CN102031147B - Catalytic conversion method for producing diesel and propylene in high yield - Google Patents
Catalytic conversion method for producing diesel and propylene in high yield Download PDFInfo
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Abstract
The invention provides a catalytic conversion method for producing diesel and propylene in high yield. In the method, raw oil is contacted with a catalyst to react in a reactor; the reacting temperature, the weight hourly space velocity and the weight ratio of the catalyst to the raw oil sufficiently ensure that a reaction product of catalytic wax oil, which accounts for 12 to 60 weight percent of the raw oil, is obtained; and the catalytic wax oil enters a hydrocracking device for further treatment, and the hydrocracked tail oil of the obtained catalytic wax oil is used as a raw material for a high-yield diesel producing device. The catalytic cracking process, the hydrocracking process and the high-yield diesel producing process are integrated, alkane, alkyl side chain and other hydrocarbons in the raw material are subjected to selective cracking and isomerization catalysis, the aromatic hydrocarbon in the raw material is furthest prevented from entering diesel fraction, other components in the product are prevented from generating aromatic hydrocarbon through aromatization and other reactions and retaining in the diesel fraction, and the yield of dry gas and coke is greatly reduced when the raw material is converted into diesel with high cetane number and propylene, so that the effective utilization of petroleum resources is realized.
Description
Technical field
The invention belongs to the catalysis conversion method of hydrocarbon ils in the absence of hydrogen, more particularly, is a kind of catalysis conversion method heavy feed stock being converted into high hexadecane value diesel oil and propylene.
Background technology
The demand of the current whole world to high-quality gasoline increases day by day, and voluminous high-quality gasoline technology develops rapidly, produces high hexadecane value biodiesel technology and develops then relatively slow.Although vapour, diesel oil demand are with different from different places, the whole world will exceed gasoline demand rate of growth gradually to the rate of growth of diesel oil demand generally.Diesel cetane-number that conventional catalyst cracking technique is produced is relatively low, is therefore often used as the blend component of diesel oil.In order to meet the demand of high-quality diesel oil, need to carry out upgrading to catalysis solar oil.
In prior art, hydrotreatment and alkylation are mainly comprised to the method for catalysis solar oil upgrading.CN1289832A discloses a kind of method adopting hydrotreatment to come catalytic cracking diesel oil upgrading equally, is that the Hydrobon catalyst making raw material be connected by single hop successively under hydroconversion condition is separated without centre with hydrocracking catalyst.The method make the cetane value of product diesel oil distillate comparatively raw material improve more than 10 units, its sulphur, nitrogen content significantly reduce.
CN1900226A discloses assisted catalyst for catalyzing cracking of a kind of high-yield diesel oil and preparation method thereof, add this promotor a certain amount of, can when not changing original the adopted catalyzer of oil refining apparatus, improve the diesel yield of FCC catalytic unit, improve product slates, but the method does not mention the improvement of diesel oil character.
The low-carbon alkenes such as propylene are important Organic Chemicals, and propylene is the synthon of the product such as polypropylene, vinyl cyanide.Along with increasing rapidly of the derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in World Propylene market has been increased to 5,120 ten thousand tons of 2000 from 1,520 ten thousand before 20 years ton, average growth rate per annum reaches 6.3%.The demand expecting propylene in 2010 will reach 8,600 ten thousand tons, and average growth rate per annum is about 5.6% therebetween.
Produce method mainly steam cracking and the catalytic cracking (FCC) of propylene, wherein steam cracking with lightweight oils such as petroleum naphthas for raw material produces ethene, propylene by thermo-cracking, but the productive rate of propylene be only 15 heavy about %, FCC then with mink cell focuses such as vacuum gas oils (VGO) for raw material.At present, the byproduct of ethene produced by the propylene of 61% from steam cracking in the world, and 34% produces the byproduct of vapour, diesel oil from refinery FCC, and a small amount of (about 5%) is obtained by dehydrogenating propane and Ethylene/Butylene metathesis reaction.
If petrochemical complex walks traditional preparing ethylene by steam cracking, propylene route, several large restraining factors such as the shortage of lightweight material oil, inefficiency of production and high cost will be faced.
FCC comes into one's own day by day due to advantages such as its adaptability to raw material is wide, flexible operations.In the U.S., almost 50% of propylene market demand all derive from FCC apparatus.The catalytic cracking improvement opportunity development of propylene enhancing is very fast.
US4,422,925 disclose the multiple hydro carbons with different cracking performance contacts with hot regenerated catalyst and the method transformed, hydro carbons described in the method is at least containing a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material, the method has different cracking performance according to different hydrocarbon molecules, reaction zone is divided into multiple reaction zone and carries out cracking reaction, with voluminous low-molecular olefine.
CN1279270A discloses the catalysis conversion method of a kind of high-yield diesel oil and liquefied gas, the method has in the riser tube of four sections or fluidized-bed reactor at one to carry out, gasoline stocks, traditional cracking raw material and reaction terminating agent inject different positions, and the method can improve the yield of liquefied gas and diesel oil simultaneously.But the method dry gas and coke yield are relatively high.
For a long time, those of ordinary skill in the art think, the transformation efficiency of heavy oil fluid catalytic cracking is more high better.But contriver is through creatively thinking and repeatedly test discovery, and the transformation efficiency of heavy oil fluid catalytic cracking is not more high better, when transformation efficiency height to a certain extent, object product increases seldom, and the productive rate of dry gas and coke but increases considerably.
In order to efficiency utilization inferior heavy oil resource, meet the demand of growing light-weight fuel oil, be necessary to develop a kind of catalysis conversion method heavy oil feedstock being converted into a large amount of clean diesel and propylene.
Summary of the invention
The object of the invention is on prior art basis, a kind of method mink cell focus being converted into high hexadecane value diesel oil and propylene is provided.It mainly passes through the hydro carbons such as alkane, alkyl group side chain in optionally cracking and isomerization catalytic raw material, the aromatic hydrocarbons reduced in raw material enters diesel oil distillate to greatest extent simultaneously, and avoid other component in product generate aromatic hydrocarbons by reactions such as aromizing and remain in diesel oil distillate, while cracking stock is converted into high hexadecane value diesel oil and propylene, the productive rate of dry gas and coke significantly reduces, thus realizes effective utilization of petroleum resources.
In one embodiment of the present invention, provide a kind of catalysis conversion method, wherein stock oil reacts with catalyst exposure in reactor, it is characterized in that temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make to be obtained by reacting the reaction product comprising and account for the heavy % catalytic wax oil of stock oil 12 ~ 60, wherein said weight hourly space velocity is 25 ~ 100h
-1, described temperature of reaction is 450 ~ 600 DEG C, and described catalyzer and stock oil weight ratio are 1 ~ 30; Catalytic wax oil enters hydroeracking unit and processes further, and gained hydrocracking tail oil is as the raw material of high-yield diesel oil device.
In a more preferred embodiment, temperature of reaction is 450 ~ 600 DEG C, preferably, and 460 ~ 580 DEG C, more preferably, 480 ~ 540 DEG C.
In a more preferred embodiment, weight hourly space velocity is 30 ~ 80h
-1, preferably, 40 ~ 60h
-1.
In a more preferred embodiment, catalyzer and stock oil weight ratio are 1 ~ 30, preferably, and 2 ~ 25, more preferably, 3 ~ 14.
In a more preferred embodiment, reaction pressure is 0.10MPa ~ 1.0MPa.
In a more preferred embodiment, described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, its 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, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, shale oil.
In a more preferred embodiment, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % of the heavy % of zeolite 1 ~ 50, the heavy % of inorganic oxide 5 ~ 99, clay 0 ~ 70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51 ~ 100 heavy % of zeolite gross weight, preferably the 70 heavy % in heavy % ~ 100.Large pore zeolite accounts for 0 ~ 49 heavy % of zeolite gross weight, preferably the 0 heavy % in heavy % ~ 30.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from Y-series zeolite.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
In a more preferred embodiment, a position, described stock oil is introduced in reactor, or described stock oil is introduced in reactor by the position of identical or different height more than one.
In a more preferred embodiment, described method also comprises and reaction product being separated with catalyzer, and catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, diesel oil and catalytic wax oil.
In a more preferred embodiment, described catalytic wax oil is the cut that initial boiling point is not less than 260 DEG C, and hydrogen richness is not less than 10.5 heavy %.
In a more preferred embodiment, described catalytic wax oil is the cut that initial boiling point is not less than 330 DEG C, and hydrogen richness is not less than 10.8 heavy %.
The reactive system of hydroeracking unit generally includes refining reaction device and cracking case, be fixed-bed reactor, refining reaction device loads hydrotreating catalyst usually, this hydrotreating catalyst be load at unformed aluminum oxide or/and the group vib in silica-alumina supports is or/and VIII non-precious metal catalyst; Hydrocracking catalyst is that the group vib of load in Y-type zeolite molecular sieve is or/and VIII non-precious metal catalyst.Wherein said group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.
The processing condition of described hydrocracking are: hydrogen dividing potential drop 4.0 ~ 20.0MPa, temperature of reaction 280 ~ 450 DEG C, volume space velocity 0.1 ~ 20h
-1, hydrogen-oil ratio 300 ~ 2000v/v.
In a more preferred embodiment, high-yield diesel oil device is the catalytic cracking unit of high-yield diesel oil.
In a more preferred embodiment, the catalytic cracking unit temperature of reaction of high-yield diesel oil is 400 ~ 650 DEG C, preferred 430 ~ 500 DEG C, preferred 430 ~ 480 DEG C; The oil gas residence time is 0.05 ~ 5 second, preferably, and 0.1 ~ 4 second; Reaction pressure is 0.10MPa ~ 1.0MPa.
In a more preferred embodiment, described high-yield diesel oil catalyzer comprises zeolite, inorganic oxide, clay.In butt, each component accounts for total catalyst weight respectively: zeolite 5 is heavy ~ and 60 heavy %, preferably 10 is heavy ~ 30 heavy %; Inorganic oxide 0.5 is heavy ~ 50 heavy %; Clay 0 is heavy ~ 70 heavy %.Its mesolite is lived as activity and is divided, and is selected from large pore zeolite.One or more mixture in this group zeolite that described large pore zeolite refers to the super steady Y obtained by Rare Earth Y, rare earth hydrogen Y, different methods, high silicon Y is formed.
Inorganic oxide, as matrix, is selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).In butt, in inorganic oxide, silicon-dioxide accounts for the heavy % in 50 heavy ~ 90, and aluminium sesquioxide accounts for 10 heavy ~ 50 heavy %.
Clay, as caking agent, is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.
In a more preferred embodiment, described high-yield diesel oil reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
In a more preferred embodiment, a position, described hydrocracking tail oil is introduced in high-yield diesel oil reactor, or described hydrocracking tail oil is introduced in high-yield diesel oil reactor by the position of identical or different height more than one.
In a more preferred embodiment, described high-yield diesel oil method also comprises and reaction product being separated with high-yield diesel oil catalyzer, high-yield diesel oil catalyzer returns high-yield diesel oil reactor after stripping, coke burning regeneration, and the product after separation comprises high hexadecane value diesel oil and propylene.
In another embodiment of the invention, provide a kind of catalysis conversion method, wherein stock oil reacts with catalyst exposure in reactor, it is characterized in that
(1) stock oil comprises cracking stock oil and cracking stock oil again, is introduced in reactor by described stock oil a position, or described stock oil is introduced in reactor by the position of identical or different height more than one;
(2) cracking stock oil is not later than cracking stock oil and reacts in reactor again;
(3) temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make to be obtained by reacting the reaction product comprising and account for the heavy % catalytic wax oil of stock oil 12 ~ 60;
(4) the described weight hourly space velocity of cracking stock oil is 5 ~ 100h
-1;
(5) catalytic wax oil enters catalytic wax oil hydroeracking unit;
(6) hydrocracking tail oil that obtains of hydrocracking is as the raw material of high-yield diesel oil device.
In a more preferred embodiment, the grease separation of described cracking stock again from or one or more the mixture that comprises in dry gas, liquefied gas, gasoline.
In a more preferred embodiment, described cracking stock grease separation from or comprise petroleum hydrocarbon and/or other mineral oil, its 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, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, shale oil.
In a more preferred embodiment, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % of the heavy % of zeolite 1 ~ 50, the heavy % of inorganic oxide 5 ~ 99, clay 0 ~ 70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51 ~ 100 heavy % of zeolite gross weight, preferably the 70 heavy % in heavy % ~ 100.Large pore zeolite accounts for 0 ~ 49 heavy % of zeolite gross weight, and mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from Y-series zeolite.
In a more preferred embodiment, described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
In a more preferred embodiment, then the reaction conditions of cracking stock oil be: temperature of reaction 600 ~ 750 DEG C, weight hourly space velocity 100 ~ 800h
-1, reaction pressure 0.10 ~ 1.0MPa, catalyzer and cracking stock oil again weight ratio 30 ~ 150, water vapor is 0.05 ~ 1.0 with the weight ratio of cracking stock oil again.
In a more preferred embodiment, the reaction conditions of cracking stock oil is: temperature of reaction 450 ~ 600 DEG C, weight hourly space velocity 5 ~ 100h
-1, reaction pressure 0.10 ~ 1.0MPa, catalyzer and cracking stock oil weight ratio 1.0 ~ 30, the weight ratio of water vapor and cracking stock oil is 0.05 ~ 1.0.
In a more preferred embodiment, the temperature of reaction of cracking stock oil is 460 ~ 580 DEG C, and weight hourly space velocity is 10 ~ 90h
-1, be preferably 20 ~ 60h
-1, be more preferably 30 ~ 50h
-1, catalyzer and stock oil weight ratio are 3 ~ 14.
In a more preferred embodiment, described method also comprises and reaction product being separated with catalyzer, and catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, high hexadecane value diesel oil and catalytic wax oil.
In a more preferred embodiment, described catalytic wax oil is the cut that initial boiling point is not less than 260 DEG C, and hydrogen richness is not less than 10.5 heavy %.
In a more preferred embodiment, described catalytic wax oil is the cut that initial boiling point is not less than 330 DEG C, and hydrogen richness is not less than 10.8 heavy %.
The reactive system of hydroeracking unit generally includes refining reaction device and cracking case, be fixed-bed reactor, refining reaction device loads hydrotreating catalyst usually, this hydrotreating catalyst be load at unformed aluminum oxide or/and the group vib in silica-alumina supports is or/and VIII non-precious metal catalyst; Hydrocracking catalyst is that the group vib of load in Y-type zeolite molecular sieve is or/and VIII non-precious metal catalyst.Wherein said group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.
The processing condition of described hydrocracking are: hydrogen dividing potential drop 4.0 ~ 20.0MPa, temperature of reaction 280 ~ 450 DEG C, volume space velocity 0.1 ~ 20h
-1, hydrogen-oil ratio 300 ~ 2000v/v.
In a more preferred embodiment, high-yield diesel oil device is the catalytic cracking unit of high-yield diesel oil.
In a more preferred embodiment, the catalytic cracking unit temperature of reaction of high-yield diesel oil is 400 ~ 650 DEG C, preferred 430 ~ 500 DEG C, preferred 430 ~ 480 DEG C.The oil gas residence time is 0.05 ~ 5 second, preferably, and 0.1 ~ 4 second.Reaction pressure is 0.10MPa ~ 1.0MPa.
In a more preferred embodiment, described high-yield diesel oil catalyzer comprises zeolite, inorganic oxide, clay.In butt, each component accounts for total catalyst weight respectively: zeolite 5 is heavy ~ and 60 heavy %, preferably 10 is heavy ~ 30 heavy %; Inorganic oxide 0.5 is heavy ~ 50 heavy %; Clay 0 is heavy ~ 70 heavy %.Its mesolite is lived as activity and is divided, and is selected from large pore zeolite.One or more mixture in this group zeolite that described large pore zeolite refers to the super steady Y obtained by Rare Earth Y, rare earth hydrogen Y, different methods, high silicon Y is formed.
Inorganic oxide, as matrix, is selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).In butt, in inorganic oxide, silicon-dioxide accounts for the heavy % in 50 heavy ~ 90, and aluminium sesquioxide accounts for 10 heavy ~ 50 heavy %.
Clay, as caking agent, is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.
In a more preferred embodiment, described high-yield diesel oil reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
In a more preferred embodiment, a position, described hydrocracking tail oil is introduced in high-yield diesel oil reactor, or described hydrocracking tail oil is introduced in high-yield diesel oil reactor by the position of identical or different height more than one.
In a more preferred embodiment, described high-yield diesel oil method also comprises and reaction product being separated with high-yield diesel oil catalyzer, high-yield diesel oil catalyzer returns high-yield diesel oil reactor after stripping, coke burning regeneration, and the product after separation comprises high hexadecane value diesel oil and propylene.
In order to increase the agent-oil ratio of reaction catchment, improve the catalytic activity of catalyzer, by supplemental heat or cold regenerated catalyst, semi regeneration catalyzer, catalyzer to be generated, live catalyst.The regenerated catalyst of cooling and the semi regeneration catalyzer of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration, regenerated catalyst carbon content is 0.1 heavy below %, be preferably 0.05 heavy below %, semi regeneration coke on regenerated catalyst is the 0.1 heavy % in heavy % ~ 0.9, and best carbon content is the 0.15 heavy % in heavy % ~ 0.7; Reclaimable catalyst carbon content is 0.9 heavy more than %, and best carbon content is the 0.9 heavy % in heavy % ~ 1.2.
From reaction product, the method such as separation of propylene is identical with the method that those of ordinary skill in the art know; Be greater than the stock oil of cut (or being greater than the cut of 330 DEG C) as catalytic cracking unit of 250 DEG C or 260 DEG C, or catalytic wax oil (or being greater than the catalytic wax oil of 330 DEG C) the hydrocracking mode being greater than 250 DEG C or 260 DEG C adopts catalytic wax oil hydroeracking unit.
The techniques such as catalytic pyrolysis, catalytic wax oil hydrocracking organically combine by this technical scheme, produce high hexadecane value diesel oil low-carbon alkene to greatest extent, especially propylene from the heavy feed stock that hydrogen richness is lower.The present invention compared with prior art has following technique effect:
1, while high-yield diesel oil, productivity of propylene and the propylene selectivity in liquefied gas increases considerably;
2, diesel yield increases significantly, and diesel cetane-number improves significantly;
3, when productivity of propylene and diesel oil increase considerably, dry gas yied and coke reduce significantly;
4, yield of light oil increases significantly, and slurry oil productive rate reduces significantly, thus petroleum resources utilising efficiency improves;
5, the hydrotreater operational cycle is improved significantly.
Accompanying drawing explanation
Accompanying drawing is the schematic diagram of a kind of embodiment of the present invention.
Accompanying drawing is intended to the present invention is schematically described and unrestricted the present 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 the schematic diagram of the first embodiment of the present invention.
Its technical process is as follows:
Pre-lift medium enters by bottom riser reactor 2 through pipeline 1, from the regenerated catalyst of pipeline 16 under the castering action of pre-lift medium along riser tube upwards accelerated motion, cracking stock oil is through the bottom of pipeline 3 injecting lift pipe 2 reaction zone I together with the atomizing steam from pipeline 4 again, mix with the existing logistics of riser reactor, there is cracking reaction in cracking stock again on the catalyzer of heat, and upwards accelerated motion.Cracking stock oil is through the middle and lower part of pipeline 5 injecting lift pipe 2 reaction zone I together with the atomizing steam from pipeline 6, mix with the existing logistics of riser reactor, cracking reaction is there is containing on the catalyzer of certain charcoal in cracking stock lower, and upwards accelerated motion enters reaction zone II continuation reaction, the oil gas generated and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 8 through pipeline 7, realize being separated of reclaimable catalyst and oil gas, oil gas enters collection chamber 9, and catalyst fines returns settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 10, contacts with the steam from pipeline 11.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 9 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, the coke on burning-off reclaimable catalyst, and the reclaimable catalyst of inactivation is regenerated, and flue gas enters cigarette machine through pipeline 15.Catalyzer after regeneration enters riser tube through inclined tube 16.
Oil gas in collection chamber 9, through main oil gas piping 17, enters follow-up separation system 18, is separated the propylene obtained and draws through pipeline 19, is separated the propane obtained and draws through pipeline 28; And C_4 hydrocarbon is drawn through pipeline 20, also riser tube 2 can be returned; Catalytic pyrolysis dry gas is drawn through pipeline 21; Catalytic cracking gasoline is drawn through pipeline 27, and preferred boiling range is less than 65 ~ 110 DEG C of gasoline fractions and draws conduct cracking stock Returning reactor again through pipeline 22; Diesel oil distillate is drawn through pipeline 29, also heavy gas oil cut can be drawn together with catalytic wax oil and enter Hydrocracking unit; Catalytic wax oil raw material is drawn out to Hydrocracking unit 24 through pipeline 23, and isolated hydrocracked product divides through pipeline 25, and hydrocracking tail oil sends into high-yield diesel oil device 27 through pipeline 26.The oil gas that high-yield diesel oil device generates can enter fractionating system 18 through gas pipeline 28 or/and enter other fractionating system and be separated.Wherein each cut boiling range regulates according to refinery's actual needs.
The following examples will be further described present method, but therefore not limit present method.
Stock oil used in embodiment is VGO, and its character is as shown in table 1.
Catalytic cracking catalyst preparation method used in embodiment is summarized as follows:
Catalyzer CAT-MP preparation method
1), by 20gNH
4cl is dissolved in 1000g water, and in this solution, adding 100g (butt) crystallization product ZRP-1 zeolite, (Qilu Petrochemical Company's catalyst plant is produced, SiO
2/ Al
2o
3=30, content of rare earth RE
2o
3=2.0 heavy %), after exchanging 0.5h at 90 DEG C, filter to obtain filter cake; Add 4.0gH
3pO
4(concentration 85%) and 4.5gFe (NO
3)
3be dissolved in 90g water, dry with filter cake hybrid infusion; Then within 2 hours, obtain phosphorous and MFI structure mesopore zeolite that is iron 550 DEG C of roasting temperature process, 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 by 75.4kg halloysite (Suzhou china clay company Industrial products, the heavy % of solid content 71.6) making beating, add 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, the heavy % of solid content 63) again, with hydrochloric acid, its PH is adjusted to 2 ~ 4, stir, at 60 ~ 70 DEG C, leave standstill aging 1 hour, keep PH to be 2 ~ 4, cool the temperature to less than 60 DEG C, add 41.5Kg Alumina gel (Qilu Petrochemical Company's catalyst plant product, Al
2o
3content is 21.7 heavy %), stir 40 minutes, obtain mixed serum.
3), by step 1) the MFI structure mesopore zeolite (butt is 22.5kg) of phosphorous and iron prepared and DASY zeolite (Qilu Petrochemical Company's catalyst plant Industrial products, 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 1 heavy %) washing, wash away free Na
+, be drying to obtain catalytic cracking catalyst sample CAT-MP, the MFI structure mesopore zeolite consisting of the phosphorous and iron of 18 heavy % of this catalyzer, 2 heavy %DASY zeolites, 28 heavy % pseudo-boehmites, 7 heavy % Alumina gel and balance kaolin.
High-yield diesel oil method for preparing catalyst used in embodiment is summarized as follows:
Catalyzer CAT-MD preparation method
1), the water glass solution that 2 liters of silica concentrations are 155g/l is configured and 1 liter of free acid is 148g/L, Al
2o
3content is the acidified aluminum sulfate solution of 20g/L, and above-mentioned two kinds of solution enter flash mixer reaction simultaneously, obtain silicon sol.
2), in the silicon sol of above-mentioned preparation, add 465g kaolin (Kaolin of Suzhou company, solid content 80 % by weight), pull an oar and obtain kaolin-silicon sol in 1 hour.
3), containing Al
2o
3pseudo-boehmite (Shandong Aluminum Plant, the Al of 124g
2o
3content is 33 % by weight) and 450g deionized water mixing making beating 30 minutes, then add hydrochloric acid (acid/Al that 25 ml concns are 31 % by weight
2o
3mol ratio is 0.2) peptization, continue making beating 2 hours, then adding 656g molecular sieve content is 32 % by weight ground DASY0.0 molecular sieve pulp (Shandong catalyst plant productions, lattice constant is 2.445nm), pull an oar 30 minutes, obtain the mixed serum of pseudo-boehmite and molecular sieve.
4), by the mixed serum mixing making beating 10 minutes of the pseudo-boehmite of the kaolin of above-mentioned preparation-silicon sol slurries and above-mentioned preparation and molecular sieve, obtain catalyst slurry, the slurries obtained are spray dried to the particle that diameter is 20 ~ 120 microns, silica content is 29.9 % by weight, kaolin content is 35.9 % by weight, alumina content is 13.9 % by weight, molecular sieve content is 20.3 % by weight, drying temperature is 180 DEG C.With deionized water wash to without sodium ion for detecting, 150 DEG C of oven dry, obtain prepared catalyzer CAT-MD.
Hydrobon catalyst used in embodiment and the trade names of hydrocracking catalyst are respectively RN-2 and RT-1, produce by Sinopec catalyzer branch office Chang Ling catalyst plant.
Embodiment 1
This embodiment is tested according to the flow process of accompanying drawing, cracking stock oil A is directly as the raw material of catalytic pyrolysis, adopt catalyzer CAT-MP, the middle-scale device of riser reactor is tested, cracking stock enters I middle and upper part, reaction zone, butylene enters bottom the I of reaction zone as cracking stock again, and bottom the I of reaction zone, then the raw material of cracking is at temperature of reaction 610 DEG C, weight hourly space velocity 175h
-1, the weight ratio 70 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material is carry out cracking reaction under 0.20 condition; In I middle and upper part, reaction zone, fcc raw material is at temperature of reaction 530 DEG C, weight hourly space velocity 40h
-1the weight ratio 4 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material is carry out cracking reaction under 0.15 condition, at reaction zone II, oil gas carries out cracking reaction under the weight ratio of temperature of reaction 480 DEG C, water vapor and raw material is 0.15 condition, oil gas with treat that the catalyzer of charcoal is separated at settling vessel, product cuts by boiling range in separation system, thus obtains propylene, butylene, gasoline, diesel oil and catalytic wax oil cut.Catalytic wax oil delivers to hydroeracking unit process, and the reactive system of this hydroeracking unit comprises refining reaction device and cracking case two reactors, at hydrogen dividing potential drop 17.9/17.4MPa, temperature of reaction 373/371 DEG C, volume space velocity 0.95/1.2h
-1reaction conditions under carry out hydrotreatment, the hydrocracking tail oil after hydrogenation is delivered to high-yield diesel oil catalytic cracking unit and carries out catalyzed conversion.Operational condition and product slates list in table 2.
As can be seen from Table 2, productivity of propylene is up to 13.10 heavy %, and diesel yield is 11.36 heavy %, and diesel cetane-number is up to 52, and rocket engine fuel is 13.33 heavy %.
Table 1
| Type of feed | A |
| Density (20 DEG C), kg/m 3 | 858.6 |
| Kinematic viscosity (100 DEG C), millimeter 2/ second | 4.9 |
| Carbon residue, heavy % | 0.03 |
| Total nitrogen, heavy % | 0.05 |
| Sulphur, heavy % | 0.06 |
| Carbon, heavy % | 86.3 |
| Hydrogen, heavy % | 13.64 |
| Heavy metal content, ppm | |
| Nickel | ＜0.1 |
| Vanadium | ＜0.1 |
| Boiling range, DEG C | |
| Initial boiling point | 290 |
| 10％ | 372 |
| 30％ | 415 |
| 50％ | 440 |
| 70％ | 470 |
| 90％ | 502 |
| Final boiling point | - |
Table 2
| Embodiment 1 | |
| Stock oil is numbered | A |
| Catalyst cracking unit | |
| Catalyzer | CAT-MP |
| Operational condition | |
| Riser reaction zone II | |
| Temperature of reaction, DEG C | 480 |
| The weight ratio of water vapor/stock oil | 0.15 |
| Riser reaction zone I | |
| Medial temperature, DEG C | 610/530 |
| Agent-oil ratio, m/m | 70/4 |
| Weight hourly space velocity, h -1 | 175/40 |
| The weight ratio of water vapor/stock oil | 0.2/0.15 |
| Hydrocracking unit | |
| Hydrogen dividing potential drop, MPa | 17.9/17.4 |
| Temperature of reaction, DEG C | 374/371 |
| Volume space velocity, h -1 | 0.95/1.2 |
| High-yield diesel oil catalytic cracking unit | |
| Catalyzer | CAT-MD |
| Temperature of reaction, DEG C | 480 |
| Agent-oil ratio, m/m | 3 |
| Product slates, m% | |
| Dry gas | 4.65 |
| Liquefied gas | 36.96 |
| Propylene | 13.10 |
| Gasoline | 29.33 |
| Rocket engine fuel | 13.33 |
| Diesel oil | 11.36 |
| Coke | 4.65 |
| Loss | 0.50 |
| Add up to | 100.78 |
| Diesel cetane-number | 52 |
Claims (43)
1. the catalysis conversion method of a high-yield diesel oil and propylene, wherein stock oil reacts with catalyst exposure in reactor, it is characterized in that temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make to be obtained by reacting the reaction product comprising and account for the heavy % catalytic wax oil of stock oil 12 ~ 60, wherein said weight hourly space velocity is 25 ~ 100h
-1, described temperature of reaction is 450 ~ 600 DEG C, and described catalyzer and stock oil weight ratio are 1 ~ 30, and catalytic wax oil enters hydroeracking unit and processes further, and gained hydrocracking tail oil is as the raw material of high-yield diesel oil device; Described hydrocracking process condition is: hydrogen dividing potential drop 4.0 ~ 20.0MPa, temperature of reaction 280 ~ 450 DEG C, volume space velocity 0.1 ~ 20h
-1, hydrogen-oil ratio 300 ~ 2000v/v, hydrocracking catalyst is that the group vib of load in Y-type zeolite molecular sieve is or/and VIII non-precious metal catalyst.
2. according to the method for claim 1, it is characterized in that described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, its 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, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, shale oil.
3. according to the method for claim 1, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % of the heavy % of zeolite 1 ~ 50, the heavy % of inorganic oxide 5 ~ 99, clay 0 ~ 70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51 ~ 100 heavy % of zeolite gross weight, large pore zeolite accounts for 0 ~ 49 heavy % of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from Y-series zeolite.
4. according to the method for claim 1, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
5., according to the method for claim 1, it is characterized in that a position, described stock oil being introduced in reactor, or described stock oil is introduced in reactor by the position of identical or different height more than one.
6., according to the method for claim 1, it is characterized in that temperature of reaction is 460 ~ 580 DEG C, weight hourly space velocity is 30 ~ 80h
-1, catalyzer and stock oil weight ratio be 2 ~ 15.
7., according to the method for claim 1, it is characterized in that temperature of reaction is 480 ~ 540 DEG C.
8., according to the method for claim 1, it is characterized in that weight hourly space velocity is 40 ~ 60h
-1.
9., according to the method for claim 1, it is characterized in that catalyzer and stock oil weight ratio are 3 ~ 14.
10., according to the method for claim 1, it is characterized in that described reaction is carried out under pressure is 0.10MPa ~ 1.0MPa.
11. according to the method for claim 1, and it is characterized in that described method also comprises and reaction product be separated with catalyzer, catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, high hexadecane value diesel oil and catalytic wax oil.
12., according to the method for claim 1, is characterized in that described catalytic wax oil is the cut that initial boiling point is not less than 260 DEG C, and hydrogen richness is not less than 10.5 heavy %.
13., according to the method for claim 12, is characterized in that described catalytic wax oil is the cut that initial boiling point is not less than 330 DEG C, and hydrogen richness is not less than 10.8 heavy %.
14. according to the method for claim 1, it is characterized in that high-yield diesel oil device adopts the catalytic cracking unit of high-yield diesel oil.
15. according to the method for claim 1, and it is characterized in that the catalytic cracking unit temperature of reaction of high-yield diesel oil is 400 ~ 650 DEG C, the oil gas residence time is 0.05 ~ 5 second, and reaction pressure is 0.10MPa ~ 1.0MPa.
16. according to the method for claim 14, and it is characterized in that the catalyzer that high-yield diesel oil device uses comprises zeolite, inorganic oxide, clay, in butt, each component accounts for total catalyst weight respectively: zeolite 5 is heavy ~ and 60 heavy %; Inorganic oxide 0.5 is heavy ~ 50 heavy %; Clay 0 is heavy ~ 70 heavy %, and its mesolite to be lived point as activity, is selected from large pore zeolite, described large pore zeolite refers to the super steady Y obtained by Rare Earth Y, rare earth hydrogen Y, different methods, one or more mixture in this group zeolite that high silicon Y is formed.
17., according to the method for claim 16, is characterized in that described inorganic oxide is as matrix, is selected from silicon-dioxide and/or aluminium sesquioxide; When inorganic oxide be silicon-dioxide and aluminium sesquioxide time, in butt, in inorganic oxide, silicon-dioxide accounts for the heavy % in 50 heavy ~ 90, and aluminium sesquioxide accounts for 10 heavy ~ 50 heavy %.
18. according to the method for claim 16, it is characterized in that described clay is as caking agent, is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.
19. according to the method for claim 1, it is characterized in that described high-yield diesel oil device reactor used be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
20. according to the method for claim 1, it is characterized in that being introduced in high-yield diesel oil reactor by described hydrocracking tail oil a position, or more than one the position of identical or different height by described hydrocracking tail oil introducing high-yield diesel oil reactor.
21. according to the method for claim 1, it is characterized in that described method also comprises reaction product is separated with high-yield diesel oil catalyzer, high-yield diesel oil catalyzer returns high-yield diesel oil reactor after stripping, coke burning regeneration, and the product after separation comprises high hexadecane value diesel oil and propylene.
22. 1 kinds of catalysis conversion methods, wherein stock oil reacts with catalyst exposure in reactor, it is characterized in that
(1) stock oil comprises cracking stock oil and cracking stock oil again, is introduced in reactor by described stock oil a position, or described stock oil is introduced in reactor by the position of identical or different height more than one;
(2) cracking stock oil is not later than cracking stock oil and reacts in reactor again;
(3) weight ratio of temperature of reaction, weight hourly space velocity, catalyzer and stock oil is enough to make to be obtained by reacting the reaction product comprising and account for the heavy % catalytic wax oil of cracking stock oil 12 ~ 60;
(4) the described weight hourly space velocity of cracking stock oil is 5 ~ 100h
-1;
(5) catalytic wax oil enters hydroeracking unit;
(6) hydrocracking tail oil that obtains of hydrocracking is as the raw material of high-yield diesel oil device.
23. according to the method for claim 22, described in it is characterized in that again cracking stock grease separation from or comprise slurry oil, diesel oil, gasoline, carbonatoms are one or more mixture in the hydrocarbon of 4 ~ 8.
24. according to the method for claim 22, it is characterized in that described cracking stock grease separation from or comprise petroleum hydrocarbon and/or other mineral oil, its 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, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, shale oil.
25. according to the method for claim 22, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % of the heavy % of zeolite 1 ~ 50, the heavy % of inorganic oxide 5 ~ 99, clay 0 ~ 70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for 51 ~ 100 heavy % of zeolite gross weight, large pore zeolite accounts for 0 ~ 49 heavy % of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from Y-series zeolite.
26. according to the method for claim 22, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
27., according to the method for claim 22, is characterized in that the reaction conditions of cracking stock oil is again: temperature of reaction 600 ~ 750 DEG C, weight hourly space velocity 100 ~ 800h
-1, reaction pressure 0.10 ~ 1.0MPa, catalyzer and cracking stock oil again weight ratio 30 ~ 150, water vapor is 0.05 ~ 1.0 with the weight ratio of cracking stock oil again.
28., according to the method for claim 22, is characterized in that the reaction conditions of cracking stock oil is: temperature of reaction 450 ~ 600 DEG C, weight hourly space velocity 5 ~ 100h
-1, reaction pressure 0.10 ~ 1.0MPa, catalyzer and cracking stock oil weight ratio 1.0 ~ 30, the weight ratio of water vapor and cracking stock oil is 0.05 ~ 1.0.
29., according to the method for claim 22, is characterized in that the temperature of reaction of cracking stock oil is 460 ~ 560 DEG C.
30., according to the method for claim 22, is characterized in that weight hourly space velocity is 10 ~ 90 h
-1.
31., according to the method for claim 22, is characterized in that catalyzer and stock oil weight ratio are 1 ~ 14.
32. according to the method for claim 22, and it is characterized in that described method also comprises and reaction product be separated with catalyzer, catalyzer is Returning reactor after stripping, coke burning regeneration, and the product after separation comprises propylene, high hexadecane value diesel oil and catalytic wax oil.
33., according to the method for claim 22, is characterized in that described catalytic wax oil is the cut that initial boiling point is not less than 260 DEG C, and hydrogen richness is not less than 10.5 heavy %.
34., according to the method for claim 33, is characterized in that described catalytic wax oil is the cut that initial boiling point is not less than 330 DEG C, and hydrogen richness is not less than 10.8 heavy %.
35. according to the method for claim 22, it is characterized in that high-yield diesel oil device adopts the catalytic cracking unit of high-yield diesel oil.
36. according to the method for claim 22, and it is characterized in that the catalytic cracking unit temperature of reaction of high-yield diesel oil is 400 ~ 650 DEG C, the oil gas residence time is 0.05 ~ 5 second, and reaction pressure is 0.10MPa ~ 1.0MPa.
37. according to the method for claim 22, and it is characterized in that described high-yield diesel oil device used catalyst comprises zeolite, inorganic oxide, clay, in butt, each component accounts for total catalyst weight respectively: zeolite 5 is heavy ~ and 60 heavy %; Inorganic oxide 0.5 is heavy ~ 50 heavy %; Clay 0 is heavy ~ 70 heavy %, and its mesolite to be lived point as activity, is selected from large pore zeolite, described large pore zeolite refers to the super steady Y obtained by Rare Earth Y, rare earth hydrogen Y, different methods, one or more mixture in this group zeolite that high silicon Y is formed.
38., according to the method for claim 37, is characterized in that described inorganic oxide is as matrix, is selected from silicon-dioxide or aluminium sesquioxide.
39., according to the method for claim 37, is characterized in that described inorganic oxide is as matrix, is selected from silicon-dioxide and aluminium sesquioxide, and in butt, in inorganic oxide, silicon-dioxide accounts for 50 heavy ~ 90 heavy %, and aluminium sesquioxide accounts for 10 heavy ~ 50 heavy %.
40. according to the method for claim 37, it is characterized in that described clay is as caking agent, is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.
41. according to the method for claim 22, it is characterized in that described high-yield diesel oil device reactor used be selected from riser tube, etc. one or more the combination in the fluidized-bed of linear speed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes, or the two or more combination of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
42. according to the method for claim 22, it is characterized in that being introduced in high-yield diesel oil reactor by described hydrocracking tail oil a position, or more than one the position of identical or different height by described hydrocracking tail oil introducing high-yield diesel oil reactor.
43. according to the method for claim 22, it is characterized in that described method also comprises reaction product is separated with high-yield diesel oil catalyzer, high-yield diesel oil catalyzer returns high-yield diesel oil reactor after stripping, coke burning regeneration, and the product after separation comprises high hexadecane value diesel oil and propylene.
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| CN200910177173.XA CN102031147B (en) | 2009-09-28 | 2009-09-28 | Catalytic conversion method for producing diesel and propylene in high yield |
| US12/888,780 US8529754B2 (en) | 2009-09-28 | 2010-09-23 | Catalytic conversion process for producing more diesel and propylene |
| RU2010139596/04A RU2562238C2 (en) | 2009-09-28 | 2010-09-27 | Method of catalytic conversion for production of additional quantity of diesel fuel and propylene |
| KR1020100093230A KR101796132B1 (en) | 2009-09-28 | 2010-09-27 | A catalytic conversion process for producing more diesel and propylene |
| GB1016294.9A GB2474119B (en) | 2009-09-28 | 2010-09-28 | A catalytic conversion process for producing more diesel and propylene |
| JP2010216780A JP5806458B2 (en) | 2009-09-28 | 2010-09-28 | Catalyst modification process to produce more diesel and propylene |
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| CN101191081A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic conversion method for hydrocarbon oil raw material |
| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
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| CN101191081A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic conversion method for hydrocarbon oil raw material |
| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
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