CN102220165A - Process for delaying coking - Google Patents

Process for delaying coking Download PDF

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Publication number
CN102220165A
CN102220165A CN2010101449024A CN201010144902A CN102220165A CN 102220165 A CN102220165 A CN 102220165A CN 2010101449024 A CN2010101449024 A CN 2010101449024A CN 201010144902 A CN201010144902 A CN 201010144902A CN 102220165 A CN102220165 A CN 102220165A
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Prior art keywords
coking
tower
coking tower
oil
weight
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Inventor
王龙延
李和杰
秦如意
黄新龙
徐江华
王晨涯
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China Petrochemical Corp
Sinopec Luoyang Guangzhou Engineering Co Ltd
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Sinopec Luoyang Petrochemical Engineering Corp
China Petrochemical Corp
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Abstract

The invention provides a process for delaying coking, which comprises the following steps that raw oil is heated through a heating furnace to be divided into two parts, wherein one part enters a coking tower from the top part or the side of the coking tower, and the other part enters the coking tower from the bottom part of the coking tower, the two parts react in the coking tower to generate oil gas, the oil gas flows out of the top part or the upper part of the coking tower to enter a coking fractionating tower, and generated coke is maintained in the coking tower; and a distributor is arranged at the raw oil inlet in the coking tower, so that the raw material entering the coking tower from the upper part of the coking tower becomes small liquid drops through the distributor, the evaporation area and vapor pressure of the raw oil can be increased, the gasification of the raw oil and the generated oil is facilitated, the occurrence of the secondary reaction can be reduced, further, the liquid yield of the process for delaying coking can be increased, and the height of the foam layer in the coking tower can be reduced.

Description

A kind of delay coking process
Technical field
The invention belongs to the Petroleum Processing Technology field, relate to a kind of delay coking process that improves liquid yield.Specifically, relate to a kind of delay coking process that improves liquid yield by the feeding manner that improves coking tower.
Background technology
The delayed coking technology is heavy oil lighting means important in the petroleum refining process.Its outstanding feature is that adaptability to raw material is strong, can process the inferior heavy oil that other heavy oil upgrading technology can't be processed, even can process sump oil, greasy filth.Along with the lasting exploitation of crude oil, the trend of the poor qualityization of crude oil and heaviness is more and more obvious, and the amount of heavy oil and inferior heavy oil can be more and more many, and delay coking process is just more and more important.
The raw material of delay coking process generally is the residual oil behind the crude oil process atmospheric and vacuum distillation, and its boiling range scope is usually greater than 500 ℃.Residual oil usually and delayed coking turning oil pass through process furnace together and be heated to the coking tower that enters delayed coking about 500 ℃, under 450~480 ℃ temperature, carry out thermally splitting and condensation reaction.Crackate is dry gas, liquefied gas, petroleum naphtha, intermediate oil and wax tailings normally.Condensation product is a coke.Usually petroleum naphtha, intermediate oil and wax tailings yield and, be called the liquid yield of delay coking process.Liquid yield is the most important technico-economical comparison of delay coking process.
In addition, in delayed coking process, in the coking tower because oil gas generation foam layer.Foam layer has influenced the utilization ratio of coking tower, can cause when serious and confusingly bring Jiao into coking fractional distillation column towards the tower accident, causes pipeline and coking fractional distillation column coking, obstruction, makes the improper shut-down of device.The method of generally using is to inject defoamer in coking tower now.
Patent CN101638585A discloses a kind of delayed coking method that relates to charging, and its main purpose is to improve the green coke cycle that decoking shortens coking tower simultaneously.The core of this technology is, when the temperature of coke was also quite high, coke was can mobile, by inject a kind of rare gas element in tower coke is extruded.This patent does not relate to liquid yield.
Patent CN200610106994.0 discloses a kind of method that improves the delayed coking liquid yield.This method is to add the liquid yield that a kind of auxiliary agent improves delay coking process in delayed coking process.This auxiliary agent is made up of the alkyl nitric ether of 20~40 weight %, the Fatty Alcohol(C12-C14 and C12-C18) of 10~30 weight %, dimethyl polysiloxane and the balance solvent of 10~20 weight %.Use this invention can obviously improve the yield of delayed coking liquid, reduce coke yield.This method will make used additives, and the raw material of production auxiliary agent is all somewhat expensive, also injecting equipment will be arranged, and can improve the tooling cost of delayed coking, also can increase the complicacy of operation.
Patent CN03133538.1 discloses a kind of method that the delayed coking light oil yield reduces coke yield that improves.This method uses coal tar fraction as anticoking agent, and add-on ranges up to 10%, has improved yield of light oil, has reduced coke yield.This method need be used coal tar as anticoking agent, and is the benzoline of coal tar, and cutting coal tar certainly will increase energy consumption.And the treatment capacity of meeting reduction delayed coking behind the adding coal tar.
The disclosed technology of patent CN02139673.6 is that a kind of lower boiling hydro carbons of adding can improve the liquid yield of delayed coking in coking.But this method can cause the flow process complexity, and increases the load of separation column, causes energy consumption to increase.
Patent CN99119740.2 discloses a kind of method that reduces the coking tower foam layer height.When foam layer is low, do not annotate defoamer, when foam layer height is higher, inject defoamer, can reduce the silicone content that generates in the oil.This can make operation become complicated.
Summary of the invention
The invention provides a kind of delay coking process, overcome the deficiencies in the prior art, under investment and process cost situation about not increasing substantially, improve the liquid yield of delay coking process, do not increase energy consumption, can also reduce the interior foam layer height of coking tower.
In addition, use the present invention not influence the use of other patented technology.That is to say,, can also continue to use technology of the present invention even used other increase liquid receipts technology.The present invention can receive on the basis of technology at the existing liquid that increases, and increases the liquid yield of delay coking process again.
Delay coking process provided by the invention comprises the steps:
(a) stock oil mixes after process furnace is heated to 450~550 ℃ separately or with turning oil, and this temperature is the furnace outlet temperature;
(b) stock oil that comes from step (a) is divided into two portions, and a part enters coking tower from the top of coking tower (other coking tower is in other as processes such as decoking, warm towers) or the side of coking tower; Another part enters coking tower from the bottom of coking tower; Wherein the inlet amount that enters coking tower from the top or the side of coking tower accounts for the 50 weight %~99.99 weight % of coking total feed, and the inlet amount that enters coking tower from the bottom of coking tower accounts for the 0.01 weight %~50 weight % of coking total feed;
(c) coking raw material from step (b) carries out thermally splitting and condensation reaction in coking tower;
(d) from step (b) and the coking that (c) produces generate oil gas and flow out from the coking tower top or near the side at top, enter coking fractional distillation column;
(e) from step (b) and the coke that (c) generates then stay in the coking tower;
(f) behind the green coke certain hour, charging is switched to the coking tower that has been ready to charging in addition, carry out decoking with conventional decoking and filled burnt coking tower; Decoking finish after seal, standby behind the conventional steps such as warm tower; Circulation is switched between the coking tower, and process is able to continuously.
As the technical scheme of further optimization, described furnace outlet temperature is preferably 480~520 ℃, and the ratio that the described inlet amount that enters coking tower from the top or the side of coking tower accounts for the coking total feed is preferably 70 weight %~99.9 weight %; The ratio that the inlet amount that enters coking tower from the bottom of coking tower accounts for the coking total feed is preferably 0.1 weight %~30 weight %; In order to reach better dispersion effect, also can be in coking tower stock oil ingress install at least one feed distributor to from the coking tower top or the side stock oil that enters coking tower disperse.
Core of the present invention is the feeding manner of coking tower.With regard to existing delayed coking technology, the charging of coking tower all is the bottom feed from coking tower, and does not adopt any special measure; Feeding manner of the present invention then is to tell top or the side-fed of a part of raw material from coking tower, before raw material advances coking tower and generate the technical process that oil gas advances behind the separation column and can adopt existing known technology or existing patented technology.
The principle that employing the present invention increases liquid yield is as follows: form in coking tower the process of dispersive drop and whereabouts through feed distributor from the stock oil of coking tower top charging, because raw material is disperseed, increased the evaporation of liquid area, simultaneously because the increase of the drip gauge curvature of face, vapour pressure also increases, and certainly will make the amount of vaporization of stock oil in the decline process increase greatly.There is not the liquid of gasification to continue cracking and condensation in coking tower.So not only can reduce the secondary reaction that generates oil gas, reduce the productive rate of dry gas, reduce owing to entering the raw material that participates in condensation reaction in the tower simultaneously, will reduce the productive rate of coke, increase the yield of liquid.Also owing to generate oil gas and in the decline process of drop, gasify and fallen a part, make that the escaping gas amount reduces in the liquid level, flow velocity reduces, and will make foam layer height decline in the coking tower.
Compared with prior art, under the situation that needn't change coking tower fractionating system and reheat furnace system, just feed entrance point is changed and the increase feed distribution system, just can be improved the liquid yield of technology and lower the coking tower foam layer height, will produce bigger economic benefit.
Description of drawings
The present invention will be further described below in conjunction with accompanying drawing:
Fig. 1 is a delay coking process general flow chart of the present invention;
Fig. 2 is medium-sized delayed coking testing apparatus schema;
Fig. 3 is the medium-sized delayed coking unit schema that has adopted delay coking process of the present invention.
Embodiment
As shown in Figure 1, coking raw material oil 1 enters the convection zone and the radiation section of process furnace 2.After radiation section is heated to 480~550 ℃, separated into two parts, a part (accounting for the 50 weight %~99.99 weight % of coking total feed) enters the top of coking tower 7 through transfer line 3, and the divider 5 through installing on the top of coking tower enters coking tower; Another part (accounting for the 0.01 weight %~50 weight % of coking total feed) enters coking tower through transfer line 4 from the bottom of coking tower 7.The coking raw material that enters coking tower from the top of coking tower 7 disperses coking raw material through divider 5, in this part stock oil not the liquid of gasification be dispersed into drop even droplet, fall into the bottom of coking tower, carry out thermally splitting and condensation reaction.And the raw material that enters coking tower from coking tower 7 bottoms carries out pyrogenic reaction in the pyrogenic mode of routine.The effect of advancing a part of raw material from coking tower 7 bottoms is to keep the passage that steams out with cold Jiao, so that use conventional decoking technology to carry out decoking.The oil-feed time of coking tower 7 is 6~36 hours, switches to coking tower 8 oil-feeds then, by divider 6 coking raw material is disperseed, and repeats said process.Carry out decoking with conventional method behind the conventional process such as 7 processes of coking tower steam out, cold Jiao.Prepare oil-feed again after decoking finishes, so circulate.
The oil gas 9 that generates is the same with conventional delayed coking, enters follow-up coking fractionating system fractionating method routinely and separates.
The present invention will be further described for the following examples, but do not limit the present invention.
The comparative example 1
As shown in Figure 2, on medium-sized delayed coking testing apparatus, certain vacuum residuum has been carried out the conventional delayed coking experiment of one way.Stock oil pumps in the process furnace 5 after the water vapor that pump 3 is extracted out and water vapor producer 6 produces mixes from material tank 1, and through pump 4 extractor pump entry Steam generating furnaces 6, the stock oil that the steam of generation and pump 3 come out mixes deionized water from water pot 2 simultaneously.The mixture of stock oil and water vapor enters coking tower from the bottom of coking tower 7 and carries out cracking and condensation reaction after process furnace 5 is heated to coking temperature.Coking generates oil gas and flows out from the top of coking tower 7, after condenser 8 condensations, enter and generate oily receiving tank 9, uncooled gas through cold well 10 further condensation coolings after wet test meter measures post-sampling emptying.The coking that receiving tank 9 and cold well 10 are collected generates oil and obtain petroleum naphtha, intermediate oil, wax tailings after the distillation of FY-III type true boiling point device.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
The comparative example 2
As shown in Figure 2, on medium-sized delayed coking testing apparatus, certain vacuum residuum has been carried out conventional belt circulation delay coking experiment.Stock oil and turning oil prepare in the charging feedstock oil tank 1 by a certain percentage in advance.Thereafter process is with comparative example 1.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
Embodiment 1
As shown in Figure 3, on the medium-sized delayed coking unit that adopts delay coking process of the present invention, certain vacuum residuum has been carried out one way delayed coking experiment.Stock oil pumps in the process furnace 5 after the water vapor that pump 3 is extracted out and water vapor producer 6 produces mixes from material tank 1, and through pump 4 extractor pump entry Steam generating furnaces 6, the stock oil that the steam of generation and pump 3 come out mixes deionized water from water pot 2 simultaneously.The mixture of stock oil and water vapor is separated into two parts after process furnace 5 is heated to coking temperature, the 75 weight % that a part accounts for total feed enter coking tower from the top from coking tower 7 after divider disperses, the 25 weight % that another part accounts for total stuff amount enter coking tower from the bottom of coking tower 7, and these two strands of materials carry out cracking and condensation reaction in coking tower 7.Coking generates oil gas and flows out from the top of coking tower 7, after condenser 8 condensations, enter and generate oily receiving tank 9, uncooled gas through cold well 10 further condensation coolings after wet test meter measures post-sampling emptying.The coking that receiving tank 9 and cold well 10 are collected generates oil and obtain petroleum naphtha, intermediate oil, wax tailings after the distillation of FY-III type true boiling point device.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
Embodiment 2
As shown in Figure 3, on the medium-sized delayed coking unit that adopts delay coking process of the present invention, certain vacuum residuum has been carried out circulation delay coking experiment.Stock oil and turning oil prepare in the charging feedstock oil tank 1 by a certain percentage in advance.Thereafter process is still cut turning oil just with embodiment 1 when distillation.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
By table 1, table 2 and table 3 as seen, the density of stock oil is 990.9kg/m 3, carbon residue is 16.6%.Comparative example 1 is identical with the operational condition of embodiment 1, and comparative example 2 is identical with the operational condition of embodiment 2.After adopting technology of the present invention, pass through (recycle ratio is 0, embodiment 1 and comparative example 1) for one way, liquid yield has increased by 1.61 percentage points, and foam layer height has reduced by 19%; After adopting technology of the present invention, for circulation coking (recycle ratio is 0.3, embodiment 2 and comparative example 2), liquid yield has increased by 2.16 percentage points, and foam layer height has reduced by 18.9%.Table 4~8 have been listed the composition and the character of cooking gas, coking naphtha, coking intermediate oil, wax tailings and coke among each embodiment respectively.
Table 1 stock oil character
Density (20 ℃), kg/m 3 991.1
Carbon residue, % 16.8
Sulphur content, % 2.25
Stable hydrocarbon, % 17.1
Aromatic hydrocarbons, % 56.1
Colloid+bituminous matter 26.8
Table 2 operational condition
The pyrogenic reaction condition Embodiment 1 The comparative example 1 Embodiment 2 The comparative example 2
The furnace outlet temperature, ℃ 497 ?497 497 ?497
The coking column bottom temperature, ℃ 490 ?490 490 ?490
The coking tower top pressure, MPa 0.17 ?0.17 0.17 ?0.17
Water injection rate, % 2.1 ?2.1 2.1 ?2.1
Top inlet amount: underfeed amount 3∶1 ?- 3∶1 ?-
Recycle ratio 0 ?0 0.30 ?0.31
Table 3 product distributes
Project Embodiment 1 The comparative example 1 Embodiment 2 The comparative example 2
Gas 6.54 ?6.92 7.80 8.37
Petroleum naphtha (C5~180 ℃) 7.53 ?8.18 12.87 13.23
Intermediate oil (180~360 ℃) 24.91 ?26.41 30.39 31.09
Wax tailings 39.01 ?35.23 23.99 20.77
Coke 21.53 ?22.67 24.36 25.98
Loss 0.48 ?0.59 0.59 0.56
Liquid yield, % 71.45 ?69.82 67.25 65.09
Liquid is received to be increased, percentage point 1.63 2.16
Foam layer height, relatively 81 ?100 73 90
The composition of table 4 cooking gas
Component, m% Embodiment 1 The comparative example 1 Embodiment 2 The comparative example 2
H 2S H 2 C 1 0 C 2 0 C 2 C 3 0 C 3 i-C 4 0 n-C 4 0 n-C 4 i-C 4 t-C 4 c-C 4 C 4 == 8.69 0.56 24.84 18.65 3.15 17.64 9.60 1.50 8.37 0.99 2.89 1.69 1.23 0.20 100.00 ?8.90?0.70?25.91?18.48?3.15?17.58?8.42?1.70?8.54?0.78?3.02?1.61?1.06?0.15?100.00 8.95 0.70 26.79 19.61 3.28 17.11 8.21 1.54 8.63 0.57 2.26 1.47 0.78 0.10 100.00 ?9.01?0.72?28.93?20.18?3.32?15.46?7.71?1.65?7.86?0.62?2.39?1.26?0.85?0.04?100.00
Table 5 coking naphtha character
Project name Embodiment 1 The comparative example 1 Embodiment 2 The comparative example 2
Density (20 ℃), kg/m 3Acidity, the mgKOH/100ml sulphur content, μ g/g nitrogen content, μ g/g hydrocarbon system forms, m% stable hydrocarbon alkene aromatic hydrocarbons 738.3 3.84 4963 91 47.35 44.83 7.82 ?738.7?4.15?4900?85 46.53?45.20?8.27 738.9 3.67 4905 83 44.31 46.37 9.32 ?740.1?3.71?5211?77 42.02?48.16?9.82
Table 6 coking middle runnings oil nature
Analysis project Embodiment 1 The comparative example 1 Embodiment 2 The comparative example 2
Density (20 ℃), kg/m 3Acidity, mgKOH/100ml sulphur content, m% nitrogen content, μ g/g cetane index 854.8 4.05 1.16 1051 47 ?854.7?4.13?1.19?953?47 854.9 4.11 1.31 1010 47 ?855.1?3.78?1.26?987?46
Table 7 wax tailings character
Project name Embodiment 1 The comparative example 1 Embodiment 2 The comparative example 2
Density (20 ℃), kg/m 3Condensation point, ℃ acid number, mgKOH/g sulphur content, m% nitrogen content, μ g/g 934.4 29 0.05 1.91 4480 ?934.5?30?0.06?1.82?4364 934.7 30 0.05 1.81 4823 ?934.6?29?0.05?1.73?4390
Table 8 coke property
Project name Embodiment 1 The comparative example 1 Embodiment 2 The comparative example 2
Sulphur content, m% volatile matter, m% ash content, m% 2.85 8.91 0.81 ?2.79?8.88?0.78 2.93 9.17 0.71 2.79 9.26 0.69

Claims (5)

1. a delay coking process is characterized in that comprising the steps:
(a) stock oil mixes after process furnace is heated to 450~550 ℃ separately or with turning oil, and this temperature is the furnace outlet temperature;
(b) stock oil that comes from step (a) is divided into two portions, and a part enters coking tower from the top of coking tower or the side of coking tower; Another part enters coking tower from the bottom of coking tower; Wherein the inlet amount that enters coking tower from the top or the side of coking tower accounts for the 50 weight %~99.99 weight % of coking total feed, and the inlet amount that enters coking tower from the bottom of coking tower accounts for the 0.01 weight %~50 weight % of coking total feed;
(c) coking raw material from step (b) carries out thermally splitting and condensation reaction in coking tower;
(d) from step (b) and the coking that (c) produces generate oil gas and flow out from the coking tower top or near the side at top, enter coking fractional distillation column;
(e) from step (b) and the coke that (c) generates then stay in the coking tower;
(f) behind the green coke certain hour, charging is switched to the coking tower that has been ready to charging in addition, carry out decoking with conventional decoking and filled burnt coking tower; Decoking finish after seal, standby behind the conventional steps of warm tower; Circulation is switched between the coking tower, and process is able to continuously.
2. delay coking process according to claim 1, it is characterized in that in coking tower stock oil ingress install at least one feed distributor to from the coking tower top or the side stock oil that enters coking tower disperse.
3. delay coking process according to claim 1 and 2, it is characterized in that the ratio that the described inlet amount that enters coking tower from the top or the side of coking tower accounts for the coking total feed is 70 weight %~99.9 weight %, the ratio that the inlet amount that enters coking tower from the bottom of coking tower accounts for the coking total feed is 0.1 weight %~30 weight %.
4. delay coking process according to claim 1 and 2 is characterized in that described furnace outlet temperature is 480~520 ℃.
5. delay coking process according to claim 3 is characterized in that described furnace outlet temperature is 480~520 ℃.
CN2010101449024A 2010-04-13 2010-04-13 Process for delaying coking Pending CN102220165A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104164254A (en) * 2013-05-15 2014-11-26 中石化洛阳工程有限公司 Heavy oil processing process
CN104164253A (en) * 2013-05-15 2014-11-26 中石化洛阳工程有限公司 Heavy oil processing method
CN105586078A (en) * 2014-10-21 2016-05-18 中国石油化工股份有限公司 Heavy oil coking method
CN105586079A (en) * 2014-10-21 2016-05-18 中国石油化工股份有限公司 Heavy oil coking method
CN105623692A (en) * 2014-10-31 2016-06-01 中国石油化工股份有限公司 Method for preparing raw material for needle-like coke
CN105623691A (en) * 2014-10-31 2016-06-01 中国石油化工股份有限公司 Method for preparing raw material for needle-like coke
CN105623693A (en) * 2014-10-31 2016-06-01 中国石油化工股份有限公司 Method for preparing raw material for needle-like coke
CN110513669A (en) * 2019-08-23 2019-11-29 七台河宝泰隆新能源有限公司 A kind of steam generator heavy oil temperature regulating device
CN114540068A (en) * 2020-11-26 2022-05-27 中国石油天然气集团有限公司 Slurry treatment equipment

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Publication number Priority date Publication date Assignee Title
US4501654A (en) * 1983-11-17 1985-02-26 Exxon Research & Engineering Co. Delayed coking process with split fresh feed and top feeding
CN86102643A (en) * 1985-05-13 1986-11-12 东洋工程株式会社 The treating processes of heavy oil residue
CN101638585A (en) * 2009-06-25 2010-02-03 中国石油化工集团公司 Delayed coking method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4501654A (en) * 1983-11-17 1985-02-26 Exxon Research & Engineering Co. Delayed coking process with split fresh feed and top feeding
CN86102643A (en) * 1985-05-13 1986-11-12 东洋工程株式会社 The treating processes of heavy oil residue
CN101638585A (en) * 2009-06-25 2010-02-03 中国石油化工集团公司 Delayed coking method

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104164254A (en) * 2013-05-15 2014-11-26 中石化洛阳工程有限公司 Heavy oil processing process
CN104164253A (en) * 2013-05-15 2014-11-26 中石化洛阳工程有限公司 Heavy oil processing method
CN105586078A (en) * 2014-10-21 2016-05-18 中国石油化工股份有限公司 Heavy oil coking method
CN105586079A (en) * 2014-10-21 2016-05-18 中国石油化工股份有限公司 Heavy oil coking method
CN105586078B (en) * 2014-10-21 2017-11-03 中国石油化工股份有限公司 A kind of heavy oil coking method
CN105586079B (en) * 2014-10-21 2017-11-03 中国石油化工股份有限公司 A kind of heavy oil coking method
CN105623693A (en) * 2014-10-31 2016-06-01 中国石油化工股份有限公司 Method for preparing raw material for needle-like coke
CN105623691A (en) * 2014-10-31 2016-06-01 中国石油化工股份有限公司 Method for preparing raw material for needle-like coke
CN105623692A (en) * 2014-10-31 2016-06-01 中国石油化工股份有限公司 Method for preparing raw material for needle-like coke
CN105623693B (en) * 2014-10-31 2018-07-31 中国石油化工股份有限公司 A method of preparing needle-shape coke raw material
CN110513669A (en) * 2019-08-23 2019-11-29 七台河宝泰隆新能源有限公司 A kind of steam generator heavy oil temperature regulating device
CN110513669B (en) * 2019-08-23 2021-02-26 七台河宝泰隆新能源有限公司 Heavy oil temperature adjusting device of steam generator
CN114540068A (en) * 2020-11-26 2022-05-27 中国石油天然气集团有限公司 Slurry treatment equipment

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