CN1246514A - Improved delay coking process - Google Patents
Improved delay coking process Download PDFInfo
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- CN1246514A CN1246514A CN 98117811 CN98117811A CN1246514A CN 1246514 A CN1246514 A CN 1246514A CN 98117811 CN98117811 CN 98117811 CN 98117811 A CN98117811 A CN 98117811A CN 1246514 A CN1246514 A CN 1246514A
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Abstract
An improved delay coking process features that the raw oil takes part in buffered thermocracking in reactor at first to obtain 5-15 vol% of low-boiling-point substance used as oxygen-supplying agent and diluent, which is then introduced to coking tower for further thermocracking. Its advantages are the improved distribution structure of products, minimal recirculating ratio of delay coking and higher treating ability of equipment.
Description
The present invention is the improvement that belongs to delay coking process.More particularly, be the distributed architecture that improves the delayed coking product, improve the coking liquid yield, realize a kind of technology of delayed coking minimal circulation ratio, raising device processing power simultaneously.
Delayed coking is the comparatively ideal technology of residual oil deep processing, it has characteristics such as reduced investment, flow process are simple, technology maturation, bottoms conversion height, and existing delayed coking major equipment is process furnace, coke drum, separation column and mechanical facilities such as corresponding decoking, accumulating.
Up to the present, for the delayed coking unit of producing non-superpower electrode coke,,, increase the yield of liquid product so all wish to reduce the productive rate of coke because liquid product has higher value than coke.
USP4,455,219th, by reducing recycle ratio, reduce the quantity of circulation heavy recycle stock, in raw material, add the lower boiling component of part simultaneously, reach and improve the purpose that total liquid is received (being gasoline, diesel oil and wax oil yield sum), reduced coking yield.
USP4,518,487th, by lower boiling component being substituted heavy recycle stock fully, reaches the purpose that improves total liquid receipts, reduces coking yield.
USP4,661,241st, under the prerequisite of single-pass operation, the low-boiling point material that adds different range is respectively realized the different choice to product yield as hydrogen supply agent.
Above-mentioned patent mainly is to utilize a part of lower boiling material partly or entirely to replace heavy recycle stock to the improvement of delayed coking, reaches to improve the purpose that total liquid is received, reduced coking yield; Low-boiling point material mainly is as the hydrogen supply agent of raw material and thinner, by they dissolvings to heavy arene and coke precursor body, alleviates its deposition and coking in heating furnace tube, thereby reaches the purpose that extends manufacture cycle.
USP4,443,325th, utilize visbreaking and pyrogenic combination process, after the fractionation of visbreaking distilled oil, visbreaking residue carries out coking, improves the purpose that total liquid is received thereby reach.
CN1,011,416B is a different operating method of utilizing two cover cokers, enlarges the raw material of producing needle coke, realizes the continuous production of needle coke under the not enough condition of raw material.
The objective of the invention is to provide on the basis of existing technology a kind of improved delay coking process, promptly do not mend low-boiling point material outward and produce a kind of lower boiling thinner by stock oil self, alleviate the coking of heating furnace tube, improve total liquid and receive, reduce coking yield.
Improved delay coking process provided by the invention, its processing step comprises:
(a). stock oil enters to enter after the process furnace preheating and relaxes thermally splitting in the reactor;
(b). after the stock oil that comes out from reactor enters the another one process furnace and is heated to coking temperature, enter coke drum and carry out degree of depth thermally splitting, the fractionation in separation column of coking cat head oil gas obtains gas, gasoline, diesel oil, light wax oil and wax slop;
(c). the wax slop Returning reactor of separation column mixes with stock oil.
Method provided by the invention is so concrete enforcement: after stock oil entered process furnace and is preheated to 300～460 ℃, entering in the reactor in absolute pressure was that 100～600 kPas, the residence time are to relax thermally splitting under 10～180 minutes the condition.After the stock oil that comes out from reactor enters the another one process furnace and is heated to 490～510 ℃, enter coke drum and carry out degree of depth heat cracking reaction, the inlet operating temperature of coke drum is that 490～510 ℃, pressure are 98～245 kPas (gauge pressures), to fill the burnt time be 16～40 hours.The fractionation in separation column of coking cat head oil gas obtains gas, gasoline, diesel oil, light wax oil and wax slop.The wax slop Returning reactor of separation column mixes with stock oil.The wax slop of Returning reactor and the weight ratio of stock oil (hereinafter to be referred as recycle ratio) are 0～1.0: 1.
The used stock oil of the present invention is to be selected from vacuum residuum, long residuum, fluid catalytic cracking decant oil, heavy crude, ethylene bottom oil, lubricating oil to extract one or more mixture in oil and the various poor residuums out.
Used reactor both can be a tubular reactor among the present invention, also can be tower reactor.
Give further instruction below in conjunction with 2 pairs of technologies provided by the present invention of accompanying drawing.
Stock oil enters preheating oven 1 through pipeline 6, after being warming up to 300～460 ℃, enter in the reactor 2 through pipeline 7, stock oil is that 100～600 kPas, the residence time are to relax thermally splitting under 10～180 minutes the condition in absolute pressure, and generates the low boiling component of about 5～15 volume %.For preventing stock oil a large amount of back-mixings in reactor 2, reactor 2 is provided with internals simultaneously.Pipeline 11 is the pressure equilibrium line of reactor.
The stock oil that comes out from reactor 2, enter in the process furnace 3 through pipeline 8, after being heated to 490～510 ℃, enter through pipeline 9 and to carry out degree of depth heat cracking reaction in the coke drum 4, the inlet operating temperature of coke drum is that 490～510 ℃, pressure are 98～245 kPas (gauge pressures), to fill the burnt time be 16～40 hours.The sedimentation of coke that reaction generates is in coke drum.Behind burnt full the switching, carry out decoking by the delayed coking hydraulic decoking system of routine.
Coking oil gas enters separation column 5 through pipeline 10 and is fractionated into gas, gasoline, diesel oil, light wax oil and goes out device.The part light wax oil is back to separation column 5 through pipeline 13, to regulate fractionator bottom temperature; Wax slop can all go out device, also can a part pump in the reactor 2 to regulate recycle ratio through pipeline 12.
The invention has the advantages that:
1, compares with the delay coking process of routine, reduce coke yield under the same conditions, and optimize product structure.
2, do not need the outer low boiling component of mending, required thinner and hydrogen supply agent are obtained by the mitigation thermally splitting of stock oil by self.Stock oil makes the stock oil cracking generate the low boiler cut of 5～15 volume % earlier through relaxing the process of thermally splitting, and this cut has reduced the demand that component is externally mended in operation of installing.
3, help the long period operation of delay coking heating furnace.Because the low boiler cut of 5～15 volume % has played the effect of thinner and hydrogen supply agent in stock oil, this will alleviate and suppress the deposition of coke precursor body in the delay coking heating furnace boiler tube effectively, help prolonging the on-stream time of delayed coking unit.
4, can realize the operation of " minimum recycle ratio " (recycle ratio is 0～0.01), receive, improve the processing power of device thereby increased total liquid.And conventional delayed coking recycle ratio generally can only drop to about 0.20.
5, has bigger flexibility of operation.According to the particular case of stock oil and actually operating, the present invention can realize flexible operating at different situations.For example as if being purpose with voluminous intermediate oil, the may command recycle ratio is 0.4～1.0; If with the maximum throughput is purpose, then can operate by " minimum recycle ratio ".
Accompanying drawing 1 is the schematic flow sheet of conventional delay coking process.
Accompanying drawing 2 is schematic flow sheets of improvement delay coking process provided by the invention.
Each numbering is described as follows in the accompanying drawing:
1 is preheating oven, and 2 is reactor, and 3 is process furnace, and 4 is coke drum, and 5 is separation column, and 6,7,8,9,10,11,12,13 all represent pipeline.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Stock oil used among the embodiment is vacuum residuum, and its character is listed in table 1.
Embodiment 1
Vacuum residuum enters tubular reactor after preheating oven is preheated to 425 ℃, be that 400 kPas, the residence time are to relax thermally splitting under 40 minutes the condition at pressure.The stock oil that comes out from tubular reactor enters and carries out degree of depth heat cracking reaction in the coke drum after entering and being heated to 500 ℃ the process furnace, and the inlet operating temperature of coke drum is that 500 ℃, pressure are 170 kPas (gauge pressures), to fill the burnt time be 24 hours.The sedimentation of coke that reaction generates is in coke drum.Behind burnt full the switching, carry out decoking by the delayed coking hydraulic decoking system of routine.
Coking oil gas enters separation column and is separated into gas, gasoline, diesel oil, light wax oil and goes out device.Wax slop all goes out device.
List in table 1 through relaxing the pretreated vacuum residuum character of thermally splitting, operational condition and material balance are listed in table 2.
As can be seen from Table 1, through relaxing the pretreated residual oil character of thermally splitting, the cut of boiling range scope＜525 ℃ that is to say than about increase by the 10 volume % of vacuum residuum, and vacuum residuum relaxes the low boiling component that has generated after the thermally splitting about 10 volume %.
As can be seen from Table 2, compare with Comparative Examples 1, the present invention is under 0 the condition in recycle ratio, and coke yield reduces by 4.54 heavy %, and total liquid is received increases by 5.74 heavy %.Diesel yield had increased by 3.17 heavy % during product distributed simultaneously, and the wax oil yield has increased by 6.20 heavy %.
Embodiment 2
Vacuum residuum enters tower reactor after preheating oven is preheated to 425 ℃, be that 400 kPas, the residence time are to relax thermally splitting under 40 minutes the condition at pressure.The stock oil that comes out from tower reactor enters and carries out degree of depth heat cracking reaction in the coke drum after entering and being heated to 500 ℃ the process furnace, and the inlet operating temperature of coke drum is that 500 ℃, pressure are 170 kPas (gauge pressures), to fill the burnt time be 24 hours.The sedimentation of coke that reaction generates is in coke drum.Behind burnt full the switching, carry out decoking by the delayed coking hydraulic decoking system of routine.
Coking oil gas enters separation column and is separated into gas, gasoline, diesel oil, light wax oil and goes out device.The recycle ratio of wax slop is 0.4: 1.
List in table 1 through relaxing the pretreated vacuum residuum character of thermally splitting, operational condition and material balance are listed in table 2.As can be seen from Table 2, compare with Comparative Examples 1, the present invention is under 0.4 the condition in recycle ratio, and coke yield reduces by 1.39 heavy %, and total liquid is received increases by 0.36 heavy %, and diesel yield had increased by 6.52 heavy % during product distributed simultaneously.
Comparative Examples 1
Vacuum residuum is heated to 500 ℃ in process furnace after, enters and carry out degree of depth heat cracking reaction in the coke drum, the inlet operating temperature of coke drum is that 500 ℃, pressure are 170 kPas (gauge pressures), to fill the burnt time be 24 hours.The sedimentation of coke that reaction generates is in coke drum.Behind burnt full the switching, carry out decoking by the delayed coking hydraulic decoking system of routine.
Coking oil gas enters separation column and is separated into gas, gasoline, diesel oil, light wax oil and goes out device.The recycle ratio of wax slop is 0.4: 1.Operational condition and material balance are listed in table 2.
Table 1
| Material name | Vacuum residuum | Residual oil after the pre-treatment |
| Density (20 ℃), gram per centimeter 3Kinematic viscosity (80 ℃), millimeter 2/ second carbon residue, heavy % | ????1.0014 ????11380 ????18.31 | ????0.9984 ????3367 ????18.80 |
| Boiling range, ℃ | ????384 ????497 ????525 ????555 ????560 * | ????273 ????424 ????473 ????529 ????560 |
*The rate of distillating is 22%
Table 2
| Technical process | Embodiment 1 | Embodiment 2 | Comparative Examples 1 |
| Operational condition relaxes the thermally splitting preheating temperature, ℃ absolute pressure, kPa residence time, minute degree of depth thermally splitting furnace outlet temperature, ℃ coke tower top pressure (gauge pressure), kPa fill the burnt time, hour recycle ratio | ????425 ????500 ????40 ????500 ????170 ????24 ????0 | ????425 ????500 ????40 ????500 ????170 ????24 ????0.4 | ????- ????- ????- ????500 ????170 ????24 ????0.4 |
| Product yield, heavy % natural gas liquid diesel gas oil coke | ????6.75 ????10.79 ????21.00 ????38.23 ????23.23 | ????8.98 ????13.26 ????24.35 ????27.03 ????26.38 | ????7.95 ????14.42 ????17.83 ????32.03 ????27.77 |
| Total liquid is received, heavy % | ????70.02 | ????64.64 | ????64.28 |
Claims (6)
1, a kind of improved delay coking process, its processing step comprises:
(a). stock oil enters to enter after the process furnace preheating and relaxes thermally splitting in the reactor;
(b). after the stock oil that comes out from reactor enters the another one process furnace and is heated to coking temperature, enter coke drum and carry out degree of depth thermally splitting, the fractionation in separation column of coking cat head oil gas obtains gas, gasoline, diesel oil, light wax oil and wax slop;
(c). the wax slop Returning reactor of separation column mixes with stock oil.
2, according to the technology of claim 1, it is characterized in that described in (a) stock oil be to be selected from vacuum residuum, long residuum, fluid catalytic cracking decant oil, heavy crude, ethylene bottom oil, lubricating oil to extract one or more mixture in oil and the various poor residuums out.
3,, it is characterized in that the stock oil described in (a) is preheated to 300～460 ℃ in process furnace according to the technology of claim 1.
4,, it is characterized in that the reactor described in (a) is tubular reactor or tower reactor according to the technology of claim 1.
5, according to the technology of claim 1 or 4, it is characterized in that the absolute pressure of the stock oil described in (a) in reactor is 100～600 kPas, the residence time is 10～180 minutes.
6,, it is characterized in that the wax slop of Returning reactor in (c) and the weight ratio of stock oil are 0～1.0: 1 according to the technology of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98117811 CN1115376C (en) | 1998-08-27 | 1998-08-27 | Improved delay coking process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98117811 CN1115376C (en) | 1998-08-27 | 1998-08-27 | Improved delay coking process |
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| CN1246514A true CN1246514A (en) | 2000-03-08 |
| CN1115376C CN1115376C (en) | 2003-07-23 |
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| CN 98117811 Expired - Lifetime CN1115376C (en) | 1998-08-27 | 1998-08-27 | Improved delay coking process |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386408C (en) * | 2005-07-06 | 2008-05-07 | 华东理工大学 | Delayed coking treatment method for waste biomass |
| CN1954049B (en) * | 2004-05-14 | 2012-02-29 | 埃克森美孚研究工程公司 | Viscoelastic upgrading of heavy oil by altering its elastic modulus |
| CN103045301A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Method for producing needle coke by catalytic cracking-delayed coking combination process |
| CN103113906A (en) * | 2013-01-08 | 2013-05-22 | 何巨堂 | Coking delaying method of easy-coking oil product |
| CN101928597B (en) * | 2010-02-04 | 2013-07-17 | 涿州贝尔森生化科技发展有限公司 | Vacuum residue processing method |
| CN104560152A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Coking process for production of needle coke |
| CN111320168A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Device and method for producing high-end graphite carbon material |
-
1998
- 1998-08-27 CN CN 98117811 patent/CN1115376C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954049B (en) * | 2004-05-14 | 2012-02-29 | 埃克森美孚研究工程公司 | Viscoelastic upgrading of heavy oil by altering its elastic modulus |
| CN100386408C (en) * | 2005-07-06 | 2008-05-07 | 华东理工大学 | Delayed coking treatment method for waste biomass |
| CN101928597B (en) * | 2010-02-04 | 2013-07-17 | 涿州贝尔森生化科技发展有限公司 | Vacuum residue processing method |
| CN103045301A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Method for producing needle coke by catalytic cracking-delayed coking combination process |
| CN103045301B (en) * | 2011-10-17 | 2014-10-22 | 中国石油化工股份有限公司 | Method for producing needle coke by catalytic cracking-delayed coking combination process |
| CN103113906A (en) * | 2013-01-08 | 2013-05-22 | 何巨堂 | Coking delaying method of easy-coking oil product |
| CN104560152A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Coking process for production of needle coke |
| CN104560152B (en) * | 2013-10-23 | 2017-03-22 | 中国石油化工股份有限公司 | Coking process for production of needle coke |
| CN111320168A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Device and method for producing high-end graphite carbon material |
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| CN1115376C (en) | 2003-07-23 |
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