CN101531923A - Catalytic conversion method for preparing propylene and high-octane gasoline - Google Patents
Catalytic conversion method for preparing propylene and high-octane gasoline Download PDFInfo
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Abstract
A catalytic conversion method for preparing propylene and high-octane gasoline comprises the following steps: raw materials which are difficult to be cracked are firstly contacted with a thermal regeneration catalytic cracking catalyst to carry out cracking reaction under the conditions that the reaction temperature is 600-750 DEG C and the weight hourly space velocity is 100-800h<-1>, the reactant flow is mixed with raw oil which is easy to be cracked to carry out the cracking reaction under the conditions that the reaction temperature is 450-620 DEG C and the weight hourly space velocity is 0.1-100h<-1>; the spent catalyst and reaction oil and gas are separated, the spent catalyst returns to a reactor after regeneration, the reaction oil and gas are separated to obtain propylene and gasoline, and hydrogenated heavy oil obtained by hydrotreating fractions above 260 DEG C is taken as raw oil of the catalytic cracking device or a conventional catalytic cracking device. The method improves the yield and the selectivity of the propylene, increases the yield of the high-octane gasoline, reduces the yield of dry gas, greatly increases the yield of liquid and realizes the high-efficient utilization of petroleum resources.
Description
Technical field
The invention belongs to the catalysis conversion method of hydrocarbon ils, more particularly, be by the combination of hydrocarbon oil catalytic cracking and hydroprocessing technique process just heavy feed stock be converted into the especially catalysis conversion method of propylene and stop bracket gasoline of low-carbon alkene.
Background technology
Low-carbon alkene such as ethene, propylene etc. are important Organic Chemicals, and wherein propylene is the synthon of products such as polypropylene, vinyl cyanide.Along with increasing rapidly of derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in propylene market, the world is 1,520 ten thousand tons of 5,120 ten thousand tons of being increased to 2000 before 20 years, and average growth rate per annum reaches 6.3%.The demand that expects propylene in 2010 will reach 8,600 ten thousand tons, and average growth rate per annum is about 5.6% therebetween.
The method of producing propylene mainly is steam cracking and catalytic cracking (FCC), wherein steam cracking is that raw material is produced ethene, propylene by thermo-cracking with lightweight oils such as petroleum naphthas, but the productive rate of propylene only is that FCC is a raw material with vacuum gas oil mink cell focuses such as (VGO) then about 15 heavy %.At present, 66% propylene is produced the byproduct of ethene from steam cracking in the world, and 32% produces the byproduct of vapour, diesel oil from refinery FCC, and a small amount of (about 2%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.
If petrochemical complex is walked traditional preparing ethylene by steam cracking, propylene route, will face the shortage of lightweight material oil, inefficiency of production and cost and cross high several big restraining factors.
FCC is owing to advantages such as its adaptability to raw material is wide, flexible operation come into one's own day by day.In the U.S., almost 50% of the propylene market demand all derive from FCC apparatus.It is very fast that the catalytic cracking of propylene enhancing improves technical development.
US4,980,053 disclose a kind of hydrocarbon conversion processes of producing low-carbon alkene, and raw material is petroleum fractions, residual oil or the crude oil of different boiling ranges, uses solid acid catalyst in fluidized-bed or moving-burden bed reactor, temperature 500-650 ℃, pressure 1.5-3 * 10
5Pa, weight hourly space velocity 0.2-2.0h
-1, agent-oil ratio 2-12 condition under carry out catalytic conversion reaction, reacted catalyzer Returning reactor internal recycle behind coke burning regeneration uses.The overall yield of this method propylene and butylene can reach about 40%, and wherein productivity of propylene is up to 26.34%.
WO00/31215A1 discloses a kind of catalyst cracking method of producing alkene, and this method adopts ZSM-5 and/or ZSM-11 zeolite to do active component, is the catalyzer of matrix with a large amount of inert substances, is raw material with VGO, and the productive rate of propylene also is no more than 20 heavy %.
US4,422,925 disclose the method that multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, the described hydro carbons of this method contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material at least, this method has different cracking performances according to different hydrocarbon molecules, reaction zone is divided into a plurality of reaction zones carries out cracking reaction, with voluminous low-molecular olefine.
Although these methods can producing more propylene, but increase along with liquefied gas yield or productivity of propylene, gasoline yield reduces, aromatic hydrocarbons in the gasoline and benzene content also increase considerably, if the gasoline of high benzene content without extracting or saturated, is not suitable for blended gasoline usually, the high problem of aromatic hydrocarbons in gasoline and benzene content, dry gas yied increases nearly 5 times, thereby causes the waste of heavy oil resources, and petroleum resources are unrealized and are efficiently utilized.
Along with Chinese economic development, China's gasoline car recoverable amount increases year by year, and therefore the demand to the high quality light-weight fuel oil then increases considerably, especially gasoline.And at present the world is being faced with crude oil and becomes and heavily become bad trend, and the demand of heavy fuel oil (HFO) is but gradually reduced.Therefore, residual hydrocracking is used widely as the technology of heavy oil fluid catalytic cracking stock oil.CN1382776A discloses the method for residual hydrocracking and catalytically cracking heavy oil, be that residual oil and slurry oil steam that thing, catalytic cracking heavily follow carburetion, optional distillate enters hydrotreater together, in the presence of hydrogen and hydrogenation catalyst, carry out hydrogenation reaction; After the generation oil of reaction gained steams petrol and diesel oil, hydrogenated residue enters catalytic cracking unit with optional vacuum gas oil, carry out cracking reaction in the presence of cracking catalyst, reaction gained heavy cycle oil enters residual hydrogenation equipment, and the distillation slurry oil obtains steaming thing and is back to hydrogenation unit.This method can be converted into light-end products with slurry oil and heavy cycle oil, has improved the yield of gasoline and diesel oil.Although heavy oil is by behind the hydroprocessing technique, catalytic cracking process can be produced more liquid product, and the foreign matter content of product is low, character makes moderate progress, but the density of working as heavy oil is big, and when viscosity height, heavy metal content height and colloid and asphalt content were high, the operational condition of hydrotreater was very harsh, the working pressure height, the temperature of reaction height, air speed is low, and on-stream time is short, the process cost height, and the one-time investment of device is also high.In addition, when this method is handled heavy oil, also produce the small molecules hydro carbons, especially dry gas causes the reduction of heavy oil efficiency of resource, simultaneously, when hydrogenated residue enters the catalytic cracking unit processing, still produce the heavy oil of 8～10 heavy %, cause the reduction of heavy oil efficiency of resource again.This heavy oil can return residual hydrogenation equipment, but this heavy oil and residual oil character differ bigger, and hydrogen richness is low, even through hydrotreatment, the character of this heavy oil is improved limited.
Above-mentioned prior art still exists not enough to the design of the alkane molecule cracking reaction in the stock oil, and it is excessive to other hydrocarbon molecules cracking reaction in the raw material, cause dry gas and coke yield to increase considerably, simultaneously, prior art is underused the gasoline potential content in gasoline octane rating and the diesel oil, cause productivity of propylene on the low side, there are room for improvement in gasoline yield and quality simultaneously.For the demand that satisfies growing propylene industrial chemicals and the productive rate of motor spirit, be necessary to develop and a kind of heavy feed stock be converted into a large amount of propylene and the catalysis conversion method of stop bracket gasoline.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of and heavy feed stock is converted into low-carbon alkene, especially the catalysis conversion method of propylene and stop bracket gasoline by catalytic cracking process and hydroprocessing technique organic assembling.Combined method is that catalytic cracking process is only handled alkane group in the heavy feed stock, and remaining aromatic hydrocarbon group is processed by hydroprocessing technique, thereby realizes that petroleum resources efficiently utilize.
Method provided by the invention comprises that the hydrocarbon raw material of different cracking performances contacts with catalytic cracking catalyst, and this method comprises:
Difficult cracked raw material contacts with hot regeneration catalyzing catalyst for cracking earlier, at 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10MPa～1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30～150, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05～1.0 the condition, reactant flow is mixed with easy cracked stock oil, at 450～620 ℃ of temperature of reaction, weight hourly space velocity 0.1～100h
-1, reaction pressure 0.10～1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 1.0～30, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05～1.0 the condition; Reclaimable catalyst separates by cyclonic separator with reaction oil gas, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration, reaction oil gas through separation obtain purpose product propylene, stop bracket gasoline and boiling range be 180～260 ℃ cut, 260 ℃ cut, wherein〉260 ℃ cut contacts with hydrogen, hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under carry out hydrotreatment, resulting hydrogenation heavy oil is as the stock oil of this cat-cracker or the stock oil of conventional catalytic cracking unit.
Described boiling range is that 180～260 ℃ cut returns the stock oil as this cat-cracker.
The hydrocarbon raw material of described different cracking performances is divided into easy cracking and difficult cracking stock.
Described easy cracking stock is petroleum hydrocarbon and/or other mineral oil, and wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil (VGO), atmospheric gas oil (AGO), coker gas oil (CGO), deasphalted oil (DAO), vacuum residuum (VR), long residuum (AR), the hydrogenation heavy oil.Other mineral oil is one or more in liquefied coal coil, tar sand oil, the shale oil.Preferred raw material is selected from a kind of of vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum or more than one mixture wherein.Wherein VGO, AGO, CGO, DAO, VR, AR are the full cut or the part cut of not hydrogenation, or are full cut or part cut behind the hydrogenation.
Described difficult cracking stock is selected from a kind of in hydrocarbon that diesel oil, gasoline, carbonatoms are 4-8, the cut that the boiling range scope is 180～260 ℃ or more than one mixture wherein.
Described gasoline is selected from a kind of in present method gained catalytic cracking gasoline, catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, the hydrogenated gasoline or more than one mixture wherein, and wherein catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, hydrogenated gasoline are from the outer gasoline of this device.
Described diesel oil is to be selected from a kind of in present method gained catalytic pyrolysis diesel oil, catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, the hydrogenated diesel oil or more than one mixture wherein, and wherein catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, hydrogenated diesel oil are from the outer diesel oil of this device.
Carbonatoms is that 4～8 hydrocarbon can be from catalytic cracking method of the present invention, also can be from technologies such as conventional catalytic cracking, coking, thermally splitting, hydrogenation.
Described hydrogenation heavy oil is the boiling range produced of this device or external device such as conventional catalytic cracking greater than 260 ℃ heavy oil, more preferably greater than 330 ℃ heavy oil under there is situation in hydrogen, contact with hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under to carry out hydrotreatment resultant.
Described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight respectively: the heavy % of zeolite 1 heavy %-50, the heavy % of inorganic oxide 5 heavy %-99, the heavy % of clay 0 heavy %-70.
Its mesolite is selected from mesopore zeolite and optional large pore zeolite as active ingredient, and mesopore zeolite accounts for the heavy % of 50 heavy %-100 of zeolite gross weight, and the heavy % of preferred 70 heavy %-100, large pore zeolite account for the heavy % of 0 heavy %-50 of zeolite gross weight, the heavy % of preferred 0 heavy %-30.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as non-metallic elements such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.Large pore zeolite is selected from one or more the mixture in this group zeolite that the super steady Y that is obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods, high silicon Y constitute.
Inorganic oxide is selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).
Clay is selected from kaolin and/or halloysite as matrix (being carrier).
Catalytic cracking catalyst in each reactor can be identical, also can be different.
Described fluidized-bed reactor be selected from riser tube, etc. fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, one or both series combinations of downstriker transfer limes of linear speed.Riser tube can be conventional isodiametric riser tube, also can be the riser tube of various forms reducing.Wherein the gas speed of fluidized-bed is 0.1 meter per second-2 meter per second, and the gas speed of riser tube is 2 meter per seconds-30 meter per second (disregarding catalyzer).
Preferred forms of the present invention is to carry out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.
In order to increase the agent-oil ratio of reaction catchment, improve the lytic activity of catalyzer, can be by supplemental heat or cold regenerated catalyst, half regenerated catalyst, catalyzer, live catalyst to be generated.Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7; The reclaimable catalyst carbon content is more than the 0.9 heavy %, and preferably carbon content is the heavy % in 0.9 heavy %～1.2.
Described low-carbon alkene is propylene and butylene.
Separation of propylene is identical with the method that those of ordinary skills know with the method for the butylene of choosing wantonly from reaction oil gas; From the reaction oil gas separation of C
5-C
8It is identical with the method that those of ordinary skills know as the recycle stock method to come out; Separate described 180～260 ℃ cut, preferred 190～250 ℃ cut can carry out separation method in existing FCC separation column, cut greater than 250 ℃ or 260 ℃, can be used as the stock oil of hydrotreater more preferably greater than 330 ℃ cuts, perhaps greater than the cut of 250 ℃ or 260 ℃, more preferably greater than the stock oil of 330 ℃ cuts as conventional catalytic cracking unit.
Hydrotreater be handle that this device or external device such as conventional catalytic cracking produce greater than 260 ℃ heavy oil, more preferably greater than 330 ℃ heavy oil.Under there was situation in hydrogen, this heavy oil contacted with hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under carry out hydrotreatment, resulting hydrogenation heavy oil can be used as the stock oil of this device or the stock oil of conventional catalytic cracking unit.
Described hydrotreating catalyst is group vib metal and/or the VIII family metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium carrier, preferred hydrotreating catalyst is that one or more group VIII metals, 12～39 one or more group vib metals of heavy % and surplus aluminum oxide and/or the amorphous silicon aluminium carrier by 0～10 heavy % additive, 1～9 heavy % constitutes, and wherein said additive is selected from non-metallic element and metallic elements such as fluorine, phosphorus, titanium, platinum.Described group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
This technical scheme organically combines technologies such as catalytic pyrolysis and hydrotreatment, produces low-carbon alkene to greatest extent from the heavy feed stock that hydrogen richness is lower, especially propylene and light-weight fuel oil, and stop bracket gasoline especially, thus realize that petroleum resources efficiently utilize.The present invention compared with prior art has following unforeseeable technique effect:
1, productivity of propylene and the propylene selectivity in liquefied gas increases considerably, for paraffinic base VGO, and productivity of propylene nearly 30 heavy %.
2, gasoline yield increases significantly, and gasoline octane rating improves significantly.
3, under the situation that productivity of propylene increases considerably, dry gas yied reduces significantly, can reduce to reach more than the 80 heavy %.
4, yield of light oil increases significantly, and the slurry oil productive rate reduces significantly, thereby the petroleum resources utilising efficiency improves.
5, the hydrotreater operational cycle is improved significantly, and hydrogenation heavy oil character is significantly improved.
Description of drawings
Accompanying drawing is a catalysis conversion method schematic flow sheet of producing propylene and stop bracket gasoline provided by the invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is a catalysis conversion method schematic flow sheet of producing propylene and stop bracket gasoline provided by the invention.
Its technical process is as follows:
The pre-medium that promotes is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 in the accelerated motion that makes progress of the pre-castering action lower edge riser tube that promotes medium, difficult cracking stock oil through pipeline 3 with bottom from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction takes place in difficult cracking stock on the catalyzer of heat, and upwards accelerated motion.Easily cracking stock oil through pipeline 5 with middle and lower part from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 6, mix with the existing logistics of riser reactor, easily cracking reaction takes place in cracking stock on the lower catalyzer that contains certain charcoal, and upwards accelerated motion enters reaction zone II continuation reaction, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 8 through pipeline 7, the realization reclaimable catalyst separates with oil gas, oil gas enters collection chamber 9, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 10 in the settling vessel, contacts with steam from pipeline 11.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 9 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline 15.Catalyzer after the regeneration enters riser tube through inclined tube 16.
Oil gas in the collection chamber 9 is through main oil gas piping 17, enter follow-up separation system 18, separating the propylene that obtains draws through pipeline 19, separating the propane that obtains draws through pipeline 28, and carbon four hydrocarbon are drawn through pipeline 20, also can return the reaction zone I bottom of riser tube 2, the catalytic pyrolysis dry gas is drawn through pipeline 21, catalytic cracking gasoline is drawn through pipeline 27, boiling range is 180～260 ℃ cut returns riser tube 2 through pipeline 22 reaction zone I bottom, boiling range〉260 ℃ cut enters hydrotreatment unit 24 through pipeline 23, isolates light constituent and draws through pipeline 25, and hydrogenation heavy oil returns the reaction zone I middle and lower part of riser tube 2 through pipeline 26.
The following examples will give further instruction to present method, but therefore not limit present method.
Used raw material is VGO among the embodiment, and its character is as shown in table 1.Used extraction solvent is a furfural among the embodiment.
Catalytic cracking catalyst preparation method used among the embodiment is summarized as follows:
1), with 20gNH
4Cl is dissolved in the 1000g water, and (Qilu Petrochemical company catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP-1 zeolite in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 90 ℃ of exchange 0.5h, filter filter cake; Add 4.0gH
3PO
4(concentration 85%) and 4.5gFe (NO
3)
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; Then handle at 550 ℃ of roasting temperatures and obtained phosphorous and MFI structure mesopore zeolite iron in 2 hours, its elementary analytical chemistry consists of
0.1Na
2O·5.1Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2), use 250kg decationized Y sieve water with 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%) again, its PH is transferred to 2-4 with hydrochloric acid, stir, left standstill under 60-70 ℃ aging 1 hour, maintenance PH is 2-4, cools the temperature to below 60 ℃, add 41.5Kg aluminium colloidal sol (Qilu Petrochemical company catalyst plant product, Al
2O
3Content is 21.7m%), stirred 40 minutes, obtain mixed serum.
3), the MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (the Qilu Petrochemical company catalyst plant Industrial products of the phosphorous and iron that step 1) is prepared, lattice constant is 2.445-2.448nm, butt is 2.0kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, the flush away Na that dissociates
+, being drying to obtain the catalytic cracking catalyst sample, consist of 15 heavy % MFI structure mesopore zeolite, 3 heavy %DASY zeolites, the 32 heavy % pseudo-boehmites, 6 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Hydrotreating catalyst preparation method used among the embodiment is summarized as follows: take by weighing ammonium metawolframate ((NH
4)
2W
4O
1318H
2O, chemical pure) and nickelous nitrate (Ni (NO
3)
218H
2O, chemical pure), water is made into 200mL solution.Solution is joined in alumina supporter 50 gram, at room temperature flooded 3 hours, used the ultrasonication steeping fluid 30 minutes in steeping process, cooling is filtered, and is put in the microwave oven dry about 15 minutes.Consisting of of this catalyzer: 30.0 heavy %WO
3, 3.1 heavy %NiO and surplus aluminum oxide.
Embodiment 1
This embodiment tests according to the flow process of accompanying drawing, stock oil A is directly as the raw material of catalytic pyrolysis, on middle-scale device, test by riser reactor, easily the cracked raw material enters reaction zone I middle and lower part, difficult cracked raw material enters reaction zone I bottom, in reaction zone I bottom, difficult cracked raw material is at 640 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, the weight ratio 60 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.20 condition; At reaction zone I middle part, easily the cracked raw material is at 580 ℃ of temperature of reaction, weight hourly space velocity 60h
-1, the weight ratio 10 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.15 condition, at reaction zone II, oil gas is at 540 ℃ of temperature of reaction, weight hourly space velocity 30h
-1The weight ratio of water vapor and raw material is to carry out cracking reaction under 0.15 condition, oil gas separates at settling vessel with the catalyzer for the treatment of charcoal, product cuts by boiling range in separation system, thereby obtain propylene and gasoline, part carbon four hydrocarbon, boiling range are that 180～260 ℃ cut carries out freshening, boiling range〉260 ℃ cut is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1500v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, the hydrogenation heavy oil behind the hydrogenation loops back above-mentioned kitty cracker.Operational condition and product distribute and list in table 2.
As can be seen from Table 2, productivity of propylene is up to 30.02 heavy %, and dry gas yied only is 3.32 heavy %, and liquid yield is 90.68 heavy %.
This embodiment is identical with the testing apparatus of embodiment 1, stock oil B is directly as the raw material of catalytic pyrolysis, on middle-scale device, test by riser reactor, easily the cracked raw material enters reaction zone I middle and lower part, difficult cracked raw material enters reaction zone I bottom, in reaction zone I bottom, difficult cracked raw material is at 640 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, the weight ratio 60 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.20 condition; In reaction zone I middle and lower part, easily the cracked raw material is at 580 ℃ of temperature of reaction, weight hourly space velocity 60h
-1The weight ratio 10 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.15 condition, in addition, replenish the steam stripped reclaimable catalyst of part from stripping stage and enter reaction zone II bottom, with temperature and the reaction weight hourly space velocity that reduces reaction zone II.At reaction zone II, oil gas is at 530 ℃ of temperature of reaction, weight hourly space velocity 20h
-1The weight ratio of water vapor and raw material is to carry out cracking reaction under 0.15 condition, oil gas separates at settling vessel with the catalyzer for the treatment of charcoal, product cuts by boiling range in separation system, thereby obtain propylene and gasoline, part carbon four hydrocarbon, boiling range are that 180～260 ℃ cut carries out freshening, boiling range〉260 ℃ cut is through hydrotreatment, at hydrogen dividing potential drop 10.0MPa, 450 ℃ of temperature of reaction, hydrogen to oil volume ratio 500v/v, volume space velocity 0.5h
-1Reaction conditions under carry out hydrotreatment, the hydrogenation heavy oil behind the hydrogenation loops back above-mentioned kitty cracker.Operational condition and product distribute and list in table 2.
As can be seen from Table 2, productivity of propylene is up to 27.55 heavy %, and dry gas yied only is 3.16 heavy %, and liquid yield is 90.64 heavy %.
Table 1
| Embodiment 1 | |
|
| The stock oil numbering | A | B |
| Stock oil character | ||
| Density (20 ℃), g/cm 3 | 0.8886 | 0.9134 |
| Sulphur content, ppm | 4700 | 5800 |
| Nitrogen content, ppm | 1600 | 2900 |
| Aromatic hydrocarbons, m% | 26.3 | 32.6 |
| C，m％ | 86.46 | 86.23 |
| H，m％ | 12.86 | 12.69 |
| Boiling range (ASTM D-1160), ℃ | ||
| IBP | 312 | 327 |
| 10％ | 361 | 363 |
| 30％ | 412 | 409 |
| 50％ | 452 | 450 |
| 70％ | 478 | 482 |
| 90％ | 506 | 504 |
| 95％ | 532 | 526 |
| EP | 546 | 542 |
Table 2
| Embodiment 1 | |
|
| The stock oil numbering | A | B |
| The catalytic pyrolysis unit | ||
| Operational condition | ||
| The riser tube temperature out, ℃ | 530 | 520 |
| Riser reaction zone II | ||
| Temperature of reaction, ℃ | 540 | 530 |
| Weight hourly space velocity, h -1 | 30 | 20 |
| The weight ratio of water vapor/raw material | 0.15 | 0.15 |
| Riser reaction zone I | ||
| Medial temperature, ℃ | 640/580 | 640/550 |
| Agent-oil ratio, m/m | 60/10 | 60/10 |
| Weight hourly space velocity, h -1 | 180/60 | 180/60 |
| The weight ratio of water vapor/raw material | 0.20/0.15 | 0.25/0.15 |
| The hydrotreatment unit | ||
| The hydrogen dividing potential drop, MPa | 18.0 | 10.0 |
| Temperature of reaction, ℃ | 350 | 450 |
| Hydrogen to oil volume ratio, v/v | 1500 | 500 |
| Volume space velocity, h -1 | 1.5 | 0.5 |
| Product distributes, m% | ||
| Dry gas | 3.32 | 3.16 |
| Liquefied gas | 51.23 | 48.12 |
| Propylene | 30.02 | 27.55 |
| Gasoline | 31.12 | 33.05 |
| Diesel oil | 8.33 | 9.47 |
| Coke | 6.0 | 6.2 |
| Add up to | 100.00 | 100.00 |
Claims (8)
1, a kind of catalysis conversion method of producing propylene and stop bracket gasoline is characterized in that this method comprises: difficult cracked raw material contacts with hot regeneration catalyzing catalyst for cracking earlier, at 600～750 ℃ of temperature of reaction, weight hourly space velocity 100～800h
-1, reaction pressure 0.10MPa～1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30～150, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05～1.0 the condition, reactant flow is mixed with easy cracked stock oil, at 450～620 ℃ of temperature of reaction, weight hourly space velocity 0.1～100h
-1, reaction pressure 0.10～1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 1.0～30, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05～1.0 the condition; Reclaimable catalyst separates by cyclonic separator with reaction oil gas, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration, reaction oil gas through separation obtain purpose product propylene, stop bracket gasoline and boiling range be 180～260 ℃ cut, 260 ℃ cut, wherein〉260 ℃ cut contacts with hydrogen, hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under carry out hydrotreatment, resulting hydrogenation heavy oil is as the stock oil of this cat-cracker or the stock oil of conventional catalytic cracking unit.
2,, it is characterized in that the described difficult cracking stock of described difficult cracked raw material is selected from one or more the mixture in the hydrocarbon that slurry oil, diesel oil, gasoline, carbonatoms are 4-8 according to the method for claim 1.
3, according to the method for claim 1, it is characterized in that described easy cracking stock is petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, the hydrogenation heavy oil, and other mineral oil is one or more in liquefied coal coil, tar sand oil, the shale oil.
4,, it is characterized in that described hydrogenation heavy oil is the boiling range produced of this device or conventional catalytic cracking greater than 260 ℃ heavy oil, through the hydrotreatment gained according to the method for claim 1 or 3.
5, according to the method for claim 1, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % of zeolite 1 heavy %-50, the heavy % of inorganic oxide 5 heavy %-99, the heavy % of clay 0 heavy %-70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for the heavy % of 50 heavy %-100 of zeolite gross weight, large pore zeolite accounts for the heavy % of 0 heavy %-50 of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y series zeolite.
6, according to the method for claim 1, it is characterized in that used reactor be selected from riser tube, etc. one or both series combinations in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, wherein riser tube is the conventional isodiametric riser tube or the riser tube of various forms reducing.
7,, it is characterized in that described hydrotreating catalyst is group vib metal and/or the VIII family metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium carrier according to the method for claim 1.
8,, it is characterized in that described boiling range is that 180～260 ℃ cut returns the stock oil as this cat-cracker according to the method for claim 1.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101018539A CN101531923B (en) | 2008-03-13 | 2008-03-13 | Catalytic conversion method for preparing propylene and high-octane gasoline |
| KR1020107005146A KR101546466B1 (en) | 2007-08-09 | 2008-08-07 | A catalytic conversion process |
| JP2010519326A JP5936819B2 (en) | 2007-08-09 | 2008-08-07 | Catalytic conversion process |
| DK08783625.0T DK2184335T3 (en) | 2007-08-09 | 2008-08-07 | PROCEDURE FOR CATALYTIC TRANSFORMATION |
| RU2010107891/04A RU2464298C2 (en) | 2007-08-09 | 2008-08-07 | Method for catalytic conversion (versions) |
| PCT/CN2008/001439 WO2009018722A1 (en) | 2007-08-09 | 2008-08-07 | A process of catalytic conversion |
| EP08783625.0A EP2184335B1 (en) | 2007-08-09 | 2008-08-07 | A process of catalytic conversion |
| CN200880102537.1A CN101932672B (en) | 2007-08-09 | 2008-08-07 | A process of catalytic conversion |
| TW097130151A TWI383039B (en) | 2007-08-09 | 2008-08-07 | A catalytic conversion method |
| US12/672,666 US8696887B2 (en) | 2007-08-09 | 2008-08-07 | Catalytic conversion process |
| JP2014202981A JP2015025134A (en) | 2007-08-09 | 2014-10-01 | Process of catalytic conversion |
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| CN2008101018539A CN101531923B (en) | 2008-03-13 | 2008-03-13 | Catalytic conversion method for preparing propylene and high-octane gasoline |
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