CN1205304C - Method for raising production efficiency of delayed coking liquid product - Google Patents
Method for raising production efficiency of delayed coking liquid product Download PDFInfo
- Publication number
- CN1205304C CN1205304C CN 02109408 CN02109408A CN1205304C CN 1205304 C CN1205304 C CN 1205304C CN 02109408 CN02109408 CN 02109408 CN 02109408 A CN02109408 A CN 02109408A CN 1205304 C CN1205304 C CN 1205304C
- Authority
- CN
- China
- Prior art keywords
- coking
- heat supply
- supply agent
- raw material
- production efficiency
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a delayed coking technology for producing many liquid products, which is characterized in that a low molecular hydrocarbon heat supply agent which can not be coked at high temperature and has a high enthalpy value is added to a coking tower during a delayed coking process, which enhances liquid reaction temperature in the coking tower, increases the yield of coked liquid products and lowers the yield of coke products.
Description
1, technical field
The invention belongs to delayed coking process, more particularly, is a kind of method that improves liquid product yield in the delayed coking operation process.
2, background technology
Delayed coking has been used for many years in petroleum refining industry as one of heavy oil upgrading means.This technology is to be raw material with heavy, poor residuum, enters coking tower after the process furnace heating, and thermolysis generates the liquid product and the coke product of gas products, different boiling in coking tower.
The raw material of refinery's delayed coking unit processing at present is more and more heavy, and coke yield is up to 30w%-40w%, and liquid product is quite few.Delayed coking unit is subjected to the restriction of coke yield, and increasing service temperature can only finish by process furnace.Increase furnace temp and certainly will quicken tube coking, cause boiler tube to stop up, cause shut-down.In order to improve and alleviate tube coking speed, prolong the boiler tube life cycle, former technology is the heavy gas oil circulation that adds 5w%-40w% in fresh feed oil.Although turning oil can reduce the tube coking amount, its coking result is that coke yield increases.In order to address this problem, U.S. Pat 4,455,219 disclose a kind of delayed coking method.This method is the hydro carbons attenuant replacement heavy cycle oil that is lower than heavy cycle oil with the part boiling point, and the coking liquid yield is increased, and coke yield descends.
U.S. Pat 4,518,487 at US4, on 455,219 the basis heavy cycle oil has all been obtained effect preferably with the replacement of low boiling point hydrocarbon thinner.
U.S. Pat 4,661, disclosed a kind of improved delayed coking in 241 and improved the method that liquid is received, this method is that one way is passed through (no heavy cycle oil), adds the part boiling point simultaneously and be lower than 450 ℃ hydrocarbon diluent (or in the adding of furnace outlet place) in raw material.The problem that this method has promptly been alleviated tube coking has increased liquid product yield again, reduce the coke product productive rate, but the problem that one way is passed through is a heavy constituent content height, is directed at carbon residue and heavy metal content is higher, and processing brings certain degree of difficulty to downstream unit.
The above these method has all been improved the process furnace operating mode to some extent, prolonged the life cycle of process furnace, but can not improve the liquid reactions temperature in the coking tower effectively, reach and increase considerably liquid yield, reduce the purpose of coke product productive rate.U.S. Pat 5,645,712 pairs of delay coking process have been done further improvement, this patent with a kind of hydro carbons (168-450 ℃ of cut) of high temperature noncoking as thinner.In original delay coking process flow process, set up another process furnace again, heated this thinner separately, made its temperature be higher than interior the about 10-300 of fluid temperature of coking tower, entered coking tower then, made the interior liquid starting material temperature of coking tower improve 1-50 °F at least.This improved delayed coking method has improved the about 1w% of liquid product yield, has reduced coke product productive rate 3.48%.Although this method is compared with above-mentioned patented method, obtaining bigger progress aspect raising liquid yield and the reduction coke yield, this method also exists certain deficiency.At first, the process furnace of mentioning in this method of establishing in addition is used for heating the noncoking hydrocarbon diluent separately, has increased facility investment, makes flow process complicated simultaneously; In addition, the noncoking hydrocarbon diluent that uses in this method is a 168-450 ℃ of cut, this cut has comprised part diesel oil distillate and part wax oil cut, is uneconomic with diesel oil distillate as thinner, it is little to reducing the coke yield contribution to make thinner with wax oil, this cut is heavier in addition, and the heat enthalpy value of the relative lighter fraction of heat enthalpy value is low.
3, summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, propose a kind of improved coking delay process, be intended to further improve liquid yield, reduce the coke product productive rate.
Improved coking delay process of the present invention, comprise: coking raw material is heated to 450-530 ℃, preferably 490-510 ℃, entering into coking tower reacts, its characteristics are also to inject the lighter hydrocarbons heat supply agent of about 0.1w%-20w% (accounting for fresh coking raw material), preferably 5w%-10w% in coking tower.Lighter hydrocarbons heat supply agent generally should be heated to about 500-580 ℃, preferred 510-545 ℃.Mix with the coking raw material after above-mentioned being heated (in transfer line place or coking tower), make the coking tower interior reaction temperature improve 1 ℃ at least, generally should be 3-8 ℃, owing to charged into the heat supply agent in the coking tower, make temperature of reaction in the coking tower generally at 465-525 ℃, normally 485-510 ℃, this temperature is than conventional delayed coking reaction temperature height, and working pressure generally is 0.01-1.5Mpa, preferably 0.15-0.25Mpa, recycle ratio is generally 0-1, preferably 0.15-0.45.
Recycle ratio of the present invention is meant the ratio of turning oil weight and fresh feed weight of oil, and turning oil is meant the tail oil that described separation system is told, and its initial boiling point is generally greater than 450 ℃.
Coking raw material of the present invention is weight, the residual oil raw material of initial boiling point＞350 ℃, generally can be selected from residual oil, the heavy deasphalted oil of deasphalting unit, catalytically cracked oil, viscous crude, the topped crude of atmospheric and vacuum distillation unit, certainly also can be selected from other similar raw material, the heavier hydrocarbon feeds after processing as coal, shale and oil-sand etc.
Above-described lighter hydrocarbons heat supply agent mainly is meant the detailed hydrocarbon of boiling point＜180 ℃ or do＜180 ℃ hydrocarbon mixture generally can be C
3-C
12Detailed hydrocarbon or hydrocarbon mixture in the scope, its boiling range for example can be isolating C after the pyrogenic reaction greatly about 0-180 ℃
3, C
4Cut and/or C
5Above coker gasoline partly or entirely, the cut that can certainly use other device is as lighter hydrocarbons heat supply agent of the present invention, as the catalytic cracking petroleum naphtha etc.
A principal feature of lighter hydrocarbons heat supply agent of the present invention is to be difficult for coking under the high temperature, and has the high enthalpy value.By in coking tower, injecting above lighter hydrocarbons heat supply agent, can be under the situation that does not improve the raw materials furnace and heating service temperature, to increase the coking tower interior reaction temperature, usually temperature of reaction can be improved at least 1 ℃, generally should improve 3-8 ℃ (this temperature can be measured by thermocouple at the coking tower top), thereby increased liquid cracking reaction temperature in the coking tower, increased the coking liquid yield, reduced the coke product productive rate.The consumption of described light hydrocarbon heat supply agent accounts for greatly between the 0.1%-20% of fresh coking raw material gross weight, preferred 5%-10%, and the heat supply agent generally should be heated to about 500-580 ℃ before entering coking tower, preferred 510-545 ℃.After described lighter hydrocarbons heat supply agent is heated, can by transfer line be heated after coking raw material be mixed and enter coking tower, also can enter coking tower respectively.
The heating of coking raw material of the present invention generally can be undertaken by process furnace, the heating of lighter hydrocarbons heat supply agent can adopt any suitable mode to carry out, for example also can establish a process furnace separately carries out, the radiation zone that the present invention recommends the coking raw material process furnace is sent in described lighter hydrocarbons heat supply agent heats, so promptly reduced facility investment, energy is fully used.
The reacted product of coking tower of the present invention generally can be separated into C with it after entering and separating in the separation column
4Following cut, C
5-180 ℃ of gasoline fractions, 180 ℃ of-350 ℃ of diesel oil distillates, 350 ℃ of-450 ℃ of wax oil cuts and tail oil more than 450 ℃.Certainly also can be as the case may be with C
4C in the following cut
1-C
2Cut and C
3-C
4Cut separates, with C
3-C
4Cut and C
5In-180 ℃ of cuts partly or entirely as lighter hydrocarbons heat supply agent; The sedimentation of coke that reaction generates in coking tower after coke is full of, can stop charging in coking tower at the bottom of tower, switch to another coking tower and carry out same operation (but each coking tower operate continuously 36-48 hour).In addition, can be as the case may be, tail oil at the bottom of the isolated tower in the separation system is partly or entirely looped back the device front portion to be handled with fresh coking raw material again, can certainly adopt at the bottom of the tower not cyclic process of tail oil, one-pass scheme, generally can select part round-robin mode to operate, its recycle ratio is 0.15-0.45 preferably.
Technical scheme described in the inventive method is equally applicable in other delayed coking method.U.S.P No.4 of the prior art as previously mentioned, 455,219, U.S.P No.4,518,487 and U.S.PNo.4,661,241 are specially adapted to U.S.P No5,645,712.
The present invention is not only applicable to process the coking raw material of general routine, as vacuum residuum, is applicable to the various unmanageable poor residuums in low temperature coking in the past of processing, as heavy deasphalted oil, viscosity breaking residue, catalytically cracked oil, viscous crude etc. yet.Make these inferior raw materials in the method for this invention, obtain the high value added product of higher yields.
The present invention compares with relevant patented technology and has the following advantages:
1 and US5,645,712 compare, and the inventive method can improve the about 1w%-2w% of gas yield, improve the about 1w%-3w% of liquid yield, the about 3w%-7w% of reduction coke yield.
2, the low molecular hydrocarbon class heat supply agent with high enthalpy value of noncoking enters coking raw material heating furnace high-temperature radiation zone separately under the high temperature, is heated to the temperature of hope, does not heat the heat supply agent separately and do not need to increase another process furnace, reduces facility investment.
3, the used heat supply agent of the present invention is boiling point or does low molecular hydrocarbon class less than 180 ℃, the height of its heat enthalpy value higher hydrocarbon, therefore reach with relevant patented method in temperature the time required adding amount reduce relatively; Or when identical with consumption in the relevant patented method, this heat supply agent does not need to be heated to higher temperature, thereby has reached the purpose that reduces cost.
4, among the present invention under the used high temperature low molecular hydrocarbon class heat supply agent with high enthalpy value of noncoking be light gasoline fraction from coking itself.This cut alkene and various foreign matter content are higher, and octane value is lower, can not be to be worth lower product, but its heat enthalpy value are higher relatively as commodity selling, with it as the heat supply agent than low, effective with the diesel oil distillate cost in the relevant patented method.
5, method of the present invention provides operational handiness, so that determine the variation that product distributes according to market situation, and reduces coke yield as far as possible.
4, description of drawings
Fig. 1 is employed a kind of schematic flow sheet in following examples of the present invention.
Be further explained in detail the present invention below in conjunction with accompanying drawing and specific embodiment.
5, embodiment
As shown in Figure 1, stock oil enters in the process furnace 3 through pipeline 1 and heats, low molecular hydrocarbon class heat supply agent enters the radiation zone of process furnace 3 along pipeline 2, enter in the coking charcoal 7 by pipeline 6 together through pipeline 4 and pipeline 5 respectively pyrogenic reaction takes place through being heated to stock oil after temperature required and low molecular hydrocarbon class, the pyrogenic reaction product enters separation column 11 from coking tower 7 tops by pipeline 8 and pipeline 9, isolates various products in separation column 11.C
1, C
2Through pipeline 18 take-up gears, C
3, C
4A part is through pipeline 17 take-up gears, and another part is recycled to raw materials furnace and heating hyperthermia radiation district as the heat supply agent through pipeline 20 and 21 and recycles; C
5-180 ℃ of cut parts are through pipeline 16 take-up gears, and a part is recycled to raw materials furnace and heating hyperthermia radiation district as the heat supply agent through pipeline 19 and pipeline 21 and recycles; 180-350 ℃ of diesel oil is through pipeline 15 take-up gears; Wax oil is through pipeline 14 take-up gears, is recycled to raw materials furnace and heating 3 greater than 450 ℃ of tail oils through pipeline 12 and pipeline 1 and recycles (can take whole circular treatment as the case may be greater than 450 ℃ of tail oils, or the scheme passed through of part circulation or one way).Coke product then goes out device by pipeline 10 and pipeline 13.After coking tower 7 is full of, stop charging, switch another coking tower 7a and carry out same operation, again respectively process pipeline 4 and pipeline 5 after together by pipeline 6a enter coking tower 7a through reaction raw materials after heating and lighter hydrocarbons heat supply agent this moment, reaction product enters in the pipeline 9 via pipeline 8a, and coke goes out device by pipeline 10a and pipeline 13.
Following examples describe the present invention in detail, but do not limit the present invention.All test usefulness stock oils among the embodiment, the heat supply agent is all identical, and raw materials furnace and heating temperature out, reaction pressure, recycle ratio are all identical, are intended to the influence to pyrogenic reaction of comparison heat supply agent furnace outlet temperature and add-on.
According to the described schematic flow sheet of Fig. 1, on medium-sized tester, done following experiment.Below the character of the raw materials used oil of experiment, heat supply agent sees Table 1.The raw materials furnace and heating temperature out is 500 ℃, and working pressure is 0.17Mpa, recycle ratio 0.2 (w/w).Inlet amount is 5kg/h, turns round 10 hours, stops charging, and adustion 2 hours is removed volatile matter.Heat supply agent furnace outlet temperature, add-on and experiment condition and test-results see Table 2.
The character of table 1 stock oil and heat supply agent
Project stock oil heat supply agent
Density, (20 ℃), g/cm
30.9816 0.7545
Carbon residue, w% 15.6-
Sulphur content, w% 1.18 0.045
H/C atomic ratio 1.58-
Initial boiling point, ℃ 380 48
50％，℃ 455 128
95％，℃ 535 -
Do ℃-180
Table 2 heat supply agent furnace outlet temperature, add-on and product distribute
Test number 12345
Heat supply agent furnace outlet temperature, ℃-510 510 515 515
Heat supply agent add-on, w%-5 10 5 10
The coking tower top temperature, ℃ 440 442 445 445 448
Product distributes, w%
H
2S 0.12 0.11 0.10 0.12 0.11
C
1，C
2 2.85 3.01 3.13 3.13 3.26
C
3，C
4 4.62 4.76 4.88 4.90 5.12
C
5-180℃ 13.68 13.93 14.15 14.16 14.52
180-350℃ 20.10 20.14 20.16 20.16 20.19
350-450℃ 23.81 24.07 24.36 24.37 24.51
＞450℃ 6.80 6.56 6.42 6.43 6.31
Coke 28.02 27.42 26.80 26.73 25.98
Add up to 100.00 100.00 100.00 100.00 100.00
* test 1 and be blank test.
Claims (8)
1, a kind of method that improves production efficiency of delayed coking liquid product, comprise: coking raw material is heated to 450-530 ℃, entering into coking tower reacts, its feature is being also to inject the lighter hydrocarbons heat supply agent that accounts for fresh coking raw material weight 0.1%-20% in coking tower, described lighter hydrocarbons heat supply agent should be heated to after 500-580 ℃ with coking raw material after above-mentioned being heated and mix, make the coking tower interior reaction temperature and do not add lighter hydrocarbons heat supply agent and compare, at least improve 1 ℃, temperature of reaction in the coking tower is 465-525 ℃, working pressure is 0.01-1.5Mpa, and recycle ratio is 0-1; Described lighter hydrocarbons heat supply agent is to do≤180 ℃ hydrocarbon mixture.
2, according to the method for the described raising production efficiency of delayed coking liquid product of claim 1, the consumption that it is characterized in that described lighter hydrocarbons heat supply agent is the 5%-10% of fresh coking raw material weight.
3, according to the method for the described raising production efficiency of delayed coking liquid product of claim 1, it is characterized in that described coking tower interior reaction temperature is 485-510 ℃, working pressure is 0.15-0.25Mpa, recycle ratio is 0.15-0.45.
4,, it is characterized in that described coking raw material is weight, the residual oil raw material of initial boiling point＞350 ℃ according to the method for the described raising production efficiency of delayed coking liquid product of claim 1.
5,, it is characterized in that described lighter hydrocarbons heat supply agent before entering coking tower, should be heated to 510-545 ℃ according to the method for the described raising production efficiency of delayed coking liquid product of claim 1.
6,, it is characterized in that described lighter hydrocarbons heat supply agent is to heat by the radiation zone that enters described coking raw material process furnace to reach temperature required according to the method for the described raising production efficiency of delayed coking liquid product of claim 1.
7,, it is characterized in that entering into coking tower after described coking raw material is heated to 490-510 ℃ reacts according to the method for the described raising production efficiency of delayed coking liquid product of claim 1.
8, according to the method for the described raising production efficiency of delayed coking liquid product of claim 1, it is characterized in that coking tower is injected in described lighter hydrocarbons heat supply agent after, the coking tower interior reaction temperature is compared with not adding lighter hydrocarbons heat supply agent, improves 3-8 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109408 CN1205304C (en) | 2002-04-04 | 2002-04-04 | Method for raising production efficiency of delayed coking liquid product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109408 CN1205304C (en) | 2002-04-04 | 2002-04-04 | Method for raising production efficiency of delayed coking liquid product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1448466A CN1448466A (en) | 2003-10-15 |
| CN1205304C true CN1205304C (en) | 2005-06-08 |
Family
ID=28680411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02109408 Expired - Lifetime CN1205304C (en) | 2002-04-04 | 2002-04-04 | Method for raising production efficiency of delayed coking liquid product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1205304C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457856C (en) * | 2004-10-29 | 2009-02-04 | 中国石油化工股份有限公司 | Delayed coking method for promoting light oil yield |
| CN101619238B (en) * | 2008-07-04 | 2012-08-29 | 中国石油化工股份有限公司 | Delayed coking and reduced pressure distillation combined processing method |
| CN102041013B (en) * | 2009-10-16 | 2013-07-24 | 中国石油化工股份有限公司 | Method for producing needle coke raw material by using delayed coking process |
| 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 |
| MY172621A (en) * | 2011-05-13 | 2019-12-06 | Catalytic Distillation Tech | Method for producing high vcm coke |
| CN104673371B (en) * | 2013-12-02 | 2017-04-05 | 中石化洛阳工程有限公司 | A kind of method for improving delayed coking liquid product yield |
-
2002
- 2002-04-04 CN CN 02109408 patent/CN1205304C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1448466A (en) | 2003-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6332975B1 (en) | Anode grade coke production | |
| US6207041B1 (en) | Process for converting heavy crude oil fractions, comprising an ebullating bed hydroconversion step and a hydrotreatment step | |
| US3775290A (en) | Integrated hydrotreating and catalytic cracking system for refining sour crude | |
| RU2005117790A (en) | METHOD FOR PROCESSING HEAVY RAW MATERIALS, SUCH AS HEAVY RAW OIL AND CUBE RESIDUES | |
| US6048448A (en) | Delayed coking process and method of formulating delayed coking feed charge | |
| MX2014011112A (en) | Integration of solvent deasphalting with resin hydroprocessing and with delayed coking. | |
| CN102358846A (en) | Visbreaking-coking combined process method by hydrogen generated from heavy oil | |
| JPS6337155B2 (en) | ||
| CN102899076A (en) | Delayed coking method | |
| EP0372652A1 (en) | Process for the conversion of a heavy hydrocarbonaceous feedstock | |
| CN1205304C (en) | Method for raising production efficiency of delayed coking liquid product | |
| US10934494B2 (en) | Process for production of anisotropic coke | |
| CN1171978C (en) | Process for transforming high-sulfur high-metal residual oil | |
| CN101463266A (en) | Viscosity breaking method | |
| US2853439A (en) | Combination distillation and hydrocarbon conversion process | |
| CN111647433B (en) | Method and system for producing propylene and high-octane gasoline from inferior oil | |
| CN111378491B (en) | Inferior heavy oil hydrotreating process | |
| CN111647428B (en) | Treatment method and system for inferior oil | |
| EP0156614B1 (en) | Coking residuum in the presence of hydrogen donor | |
| CN1119388C (en) | Thermocracking process for heavy oil | |
| CN111647434B (en) | Processing method and system for inferior oil | |
| CN103102983B (en) | Delayed coking-hydrorefining process for shale oil | |
| US10113122B2 (en) | Process for upgrading heavy hydrocarbon liquids | |
| RU2819187C1 (en) | Viscosity breaking unit | |
| JP2019131788A (en) | Two-stage pyrolysis method using multistage separation system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050608 |
|
| CX01 | Expiry of patent term |