CN1292044C - Method for complex optimum using oil shale - Google Patents

Method for complex optimum using oil shale Download PDF

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Publication number
CN1292044C
CN1292044C CN 200510024417 CN200510024417A CN1292044C CN 1292044 C CN1292044 C CN 1292044C CN 200510024417 CN200510024417 CN 200510024417 CN 200510024417 A CN200510024417 A CN 200510024417A CN 1292044 C CN1292044 C CN 1292044C
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shale
oil
oil shale
resinous
resinous shale
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CN1683472A (en
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姜秀民
于立军
韩向新
张超群
崔志刚
王辉
刘建国
任庚坡
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The present invention discloses a method for comprehensively utilizing oil shale in an optimization mode. Oil shale ores are crushed and sieved, wherein oil shale whose particle diameter of granules is approximately from 8mm to 80mm is conveyed into a dry distillation furnace for preparing shale oil and fuel gas. Generated oil shale semi coke waste is crushed into granule granules of less than 8mm, the oil shale semi coke waste and waste oil shale thin slag whose particle diameter is less than 8mm in the process of oil refining of the oil shale are mixed, and mixed material is formed. The mixed material is provided for a circulating fluidized bed boiler, and the circulating fluidized bed boiler is burnt. Heat generated through combustion is converted into steam, one part of steam is used as external working substances, and one part of steam drives a turbine to drive a generator to generate electricity. After the mixed material is burnt in a circulating fluidized bed, ash is generated, and the ash can be further used for preparing cement, ceramic aggregate and building blocks. The method leads oil shale resources to be comprehensively optimized and scientifically utilized, which opens up a novel path for economically, cleanly and reasonably utilizing the oil shale resources which have great storage capacity in a high efficiency mode.

Description

The resinous shale comprehensive utilization method
Technical field
The present invention relates to a kind of resinous shale comprehensive utilization method, can realize system oil, generating, the heat supply of oil shale resources, the omnibearing comprehensive utilization of building materials, belong to oil shale resources and utilize technical field.
Background technology
Resinous shale is a kind of important potential energy source, and reserves are huge, and its reserves are converted to that thermal value is only second to coal and second of row in fossil oil.If it is converted to shale oil, oil shale reserves in the world is about 4,750 hundred million tons, is equivalent to present world natural crude oil and verifies 5.4 times of workable reserve.The Application and Development of resinous shale has more than 200 year history, and the development and use of the resinous shale energy mainly are to produce shale oil.The refining process of shale oil normally adopts method for destructive distillation, and promptly resinous shale generation cracking generates shale oil gas under heating condition, and shale oil gas obtains shale oil (Chinese shale oil industry, petroleum industry press, 1984) through cooling.During the World War II, because the petroleum demand amount increases severely, oil price soars, and resinous shale exploitation upsurge had once been risen in many countries.And in peacetime after World War II, because cheap natural oil is found and a large amount of exploitation, oil price descends significantly, makes the oil shale industry of firm rise be in stagnant condition.In the later stage eighties, along with the surge of world energy sources consumption, many countries also are conceived to the development and application of various renewable energy sources or other substitute energy when energy expenditure is diversification, so formed the rise once more of oil shale industry.But, the single oil refining of resinous shale utilize mode because cost is higher, utilization of resources rate variance, the ballistic ability of anti-market economy is difficult to sustainable development.Resinous shale acts as a fuel direct direct burning in grate furnace and chamber burner and produces heat energy is another approach (Soviet Union's fuel oil shale station boiler of resinous shale energy utilization, the electric comment in east, nineteen ninety, the 1st phase, 44~51 pages), this technology is refined the intermediate conversion links of shale oil owing to having omitted, and its energy utilization rate is improved.But because have that coking in the burner hearth, radiation heating surface metallic corrosion are serious, convection heating surface dust stratification, heat loss due to combustibles in refuse are big, be difficult to use problem such as low heat value resinous shale, are difficult to development.The bubbling fluidized bed burning of resinous shale (the fluidized bed process. Chinese industrial press, nineteen sixty-five, 175~214 pages) realized the low-temperature burning of resinous shale, solved effectively that coking in the stove that grate furnace and chamber burner oil shale combustion bring, radiation heating surface metallic corrosion are serious, the convection heating surface dust stratification, be difficult to use problem such as low heat value resinous shale, but had the problem that unburned carbon in flue dust is higher and be difficult to maximize.The resinous shale circulating fluidized bed combustion has solved the problem that resinous shale comes out in grate furnace and chamber burner and bubbling fluidized bed combustion processes, be the effective means utilized of oil shale combustion (the exemplary resinous shale circulating fluidized bed of 65t/h boiler of power plant operation practice. Proceedings of the CSEE, calendar year 2001, the 2nd phase, 69~73 pages), but problem is to fail to realize the reasonable economical and efficient utilization of optimization of oil shale resources.
Summary of the invention
The objective of the invention is to utilize the deficiency of technical matters at existing oil shale resources, a kind of resinous shale comprehensive utilization method is proposed, take all factors into consideration resource, environment, economy and society benefit, realize the scientific utilization oil shale resources,, economically and reasonably comprehensive utilization efficient, clean for resinous shale provides effective way.
For realizing such purpose, the present invention is broken and screening with oil shale ore, wherein the resinous shale that grain diameter is bigger is sent into gas retort and is produced shale oil and combustion gas, the petroliferous shale carbocoal waste products that is generated after fragmentation with the oil shale oil-refining process in the thin slag of resinous shale of depleted small size particle mix the formation mixture, supply with burning in circulating fluid bed boiler, the heat that burning produces is converted into steam, and a part is as extral supporting medium, and a part of driving steam turbine drives generator for electricity generation.The lime-ash that mixture produces after circulating fluidized bed combustion further is used for producing cement, haydite and building block.
Concrete technology of the present invention is: will refine grain graininess that shale oil uses less than the resinous shale of 80mm through fragmentation and sieve apparatus, grain graininess wherein sent into from top with transfer roller greater than the resinous shale of 8mm carry out destructive distillation the vertical carbonization furnace, the needed heat of destructive distillation is from process furnace, be advisable for the pyrolysis temperature 450-550 of carbonization furnace ℃, the shale oil gas that destructive distillation produces is discharged by furnace roof and is entered shale oil air cooling radiator cooler, send into shale oil and flying dust and combustion gas tripping device again through refrigerative shale oil gas, tripping device is separated into shale oil with shale oil gas, combustion gas and flying dust, store respectively then, be used.The oil shale semi-coke that produces after the oil shale distillation is discharged through vertical carbonization furnace bottom, is cooled to about 100 ℃ through the dry cold radiator cooler, is cooled to envrionment temperature again in air.Oil shale semi-coke is broken into less than mixing with the thin slag screen underflow of resinous shale of granularity less than 8mm behind the particle of 8mm, as the fuel of supplying with circular fluid bed.Greater than 45%, the as received basis net calorific value of mixture is about 3449.4kJ/kg~14653.8kJ/kg to grain diameter less than the granular mass share of 3mm in the thin slag mixture of oil shale semi-coke and resinous shale.Mixture is sent in the circular fluid bed of heating oil shale semicockes and the thin slag mixture of resinous shale and burnt, the temperature of combustion of the thin slag mixture of oil shale semi-coke and resinous shale in circulating fluidized bed is about 850-1000 ℃, belong to low-temperature burning, so that keep cindery activity, effectively controlled heating power type NO simultaneously xFormation and avoid coking in the stove.In the circulating fluidized bed combustion process, the mass content according to the sulphur of propellant combination adds Wingdale in the propellant combination, and as desulfurization vehicle, Wingdale is calcined under operating temperature and generated CaO, the SO in CaO and the flue gas 2Reaction further generates CaSO 4, suppress SO 2Discharging, and the operating temperature of combustion unit is the optimum operation humidity province of CaO desulfurization, therefore can obtain high desulfuration efficiency, thereby has realized the purpose of the propellant combination high-efficiency low-pollution cleanburning of the thin slag composition of oil shale semi-coke and resinous shale.The addition of Wingdale look oil shale semi-coke and the thin slag propellant combination of resinous shale sulphur mass content and determine that make to add that to make the mol ratio of calcium sulphur in the propellant combination behind the Wingdale be 2~3, desulfuration efficiency can reach 90%~98%.The heat that burning is produced is used for producing thermal medium steam, and portion of hot media steam is sent into steam working medium collection case and is used for producing and heat supply, and all the other thermal medium steam are delivered to power generation assembly, and the heat energy of steam changes kinetic energy into by steam turbine, drives generator for electricity generation.The lime-ash that generates after the thin slag mixture of oil shale semi-coke and resinous shale burns in circulating fluidized bed, a part is an end slag, after the slag water cooler is cooled to 100 ℃ at the end, sends into cinder tank.Rest part is a flying dust, and flying dust is carried by flue gas and enters fly-ash separator, after fly-ash separator separates seizure flying dust is sent into cinder tank.A part of lime-ash of cinder tank is transported to the haydite production equipment produces haydite, another part is transported to cement production device and is used for producing cement, and rest part is transported to the building block production equipment and is used for the production building block.Thereby realized the science integration optimization utilization of oil shale resources.
Advantage of the present invention is: (1) has realized system oil, generating, the heat supply of oil shale resources, the omnibearing complex optimum utilization of building materials, and the scientific utilization resource has high economy, society and environmental benefit; (2) resinous shale is refined semicoke waste that depleted grain diameter in the shale oil process produces less than thin slag and the resinous shale refining shale oil process of 8mm fuel, realized the changing rejected material to useful resource efficient clean utilization in the oil shale oil-refining process as circulating fluidized bed; (3) adopt the dry and cold technology of oil shale semi-coke to make the oil shale semi-coke of discharging from vertical gas retort be cooled to 100 ℃, the oil shale semi-coke that the oil shale semi-coke water content increase of having avoided the semicoke water-cooling process to cause causes effectively utilizes the reduction of heat; (4) utilize Wingdale in the mixture combustion processes direct desulfurization, desulphurization system is simple, cost is low, desulfuration efficiency is high; (5) temperature of combustion of the thin slag mixture of oil shale semi-coke and resinous shale in circulating fluidized bed is about 850-1000 ℃, and the chamber temperature field is even, belongs to low-temperature burning, effectively controlled generation and the discharging of heating power NOx, helps keeping cindery activity simultaneously; (6) adopt Combustion technology of circulating fluidized so to use oil shale semi-coke and the thin slag mixture of resinous shale, improved efficiency of combustion, improved the utilization ratio of Wingdale simultaneously, reduced the magnitude of recruitment of medium materials.(7) resinous shale is refined the semicoke changing rejected material to useful resource clean utilization that generates in the process of depleted grain diameter in the process of shale oil, reduced the semicoke waste pollution on the environment that generates in the process of production cost in the oil shale oil-refining process and thin slag of resinous shale and resinous shale refining shale oil significantly less than the thin slag of resinous shale of 8mm and resinous shale refining shale oil.
The present invention has realized the complex optimum utilization of oil shale resources, and the scientific utilization resource has high economy, society and environmental benefit, can be applicable at resinous shale with storing up.
Description of drawings
System device and process flow diagram that Fig. 1 relates to for the inventive method.
Among Fig. 1,1 is the resinous shale hopper, 2 are fragmentation and sieve apparatus, 3 is the thin slag waste of screen underflow resinous shale hopper, 4 is that grain diameter is greater than 8mm resinous shale hopper, 5 is vertical carbonization furnace, 6 is the dry cold radiator cooler, 7 is the oil shale semi-coke storehouse, 8 is process furnace, 9 is oil shale semi-coke and the thin slag mixture of resinous shale warehouse, 10 is the Wingdale hopper, 11 is heating oil shale semicockes and the thin slag mixture of resinous shale circular fluid bed, 12 is shale oil air cooling radiator cooler, 13 is shale oil and flying dust and combustion gas tripping device, 14 is the flying dust storehouse, 15 is end slag water cooler, 16 is slag ash storehouse, the end, 17 is fly-ash separator, 18 is cinder tank, 19 are the combustion gas storage tank, 20 is the shale oil storage tank, 21 is power generation assembly, 22 is the haydite production equipment, 23 is cement production device, 24 are the building block production equipment, 25 is steam working medium collection case.
Embodiment
Below in conjunction with accompanying drawing technical matters of the present invention is further described.
Fig. 1 is a technical matters of the present invention.As shown in Figure 1, the grain graininess that the refining shale oil is used is that 0~80mm resinous shale is sent into resinous shale hopper 1, with sieve apparatus 2 grain graininess is sent into the thin slag waste of resinous shale hopper 3 less than the thin slag screen underflow of resinous shale of 8mm through broken, grain graininess is sent into resinous shale hopper 4 greater than the resinous shale of 8mm, transfer roller is sent into vertical carbonization furnace 5 with grain graininess greater than the resinous shale of 8mm and is carried out destructive distillation from the top, be advisable for the pyrolysis temperature 450-550 of carbonization furnace ℃, the needed heat of destructive distillation is from process furnace 8, the required combustion gas of process furnace is from shale oil and flying dust and combustion gas tripping device 13, the shale oil gas that destructive distillation produces is discharged by the furnace roof of carbonization furnace 5 and is entered shale oil air cooling radiator cooler 12, go into shale oil and flying dust and combustion gas tripping device 13 through refrigerative shale oil pneumatic transmission, by shale oil and flying dust and combustion gas tripping device 13 refrigerative shale oil gas is separated into shale oil, combustion gas and flying dust, shale oil is sent into shale oil storage tank 20, combustion gas storage tank 19 is sent in combustion gas, flying dust is sent into flying dust storehouse 14, be used respectively then.The oil shale semi-coke that resinous shale produces after shale oil is produced in destructive distillation is discharged by vertical carbonization furnace 5 bottoms, be cooled to through dry cold radiator cooler 6 and send into oil shale semi-coke storehouse 7 about 100 ℃, mix with the material of the thin slag waste of resinous shale hopper 3 after the material in oil shale semi-coke storehouse 7 is broken into particle below the 8mm, in the thin slag mixture of oil shale semi-coke and resinous shale grain diameter less than the granular mass share of 3mm greater than 45%, the as received basis net calorific value of mixture is 3449.4kJ/kg~14653.8kJ/kg, and mixture is sent into oil shale semi-coke and 9 storages of the thin slag mixture of resinous shale warehouse.During operation mixture is sent in the circular fluid bed 11 of the thin slag mixture of heating oil shale semicockes and resinous shale and burnt, the temperature of combustion of the thin slag mixture of oil shale semi-coke and resinous shale in circulating fluidized bed is about 850-1000 ℃, belong to low-temperature burning, keep the generation of cindery activity and inhibition heating power type nitrogen oxide.In the circulating fluidized bed combustion process, mass content according to the sulphur of propellant combination adds Wingdale in the propellant combination, as desulfurization vehicle, the mol ratio of calcium sulphur is 2~3 in the mixture that thin slag of its oil shale semi-coke and resinous shale and Wingdale constitute, and desulfuration efficiency is about 90%~98%.The required Wingdale of desulfurization comes from Wingdale hopper 10 in the combustion processes, the heat that burning is produced is used for producing thermal medium steam, portion of hot media steam is sent into steam working medium collection case 25, all the other thermal medium steam are delivered to power generation assembly 21, the heat energy of steam changes kinetic energy into by steam turbine, drives generator for electricity generation.The lime-ash that generates after the thin slag mixture of oil shale semi-coke and resinous shale burns in circulating fluidized bed, a part is an end slag, after end slag water cooler 15 is cooled to 100 ℃, sends into slag ash storehouse 16, the end, then sends into cinder tank 18.Rest part is that flying dust is carried by flue gas and enters fly-ash separator 17, separates through fly-ash separator and flying dust is sent into cinder tank 18 after catching.A part of lime-ash of cinder tank is transported to haydite production equipment 22 is used for producing haydite, another part is transported to cement production device 23 and is used for producing cement, and rest part is transported to building block production equipment 24 and is used for the production building block.Thereby realized the science integration optimization utilization of oil shale resources.

Claims (3)

1. resinous shale comprehensive utilization method, it is characterized in that grain graininess less than the resinous shale of 80mm through broken and sieve apparatus (2), grain graininess wherein sent in the vertical carbonization furnace (5) greater than the resinous shale of 8mm carry out destructive distillation, pyrolysis temperature 450-550 ℃, the shale oil gas that destructive distillation produces enters shale oil air cooling radiator cooler (12), send into shale oil and flying dust and combustion gas tripping device (13) again through refrigerative shale oil gas, shale oil gas is separated into shale oil, combustion gas and flying dust, and storage is used respectively; Produce the oil shale semi-coke of discharging after the oil shale distillation and be cooled to 100 ℃ through dry cold radiator cooler (6), be broken into again less than mixing with the thin slag of resinous shale of granularity behind the particle of 8mm less than 8mm, constitute mixture, mixture sent in the circular fluid bed (11) burn, temperature of combustion is 850-1000 ℃, adding Wingdale in the combustion processes, to make the mol ratio of calcium sulphur in the propellant combination be 2~3, the heat that burning is produced is used for producing thermal medium steam, portion of hot media steam is sent into steam working medium collection case (25) and is used for producing and heat supply, and all the other thermal medium steam are delivered to power generation assembly (21); The lime-ash that generates after the thin slag mixture of oil shale semi-coke and resinous shale burns in circulating fluidized bed, a part is an end slag, be cooled to 100 ℃ after cinder tank (18) is sent in end slag ash storehouse (16) through end slag water cooler (15), all the other flying dusts are carried by flue gas and enter fly-ash separator (17), after separating seizure, fly-ash separator sends into cinder tank (18), a part of lime-ash of cinder tank is transported to haydite production equipment (22) produces haydite, another part is transported to cement production device (23) and is used for producing cement, and rest part is transported to building block production equipment (24) and is used for the production building block.
2, according to the resinous shale comprehensive utilization method of claim 1, the as received basis net calorific value that it is characterized in that the thin slag mixture of described oil shale semi-coke and resinous shale is 3449.4kJ/kg~14653.8kJ/kg.
3, according to the resinous shale comprehensive utilization method of claim 1, it is characterized in that grain diameter in the thin slag mixture of described oil shale semi-coke and resinous shale less than the granular mass share of 3mm greater than 45%.
CN 200510024417 2005-03-17 2005-03-17 Method for complex optimum using oil shale Expired - Fee Related CN1292044C (en)

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Cited By (1)

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CN107488476A (en) * 2017-08-10 2017-12-19 新奥泛能网络科技股份有限公司 The method and fuel of combusting oil shale semicoke

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CN100391891C (en) * 2006-06-13 2008-06-04 中国地质大学(武汉) Haydite prepared from dregs of oil shale, and preparation method
CN101240180A (en) * 2008-03-03 2008-08-13 江西江联能源环保股份有限公司 Oil shale oil-refining, power generation and cement triple production integrated device
CN101434847B (en) * 2008-03-10 2011-12-07 中国重型机械研究院 Oil shale retort oil extraction process
CN101440293B (en) * 2008-12-11 2012-06-27 上海交通大学 Oil shale fluidized bed dry distillation system
CN101817671B (en) * 2010-02-09 2012-07-11 广州建材企业集团有限公司 Method for burning fly ash by utilizing refuse in ceramsite production
CN101818073B (en) * 2010-05-21 2012-11-28 上海交通大学 Dry distillation and semicoke incineration integrated system for oil shale
CN102295941B (en) * 2011-07-29 2013-09-11 上海交通大学 Combined system of oil shale bubble column dry distillation and semicoke circulating fluidized bed combustion
CN102585864B (en) * 2012-03-20 2013-07-31 东北石油大学 Oil shale surface retorting and power plant boiler and steam turbine exhaust comprehensive recycling process
CN102585865B (en) * 2012-03-20 2013-07-31 东北石油大学 Cogeneration integrated system for dry distillation and power generation on oil shale in-situ mining ground
CN102690666B (en) * 2012-06-08 2014-04-16 上海交通大学 Gas-solid combined type heat-carrying oil shale fluidized bed dry distilling system
EP3055404A1 (en) * 2013-10-11 2016-08-17 Investment for Oily Shale Technologies Co. Ltd. High range temperature thermal dismantling method in processing oil shale
CN103923677A (en) * 2014-04-18 2014-07-16 上海交通大学 System and process for comprehensive utilization of oil shale destructive distillation and semicoke gasification
CN105176552A (en) * 2015-09-30 2015-12-23 东北电力大学 Novel gas heat carrier retorting and gas power generation integrated device and technology
CN105731998A (en) * 2016-01-15 2016-07-06 陕西省能源化工研究院 Light ceramsite prepared from oil shale semi-coke and preparation method thereof
CN106607183B (en) * 2017-02-09 2019-11-08 中国矿业大学 A kind of modular high-density coal measures oil shale process for upgrading and upgrading system
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CN114477807A (en) * 2022-04-03 2022-05-13 润鑫(杭州)新材料科技有限公司 Method for recycling oil shale slag and calcining device thereof
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