CN102816595A - Residuum hydrotreatment-catalytic cracking combination technology - Google Patents
Residuum hydrotreatment-catalytic cracking combination technology Download PDFInfo
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Abstract
A residuum hydrotreatment-catalytic cracking combination technology of catalytic cracking recycle oil is characterized in that a material inlet is arranged in front of a metal removal agent bed layer, a desulfurizer bed layer, and a residual carbon removal agent bed layer of a device respectively, residuum and hydrogen enter the device to react through a device raw material port, hydrogenated residuum enters a catalytic cracking device and continuously reacts, one part of the recovery oil of the catalytic cracking device enters a hydrogenation device to react through one or more of four material inlets of a hydrotreatment device, and the residual recovery oil of the catalytic cracking device is cycled to the catalytic cracking device and enters the catalytic cracking device together with the hydrogenated residuum. The technology enables the operations of the residuum hydrotreatment-catalytic cracking combination technology to be flexible and efficient, and has the advantages of prolongation of the operation period of the residuum hydrotreatment device, improvement of the impurity removal rates of residuum hydrogenation products, reduction of the application amount of cold hydrogen, and increase of the yield of light oil having high added values.
Description
Technical field
The present invention relates to a kind of residual hydrocracking and catalytic cracking combined technique.
Background technology
Current, oil refining processing industry in the world is being faced with the crude resources severe challenge of heaviness and poor qualityization day by day.2008,3.42 hundred million tons of crude oil in China amount of finish, wherein the heavy crude amount of finish reaches 1.37 hundred million tons, accounts for total amount more than 40%.As everyone knows, residual oil accounts for the crude oil ratio usually 45～75%, and its character significantly is inferior to the lower gas wet goods cut of boiling range, and therefore, the crude oil deep processing is made every effort to maximize the pressure of producing light-end products and industrial chemicals and just dropped on the residual oil naturally.
In the optional technological line of residual oil deep processing, residual oil hydrogenation-catalytic cracking combined technological is a kind of good technology.Residual oil has improved hydrogen richness after removing impurity such as metal, sulphur, nitrogen through hydrotreatment, can be used as fine RFCC raw material, and residual oil is transformed fully.This technology has obtained increasing application, but in this combination common process, catalytic cracking recycle oil is to be circulated to further processing in the catalytic cracking.Because contain polycyclic aromatic hydrocarbons in the heavy cycle oil, thereby light oil yield is low, the green coke amount is big, has increased the revivifier load, has reduced unit capacity and economic benefit.
US4; 713,221 disclose on conventional residual hydrogenation and catalytic cracking combined basis, and the heavy cycle oil of catalytic cracking (comprising gas oil catalytic cracking and RFCC) is circulated to residual hydrogenation equipment; With carry out hydrogenation after topped crude mixes, hydrogenated residue gets into CCU.The change that this is little can make the benefit of one barrel of crude oil of the every processing in refinery have a net increase of 0.29 dollar.
CN1119397C discloses a kind of residual hydrocracking---catalytic cracking combination process, is that residual oil and clarified oil get into the residual hydrocracking device together, in the presence of hydrogen and hydrogenation catalyst, carries out hydrogenation reaction; The hydrogenated residue that obtains of reaction gets into CCU, in the presence of cracking catalyst, carries out cracking reaction, and heavy cycle oil is in the CCU circulating inside, react slurry oil obtain clarified oil through separation, be back to hydrogenation unit.
CN101210200A discloses a kind of residual hydrocracking and catalytic cracking combination process; The thing that steams of residual oil, the heavy catalytic cycle oil that removes solid impurity, optional distillate and optional catalytically cracked oil gets into the residual hydrocracking device together; The hydrogenated residue of gained gets into CCU with optional vacuum gas oil, obtains various products; The catalytic cracking turning oil that removes impurity is circulated to the residual hydrocracking device; Catalytically cracked oil is carried out fractionation by distillation, and be circulated to the residual hydrocracking device.
In above combined method, recycle stock all is to get into the residual hydrocracking device with raw material residual oil, and inconvenient running condition and oil property according to device adjusted.
Summary of the invention
The objective of the invention is on existing basis, to provide the freshening method of a kind of catalytic cracking recycle oil in residual hydrocracking-catalytic cracking combined technique.
Method provided by the invention is:
Before the metal remover bed of conventional residual hydrocracking device, before the sweetening agent bed and before taking off the carbon residue beds, increase an opening for feed respectively; Catalyst loading still adopts catalyzer grating technology; Filling comprises protective material, metal remover, sweetening agent and takes off the multiclass catalyzer of carbon residue agent that different catalysts is seated in different beds.Under hydrogen existence and hydrotreatment reaction conditions, residual oil contacts with residual oil hydrocatalyst and carries out the hydrotreatment reaction, and the product separation obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue.
Hydrogenated residue directly or get into CCU together with other optional conventional catalytically cracked stock and further react, reaction product is separated and is obtained dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil.With in heavy catalytic cycle oil and the slurry oil one or both as catalytic cracking recycle oil.
Part catalytic cracking recycle oil is handled the back through the one or more entering residual hydrogenation equipments processing in four opening for feeds on the residual hydrocracking device through removing solid impurity, and another part catalytic cracking recycle oil direct cycles to CCU.
Method provided by the invention specifies as follows:
(1) residual hydrogenation part
Residual hydrogenation of the present invention part is the same with traditional residual hydrogenation equipment, and different is before the metal remover bed, before the sweetening agent bed and take off the carbon residue beds and increase an opening for feed before respectively.Install employed residual oil and be one or more the mixture in long residuum and the vacuum residuum.The catalyzer grating of residual hydrogenation equipment and filling need not change, and filling simultaneously comprises protective material, metal remover, sweetening agent, takes off the multiple catalyzer of carbon residue catalyzer.Different catalysts is divided the bed filling, can load in the reactor drum, also can be contained in a plurality of reactor drums.Catalyzer generally is to be carrier with porous inorganic oxide such as aluminum oxide, and group vib and VIII family metal oxide such as W, Mo, Co optionally add the catalyzer of P, Si or F auxiliary agent or/and the oxide compound of Ni is a carrier.The protective material bed can adopt fixed-bed reactor, also can adopt up-flow reactor, and other beds adopts fixed-bed reactor.
The normal operating condition of residual hydrocracking device is:: hydrogen partial pressure 10～22MPa, temperature of reaction is 310～435 ℃, volume space velocity 0.1～2.5hr
-1, the volume ratio of hydrogen and residual oil is 500～2000, by weight, catalytic cracking recycle oil is 0.1～45% of a raw material residual oil.
Residual oil and hydrogen carry out the hydrotreatment reaction from residual hydrogenation equipment opening for feed access to plant, and reaction product can be separated into dry gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue.
(2) catalytic cracking part
The hydrogenated residue of step (1) gained separately or get into CCU together with other optional conventional catalytically cracked stock and further react, reaction product is separated and is obtained dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil.Described catalytic cracking can be a catalytic cracking family, like cover such as one in RFCC, catalytic pyrolysis, the voluminous isoparaffin catalytic cracking etc. or several covering devices.
The condition of catalytic cracking is: 470～650 ℃ of temperature of reaction, 0.5～5 second reaction times, the weight ratio 3～10 of catalyzer and raw oil, 650～800 ℃ of regeneration temperatures.
(3) catalytic cracking recycle oil
Catalytic cracking recycle oil is one or both in heavy catalytic cycle oil and the slurry oil; Catalytic cracking recycle oil is 0.1%～45% of a raw material residual oil, and a part of catalytic cracking recycle oil is through removing after the solid impurity pre-treatment through the one or more accesss to plant processing in four opening for feeds on the residual hydrocracking device; Another part catalytic cracking recycle oil direct cycles to CCU.Solid impurity content needs less than 5ppm after the pre-treatment of recycle stock process, and pretreatment process can be one or more in filtration, distillation, the rotation separation etc.Get into of the running condition decision of the ratio of each several part recycle stock according to oil property and device.For example, when metal content is higher in the recycle stock, can before feed(raw material)inlet and metal remover bed, get into more; When the sweetening agent bed with take off carbon residue agent bed temperature higher with carbon deposit more for a long time, can select to introduce the part recycle stock before these two beds, reduce temperature of reaction, reduce carbon deposit.
Compare with existing method, method advantage provided by the invention mainly contains:
(1) combined method is more flexible, can adjust the ratio of various piece recycle stock according to oil property, device running condition neatly, increases the treatment capacity of device.
(2) because recycle stock kinematic viscosity is lower; On residual hydrogenation equipment, introduce recycle stock, can improve liquid-flow, distribution in the reactor drum, reduce raw oil viscosity; Raising residual oil molecule is internal diffusion speed in the catalyzer duct, and then improve the impurity removal percentage of device.
(3) because the recycle stock aromaticity is higher; On residual hydrogenation equipment, introduce recycle stock; Particularly, can improve the aromaticity of oil plant, promote the bitum dissolving of separating out gradually because of hydrogenation in the residual oil through advance inlet and take off before the carbon residue agent inlet and introduce recycle stock of sweetening agent; Reduce the deposition of bituminous matter on catalyzer, and then reduce the coke content on the catalyzer.
(4) operation is more flexible, on industrial reactor, can adjust reaction bed temperature through the feeding temperature of regulating the recycle stock that respectively enters the mouth, reduces cold hydrogen usage quantity.
Description of drawings
Fig. 1 freshening method flow provided by the invention synoptic diagram
Embodiment
Accompanying drawing is a freshening method flow synoptic diagram provided by the invention; The residual hydrocracking device adopts catalyzer grating technology; Every kind of catalyzer is contained in the different reactor drums; Be respectively protective material reactor drum, metal remover reactor drum, reactive desulfurizing agent device and take off residual hydrogen-catalyst reactor, take off in the carbon residue hydrogen-catalyst reactor and to remove filling and take off the carbon residue agent and can also load in the catalyzer such as denitrfying agent.Before the metal remover bed, before the sweetening agent bed, before taking off the carbon residue beds, respectively increase a feed entrance.Different catalysts has been contained in four reactor drums in the synoptic diagram, in reality, also can be contained in one or two or three or five reactor drums.
Get into residual hydrogenation equipment through preheating after mixing from the residual oil of pipeline 01 with from the hydrogen of pipeline 02, contact with hydrogenation catalyst and carry out hydrotreatment and react; The product of residual hydrogenation gets into tripping device through pipeline 06; Obtain dry gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Dry gas, hydrotreated naphtha, hydrogenated diesel oil pass through pipeline 07,08,09 caterpillar respectively, and hydrogenated residue gets into CCU through pipeline 10.Hydrogenated residue contacts with catalytic cracking catalyst in CCU and reacts; Obtain dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil; Dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil are respectively through pipeline 11,12,13,14 caterpillars, and heavy catalytic cycle oil and slurry oil are respectively through 15,16 caterpillars.With in heavy cycle oil and the slurry oil one or both as recycle stock; A part of recycle stock process pipeline 19 is got into CCUs through pipeline 10 together with hydrogenated residue, with the one or more entering residual hydrogenation equipments in another part recycle stock process pipeline 17, pre-treatment, the pipeline 18 process pipelines 03,04,05,20.Can regulate the temperature of reaction of each bed through the feeding temperature of recycle stock.
One liter of four anti-pilot plant of fixed bed residual hydrogenation that the residual hydrogenation equipment that uses in embodiment and the Comparative Examples is produced as U.S. Xytel company, device is totally four reactor drums, loads protective material, metal remover, sweetening agent respectively and takes off the carbon residue agent.Comparative Examples is the same with catalyzer among the embodiment, and a level mixing ratio is 5: 40: 30: 25, and catalyzer is that independently develop in the laboratory.In order to carry out experiment, before the reactor drum of filling metal remover, before the reactor drum of filling sweetening agent and filling increased each opening for feed before taking off the reactor drum of carbon residue agent.Comparative Examples is the same with operational condition among the embodiment, sees table 1.
Catalytic cracking is tested on the small-sized riser reactor pilot plant that designs voluntarily in the laboratory and is carried out in embodiment and the Comparative Examples, and the catalyzer that uses is developed as the laboratory voluntarily.Comparative Examples is the same with operational condition among the embodiment, sees table 1.
The residual oil that uses in embodiment and the Comparative Examples is Kuwait's long residuum, and catalytic cracking recycle oil is circulated to residual hydrogenation equipment and partly carries out fine filtering, and solid impurity content is less than 5ppm.
The main operational condition of table 1
Table 2 test raw material oil (Kuwait's long residuum) main character
| Density (20 ℃), kg/m 3 | 0.977 |
| S，m％ | 4.43 |
| N，m％ | 0.37 |
| Carbon residue (MCR), m% | 13.2 |
| Metal (Ni+V), ppm | 78.5 |
| Bituminous matter, m% | 4.1 |
| Aromatic hydrocarbon, m% | 40.7 |
Comparative Examples 1
Kuwait's residual oil and hydrogen get into the residual hydrogenation pilot plant together, through residual hydrocracking, react according to the condition in the table 1, and reaction product is separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Hydrogenated residue gets into CCU; Condition according in the table 1 is reacted; Catalytic cracking production is divided into dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil; Recycle stock adopts heavy cycle oil, recycle stock all to be circulated to CCU and gets into CCU together with hydrogenated residue and react, and table 3 is seen in the product distribution.
Comparative Examples 2
Kuwait's residual oil and hydrogen get into the residual hydrogenation pilot plant together, through residual hydrocracking, react according to the condition in the table 1, and reaction product is separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Hydrogenated residue gets into CCU; Condition according in the table 1 is reacted; Catalytic cracking production is divided into dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil, and recycle stock adopts heavy cycle oil, and recycle stock all is circulated to residual hydrogenation equipment; Get into the residual hydrocracking device together with residual oil and react, product distributes and sees table 3.
Embodiment 1
Kuwait's residual oil and hydrogen get into the residual hydrogenation pilot plant together, through residual hydrocracking, react according to the condition in the table 1, and reaction product is separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Hydrogenated residue gets into CCU; Condition according in the table 1 is reacted; Catalytic cracking production be divided into dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil and, heavy catalytic cycle oil and slurry oil, recycle stock adopts heavy cycle oil, 40% recycle stock is circulated to CCU and hydrogenated residue and gets into CCU together and react; 60% recycle stock is through fine filtering; Be equally divided into four parts and hydrogen respectively before residual hydrogenation equipment feed(raw material)inlet, metal remover bed inlet, inlet before the sweetening agent bed, enter the mouth before taking off the carbon residue beds, get into the residual hydrogenation equipment reaction, product distributes and sees table 3.
Embodiment 2
Kuwait's residual oil and hydrogen get into the residual hydrogenation pilot plant together, through residual hydrocracking, react according to the condition in the table 1, and reaction product is separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Hydrogenated residue gets into CCU; Condition according in the table 1 is reacted; Catalytic cracking production is divided into dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil, and recycle stock adopts heavy cycle oil, 40% recycle stock to be circulated to CCU and hydrogenated residue and gets into CCU together and react; 60% recycle stock is through fine filtering; Be equally divided into two portions and hydrogen respectively before residual hydrogenation equipment feed(raw material)inlet, sweetening agent bed inlet, enter the mouth before taking off the carbon residue beds, get into the residual hydrogenation equipment reaction, product distributes and sees table 3.
We can know through table 3 contrast; Move after 4000 hours; Hydrogenated residue character among the embodiment 1,2 obviously is superior to Comparative Examples 1,2, and the carbon deposit on sweetening agent HDS1, HDS2 and the denitrfying agent HDN is starkly lower than Comparative Examples, estimates that runtime is higher 4 months and 2 months than Comparative Examples 1,2 respectively; In the catalytic cracking product, embodiment 1,2 each item yields are approaching, and diesel yield is higher 1.7 and 0.4 percentage points respectively than Comparative Examples 1,2, and are high 1.4 percentage points in the steam oil ratio (SOR) Comparative Examples.
4000 hours residual hydrogenation product data of table 3 operation and catalyst carbon deposit situation
Claims (3)
1. residual hydrocracking and catalytic cracking combined technique, it is characterized in that: step comprises:
(1) residual hydrogenation part
The catalyst grade mixing ratio of residual hydrogenation equipment is constant, loads protective material, metal remover, sweetening agent and takes off the carbon residue catalyzer, and different catalysts is divided the bed filling; Load in the reactor drum or be contained in a plurality of reactor drums, catalyzer is to be carrier with the porous alumina, and load W, Mo, Co are or/and the oxide compound of Ni; The catalyzer that optionally adds P, Si or F auxiliary agent; The protective material bed adopts fixed-bed reactor, or adopts up-flow reactor, and other beds adopts fixed-bed reactor;
The operational condition of residual hydrocracking device is: hydrogen partial pressure 10～22MPa, temperature of reaction is 310～435 ℃, volume space velocity 0.1～2.5hr
-1, the volume ratio of hydrogen and residual oil is 500～2000;
Residual oil and hydrogen carry out the hydrotreatment reaction from residual hydrogenation equipment opening for feed access to plant, and reaction product is separated into dry gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue;
(2) catalytic cracking part
The hydrogenated residue of step (1) gained separately or get into CCU together with other optional conventional catalytically cracked stock and further react, reaction product is separated and is obtained dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil; The condition of catalytic cracking is: 470～650 ℃ of temperature of reaction, 0.5～5 second reaction times, the weight ratio 3～10 of catalyzer and raw oil, 650～800 ℃ of regeneration temperatures; Catalyzer is conventional catalytic cracking catalyst;
(3) catalytic cracking recycle oil
Catalytic cracking recycle oil is one or both in heavy catalytic cycle oil and the slurry oil; Catalytic cracking recycle oil is 0.1～45% of a raw material residual oil weight, and a part of catalytic cracking recycle oil is handled through removing after the solid impurity pre-treatment through the one or more entering residual hydrogenation equipments that are separately positioned on protective material, metal remover, sweetening agent on the residual hydrocracking device and take off in four opening for feeds at carbon residue beds place; Another part catalytic cracking recycle oil direct cycles to CCU.
2. according to described a kind of residual hydrocracking of claim 1 and catalytic cracking combined technique, it is characterized in that: described residual oil is a kind of or mixture in long residuum and the vacuum residuum.
3. according to described a kind of residual hydrocracking of claim 1 and catalytic cracking combined technique, it is characterized in that: pretreatment process is one or more in filtration, distillation, the rotation separation.
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Citations (6)
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| US4713221A (en) * | 1984-05-25 | 1987-12-15 | Phillips Petroleum Company | Crude oil refining apparatus |
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| JP2619706B2 (en) * | 1987-11-17 | 1997-06-11 | シエル・インターナショネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing light hydrocarbon fraction by hydrocracking and catalytic cracking |
| CN1119397C (en) * | 1999-01-28 | 2003-08-27 | 中国石油化工集团公司 | Hydrogenation and catalystic cracking combined process for residual oil |
| CN1144860C (en) * | 2001-07-02 | 2004-04-07 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil |
| CN1165601C (en) * | 2001-04-28 | 2004-09-08 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
-
2011
- 2011-06-10 CN CN201110156347.1A patent/CN102816595B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4713221A (en) * | 1984-05-25 | 1987-12-15 | Phillips Petroleum Company | Crude oil refining apparatus |
| JP2619706B2 (en) * | 1987-11-17 | 1997-06-11 | シエル・インターナショネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing light hydrocarbon fraction by hydrocracking and catalytic cracking |
| US5009768A (en) * | 1989-12-19 | 1991-04-23 | Intevep, S.A. | Hydrocracking high residual contained in vacuum gas oil |
| CN1119397C (en) * | 1999-01-28 | 2003-08-27 | 中国石油化工集团公司 | Hydrogenation and catalystic cracking combined process for residual oil |
| CN1165601C (en) * | 2001-04-28 | 2004-09-08 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
| CN1144860C (en) * | 2001-07-02 | 2004-04-07 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil |
Non-Patent Citations (1)
| Title |
|---|
| 牛传峰等: ""渣油加氢-催化裂化双向组合技术RICP"", 《石油炼制与化工》, vol. 33, no. 1, 8 January 2004 (2004-01-08), pages 27 - 29 * |
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