CN102086414B - Method for catalyzing and conversing hydrocarbon oil - Google Patents
Method for catalyzing and conversing hydrocarbon oil Download PDFInfo
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- CN102086414B CN102086414B CN 200910250059 CN200910250059A CN102086414B CN 102086414 B CN102086414 B CN 102086414B CN 200910250059 CN200910250059 CN 200910250059 CN 200910250059 A CN200910250059 A CN 200910250059A CN 102086414 B CN102086414 B CN 102086414B
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Abstract
The invention relates to a method for catalyzing and conversing hydrocarbon oil, comprising the following steps of inputting a heavy hydrocarbon oil raw material into a first lift pipe reactor to undergo a contact reaction with a catalyst; inputting fractionating tower top circulating oil into a second lift pipe reactor to undergo the contact reaction with the catalyst; enabling the generated oil gas and the reacted catalysts to enter a settler upwards, wherein the catalysts and the oil gas are separated in the settler, the oil gas enters a follow-up separation system to separate reaction products, the catalysts enter a regenerator to burn and regenerate, and the regenerated catalysts return to the lift pipe reactors for recycling. The first lift pipe reactor and the second lift pipe reactor share one settler and one regenerator. By utilizing the method, the yields of gasoline and liquefied gas can be increased, and meanwhile, the quality of the gasoline can be improved.
Description
Technical field
The present invention relates to a kind of method of hydrocarbon oil catalytic conversion, more particularly, is a kind of method of carrying out hydrocarbon oil catalytic conversion in duo-lift tube reactor.
Background technology
Catalytic cracking is one of important technical of heavy oil lighting, along with the stock oil heaviness and to the increase of gasoline and liquefied gas demand, the catalytic cracking process condition is harsher, as improved temperature of reaction, improving catalyst/feed oil quality ratio, causes dry gas and coke yield obviously to increase.
Adopt double lifting leg to carry out the technical development of hydrocarbon oil catalytic conversion very fast, generally on the first riser tube, carry out heavy oil fluid catalytic cracking, carry out gasoline upgrading and gasoline conversion on the second riser tube, two riser tubes can share catalyzer and oil and gas separating system (settling vessel) and subsequent separation system, also oil and gas separating system (settling vessel) and subsequent separation system can be set separately.It is to improve gasoline quality that prior art adopts the main purpose of double lifting leg, and the gasoline upgrading proposed as CN1176189C, CN1171977C, CN1100115C comprises a conventional heavy oil catalytic cracking process, and an inferior patrol catalyzed conversion upgrading process.Heavy oil carries out conventional catalytic cracking reaction at the heavy oil riser reactor, and inferior patrol carries out the catalyzed conversion upgrading at the gasoline rising pipe reactor, and two processes share a catalyst regenerator, use the same catalytic cracking catalyst.Can make the olefin(e) centent of inferior patrol reduce by 15～50 volume percentage points, gasoline octane rating (RON) improves 0.2～2 unit; Its coke and dry gas yied increase to some extent.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of hydrocarbon oil catalytic conversion, under the prerequisite that does not increase coke and dry gas yied, increases substantially gasoline and liquefied gas yield, improves the octane value of gasoline simultaneously.
A kind of method of hydrocarbon oil catalytic conversion comprises:
(1) heavy hydrocarbon oil raw material is inputted to the first riser reactor, contacted with catalyzer, react under the condition of catalytic cracking, the oil gas of generation and reacted catalyzer upwards enter settling vessel;
(2) fractionation tower top turning oil is inputted to the second riser reactor, contact with catalyzer, reacted under the condition of catalytic cracking, the oil gas of generation and reacted catalyzer upwards enter settling vessel;
(3) in settling vessel, catalyzer and gas-oil separation, oil gas removes subsequent separation system separating reaction product, and catalyzer goes revivifier to carry out coke burning regeneration, and the catalyzer after regeneration returns to riser reactor and recycles;
Wherein, the first and second riser reactors share a settling vessel and revivifier.
In the present invention, described catalyzer is catalytic cracking catalyst, and it consists of conventionally known to one of skill in the art.
In the present invention, described heavy hydrocarbon oil raw material is the petroleum hydrocarbon cut that initial boiling point is greater than 250 ℃, is preferably one or more in vacuum residue fraction, vacuum residuum solvent-deasphalted oils, hydro-cracking of vacuum residue tail oil and the vacuum residuum hydrotreatment heavy oil fraction of decompressed wax oil cut, crude oil underpressure distillation of long residuum cut, the crude oil underpressure distillation of crude oil atmospheric distillation.
In the present invention, described fractionation tower top turning oil comes from the product separation system of this device, for gasoline reform, divides and the mixture of diesel oil than light constituent, and boiling range is between 40～350 ℃.
In method of the present invention, the reaction conditions of the first riser tube is: temperature of reaction is 450～650 ℃, reaction pressure is 80～450KPa, catalyzer and stock oil mass ratio are (3～20): 1, the mass ratio of water vapor and stock oil is (0.02～0.5): 1, and the reaction times is 0.1～30 second.The reaction conditions of the second riser tube is: temperature of reaction is 400～560 ℃, reaction pressure is 80～450KPa, catalyzer and stock oil mass ratio are (3～20): 1, and the mass ratio of water vapor and stock oil is (0.02～0.5): 1, the reaction times is 0.1～30 second.
In method of the present invention, the preferred reaction conditions of the first riser tube is: temperature of reaction is 480～550 ℃, reaction pressure is 100～300KPa, catalyzer and stock oil mass ratio are (3～10): 1, the mass ratio of water vapor and stock oil is (0.02～0.3): 1, and the reaction times is 0.1～10 second.The preferred reaction conditions of the second riser tube is: temperature of reaction is 450～550 ℃, reaction pressure is 100～300KPa, catalyzer and stock oil mass ratio are (3～10): 1, and the mass ratio of water vapor and stock oil is (0.02～0.5): 1, the reaction times is 0.1～5 second.
The present invention adopts duo-lift tube reactor to carry out the catalytic conversion reaction of hydrocarbon ils, by carry out the catalyzer cracking reaction of heavy hydrocarbon oil raw material in the first riser tube, carry out the catalytic conversion reaction of tower top turning oil in the second riser tube, under coke and the substantially constant prerequisite of dry gas yied, reduced low-cetane diesel yield, gasoline yield and the liquefied gas yield of high value have significantly been improved, and make that Aromatic Hydrocarbon in Gasoline content increases, octane value improves, the quality of gasoline be improved significantly.
The accompanying drawing explanation
Accompanying drawing is the structural representation of the present invention for the riser reactor of hydrocarbon oil catalytic conversion.
Embodiment
Below elaborate the present invention.
Method of the present invention is carried out in the device that comprises two riser reactors, heavy hydrocarbon oil raw material after preheating and pre-lift medium are introduced to the first riser reactor by bottom, contact and carry out catalytic cracking reaction with the high temperature catalyst come from revivifier, and upwards flow together, reaction product is drawn reactor with the reclaimable catalyst with coke by the top outlet, enters settling vessel; Fractionation tower top turning oil and pre-lift medium are inputted to the second riser reactor bottom, with the high temperature catalyst contact reacts of coming from revivifier, and upwards flow together, reaction product is drawn reactor with the reclaimable catalyst with coke by the top outlet, enters settling vessel; Reaction oil gas from two riser tubes separates in same settling vessel with reclaimable catalyst, isolated catalyzer enters the revivifier coke burning regeneration after stripping, regenerated catalyst returns to riser reactor and recycles, isolated reaction oil gas enters subsequent separation system and carries out product separation, by part or all of input second riser reactor of the fractionation tower top turning oil of subsequent separation system.
In the present invention, described heavy hydrocarbon oil raw material is the petroleum hydrocarbon cut that initial boiling point is greater than 250 ℃, is preferably one or more in vacuum residue fraction, vacuum residuum solvent-deasphalted oils, hydro-cracking of vacuum residue tail oil and the vacuum residuum hydrotreatment heavy oil fraction of decompressed wax oil cut, crude oil underpressure distillation of long residuum cut, the crude oil underpressure distillation of crude oil atmospheric distillation.
In the present invention, described fractionation tower top turning oil is that gasoline reform is divided and the mixture of diesel oil than light constituent, and boiling range is between 40～350 ℃.
The mass ratio of fractionation tower top turning oil and heavy hydrocarbon oil raw material is 1: (1～10) is preferably 1: (2～5).
In the present invention, described catalyzer is catalytic cracking catalyst, and it consists of conventionally known to one of skill in the art.Catalytic cracking catalyst contains molecular sieve and heat-resistant inorganic oxide usually, and alternative contains clay.Molecular sieve is generally y-type zeolite, has the supersiliceous zeolite of five-membered ring structure, one or more in β zeolite, mordenite, omega zeolite, and the supersiliceous zeolite with five-membered ring structure comprises ZSM-5 zeolite and ZRP zeolite.Heat-resistant inorganic oxide is generally one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, alkaline earth metal oxide.Clay is generally one or more in ridge soil, halloysite, polynite, diatomite, halloysite, saponite, tired de-soil, sepiolite, attapulgite, hydrotalcite, boron-moisten soil.
The reaction conditions of the first riser tube is: temperature of reaction is 450～650 ℃, reaction pressure is 80～450KPa, catalyzer and stock oil mass ratio are (3～20): 1, and the mass ratio of water vapor and stock oil is (0.02～0.5): 1, the reaction times is 0.1～30 second.Optimum condition is: temperature of reaction is 480～550 ℃, and reaction pressure is 100～300KPa, and catalyzer and stock oil mass ratio are (3～10): 1, and the mass ratio of water vapor and stock oil is (0.02～0.3): 1, the reaction times is 0.1～10 second.
The reaction conditions of the second riser tube is: temperature of reaction is 400～560 ℃, reaction pressure is 80～450KPa, catalyzer and stock oil mass ratio are (3～20): 1, and the mass ratio of water vapor and stock oil is (0.02～0.5): 1, the reaction times is 0.1～30 second.。Optimum condition is: temperature of reaction is 450～550 ℃, and reaction pressure is 100～300KPa, and catalyzer and stock oil mass ratio are (3～10): 1, and the mass ratio of water vapor and stock oil is (0.02～0.5): 1, the reaction times is 0.1～5 second.
In the present invention, the volume ratio of the first riser reactor and the second riser reactor is 1: (0.1～1) is preferably 1: (0.2～0.5).Two riser reactor diameters can be identical, also can be different, when the diameter of each reaction zone of riser reactor is identical, the aspect ratio of the first riser reactor and the second riser reactor is volume ratio, therefore, when the riser reactor diameter is identical, the aspect ratio of the first riser reactor and the second riser reactor is 1: (0.1～1) is preferably 1: (0.2～0.5).
Described pre-lift medium is various pre-lift medium well known to those skilled in the art, as one or more in water vapor, refinery dry gas, light paraffins, light olefin.The effect of pre-lift medium is to make catalyzer accelerate to rise, and forms the catalyst activity plug flow of even density in the riser reactor bottom.The consumption of pre-lift medium is well known for the person skilled in the art, and in general, the consumption of pre-lift medium accounts for 1～30 % by weight of hydrocarbon ils total amount, preferably 2～15 % by weight.
In the present invention, in stripper, adopt water vapor to carry out stripping, its effect be by between granules of catalyst and the oil gas be full of in the particle hole cement out, improve the oil product productive rate.Amount for steam stripped water vapor is well known for the person skilled in the art.In general, account for 0.1～0.8 % by weight of catalyst recirculation amount for steam stripped water vapor amount, preferably 0.2～0.4 % by weight.
The carbon content of described reclaimable catalyst is about 0.5～1.2 % by weight.The catalyzer that regenerated catalyst is holomorphosis, this coke on regenerated catalyst is about 0.01～0.05 % by weight.
Below in conjunction with accompanying drawing, by embodiment, further set forth the present invention.
Catalytic cracking catalyst LV-23 used in Comparative Examples and embodiment is produced by China National Petroleum Corporation's Lanzhou catalyst plant, and character is listed in table 1; Tower top turning oil used is the fractionator overhead turning oil of catalytic cracking unit own, and character is listed in table 2, and long residuum is taken from Cangzhou branch office of China PetroChemical Corporation, and character is listed in table 3.
Comparative Examples
This Comparative Examples adopts the middle scale riser reactor, and this riser reactor is that total height is 10 meters, the cylindrical structure that diameter is 25 centimetres, and this riser tube foot is pre lift zone.Catalyzer is used the LV-23 of table 1, the long residuum that the raw material of processing is table 3.
Concrete implementation step is: the long residuum after preheating enters riser reactor 1 bottom by atomizing nozzle 2, with under 3 effects of pre-lift medium, from revivifier 15, the regenerated catalyst by regeneration pipeline 14 mixes, upwards to the riser reactor outlet, enter settling vessel 8 along riser tube, through cyclonic separator group 9 separating catalysts and reaction product, reaction product enters the subsequent separation system product separation by pipeline 13, catalyzer obtains reclaimable catalyst through stripper 7 strippings, reclaimable catalyst enters after revivifier 15 burns activity recovery and recycles through pipeline 12 to be generated.
Main operational condition is: 670 ℃ of regenerator temperature, 502 ℃ of outlet temperature of risers, 140 kPas of pressure, 200 ℃ of raw material preheating temperatures, the 5wt% that the atomizing steam amount is stock oil, the 5wt% that the pre-lift quantity of steam is raw material stock oil, agent-oil ratio 6, the residence time (reaction times) 4 second of stock oil in riser tube.
The product distribution results is listed in table 4, and gasoline forms and character is listed in table 5.
Embodiment
The present embodiment adopts medium-sized duo-lift tube reactor, and the first riser reactor 1 is 10 meters for total height, the cylindrical structure that diameter is 25 centimetres, and this riser tube foot is pre lift zone.Catalyzer is used the LV-23 of table 1, the long residuum that the raw material of processing is table 3.The second riser reactor 5 is 8 meters for total height, the cylindrical structure that diameter is 25 centimetres, and this riser tube foot is pre lift zone.Catalyzer is used the LV-23 of table 1, the catalytic cracking fractionating tower top turning oil that the raw material of processing is table 2.
Concrete implementation step is: the long residuum after preheating enters the first riser tube 1 reactor bottom by atomizing nozzle 2, with under 3 effects of pre-lift medium, from revivifier, the regenerated catalyst by regeneration pipeline 14 mixes, upwards to the riser reactor outlet, enter settling vessel 8 along riser tube, through cyclonic separator group 9 separating catalysts and reaction product, reaction product enters the subsequent separation system product separation by pipeline 13, catalyzer obtains reclaimable catalyst through stripper 7 strippings, reclaimable catalyst enters after revivifier 15 burns activity recovery and recycles through pipeline 12 to be generated.
Separation system fractionator overhead turning oil is entered to the second riser reactor 4 bottoms by atomizing nozzle 5, with under 6 effects of pre-lift medium, from revivifier, the regenerated catalyst by regeneration pipeline 11 mixes, upwards to the riser reactor outlet, enter settling vessel 8 along riser tube, through cyclonic separator group 10 separating catalysts and reaction product, reaction product enters the subsequent separation system product separation through pipeline 13, catalyzer obtains reclaimable catalyst through stripper 7 strippings, catalyzer obtains reclaimable catalyst through stripper 7 strippings, reclaimable catalyst enters after revivifier 15 burns activity recovery and recycles through pipeline 12 to be generated.
Main operational condition is: 670 ℃ of regenerator temperature, the first 502 ℃ of outlet temperature of risers, 140 kPas of pressure, 200 ℃ of raw material preheating temperatures, the 5wt% that the atomizing steam amount is stock oil, the 5wt% that the pre-lift quantity of steam is raw material stock oil, agent-oil ratio 6, the residence time (reaction times) 4 second of stock oil in riser tube.The second 505 ℃ of outlet temperature of risers, 140 kPas of pressure, 100 ℃ of raw material preheating temperatures, the 3wt% that the atomizing steam amount is stock oil, the 3wt% that the pre-lift quantity of steam is raw material stock oil, agent-oil ratio 6, the residence time (reaction times) 3 second of stock oil in riser tube.
The product distribution results is listed in table 4, and gasoline forms and character is listed in table 5.
Table 1
Table 2
Table 3
Table 4
From table 4, adopt method of the present invention to carry out the catalyzed conversion of hydrocarbon ils, coke and dry gas yied are substantially constant, and gasoline and liquefied gas yield obviously increase.
Table 5
From table 5, adopt method of the present invention to carry out the catalyzed conversion of hydrocarbon ils, Aromatic Hydrocarbon in Gasoline content obviously increases, olefin(e) centent descends, octane value increases, and gasoline quality obviously improves.
Claims (7)
1. the method for a hydrocarbon oil catalytic conversion comprises:
(1) heavy hydrocarbon oil raw material is inputted to the first riser reactor, contacted with catalyzer, react under the condition of catalytic cracking, the oil gas of generation and reacted catalyzer upwards enter settling vessel;
(2) fractionation tower top turning oil is inputted to the second riser reactor, contact with catalyzer, reacted under the condition of catalytic cracking, the oil gas of generation and reacted catalyzer upwards enter settling vessel;
(3) in settling vessel, catalyzer and gas-oil separation, oil gas removes subsequent separation system separating reaction product, and catalyzer goes revivifier to carry out coke burning regeneration, and the catalyzer after regeneration returns to riser reactor and recycles;
Wherein, the first and second riser reactors share a settling vessel and revivifier; Described heavy hydrocarbon oil raw material is the petroleum hydrocarbon cut that initial boiling point is greater than 250 ℃;
The reaction conditions of the first riser tube is: temperature of reaction is 450～650 ℃, and reaction pressure is 80～450KPa, and catalyzer and stock oil mass ratio are 3～20: 1, and the mass ratio of water vapor and stock oil is 0.02～0.5: 1, and the reaction times is 0.1～30 second; The reaction conditions of the second riser tube is: temperature of reaction is 400～560 ℃, and reaction pressure is 80～450KPa, and catalyzer and stock oil mass ratio are 3～20: 1, and the mass ratio of water vapor and stock oil is 0.02～0.5: 1, and the reaction times is 0.1～30 second.
2. in accordance with the method for claim 1, it is characterized in that one or more in the vacuum residue fraction of the long residuum cut that described heavy hydrocarbon oil raw material is crude oil atmospheric distillation, the decompressed wax oil cut of crude oil underpressure distillation, crude oil underpressure distillation, vacuum residuum solvent-deasphalted oils, hydro-cracking of vacuum residue tail oil and vacuum residuum hydrotreatment heavy oil fraction.
3. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the first riser tube is: temperature of reaction is 480～550 ℃, reaction pressure is 100～300KPa, catalyzer and stock oil mass ratio are 3～10: 1, the mass ratio of water vapor and stock oil is 0.02～0.3: 1, and the reaction times is 0.1～10 second; The reaction conditions of the second riser tube is: temperature of reaction is 450～550 ℃, and reaction pressure is 100～300KPa, and catalyzer and stock oil mass ratio are 3～10: 1, and the mass ratio of water vapor and stock oil is 0.02～0.5: 1, and the reaction times is 0.1～5 second.
4. in accordance with the method for claim 1, it is characterized in that, the mass ratio of fractionation tower top turning oil and heavy hydrocarbon oil raw material is 1: 1～10.
5. in accordance with the method for claim 4, it is characterized in that, the mass ratio of fractionation tower top turning oil and heavy hydrocarbon oil raw material is 1: 2～5.
6. in accordance with the method for claim 1, it is characterized in that, the volume ratio of the first riser reactor and the second riser reactor is 1: 0.1～1.
7. in accordance with the method for claim 6, it is characterized in that, the volume ratio of the first riser reactor and the second riser reactor is 1: 0.2～0.5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194227A (en) * | 1991-10-02 | 1993-03-16 | Ashland Oil, Inc. | Multiple wye catalytic cracker and process for use |
| CN101314736A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for producing high-octane gasoline with bastard crude oil |
| CN201161998Y (en) * | 2008-02-25 | 2008-12-10 | 石宝珍 | Petroleum hydrocarbon raw materials catalytic conversion reaction-regeneration apparatus |
| CN201161999Y (en) * | 2008-02-25 | 2008-12-10 | 石宝珍 | Petroleum hydrocarbon raw materials catalytic conversion reaction-regeneration apparatus |
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2009
- 2009-12-03 CN CN 200910250059 patent/CN102086414B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194227A (en) * | 1991-10-02 | 1993-03-16 | Ashland Oil, Inc. | Multiple wye catalytic cracker and process for use |
| CN101314736A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for producing high-octane gasoline with bastard crude oil |
| CN201161998Y (en) * | 2008-02-25 | 2008-12-10 | 石宝珍 | Petroleum hydrocarbon raw materials catalytic conversion reaction-regeneration apparatus |
| CN201161999Y (en) * | 2008-02-25 | 2008-12-10 | 石宝珍 | Petroleum hydrocarbon raw materials catalytic conversion reaction-regeneration apparatus |
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