CN106336928A - Method for vacuum reinforced desulfurization of high sulfur petroleum coke - Google Patents

Method for vacuum reinforced desulfurization of high sulfur petroleum coke Download PDF

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Publication number
CN106336928A
CN106336928A CN201610882719.1A CN201610882719A CN106336928A CN 106336928 A CN106336928 A CN 106336928A CN 201610882719 A CN201610882719 A CN 201610882719A CN 106336928 A CN106336928 A CN 106336928A
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China
Prior art keywords
petroleum coke
desulfurization
sulfur
vacuum
coke
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CN201610882719.1A
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Chinese (zh)
Inventor
马文会
陈正杰
魏奎先
伍继君
李绍元
秦博
雷云
谢克强
杨斌
戴永年
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Priority to CN201610882719.1A priority Critical patent/CN106336928A/en
Publication of CN106336928A publication Critical patent/CN106336928A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/08Treating solid fuels to improve their combustion by heat treatments, e.g. calcining

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Industrial Gases (AREA)

Abstract

The invention relates to a method for vacuum reinforced desulfurization of high sulfur petroleum coke and belongs to the technical field of vacuum metallurgy. First petroleum coke is ground and screened to the granularity of 45-450 [mu]m, and the thickness is controlled to be 10-100 mm; under the vacuum degree of 10<-3>Pa to 100 Pa, the temperature rises to 1000-1600 DEG C at a heating rate of 10-50 DEG C and preserving heat for 10-90 min, the petroleum coke desulfurization efficiency reaches 70% or above, and elemental sulfur with a purity of 90% or above is collected in a condensation device at the top. According to the method, a low ash content of the petroleum coke is guaranteed without adding of an additive while a high desulfurization rate is achieved, it is also guaranteed that the petroleum coke has a high recovery rate after being desulfurized, the elemental sulfur can further be obtained in the process, and the problem that plenty of harmful SO2 gas unfavorable for collection is generated according to most of petroleum coke desulfurization methods is solved.

Description

A kind of method that vacuum strengthens high sulfur petroleum coke desulfurization
Technical field
The present invention relates to a kind of method that vacuum strengthens high sulfur petroleum coke desulfurization, belong to vacuum metallurgy technology field.
Background technology
Petroleum coke belongs to one kind and is easy to graphitized carbon material, thus being widely used in the industry such as metallurgy, chemical industry as graphite Electrode.In addition, petroleum coke is higher because of fixing carbon content, volatile matter content is relatively low, and combustion heat value is higher, thus being widely used In smelting industrial silicon with compound carbonaceous reductant (mass ratio is more than 30%), during smelting industrial silicon, you can to pass through Burning provides substantial amounts of heat, and its higher fixed carbon is the primary reducing agent of silicon dioxide carbon thermal reduction again.But petroleum coke exists Higher sulfur content in combustion process, especially petroleum coke (petroleum coke sulfur content even as high as more than 8%) will produce substantial amounts of so2Harmful gass, thus polluting environment, and also can have a strong impact on mineral hot furnace fortune in smelting industrial silicon process because sulfur content is higher The stability of row, and then affect the quality of silicon product.Generally, according to sulfur in petroleum coke content height, petroleum coke can be divided into height Sulfur burnt (sulfur content is higher than 4%), middle sulfur Jiao (sulfur content 2%~4%) and low-sulfur burnt (sulfur content is less than 2%).With petroleum A large amount of exploit, the quality of petroleum declines continuous, and petroleum coke is as one of the principal by product of petroleum refining process, its Middle impurities increase also with impurity content in refinery feedstock and increase, especially wherein sulfur content, so high-sulfur in recent years The yield of petroleum coke gets more and more.Entirely different for the different petroleum coke price of sulfur content, petroleum coke sulfur content is low one hundred Branch, cost will rise hundreds of yuan.So high for a kind of desulfurization degree of high sulfur petroleum coke research invention, cost is relatively low, work Skill is simple, it is easy to accomplish sulfur in petroleum coke content is metallurgical to China and its health of chemical industry every profession and trade to reduce for industrialized method Development is very important.
For this reason, reporting a lot of methods with regard to desulfurizing petrol coke both at home and abroad.High-temperature calcination is the conventional of desulfurizing petrol coke Method, when calcining heat is less than 1000 DEG C, sulfur in petroleum coke will not remove substantially, even if calcining petroleum coke temperature reaches 1400 DEG C, the desulfurization degree of petroleum coke also can only achieve 70% about, raises with calcining heat, and desulfurization degree is in increase, but this desulfurization Technology not only needs to put into very big energy source and power expense, and in calcination process due to so producing2Gas content is relatively low and sharp In collection, if it is directly discharged environment will be brought with serious pollution." ionic liquid is used for the de- of petroleum coke to patent of invention Sulfur method " (application number cn200710064515.8) is related to a kind of method of removing sulfur in petroleum coke, by using alkali ion For adjuvant, it is added in petroleum coke and so that petroleum coke structure is changed, be conducive to sulfur in petroleum coke to remove, but the method is in stone With the addition of additive in oil coke will increase content of ashes in petroleum coke, and desulfurization degree is not high.Belong to ionic liquid its from Son belongs to a kind of patent of invention " method of removing sulfur in petroleum coke and its desulfurizing agent " (application number of acid ion Cn201010153531.6 report in) by the use of mixed acid as desulfurizing agent, directly sulfur content is placed in 3~7% petroleum coke Soak in desulfurizing agent, be then peeled off washing, 45~60%, the method will produce substantial amounts of discarded acid solution to desulfurizing petrol coke rate, And production process is more complicated, so the cost of desulfurizing petrol coke can be improved.Patent of invention " refinery coke desulfurating epuration method and Industrial furnace " (patent No.: 98114600.7) report a kind of sulfur method, first by petroleum coke in 600~1200 DEG C of temperature calcination, Again petroleum coke is placed in temperature in electric furnace to calcine at 1700~2300 DEG C, finally can obtain the low sulfur petroleum that sulfur content is 0.1% Jiao, this technology desulfurization degree is higher, but production process is excessively complicated, and requires temperature very high, thus cost is higher, and upper State and there is same, so of generation2Harmful gass are unfavorable for collecting.Patent of invention " petroleum coke gasification hydrogen-producing coupled desulfurization Method " (application number cn200710064514.3) reports a kind of desulfurizing petrol coke technology, and this technology is hydrodesulfurization, can obtain To low-sulfur content petroleum coke, in this sulfur method, need to be passed through hydrogen, hydrogen brings a lot of potential safety hazards to production process, no Beneficial to industrialized production.And the United States Patent (USP) " us3598528a " with same problem proposes first to carry out preheating, in advance by petroleum coke Oxidation, is allowed to gasify, thus changing the structure of petroleum coke particles, then again the petroleum coke after processing is placed in hydrogenation anti- Answer in device, the hydrogen being introduced in gasification reactor carries out the desulfurization of petroleum coke, this desulfurization technology belongs to hydrodesulfurization technology, skill Art operation is equally complicated.
Content of the invention
For the desulfurization inventive technique of above-mentioned domestic and international petroleum coke, there is high cost, technics comparing in the high technology of desulfurization degree Complicated;And the desulfurization technology of low cost, desulfurization degree is not high, and the present invention provides a kind of vacuum to strengthen the side of high sulfur petroleum coke desulfurization Method.While the method can reach compared with high desulfurization rate, not outer doping ensures the relatively low ash content of petroleum coke, also ensure that There is after desulfurizing petrol coke the higher response rate, elemental sulfur can also be obtained in the process, solve because of most desulfurizing petrol cokes Method produces so being unfavorable in a large number collecting2Harmful gass, the present invention is achieved through the following technical solutions.
A kind of method that vacuum strengthens high sulfur petroleum coke desulfurization, it specifically comprises the following steps that and first petroleum coke is ground screening To 45~450 μm of granularity, control thickness is 10~100mm, is 10 in vacuum-3Under the conditions of pa~100pa, with 10~50 ° of c/ The heating rate of min is warmed up to 1000~1600 ° of c and is incubated 10~90min, collects purity in the condensing plant at top simultaneously More than 90% elemental sulfur.
Described high sulfur petroleum coke sulfur content > 4%.
Above-mentioned desulfurizing petrol coke rate reaches more than 70%.
The invention has the beneficial effects as follows:
(1) petroleum coke of the method for the invention sulfur content up to more than 4% carries out simple desulfurization process, and desulfurization degree can reach More than 70%, due to carrying out desulfurization process under oxygen lean conditions, petroleum coke ablating rate ratio is relatively low, and yield is more than 75%;
(2) desulfurizing petrol coke method of the present invention can avoid because petroleum coke produces in combustion, environment being had seriously So of pollution2The discharge of gas, and the chemical productss sulphur simple substance of another high purity more than 90% can be obtained;
(3) petroleum coke process for deep desulphurization desulfurization degree of the present invention is higher, process is simple, and production procedure is comparatively short, cost Relatively low, it is easy to accomplish industrialization.
Brief description
Fig. 1 is present invention process flow chart.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
The method that this vacuum strengthens desulfurizing petrol coke, it specifically comprises the following steps that first by high sulfur petroleum coke (from Yunnan silicon industry Company, petroleum coke sulfur content is in 8.21wt%) grind and be sized to granularity 350 ~ 450 m, controls thickness is 10mm, in vacuum is Under the conditions of 100pa, 1600 ° of c insulation 10min are warmed up to the heating rate of 10 ° of c/min, prepare desulfurization petroleum coke, simultaneously The elemental sulfur of purity more than 90% is collected in the condensing plant at top.
Above-mentioned desulfurization desulfurizing petrol coke rate is 80.02%.
Embodiment 2
The method that this vacuum strengthens high sulfur petroleum coke desulfurization, it specifically comprises the following steps that first by high sulfur petroleum coke (from Yunnan Gui Ye company, petroleum coke sulfur content is in 8.21wt%) grind and be sized to granularity 250 ~ 350 m, controls thickness is 30mm, in vacuum Under the conditions of spending for 1.0pa, 1400 ° of c insulation 30min are warmed up to the heating rate of 20 ° of c/min, prepare desulfurization petroleum coke, Collect the elemental sulfur of purity more than 92% in the condensing plant at top simultaneously.
Above-mentioned desulfurization desulfurizing petrol coke rate is 75.3%.
Embodiment 3
The method that this vacuum strengthens high sulfur petroleum coke desulfurization, it specifically comprises the following steps that first by high sulfur petroleum coke (from Yunnan Gui Ye company, petroleum coke sulfur content is in 8.21wt%) grind and be sized to granularity 150 ~ 250 m, controls thickness is 50mm, in vacuum Spend for 10-1Under the conditions of pa, 1300 ° of c insulation 50min are warmed up to the heating rate of 30 ° of c/min, prepare desulfurization petroleum coke, Collect the elemental sulfur of purity more than 91.2% in the condensing plant at top simultaneously.
Above-mentioned desulfurization desulfurizing petrol coke rate is 76.5%.
Embodiment 4
The method that this vacuum strengthens high sulfur petroleum coke desulfurization, it specifically comprises the following steps that first by high sulfur petroleum coke (from Yunnan Gui Ye company, petroleum coke sulfur content is in 8.21wt%) grind and be sized to granularity 50 ~ 100 m, controls thickness is 100mm, in vacuum Spend for 10-3Under the conditions of pa, 1000 ° of c insulation 90min are warmed up to the heating rate of 50 ° of c/min, prepare desulfurization petroleum coke, Collect the elemental sulfur of purity more than 90.3% in the condensing plant at top simultaneously.
Above-mentioned desulfurization desulfurizing petrol coke rate is 70.54%.
Above the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party Formula, in the ken that those of ordinary skill in the art possess, can also make on the premise of without departing from present inventive concept Go out various change.

Claims (2)

1. petroleum coke is ground first by a kind of method of vacuum strengthening high sulfur petroleum coke desulfurization it is characterised in that specifically comprising the following steps that Mill is sized to 45~450 μm of granularity, and control thickness is 10~100mm, is 10 in vacuum-3Under the conditions of pa~100pa, with 10~ The heating rate of 50 ° of c/min is warmed up to 1000~1600 ° of c and is incubated 10~90min, collects in the condensing plant at top simultaneously Elemental sulfur to purity more than 90%.
2. vacuum according to claim 1 strengthen high sulfur petroleum coke desulfurization method it is characterised in that: described high-sulfur oil Burnt sulfur content > 4%.
CN201610882719.1A 2016-10-10 2016-10-10 Method for vacuum reinforced desulfurization of high sulfur petroleum coke Pending CN106336928A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197742A (en) * 2022-07-18 2022-10-18 昆明理工大学 Method for desulfurizing petroleum coke by vacuum strengthening additive

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2561921A1 (en) * 2011-08-23 2013-02-27 Haldor Topsøe A/S Process for removal of NOx and SO2 in flue gas boilers
CN102976309A (en) * 2012-12-14 2013-03-20 中国铝业股份有限公司 Method for producing calcined coke
CN103086347A (en) * 2011-10-31 2013-05-08 东北大学 Method for removing sulfur components in petroleum coke through using sodium hydroxide/potassium carbonate melting process
CN104651011A (en) * 2015-02-05 2015-05-27 昆明理工大学 Method for catalyzing deep desulfurization of high sulfur petroleum coke by using alkali carbonate
CN105603216A (en) * 2016-02-25 2016-05-25 沈阳北冶冶金科技有限公司 Aluminum industry solid waste recovery/petroleum coke high-temperature desulphurization device and using method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2561921A1 (en) * 2011-08-23 2013-02-27 Haldor Topsøe A/S Process for removal of NOx and SO2 in flue gas boilers
CN103086347A (en) * 2011-10-31 2013-05-08 东北大学 Method for removing sulfur components in petroleum coke through using sodium hydroxide/potassium carbonate melting process
CN102976309A (en) * 2012-12-14 2013-03-20 中国铝业股份有限公司 Method for producing calcined coke
CN104651011A (en) * 2015-02-05 2015-05-27 昆明理工大学 Method for catalyzing deep desulfurization of high sulfur petroleum coke by using alkali carbonate
CN105603216A (en) * 2016-02-25 2016-05-25 沈阳北冶冶金科技有限公司 Aluminum industry solid waste recovery/petroleum coke high-temperature desulphurization device and using method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197742A (en) * 2022-07-18 2022-10-18 昆明理工大学 Method for desulfurizing petroleum coke by vacuum strengthening additive

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