CN103555363B - A kind of high containing acid starting material oil hydrogen supply delayed coking method - Google Patents
A kind of high containing acid starting material oil hydrogen supply delayed coking method Download PDFInfo
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Abstract
The present invention is a kind of high containing acid starting material oil hydrogen supply delayed coking method, be characterised in that: add hydrogen supply agent as mixing raw material in conventional high containing in sour coking raw material, carry out hydrogen supply delayed coking reaction, the oil gas heat exchange of mixing raw material and coke drum top after process furnace heats, enter coke drum reaction, the coke generated is stayed in coke drum, after the oil gas extracted out from top of coke tower and coking raw material heat exchange cool, separation obtains cooking gas, coker gasoline, coker gas oil, wax tailings, and in coking, recycle ratio is 0.The technical process that the method adopts coker zero to circulate, improve coker treatment capacity, reduce high-acid-value material to the corrosion of delayed coking unit, improve liquid product yield to greatest extent, reduce cooking gas and coke yield, reduce tube coking tendency, extend the furnace operation cycle, reach process optimization, improve the object of device economic benefit.
Description
Technical field
The present invention relates to oil refining technical field, for a kind of high containing acid starting material oil hydrogen supply delayed coking method, specifically, a kind of passing through in the conventional high method containing adding hydrogen supply agent raising coking liquid yield, reduction cooking gas and coke yield in acid starting material oil is related to.
Background technology
Crude oil is a kind of non-renewable energy, and along with the fast development of world economy, the degree of dependence of people to crude oil improves constantly.Through Fast Algorithm for Mining for many years, crude oil constantly presents the trend of heaviness, in poor quality.The output of world's high-acid crude oil in 2007 accounts for 10% of crude oil ultimate production, and presents the trend risen year by year.In the course of processing of crude oil, the height of acid content is an important factor that can not be ignored.Petroleum acid corrodes production and refining equipment and rot-resistant research shows, when the total acid value in oil is more than 1mgKOH/g, acid corrosion will be quite serious.After atmospheric and vacuum distillation not only in distillate containing higher acidic substance, and the acid number of long residuum and vacuum residuum is also very high, causes heavy corrosion to such as the delayed coking of following process device.
Delayed coking have investment and process cost low, to different material strong adaptability, the features such as technology maturation, delayed coking is still one of topmost working method of residual oil weight-lightening, is subject to people's most attention.At present, doing large quantifier elimination and industrial application work both at home and abroad, groundwork concentrates on the aspects such as device selection, process optimization, but reduce high containing acid starting material delayed coking unit burn into improved to technological process liquid yield, reduce ordinary coke productive rate and slow down in heating furnace tube coking rate etc. and still have many deficiencies.
CN101629093A discloses a kind of the delayed coking equipment and the delayed coking method that contain acid starting material oil for height, the delayed coking equipment that this patent adopts comprises process furnace, separation column and coke drum, and process furnace comprises convection tubes, radiator tube, radiation section inlet line and radiation section egress line; Wherein, the material of convection tubes and radiator tube is T9 and/or 321H, and the material of radiation section inlet line is 1CRMO5 and/or 321, and the material of radiation section egress line is P9 and/or 316L.The delayed coking apparatus processing height adopting this patent to provide, containing acid starting material oil, can effectively solve high containing the problem of acid starting material oil to delayed coking equipment corrosion.But the use of special substance must improve the cost of equipment; In addition, this patent do not mention whether can improve technological process liquid yield, reduce ordinary coke productive rate and slow down heating furnace tube coking rate etc.
CN1580193A discloses a kind of delayed coking method of high acid value hydrocarbon ils, raw material is first after the preheating of coking heater convection zone, enter after process furnace radiation section top is heated to 350 ~ 450 DEG C further again, enter and relax cracking case reaction, from reactor top light petroleum hydrocarbon out, gas enters separation column and carries out fractionation, from reactor top, heavy cracked product out enters and enters coke drum after process furnace radiation section middle and lower part is heated to 480 ~ 510 DEG C further and carry out pyrogenic reaction, fractionation coking oil gas obtains cooking gas, gasoline, diesel oil, wax oil and cycle oil fraction.The method can utilize the raw materials such as delayed coking unit processing crude oil with high acid value, reduces high-acid-value material to the corrosion of delayed coking unit, extends coking on-stream time.But this patent does not mention the impact of technological process on liquid yield and coke yield etc. of improvement equally.
CN101638588A discloses the combined technical method of a kind of delayed coking and hydrotreatment, and coking raw material enters coke drum reaction through heating up, and oil gas is overflowed from top of coke tower, isolates gaseous fraction and liquid ingredient, and in coking, recycle ratio is 0; Liquid ingredient and hydrogen are blended in hydrogenator and react, the hydrogenation reaction effluent of fractionation gained, and obtain hydrotreated naphtha, hydrogenated diesel oil and hydrogenation wax oil, hydrogenation wax oil enters catalytic cracking unit or hydroeracking unit as high quality raw material.CN103102986A discloses a kind of Zha oil Jia hydrogen Chu Li – delayed coking combined technical method, residual oil, wax tailings and hydrogen are mixed together, hydrotreater reaction is entered under catalyzer existent condition, be separated the reaction product after hydrogenation, residual oil wherein after hydrogenation mixes with isolated vacuum gas oil or enter delayed coking unit together with other convenient source, be separated coking product, wherein coker gas oil is all circulated to residual hydrogenation equipment.CN1676573A discloses a kind of hydrogenation delayed coking method, coking raw material, optional coking recycle oil are before entering coke drum, with hydrogen, catalyst exposure, hydrogenated oil enters after coking heater is heated to coking temperature and enters coke drum after step-down, the coke generated is stayed in coke drum, and coking oil gas is isolated to cooking gas, coker gasoline, coker gas oil and wax tailings.But above-mentioned technological process does not change the processing condition of delayed coking unit itself, the liquid yield of cracking units and coke yield etc. do not change; And, owing to adopting hydrogenation means to improve delayed coking liquid yield, substantially increase cost of investment.
Summary of the invention
In order to overcome prior art deficiency, the invention provides a kind of high containing acid starting material oil hydrogen supply delayed coking method.Adopt in the conventional high technical process containing adding hydrogen supply agent and delayed coking unit zero circulation in acid starting material oil, improve coker treatment capacity, reduce high-acid-value material to the corrosion of delayed coking unit, improve liquid product yield to greatest extent, reduce cooking gas and coke yield, reduce tube coking tendency, extend the furnace operation cycle, reach process optimization, improve the object of device economic benefit.
The present invention is a kind of high containing acid starting material oil hydrogen supply delayed coking method, it is characterized in that: comprise the following steps:
Hydrogen supply agent is added as mixing raw material in conventional high containing in acid starting material oil, carry out hydrogen supply delayed coking reaction, the oil gas heat exchange of mixing raw material and coke drum top after process furnace heats, enter coke drum reaction, the coke generated is stayed in coke drum, after the oil gas extracted out from top of coke tower and coking raw material heat exchange cool, be separated and obtain cooking gas, coker gasoline, coker gas oil, wax tailings, in coking, recycle ratio is 0;
Described height is containing one or more the mixture of acid starting material grease separation in crude oil with high acid content, vacuum residuum, long residuum, visbroken resids, fluid catalytic cracking decant oil, thermal cracking residue, and these are high containing the mixture of acid starting material oil with common raw material oil, acid number is greater than 1.0mgKOH/g;
Described hydrogen supply agent is the oil product that in catalytic cracking distillate hydrogenation reaction effluent or its sepn process, gained is rich in fractional saturation aromatic hydrocarbons, and boiling range scope is between 200 ~ 500 DEG C, and fractional saturation aromaticity content is 20 ~ 100%;
The temperature in of described coke drum is 430 ~ 520 DEG C, and top of coke tower pressure is 0.1 ~ 0.5MPa, and filling the burnt time is 16 ~ 40 hours;
According to method of the present invention, it is characterized in that, the fractional saturation aromatic hydrocarbons of described hydrogen supply agent is the above aromatic hydrocarbons of dicyclo that double ring arene that partial hydrogenation is saturated and partial hydrogenation are saturated; Boiling range scope is between 220 ~ 480 DEG C, and fractional saturation aromaticity content is 25 ~ 90%;
According to method of the present invention, it is characterized in that, the add-on of described hydrogen supply agent is 5.0 ~ 50% of coking raw material weight.
Described hydrogen supply agent is the oil product that in catalytic cracking distillate hydrogenation reaction effluent or its sepn process, gained is rich in fractional saturation aromatic hydrocarbons, and acid number is extremely low, and mix containing acid starting material oil with height and can reduce its acid number, reduction coking raw material is to the corrosion of device; In addition, hydrogen supply agent aromaticity content is higher, and can well dissolve the green coke such as colloid, bituminous matter presoma, coking raw material stability obtains larger raising, plays the effect delaying green coke; And hydrogen supply agent has good hydrogen supply capacity, owing to containing a large amount of dicyclos and the above aromatic hydrocarbons of dicyclo in catalytic cracking distillate, formed after hydrotreatment and have a large amount of virtue and cycloalkane structure, thermal dehydrogenation aromizing can provide reactive hydrogen, as hydrogen donator; Coking raw material is the basic reason of the hot green coke of residual oil by the cracking caused by thermogenetic free radical and condensation reaction, the reactive hydrogen that hydrogen supply agent provides can close high aromaticity macromolecular radical by hydrogen supply in time, reduce number of free radical, reduce the macromolecular polymerization of aromaticity, thus suppress generation burnt in residual oil thermal response, extend not coke induction period to greatest extent, thus improve cracking transformation efficiency, increase yield of light oil.
Compared with prior art, the advantage of the inventive method is:
(1) technical process adopting delayed coking unit zero to circulate, improve coker treatment capacity, reduce the corrosion of high acid value coking recycle oil to delayed coking unit, avoid in coking distillate component loops process simultaneously occur that the liquid yield that thermally splitting causes declines, the problem such as gas and coke yield rising;
(2) adopt at height containing the method adding hydrogen supply agent in acid starting material oil, because hydrogen supply agent is that catalytic cracking distillate is through hydrotreatment after product, acid number is extremely low, significantly can reduce the acid number of coker feedstock, reduce raw material to the corrosion of device with height containing acid starting material oil after mixing;
(3) the hydrogen supply agent aromaticity content selected is higher, the green coke presomas such as the colloid in heavy coked raw material, bituminous matter can well be dissolved, greatly improve the stability of coking raw material, delay the hot green coke starting point of residual oil, suppress the generation of heating furnace tube residual oil thermal response coke, improve device running period, finally improve thermally splitting transformation efficiency;
(4) hydrogen supply agent selected is rich in virtue and cycloalkane structure hydrocarbon, there is good hydrogen supply capacity, the reactive hydrogen provided can close coking raw material by thermogenetic high aromaticity macromolecular radical by hydrogen supply in time, reduce number of free radical, reduce the macromolecular polymerization of aromaticity, extend not coke induction period to greatest extent, suppress the generation of coke in residual oil thermal response, improve cracking transformation efficiency, reach the object increasing yield of light oil and reduce coke yield.
Accompanying drawing explanation
Fig. 1 is that the present invention is a kind of high containing acid starting material oil hydrogen supply delayed coking method schematic flow sheet.
Wherein 1 is high oily containing acid starting material, and 2 is external hydrogen supply agent, and 3 is process furnace, the coking raw material after 4 heating, 5 is coking tower, and 6 is coke, and 7 is coking oil gas, and 8 is coking dry gas, 9 is coker gasoline, and 10 is coker gas oil, and 11 is coker gas oil, and 12 is coking fractional distillation column.
Embodiment
Accompanying drawing illustrates a kind of high containing acid starting material oil hydrogen supply delayed coking method flow process, and the shape and size of equipment and pipeline not by the restriction of accompanying drawing, but are determined as the case may be.
First the high acid starting material oil that contains mix with hydrogen supply agent, together after the radiation chamber heating of process furnace 3, enter coking tower 5 and carry out pyrogenic reaction, the coking oil gas 7 of generation enters coking fractional distillation column 12, the coking dry gas that fractionation obtains, coker gasoline, coker gas oil and coker gas oil.
Height provided by the invention enters the technical process of coker and zero circulation by additional hydrogen supply agent containing acid starting material oil hydrogen supply delayed coking method, reduce high containing the corrosion of acid starting material oil to equipment, delay coking heater coking tendency, improve the heavy oil upgrading degree of depth, improve liquid product yield to greatest extent, decrease coke yield, improve coking tower treatment capacity simultaneously.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Testing coking raw material used is vacuum residuum (> 540 DEG C) after crude oil with high acid content atmospheric and vacuum distillation, and acid number is 1.2mgKOH/g, and coking raw material oil and hydrogen supply agent character list in table 1.
Embodiment 1
High containing after sour vacuum residuum mixes with hydrogen supply agent carries out delay coking process processing, and the add-on of hydrogen supply agent is 8.0% of vacuum residuum feed weight, and the reaction conditions of coking is: temperature of reaction 510 DEG C, coke drum tower top pressure 0.18MPa, recycle ratio is 0.The product yield that result obtains is: coking yield 25.71%, cooking gas yield 7.21%, coking liquid yield 67.08% (wherein coker gasoline 20.66%, coker gas oil 22.18%, wax tailings 24.24%).
After delayed coking equipment operates 1 year continuously, according to the method test etching extent of Shandong chemical industry the 35th volume 4 phase 13-16 page in 2006, find, the etching extent of heated convection pipe is 0.02 millimeter, the etching extent of separation column tower body is 0.01 millimeter, and the etching extent of coke drum upper and lower is respectively 0.01 millimeter and 0.02 millimeter.
Embodiment 2
High containing after sour vacuum residuum mixes with hydrogen supply agent carries out delay coking process processing, and the add-on of hydrogen supply agent is 25.0% of coking raw material weight, and the reaction conditions of coking is with embodiment 1.The product yield that result obtains is: coking yield 24.95%, cooking gas yield 6.23%, coking liquid yield 68.82% (wherein coker gasoline 19.92%, coker gas oil 22.05%, wax tailings 26.85%).
After delayed coking equipment operates 1 year continuously, according to the method test etching extent of Shandong chemical industry the 35th volume 4 phase 13-16 page in 2006, find, the etching extent of heated convection pipe is 0.01 millimeter, the etching extent of separation column tower body is 0.01 millimeter, and the etching extent of coke drum upper and lower is respectively 0.01 millimeter and 0.02 millimeter.
Embodiment 3
High containing after sour vacuum residuum mixes with hydrogen supply agent carries out delay coking process processing, and the add-on of hydrogen supply agent is 48.0% of coking raw material weight, and the reaction conditions of coking is with embodiment 1.The product yield that result obtains is: coking yield 24.68%, cooking gas yield 5.96%, coking liquid yield 69.36% (wherein coker gasoline 19.71%, coker gas oil 21.83%, wax tailings 27.82%).
After delayed coking equipment operates 1 year continuously, according to the method test etching extent of Shandong chemical industry the 35th volume 4 phase 13-16 page in 2006, find, the etching extent of heated convection pipe is 0.01 millimeter, the etching extent of separation column tower body is 0.01 millimeter, and the etching extent of coke drum upper and lower is respectively 0.01 millimeter and 0.01 millimeter.
Comparative example 1
Height is directly processed by the condition of delayed coking in embodiment 1, unlike not adding hydrogen supply agent containing sour vacuum residuum.The reaction conditions of coking is: temperature of reaction 510 DEG C, coke drum tower top pressure 0.18MPa, recycle ratio is 0.Product yield is: coking yield 27.36%, cooking gas yield 8.29%, coking liquid 64.35% (wherein coker gasoline 21.33%, coker gas oil 22.66%, wax tailings 20.36%).Compared with comparative example 1, embodiment 1 can improve liquid yield 2.73%, reduces coking yield 1.65%, reduces cooking gas yield 1.08%.
After delayed coking equipment operates 1 year continuously, according to the method test etching extent of Shandong chemical industry the 35th volume 4 phase 13-16 page in 2006, find, the etching extent of heated convection pipe is 0.01 millimeter, the etching extent of separation column tower body is 0.02 millimeter, and the etching extent of coke drum upper and lower is respectively 0.02 millimeter and 0.02 millimeter.
Comparative example 2
Height is directly processed by the condition of delayed coking in embodiment 1 containing sour vacuum residuum, unlike not adding hydrogen supply agent, and part wax tailings is circulated, recycle ratio is 0.2, and the reaction conditions of coking is: temperature of reaction 510 DEG C, coke drum tower top pressure 0.18MPa.Product yield is: coking yield 28.05%, cooking gas yield 8.81%, coking liquid yield 63.14% (wherein coker gasoline 20.63%, coker gas oil 22.95%, wax tailings 19.56%).Compared with comparative example 2, embodiment 1 can improve liquid yield 3.94%, reduces coking yield 2.34%, reduces cooking gas yield 1.60%.
After delayed coking equipment operates 1 year continuously, according to the method test etching extent of Shandong chemical industry the 35th volume 4 phase 13-16 page in 2006, find, the etching extent of heated convection pipe is 0.02 millimeter, the etching extent of separation column tower body is 0.02 millimeter, and the etching extent of coke drum upper and lower is respectively 0.02 millimeter and 0.02 millimeter.
Can find out, adopt height of the present invention containing acid starting material oil hydrogen supply delayed coking method, namely the technical process of coker and zero circulation is entered by additional hydrogen supply agent, compared with traditional delayed coking combination process, the etching extent of each key equipment of coker significantly reduces, can liquid yield be significantly improved simultaneously, reduce cooking gas and coke yield, obvious to the effect of raising device whole economic efficiency.
Table 1 test raw material and hydrogen supply agent character
Claims (3)
1. high containing an acid starting material oil hydrogen supply delayed coking method, it is characterized in that: comprise the following steps:
Hydrogen supply agent is added as mixing raw material in conventional high containing in acid starting material oil, carry out hydrogen supply delayed coking reaction, the oil gas heat exchange of mixing raw material and coke drum top after process furnace heats, enter coke drum reaction, the coke generated is stayed in coke drum, after the oil gas extracted out from top of coke tower and coking raw material heat exchange cool, be separated and obtain cooking gas, coker gasoline, coker gas oil, wax tailings, in coking, recycle ratio is 0;
Described height is containing one or more the mixture of acid starting material grease separation in crude oil with high acid content, vacuum residuum, long residuum, visbroken resids, fluid catalytic cracking decant oil, thermal cracking residue, and these are high containing the mixture of acid starting material oil with common raw material oil, acid number is greater than 1.0mgKOH/g;
Described hydrogen supply agent is the oil product that in catalytic cracking distillate hydrogenation reaction effluent or its sepn process, gained is rich in fractional saturation aromatic hydrocarbons, and boiling range scope is between 200 ~ 500 DEG C, and fractional saturation aromaticity content is 20 ~ 100%;
The temperature in of described coke drum is 430 ~ 520 DEG C, and top of coke tower pressure is 0.1 ~ 0.5MPa, and filling the burnt time is 16 ~ 40 hours.
2. height according to claim 1 is containing acid starting material oil hydrogen supply delayed coking method, it is characterized in that, the fractional saturation aromatic hydrocarbons of described hydrogen supply agent is the above aromatic hydrocarbons of dicyclo that double ring arene that partial hydrogenation is saturated and partial hydrogenation are saturated; Boiling range scope is between 220 ~ 480 DEG C, and fractional saturation aromaticity content is 25 ~ 90%.
3. height according to claim 1 is containing acid starting material oil hydrogen supply delayed coking method, and it is characterized in that, the add-on of described hydrogen supply agent is 5.0 ~ 50% of coking raw material weight.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104927920B (en) * | 2014-03-21 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of residuum coking method |
| CN104830366B (en) * | 2015-05-13 | 2017-05-10 | 湖南长岭石化科技开发有限公司 | Method for enhancing crude oil distillation pull-out rate and improving residual oil properties |
| CN104946294B (en) * | 2015-06-01 | 2017-03-15 | 湖南长岭石化科技开发有限公司 | Improve the coking method of liquid yield |
| CN111808626A (en) * | 2020-07-14 | 2020-10-23 | 山东京博石油化工有限公司 | Method for improving liquid yield of delayed coking device |
| CN114437769A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Delayed coking method and device for blending deoiled asphalt and method for processing heavy oil |
| CN113278441B (en) * | 2021-07-06 | 2022-11-29 | 山东京博石油化工有限公司 | Auxiliary agent for optimizing product distribution in delayed coking or visbreaking process and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217372A (en) * | 1997-11-19 | 1999-05-26 | 中国石油化工总公司 | Method for inhibiting coke generation of heating-furnace |
| CN1552799A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Delayed coking method for increasing light oil yield |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217372A (en) * | 1997-11-19 | 1999-05-26 | 中国石油化工总公司 | Method for inhibiting coke generation of heating-furnace |
| CN1552799A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Delayed coking method for increasing light oil yield |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161009 Address after: 300131, No. 6, East Street, Hongqiao District, Tianjin Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |