31 |
| Octane value: RON MON | 91.5 78.5 | / / |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% 90% 95% is done | 47 65 74 97 119 143 169 180 192 | 222 230 233 242 254 272 299 309 324 |
Claims (16)
1, a kind of catalyst cracking method of heavy petroleum hydrocarbon, cracking catalyst after it is characterized in that regenerating enters by the close phase finish of no back-mixing contact segment after the cooling of thermal equilibrium setter, the up conversion zone of short contact, in four sections placed in-line riser reactors that short contact horizontal section and gas-solid quickly separating section constitute, contact with the heavier hydrocarbon feeds after the preheating, at 500～550 ℃, 130～350Kpa, agent-oil ratio 5～20, react under the condition in 1～4 second reaction times, reacted spent agent is through stripping, enter after the regeneration in the thermal equilibrium setter and reduce temperature, the cracking catalyst Returning reactor after the cooling recycles; Finish mixing temperature in the close phase finish of the described no back-mixing contact segment is 530～600 ℃, and agent-oil ratio is 5～20, and finish duration of contact is 0.1～0.4 second; The finish residence time in the up conversion zone of described short contact is 0.3～1.5 second; The finish residence time in the described short contact horizontal section should be less than 1 second; The temperature of described gas-solid quickly separating section internal reaction logistics is 490～530 ℃, and the residence time is 0.1～0.5 second.
2, in accordance with the method for claim 1, it is characterized in that described thermal equilibrium setter is one to be positioned at revivifier downstream, container that material is identical with revivifier; Regenerated catalyst in this thermal equilibrium setter is that the form with dense bed exists, and with oxygen-containing gas as fluidizing medium; Heat collector and/or external warmer in this thermal equilibrium setter is provided with.
3, in accordance with the method for claim 1, it is characterized in that the length of the close phase finish of described no back-mixing contact segment should be 3～6 meters, diameter should be 1～2 meter, and aspect ratio is 3～6; Beds density in this section is 250～600Kg/m
3
4, in accordance with the method for claim 3, it is characterized in that the beds density in the close phase finish of the described no back-mixing contact segment is 350～450Kg/m
3
5, in accordance with the method for claim 1, it is characterized in that the diameter of the diameter of the up conversion zone of described short contact less than the close phase finish of no back-mixing contact segment, the two diameter ratio is 0.50～0.75; The length of the up conversion zone of short contact is 20～50 meters.
6, in accordance with the method for claim 1, it is characterized in that the finish residence time in the up conversion zone of described short contact is 0.3～1.5 second.
7, in accordance with the method for claim 1, it is characterized in that being the radial shrinkage transition portion between described no back-mixing close phase finish contact segment and the up conversion zone of short contact that its angle of throat is 15～60 °, contracted length is 0.2～0.5 meter.
8, in accordance with the method for claim 1, it is characterized in that the diameter of described short contact horizontal section should be greater than the diameter of the up conversion zone of short contact, and the two diameter ratio is 1.33～2.00.
9, in accordance with the method for claim 1, it is characterized in that the finish residence time in the described short contact horizontal section is 0.1～0.5 second.
10, in accordance with the method for claim 1, it is characterized in that the junction injecting lift pipe reactor of scorch retarder from short contact horizontal section and the up conversion zone of short contact, described scorch retarder is selected from one or more in water, steam, raw gasline, the recycle stock, and the injection rate of scorch retarder accounts for 0～20 heavy % of total feed.
11, in accordance with the method for claim 10, it is characterized in that described scorch retarder is selected from sour water or raw gasline, the injection rate of scorch retarder accounts for 5～15 heavy % of total feed.
12, in accordance with the method for claim 1, the reaction conditions that it is characterized in that described heavier hydrocarbon feeds is: 500～530 ℃, 130～300Kpa, agent-oil ratio 5～15,1.5～3.5 seconds reaction times.
13, according to the method for claim 1, it is characterized in that described heavier hydrocarbon feeds is selected from: the time processing distillate comprises decompressed wax oil, long residuum, vacuum residuum; The mixture of the arbitrary proportion of two or more above-mentioned time processing distillate; Be mixed with the time processing distillate of part wax tailings, deasphalted oil or other secondary processing distillate or its mixture; Be mixed with the time processing distillate of recycle stock and/or reprocessed oil slurry or the mixture of time processing distillate and secondary processing distillate.
14, in accordance with the method for claim 13, it is characterized in that described heavier hydrocarbon feeds is vacuum residuum or the heavier petroleum fraction with vacuum residuum physico-chemical property.
15, according to the method for claim 1, it is characterized in that described cracking catalyst contain faujusite 10～60 heavy %, in phosphorus 0.01～1.5 heavy % of Vanadium Pentoxide in FLAKES, in rare earth 0.1～5 heavy % of rare earth oxide, al binder 10～60 heavy %, clay 0～75 heavy % in aluminum oxide; The double aluminium binder that described al binder is made up of pseudo-boehmite and aluminium colloidal sol, and in aluminum oxide, the weight ratio of pseudo-boehmite and aluminium colloidal sol is 0.1～10.
16, according to the method for claim 15, it is characterized in that described faujusite is the mixture of following two kinds of zeolites: zeolite a is the persilicic rare earth Y type zeolite, and its relative crystallinity is 65～85%, and its second hole volume accounts for 20～80% of total pore volume, with RE
2O
3The content of rare earth of meter is 1～17 heavy %, and described rare earth element is La or Ce or based on the mixed rare-earth elements of La and/or Ce; Zeolite b is that the unit empirical formula is (RE
wAl
xR
y) O
2Contain the rare earth zeolite, in the formula, RE represents one or more in the rare earth element, and at least a portion of rare earth element exists with the form of skeleton rare earth, R represents silicon, boron or phosphorus atom, and w, x and y represent the molar fraction of the RE, aluminium and the R that exist with the tetrahedronal oxide of skeleton unit respectively; The weight ratio of zeolite a and zeolite b is 0.1～10.
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