CN203938647U - The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system - Google Patents
The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system Download PDFInfo
- Publication number
- CN203938647U CN203938647U CN201420310615.XU CN201420310615U CN203938647U CN 203938647 U CN203938647 U CN 203938647U CN 201420310615 U CN201420310615 U CN 201420310615U CN 203938647 U CN203938647 U CN 203938647U
- Authority
- CN
- China
- Prior art keywords
- gas
- shale
- oil
- pipeline
- outlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn - After Issue
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The utility model discloses the integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system.Described system comprises the oil shale distillation unit, shale oil gas separating unit, hydrogenation of shale oil upgrading unit and the separator that connect successively, also comprises roasting kiln, coal supercritical water gasification unit, interchanger, hydrogen purification unit and production of construction materials unit.The utility model provides heat by chip shale discarded oil shale distillation unit and unnecessary residual gas for coal supercritical water gasification reacts, the coal resources that maintain coal supercritical water gasification reaction consumption higher thermal value and high economic worth are saved, and the brown coal of the integrated use shale ore of energy association are produced the hydrogen of high economic worth, have also improved the economic benefit of process when having optimized resource distribution.
Description
Technical field
The utility model belongs to the energy and chemical technology field, is specifically related to the integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system.
Background technology
Along with Chinese society and rapid economic development, energy demand is increased day by day.For reducing the dependence to Imported oil, the energy strategy that China just actively implements diversification continues supply to ensure the energy.Resinous shale is a kind of sedimentogeneous rock, has the skeleton of inorganic mineral, and contains SOLID ORGANIC matter, is low heat value solid fossil fuel.China's oil shale resources are very abundant, and reserves reach 7,199 hundred million tons, amount to into destructive distillation oil product and are equivalent to 47,600,000,000 tons, far above 2,200,000,000 tons of crude oil proven reserve.China not only oil shale reserves is abundant, and buries more shallowly, is all conducive to the exploitation of oil shale resources.Greatly develop oil shale oil-refining technology and be conducive to alleviate China's oil resource supply and demand contradiction, provide practicable approach for realizing energy diversification.
The domestic technology of utilizing to resinous shale is mainly destructive distillation oil refining technology at present.The resinous shale obtaining by underground mining or strip mining transformation, through broken, screening, under the condition of isolated air, is heated to certain temperature range, and a series of physical-chemical reaction occurs, and finally generates shale oil, coal gas and semicoke etc.This technology is seldom used to broken shale and the higher solid waste such as semicoke and lime-ash of calorific value.This has just caused a large amount of wastes of Energy resources and the problem such as economic benefit is poor.For example, after oil shale pyrolysis oil refining or burning, forming a large amount of lime-ash (accounting for the 60-80% of oil shale processes amount) piles up and takies a large amount of soils nearby; Water for a long time pouring through rainwater, the many objectionable impuritiess that retain in lime-ash enter water system and soil with rainwater, cause its severe contamination direct influence ecological environment; The a lot of thin dirt containing in lime-ash, enters atmospheric environment, causes PM to pollute, and affects the healthy of resident.
How further to improve oil shale oil-refining process economy performance, become " bottleneck " of resinous shale processing industry.The shale oil that oil shale distillation at present obtains is mainly used in the low side primary fuels such as boiler oil, contain the non-hydrocarbons organic compound such as more unsaturated hydro carbons and sulphur, nitrogen, oxygen, these impurity very easily cause colloid in oil to become many, reduce oily stability, impurity burning simultaneously also can produce a large amount of obnoxious flavour contaminate environment.Therefore shale oil needs deep processing to remove impurity, as generated oil fuel and other chemical.To hydrogenation of shale oil processing be one compared with mature technology, day by day come into one's own containing the oil-shale eduction process of hydrogenation upgrading.The schematic diagram of this process as shown in Figure 1.But this process one-time investment is large, required equipment expense and process cost are also very high, have caused domestic deep processing of shale oil rate very low.In addition, hydrogen market value is higher at present, if adopt outsourcing hydrogen as hydrogen source, can improve undoubtedly the production cost of process, reduces the economic benefit of process.
Shale ore is normal and coal mine associated, and conventionally containing a large amount of cheap brown coal, so adopt the coal resources of resinous shale association can ensure that hydrogen feedstock coal source is sufficient.For example, be 7,000,000 tons, resinous shale in Fushun Mine Administration of China current yearly capacity of western surface mines, 2,600,000 tons, coal; East surface mines planning scale is for producing 1190 ten thousand tons, resinous shale, 800,000 tons, coal per year.But traditional coal process for making hydrogen flow process, comprises air separation unit, coal gasification unit, gas purification unit, converter unit and psa unit.Have many subject matter, if gasification product is rich carbon gas, hydrogen content is lower; Environmental pollution is serious; For the high coal of moisture content, carry out pre-treatment; Gasify bulky, system complex, the problem that investment cost is too high.
As shown in Figure 1, wherein 1 is oil shale distillation unit to the process schematic representation of oil-shale eduction process of the prior art, and 2 is shale oil gas separating unit, and 3 is hydrogenation of shale oil upgrading unit, and 4 is separator; 5～15 is logistics numbering, and wherein 5 is resinous shale, and 6 is gas-oil mixture, 8 is lime-ash, and 7 is chip shale, and 9 is circulating gas, 10 is shale oil, 11 is residual gas, and 12 is fresh hydrogen, and 13 is the mixture of hydrogenation of shale oil gas product, product oil and unreacting hydrogen, 14 is circulating hydrogen, 15 is product oil and gas product, and 16 is unreacting hydrogen, and 17 is the venting of speeding.
The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining of the utility model utilization system, as shown in Figure 2, described system comprises the oil shale distillation unit 1, shale oil gas separating unit 2, hydrogenation of shale oil upgrading unit 3 and the separator 4 that connect successively, also comprises roasting kiln 18, coal supercritical water gasification unit 19, interchanger 20, hydrogen purification unit 21 and production of construction materials unit 22;
Described oil shale distillation unit 1 is provided with the entrance that passes into resinous shale raw material, and the gas-oil mixture outlet of oil shale distillation unit 1 is connected with the gas-oil mixture feed(raw material)inlet of shale oil gas separating unit 2 by pipeline; The shale oil outlet of shale oil gas separating unit 2 is connected with the shale oil feed(raw material)inlet of hydrogenation of shale oil upgrading unit 3 by pipeline, and the circulating gas outlet of shale oil gas separating unit 2 is connected with the thermal barrier feed(raw material)inlet of oil shale distillation unit 1 by pipeline; The thick oil product outlet of rock oil hydrogenation upgrading unit 3 is connected with the thick oil product feed(raw material)inlet of separator 4 by pipeline;
The hydrogen outlet of separator 4 is divided into two passages, and a passage is connected with the circulating hydrogen entrance of hydrogenation of shale oil upgrading unit 3 by pipeline, and another passage speeds to exit for discharge;
The chip shale outlet of oil shale distillation unit 1 and the residual gas outlet of shale oil gas separating unit 2 are connected with the fuel inlet of roasting kiln 18 by pipeline respectively, the shale lime-ash outlet of roasting kiln 18 is connected with the lime-ash feed(raw material)inlet of production of construction materials unit 22 by pipeline after mixing with the lime-ash outlet of oil shale distillation unit 1, and the combustion heat that roasting kiln 18 produces provides coal supply supercritical water gasification unit 19;
Described coal supercritical water gasification unit 19 is provided with coal water slurry feed(raw material)inlet, and the syngas outlet of coal supercritical water gasification unit 19 is connected with the high-temperature gas entrance of interchanger 20 by pipeline; The normal temperature syngas outlet of interchanger 20 is connected with the hydrogen feed entrance of hydrogen purification unit 21 by pipeline; The hydrogen outlet of hydrogen purification unit 21 divides two passages, and a passage is connected with the fresh hydrogen entrance of shale hydrogenation upgrading unit 3 by pipeline, and another passage is as the outlet of product hydrogen; The circulating water outlet of hydrogen purification unit 21 is connected with the cooling water inlet of interchanger 20 by pipeline after mixing with fresh water entrance; The supercritical water outlet of interchanger 20 is connected with the supercritical water entrance of coal supercritical water gasification unit 19 by pipeline.
From Fig. 1 and Fig. 2, the utility model provides heat by chip shale discarded oil shale distillation unit and unnecessary residual gas for coal supercritical water gasification reacts, and has saved the coal resources that maintain coal supercritical water gasification reaction consumption higher thermal value and high economic worth.
The technique that realizes the integrated association hydrogen production from coal gasification of above-mentioned oil shale oil-refining utilization system, comprises the following steps:
Resinous shale 5 after crushing and screening passes into oil shale distillation unit 1 and dry distillation reactor occurs obtains gas-oil mixture 6, lime-ash 8 and unreacted chip shale 7, the gas-oil mixture obtaining 6 is passed into shale oil gas separating unit 2 and separate and obtain circulating gas 9, shale oil 10 and residual gas 11;
Wherein circulating gas 9 returns to oil shale distillation unit 1 and reacts, shale oil 10 enters hydrogenation of shale oil upgrading unit 3 and obtains the mixture 13 of hydrogenation of shale oil gas product, product oil and unreacting hydrogen, mixture 13 is separated and is obtained unreacting hydrogen 16 and product oil and gas product 15 by separator, gained unreacting hydrogen 16 is divided into two portions part and returns to hydrogenation of shale oil upgrading unit 3 and react, and a part is directly discharged;
Chip shale 7 and residual gas 11 pass into roasting kiln 18 and burn, and obtain stack gas 35, shale lime-ash 34 and the combustion heat 24; After lime-ash 8 and shale lime-ash 34 mix, pass into production of construction materials unit 22 and produce building material product 37;
After coal water slurry 23 preheatings, pass into coal supercritical water gasification unit 19 and react, obtain vapourizing furnace and work off one's feeling vent one's spleen 25, the combustion heat 24 that the heat that wherein reacts required is produced by roasting kiln provides; Gained vapourizing furnace is worked off one's feeling vent one's spleen and 25 after interchanger 20 heat exchange, is obtained cooled vapourizing furnace and work off one's feeling vent one's spleen 29, and cooled vapourizing furnace is worked off one's feeling vent one's spleen and 29 entered 21 reactions of hydrogen purification unit and obtain hydrogen 31, waste gas 30 and recirculated water 32; Wherein a part for hydrogen 31 passes into hydrogenation of shale oil upgrading unit 3 as fresh hydrogen 12 and reacts, another part, as product hydrogen 33, passes into interchanger 20 heat exchange as water coolant 27 after recirculated water 32 mixes with fresh water 26 and obtains supercritical water 28 and pass into coal supercritical water gasification unit 19 reacting.Waste gas 30 directly discharges.
In above-mentioned technique in oil shale distillation unit 1 reaction detailed process as shown in Figure 3:
Resinous shale 5 after crushing and screening is through preheater 84 preheatings, resinous shale 38 drying devices 85 after preheating remove after outside water 40, the resinous shale 39 that removes surface water enters dry distillation reactor device 86, carries out dry distillation reactor and generates the mixture flow 6 containing shale oil, carbonization gas and semicoke; Mixture flow 6 is separated into mixture 42 and the solids stream 43 of shale oil and carbonization gas through the first gas-solid separator 87;
The mixture 42 of shale oil and carbonization gas mixture 44 of shale oil and carbonization gas after the cooling condensation separation obtaining of the first water cooler 92 enters washing tower 93 and washs, obtain separating rear portion shale oil and impurity 46 and washing coal gas 45, washing coal gas 45 is divided into two bursts of logistics by splitter 94, be respectively washing coal gas 47 and washing coal gas 48, washing coal gas 48 enters gas-liquid separator 96 and obtains the coal gas 52 after shale oil 53 and purification, and the coal gas 52 after purification enters interchanger 100, washing coal gas 47 obtains cooled washing coal gas 49 through the second water cooler 95, cooled washing coal gas 49 obtains shale oil 51 and purifies rear coal gas 50 after entering separator 97, coal gas 50 coal gas 54 and residual gas 11 two portions after coal gas splitter 99 is divided into purification after purifying, after purifying, coal gas 54 enters after accumulation of heat reactor 101 mixes with air 55 and burns, then the combustion reactions gas 56 obtaining passes into interchanger 100 and the coal gas 52 after purifying is heated to 500～600 DEG C, obtain circulating gas 57 and stack gas 58 after heating, residual gas 11 enters roasting kiln 18,
Solids stream 43 enters gasifying reactor 88 and mixes generating gasification reaction with saturated air 62, the gasifying gas that reaction obtains, the mixture flow 61 of inorganic mineral and lime-ash enters after the second gas-solid separator 89 is removed lime-ash 8 (also comprising the solid matters such as semicoke) and obtains gasifying gas 60, the gasifying gas 60 obtaining is divided into gasifying gas 41 and gasifying gas 59 two portions through splitter 90, gasifying gas 41 directly passes into dry distillation reactor device 86, for retort section provides heat, gasifying gas 59 obtains circulating gas 9 with the circulating gas 57 after heating after collecting tubule 91 mixes, circulating gas 9 passes into dry distillation reactor device 86, for retort section provides heat,
Shale oil 46, shale oil 53 and shale oil 51 obtain shale oil 10 after mixing device 98 mixes.
Described in above-mentioned technique, in the charging of the gasifying reactor of oil shale distillation unit, the mass ratio of air and water vapour is 1.05～1.20.Preferred, the mass ratio of described air and water vapour is 1.13.
The detailed process of reacting in hydrogenation of shale oil upgrading unit in above-mentioned technique is as shown in Figure 4:
The mixed hydrogen 75 of circulating hydrogen 74 after the fresh hydrogen 12 that make-up hydrogen compressor comes and recycle gas compressor 108 compressions is divided into hydrogen 77 and hydrogen 76 two portions, shale oil 10 enters process furnace 102 and heats together with hydrogen 77, obtain shale oil and hydrogen mixture stream 63, the mixed mixture flow 65 of product 64 of shale oil and 63 residual hydrocrackings with A reactor 103 of hydrogen mixture stream enters second reactor 104 and carries out desulfurization, the refining reactions such as denitrogenation, concurrent first portion cracking reaction, the hydrorefined product 66 of resinous shale that second reactor 104 obtains obtains containing hydrogenation of shale oil gas product after interchanger 105 heat exchange, the mixture 13 of product oil and unreacting hydrogen, mixture 13 enters high-pressure separator 106 and obtains unreacting hydrogen 16 and hydrogenated products 69, unreacting hydrogen 16 is divided into most of hydrogen 14 and small portion hydrogen 17 through hydrogen splitter 109, most of hydrogen 14 enters recycle gas compressor 108 and recycles, small portion hydrogen 17 is as speeding to exit directly discharge, hydrogenated products 69 obtain dry gas 70, liquefied petroleum gas (LPG) 71, petroleum naphtha 72, diesel oil 73 and unconverted circulation residual oil 68 through separation column 107, circulation residual oil 68 is extracted out at the bottom of by separation column 107 towers, after mixing with hydrogen 76, enter interchanger 105 and obtain the logistics 67 after heat exchange with hydrorefined product 66 heat exchange of resinous shale, the logistics 67 after heat exchange enters A reactor 103 and carries out hydrocracking reaction.
The A reactor of described hydrogenation of shale oil upgrading unit and the temperature of reaction of second reactor are 350～400 DEG C, and pressure is 15.7MPa; The mass ratio of fresh hydrogen and shale oil is 0.03～0.04.Preferred, the temperature of reaction of described A reactor is 385 DEG C; The temperature of reaction of described second reactor is 390 DEG C.
The detailed process of reacting in coal supercritical water gasification unit described in above-mentioned technique and hydrogen purification unit is as shown in Figure 5:
Through preheater, 111 heating obtain the coal water slurry 80 after preheating to coal water slurry 23, coal water slurry 80 after preheating enters coal supercritical water gasification reactor 116 and reacts with supercritical water 28 generating gasification and obtain vapourizing furnace and work off one's feeling vent one's spleen 25, and vapourizing furnace is worked off one's feeling vent one's spleen and 25 after interchanger 20 heat exchange, obtained cooled vapourizing furnace and work off one's feeling vent one's spleen 29; Cooled vapourizing furnace is worked off one's feeling vent one's spleen and 29 is entered high-pressure separator 112 and obtain hydrogen-rich gas 81 and gas-liquid mixture 82; Hydrogen-rich gas 81 enters pressure-swing absorption apparatus 113, obtains hydrogen 31; Gas-liquid mixture 82 enters light pressure separator 114 and obtains waste gas 30 and recirculated water 32, recirculated water 32 enters interchanger 20 through fresh feed pump 115 as water coolant 27 with the mixed water 83 of fresh water 26,25 heat exchange of working off one's feeling vent one's spleen of water coolant 27 and vapourizing furnace obtain supercritical water 28, and supercritical water 28 enters the 116 generating gasification reactions of coal supercritical water gasification reactor; 24 of the combustions heat required in gasification reaction process provide by roasting kiln 18;
The chip shale 7 of described oil shale distillation unit and residual gas 11 are all crossed fuel inlet and are passed into roasting kiln 18 as fuel, produce the combustion heat 24, shale lime-ash 34 and hot flue gases 79, the stack gas 35 after hot flue gases 79 must be lowered the temperature after heat recovery boiler 110 with air 78 burnings; The hydrogen 31 that the fresh hydrogen of hydrogenation of shale oil upgrading unit is produced by coal supercritical water gasification unit provides.
In above-mentioned technique, the shale lime-ash 34 that the lime-ash 8 that described oil shale distillation unit produces and coal supercritical water gasification unit produce, all passes into production of construction materials unit 22.
In described coal supercritical gasification reaction member, the service temperature of gasifying reactor is 500～650 DEG C, and pressure is 23～27MPa; The service temperature of high-pressure separator is 25 DEG C, and pressure is 23～27MPa; The service temperature of light pressure separator is 25 DEG C, and pressure is 0.1MPa.More preferably 24MPa of described high-pressure separator press operation pressure.
Utility model content
For solving the shortcoming and defect part of prior art, the purpose of this utility model is to provide the integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system.
For realizing above-mentioned utility model object, the utility model adopts following technical scheme:
The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system, described system comprises the oil shale distillation unit, shale oil gas separating unit, hydrogenation of shale oil upgrading unit and the separator that connect successively, also comprises roasting kiln, coal supercritical water gasification unit, interchanger, hydrogen purification unit and production of construction materials unit;
Described oil shale distillation unit is provided with the entrance that passes into resinous shale raw material, and the gas-oil mixture outlet of oil shale distillation unit is connected with the gas-oil mixture feed(raw material)inlet of shale oil gas separating unit by pipeline; The shale oil outlet of shale oil gas separating unit is connected with the shale oil feed(raw material)inlet of hydrogenation of shale oil upgrading unit by pipeline, and the circulating gas outlet of shale oil gas separating unit is connected with the thermal barrier feed(raw material)inlet of oil shale distillation unit by pipeline; The thick oil product outlet of rock oil hydrogenation upgrading unit is connected with the thick oil product feed(raw material)inlet of separator by pipeline;
The hydrogen outlet of separator is divided into two passages, and a passage is connected with the circulating hydrogen entrance of hydrogenation of shale oil upgrading unit by pipeline, and another passage speeds to exit for discharge;
The chip shale outlet of oil shale distillation unit and the residual gas outlet of shale oil gas separating unit are connected with the fuel inlet of roasting kiln by pipeline respectively, the shale lime-ash outlet of roasting kiln is connected with the lime-ash feed(raw material)inlet of production of construction materials unit by pipeline after mixing with the lime-ash outlet of oil shale distillation unit, and the combustion heat that roasting kiln produces provides coal supply supercritical water gasification unit;
Described coal supercritical water gasification unit is provided with coal water slurry feed(raw material)inlet, and the syngas outlet of coal supercritical water gasification unit is connected with the high-temperature gas entrance of interchanger by pipeline; The normal temperature syngas outlet of interchanger is connected with the hydrogen feed entrance of hydrogen purification unit by pipeline; The hydrogen outlet of hydrogen purification unit divides two passages, and a passage is connected with the fresh hydrogen entrance of shale hydrogenation upgrading unit by pipeline, and another passage is as the outlet of product hydrogen; The circulating water outlet of hydrogen purification unit is connected with the cooling water inlet of interchanger by pipeline after mixing with fresh water entrance; The supercritical water outlet of interchanger is connected with the supercritical water entrance of coal supercritical water gasification unit by pipeline.
Preferably, described oil shale distillation unit includes resinous shale preheater, moisture eliminator, retort section, first point of gas-solid from device, the first water cooler, washing tower, the second water cooler, gas-liquid separator and separator; Wherein retort section comprises dry distillation reactor device, gasifying reactor, the second gas-solid separator, interchanger and accumulation of heat reactor;
Described preheater is provided with resinous shale feed(raw material)inlet, and preheater, moisture eliminator and dry distillation reactor device are connected successively by pipeline, dry distillation reactor device is provided with the resinous shale entrance that removes surface water, the air-fuel mixture outlet of dry distillation reactor device is connected with the gas-oil mixture entrance of the first gas-solid separator by pipeline, the mixture flow outlet of the oily of the first gas-solid separator is connected with the mixture flow entrance of the high temperature oily of the first water cooler by pipeline, after the condensation separation of the first water cooler, the mixture outlet of shale oil and carbonization gas is connected with washing tower mixture flow entrance, the washing gas exit of washing tower is divided into two passages, be connected with the washing gas entry of the second water cooler and gas-liquid separator by pipeline respectively, the cooled washing gas exit of the second water cooler is connected with the logistics entrance of separator by pipeline,
Gasifying reactor is provided with saturated air entrance, the solid material inlet of gasifying reactor is connected with the solid materials outlet of the first gas-solid separator by pipeline, and the gas-solid mixture spout of gasifying reactor is connected with the gas-solid mixture influx of the second gas-solid separator by pipeline; The gasification gas outlet of the second gas-solid separator is divided into two passages, one passage is directly connected with the gasifying gas entrance of dry distillation reactor device by pipeline, and the heating cycle gas exit of another passage and interchanger is connected with the thermal barrier feed(raw material)inlet of dry distillation reactor device by pipeline after mixing;
The purification gas exit of separator is divided into two passages, and a passage is connected with the purification gas entry of accumulation of heat reactor by pipeline, and another passage is connected with the fuel inlet of roasting kiln by pipeline; Accumulation of heat reactor is provided with gas inlet, and the outlet of the combustion reactions gas of accumulation of heat reactor is connected with the combustion reactions gas entrance of interchanger by pipeline, and the gas exit of the gas entry after the purification of interchanger after by the purification of pipeline and gas-liquid separator is connected.
Preferred, the purification gas exit of the washing gas exit of described washing tower, the outlet of the gasification gas of the second gas-solid separator and separator is divided into two passages by splitter, splitter, coal gas splitter respectively; Gas exit after one of them passage of gasification gas outlet and the heating of interchanger of described the second gas-solid separator mixes by collecting tubule; Washing tower, gas-liquid separator and separator are provided with shale oil outlet respectively, and the shale oil of three outlets mixes by mixing device.
In such scheme, described coal gas splitter is fluid shunting device, for according to the size adjustment splitting ratio of the required thermal load of heating cycle coal gas, regulates the coal gas amount of gas retort accumulation of heat reactor and the coal gas amount that enters roasting kiln of entering.
Preferably, described hydrogenation of shale oil upgrading unit comprises process furnace, A reactor, second reactor, interchanger, hp flash drum, separation column and compressor;
Process furnace is provided with the entrance of shale oil and hydrogen mixture stream, after the logistics outlet of the shale oil of process furnace and hydrogen mixes with the outlet of the residual hydrocracking product of A reactor, be connected with the logistics entrance of second reactor by pipeline again, the hydrorefined products export of resinous shale of second reactor is connected with the hydrorefined product inlet of resinous shale of interchanger by pipeline, the hydrogenation of shale oil gas product of interchanger, the mixture flow outlet of product oil and unreacting hydrogen is connected with the mixture flow entrance of hp flash drum by pipeline, the hydrogenated products outlet of hp flash drum is connected with the logistics entrance of separation column by pipeline, the hydrogen outlet of hp flash drum is divided into two passages, one passage is connected with the hydrogen inlet of compressor by pipeline, another passage directly discharges the venting (hydrogen) of speeding,
The hydrogen outlet of compressor is divided into two passages after mixing with fresh hydrogen entrance, one passage mixes with shale oil by pipeline, after another passage mixes with the circulation residual oil outlet of separation column bottom, be connected with the heat exchange logistics entrance of interchanger by pipeline, the heat exchange logistics outlet of interchanger is connected with the logistics entrance of A reactor by pipeline again.
Preferred, the hydrogen outlet of hp flash drum is divided into two passages by hydrogen splitter.
In such scheme, described hydrogen splitter is fluid shunting device, for according to compression power consumption and protium efficiency-adjusted splitting ratio, reduces quantity discharged and can improve protium efficiency, but can improve process energy consumption, need to be optimized and could determine best splitting ratio.
Preferably, described coal supercritical water gasification unit comprises roasting kiln, coal supercritical water gasification reactor, interchanger; Described hydrogen purification unit comprises preheater, high-pressure separator, pressure-swing absorption apparatus and light pressure separator;
Preheater is provided with coal water slurry entrance, the coal water slurry outlet of preheater is connected with the coal water slurry entrance of coal supercritical water gasification reactor by pipeline, the outlet of working off one's feeling vent one's spleen of the vapourizing furnace of coal supercritical water gasification reactor is connected by pipeline and the vapourizing furnace of the interchanger entrance of working off one's feeling vent one's spleen, the cool gasification outlet of still gas outlet of interchanger is connected with the gas feed of high-pressure separator by pipeline, the hydrogen-rich gas outlet of high-pressure separator is connected with the hydrogen-rich gas entrance of pressure-swing absorption apparatus by pipeline, the gas-liquid mixture outlet of high-pressure separator is connected with the gas-liquid mixture entrance of light pressure separator by pipeline, the circulating water outlet of light pressure separator is connected with the cooling water inlet of interchanger by fresh feed pump after mixing with fresh water entrance, the supercritical water outlet of interchanger is connected with the supercritical water entrance of coal supercritical water gasification reactor by pipeline, in coal supercritical water gasification reactor gasification reaction process, required thermal load provides by roasting kiln.
On the flue gas outlet pipeline of roasting kiln, can also be provided with heat recovery boiler.
The technique that realizes the integrated association hydrogen production from coal gasification of the utility model oil shale oil-refining utilization system is specific as follows:
Resinous shale after crushing and screening passes into oil shale distillation unit generation dry distillation reactor and obtains gas-oil mixture, lime-ash and unreacted chip shale, the gas-oil mixture obtaining is passed into the separation of shale oil gas separating unit and obtain circulating gas, shale oil and residual gas;
Wherein circulating gas returns to oil shale distillation unit process, shale oil enters hydrogenation of shale oil upgrading unit and obtains the mixture of hydrogenation of shale oil gas product, product oil and unreacting hydrogen, mixture is separated and is obtained unreacting hydrogen and product oil and gas product by separator, gained unreacting hydrogen is divided into two portions, a part is returned to hydrogenation of shale oil upgrading unit process, and a part is directly discharged;
Chip shale and residual gas pass into roasting kiln burning, obtain stack gas, shale lime-ash and the combustion heat; Lime-ash and shale lime-ash pass into production of construction materials unit and produce building material product after mixing;
After coal water slurry preheating, pass into the unit process of coal supercritical water gasification, obtain vapourizing furnace and work off one's feeling vent one's spleen, the combustion heat that the heat that wherein reacts required is produced by roasting kiln provides; Gained vapourizing furnace is worked off one's feeling vent one's spleen and after interchanger heat exchange, is obtained cooled vapourizing furnace and work off one's feeling vent one's spleen, and cooled vapourizing furnace is worked off one's feeling vent one's spleen and entered hydrogen purification unit process and obtain hydrogen, waste gas and recirculated water; Wherein a part for hydrogen passes into hydrogenation of shale oil upgrading unit process as fresh hydrogen, another part, as product hydrogen, passes into interchanger heat exchange as water coolant after recirculated water mixes with fresh water and obtains supercritical water and pass into the unit process of coal supercritical water gasification.
Preferably, described resinous shale particle diameter after crushing and screening is 8～75mm; In described oil shale distillation unit, the temperature of dry distillation reactor is 500～600 DEG C, pressure 0.1MPa.
Preferred, described temperature of reaction is 525 DEG C.
Preferably, the temperature of reaction of described hydrogenation of shale oil upgrading unit is 350～400 DEG C, and pressure is 15.7MPa.
What preferably, the feed coal of described coal water slurry adopted is the brown coal of resinous shale association.
In such scheme, in resinous shale charging, particle diameter enters oil shale distillation unit at the resinous shale of 8～75mm scope, and the shale that particle diameter is less than 8mm enters roasting kiln with the residual gas that oil shale distillation process produces, for the reaction of coal supercritical water gasification provides heat; The hydrogen part being obtained by coal supercritical water gasification unit, as the hydrogen source of hydrogenation of shale oil upgrading, reduces the production cost of hydrogenation of shale oil upgrading unit, and the hydrogen of a part is exported as gas product in addition, improves the income of process; The water cycle that coal supercritical water gasification unit separator obtains after separating is used, and after mixing, enters interchanger with fresh water.
Preferred, in the charging of described oil shale distillation unit, the mass ratio of dry air and water vapour is 1.05～1.20.
Preferred, the mass ratio of described dry air and water vapour is 1.13.
Preferably, the temperature of reaction of described hydrogenation of shale oil upgrading unit is 350～400 DEG C, and pressure is 15.7MPa; The mass ratio of fresh hydrogen and shale oil is 0.03～0.04.
Preferred, in described coal supercritical gasification reaction member, service temperature is 500～650 DEG C, and pressure is 23～27MPa; The service temperature of high-pressure separator is 25 DEG C, and pressure is 23～27MPa; The service temperature of light pressure separator is 25 DEG C, and pressure is 0.1MPa.
More preferably 24MPa of described high-pressure separator press operation pressure.
Compared with prior art, the utlity model has following advantage and beneficial effect:
(1) the utility model provides heat by chip shale discarded oil shale distillation unit and unnecessary residual gas for coal supercritical water gasification reacts, and has saved the coal resources that maintain coal supercritical water gasification reaction consumption higher thermal value and high economic worth.In existing oil shale distillation process, in most of situation, the shale of chip is not utilized, unnecessary coal gas is for the lower power generation process (being generally 28～36%) of energy efficiency, and in the utility model, chip shale has all been utilized, and unnecessary coal gas is as the raw material of combustion processes, efficiency of combustion is conventionally more than 85%.
(2) brown coal of the integrated use shale ore of the utility model association are produced the hydrogen of high economic worth.For hydrogenation of shale oil upgrading unit provides stable hydrogen source, reduce the production cost of hydrogenation of shale oil process on the one hand; As output of products, greatly improve the income of resinous shale processing industry on the other hand.The income of the integrated association hydrogen production from coal gasification comprehensive utilization of a kind of oil shale oil-refining process has improved approximately 37% compared with the simple refining process of resinous shale, and total investment expenses and total cost of production have approximately improved 15% and 18%.
(3) the utility model adopts coal supercritical water gasification technology to provide stable, enough, cheap hydrogen for hydrogenation of shale oil upgrading unit.Effectively solve existing scheme, comprised that residual gas pressure swing adsorption hydrogen production exists the problem of amounts of hydrogen deficiency; There is the unsettled problem of hydrogen source in the hydrogen manufacturing of coal-seam gas methane; Tradition hydrogen production from coal gasification complex structure, the problem that investment cost is large.
(4) lime-ash that resinous shale produces through burning or retort process accounts for 60～80% of oil shale processes amount, in existing technique most of as solid waste discharge in environment, severe contamination environment.The utility model is used to this solid waste, has also improved the economic benefit of process when having optimized resource distribution.
Brief description of the drawings
Fig. 1 is the process schematic representation of current oil-shale eduction process.Wherein 1 is oil shale distillation unit, and 2 is shale oil gas separating unit, and 3 is hydrogenation of shale oil upgrading unit, and 4 is separator; 5～17 is logistics numbering, and wherein 5 is resinous shale, and 6 is gas-oil mixture, 7 is chip shale, and 8 is lime-ash, and 9 is circulating gas, 10 is shale oil, 11 is residual gas, and 12 is fresh hydrogen, and 13 is the mixture of hydrogenation of shale oil gas product, product oil and unreacting hydrogen, 14 is circulating hydrogen, 15 is product oil and gas product, and 16 is unreacting hydrogen, and 17 is the venting of speeding.
Fig. 2 is the process schematic representation of the integrated association hydrogen production from coal gasification comprehensive utilization of a kind of oil shale oil-refining of the present invention process.Wherein 18 is roasting kiln, and 19 is coal supercritical water gasification unit, and 20 is interchanger, and 21 is hydrogen purification unit, and 22 is production of construction materials unit; 23～37 is logistics numbering, and wherein 23 is coal water slurry, and 24 is the combustion heat, 25 work off one's feeling vent one's spleen for vapourizing furnace, and 26 is fresh water, and 27 is water coolant, 28 is supercritical water, and 29 work off one's feeling vent one's spleen for cooled vapourizing furnace, and 30 is waste gas, 31 is hydrogen, 32, and be recirculated water, 33 is product hydrogen, and 34 is shale lime-ash, and 35 is stack gas, 36 is lime-ash logistics, and 37 is building material product.Operating unit or logistics that all the other numberings are identical with same reference numeral in Fig. 1.
Fig. 3 is the process flow sheet of oil shale distillation process.Wherein 84 is preheater, and 85 is moisture eliminator, and 86 is dry distillation reactor device, 87 is the first gas-solid separator, and 88 is gasifying reactor, and 89 is the second gas-solid separator, 90 is splitter, and 91 is collecting tubule, and 92 is the first water cooler, 93 is washing tower, and 95 is the second water cooler, and 96 is gas-liquid separator, 97 is separator, and 98 is mixing device, and 99 is splitter, 100 is interchanger, and 101 is accumulation of heat reactor, 38-62 is logistics numbering, wherein 38 is the resinous shale after preheating, 39 for removing the resinous shale of surface water, 40 for removing water, 41 is gasifying gas, 42 is the mixture of shale oil and carbonization gas, 43 is the solids stream of inorganic mineral and semicoke etc., 44 is the mixture of shale oil and carbonization gas after condensation separation, 45 is washing coal gas, 46 for separating latter part of shale oil and impurity, 47 and 48 is washing coal gas, 49 is cooled washing coal gas, 50 for purifying coal gas, 51 is shale oil, 52 is the coal gas after purifying, 53 is shale oil, 54 is coal gas after purifying, 55 is air, 56 is combustion reactions gas, 57 is heating cycle coal gas, 58 is stack gas, 59 is gasifying gas, 60 is gasifying gas, 61 is gasifying gas, the mixture of inorganic mineral and lime-ash, 62 is saturated air.All the other number logistics identical with same reference numeral in Fig. 1.
Fig. 4 is the technical process of hydrogenation of shale oil upgrading unit.Wherein 102 is process furnace, and 103 is A reactor, and 104 is second reactor, and 105 is interchanger, and 106 is high-pressure separator, and 107 is separation column, and 108 is compressor, and 109 is splitter; 63-77 is logistics numbering, and wherein 63 is shale oil and hydrogen mixture stream, 64 products for residual hydrocracking, 65 is mixture flow, and 66 is the hydrorefined product of resinous shale, and 67 is the logistics after heat exchange, 68 is circulation residual oil, and 69 is hydrogenated products, and 70 is dry gas, 71 is liquefied petroleum gas (LPG), 72 is petroleum naphtha, and 73 is diesel oil, and 74 is the circulating hydrogen after compression, the 75th, mixed hydrogen, 76 and 77 is hydrogen.All the other number logistics identical with same reference numeral in Fig. 1.
Fig. 5 is the process flow sheet of coal supercritical water gasification unit.110 is heat recovery boiler, and 111 is preheater, and 112 is high-pressure separator, and 113 is pressure-swing absorption apparatus, and 114 is light pressure separator, and 115 is fresh feed pump, and 116 is coal supercritical water gasification reactor.78-83 is logistics numbering, and wherein 78 is air, and 79 is hot flue gases, and 80 is the coal water slurry after preheating, and 81 is hydrogen-rich gas, and 82 is gas-liquid mixture, and 83 is water.Operating unit or logistics that all the other numberings are identical with same reference numeral in Fig. 2.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the utility model is described in further detail, but embodiment of the present utility model is not limited to this.
Embodiment 1
Specifically being implemented as follows of the resinous shale of the present embodiment and association coal comprehensive utilization process thereof:
The raw material shale flow that enters the utility model technique is 322.5t/h, and that wherein enter gas retort is 275t/h, and chip shale flow is 47.5t/h.Gas retort gasification section water vapour is 1.13 with Air quality ratio.The inlet amount of brown coal is 33.91t/h.The technical analysis of resinous shale and brown coal and ultimate analysis are in table 1.The process flow sheet of the integrated association hydrogen production from coal gasification comprehensive utilization of oil shale oil-refining process is shown in Fig. 2.
The technical analysis ultimate analysis of table 1 resinous shale and brown coal
(M in table, FC, V, and A represents respectively the content of moisture in resinous shale, fixed carbon, volatile matter and ash, ar represents as received basis, wt represents massfraction)
Oil shale distillation process is as shown in Figure 3:
After crushing and screening, the resinous shale 5 of particle diameter 8～75mm is through preheater 84 preheatings, resinous shale 38 drying devices 85 after preheating remove after outside water 40, the resinous shale 39 that removes surface water enters dry distillation reactor device 86, carries out dry distillation reactor and generate the mixture flow 6 containing shale oil, carbonization gas and semicoke at 0.1MPa, 525 DEG C; Mixture flow 6 is separated into mixture 42 and the solids stream 43 of shale oil and carbonization gas through the first gas-solid separator 87;
The mixture 42 of shale oil and carbonization gas mixture 44 of shale oil and carbonization gas after the cooling condensation separation obtaining of the first water cooler 92 enters washing tower 93 and washs, obtain separating rear portion shale oil and impurity 46 and washing coal gas 45, washing coal gas 45 is divided into two bursts of logistics by splitter 94, be respectively washing coal gas 47 and washing coal gas 48, washing coal gas 48 enters gas-liquid separator 96 and obtains the coal gas 52 after shale oil 53 and purification, and the coal gas 52 after purification enters interchanger 100; Washing coal gas 47 obtains cooled washing coal gas 49 through the second water cooler 95, cooled washing coal gas 49 obtains shale oil 51 and purifies rear coal gas 50 after entering separator 97, coal gas 50 coal gas 54 and residual gas 11 two portions after coal gas splitter 99 is divided into purification after purifying, after purifying, coal gas 54 enters after accumulation of heat reactor 101 mixes with air 55 and burns, then the combustion reactions gas 56 obtaining passes into interchanger 100 and the coal gas 52 after purifying is heated to 550 DEG C, obtain circulating gas 57 and stack gas 58 after heating, residual gas 11 enters roasting kiln 18;
Solids stream 43 enters 88 and 85 DEG C of saturated airs 62 of gasifying reactor and is blended in 0.1MPa, generating gasification reaction at 850 DEG C, the gasifying gas that reaction obtains, the mixture flow 61 of inorganic mineral and lime-ash enters after the second gas-solid separator 89 is removed lime-ash 8 (also comprising the solid matters such as semicoke) and obtains gasifying gas 60, the gasifying gas 60 obtaining is divided into gasifying gas 41 and gasifying gas 59 two portions through splitter 90, gasifying gas 41 directly passes into dry distillation reactor device 86, for retort section provides heat, gasifying gas 59 obtains circulating gas 9 with the circulating gas 57 after heating after collecting tubule 91 mixes, circulating gas 9 passes into dry distillation reactor device 86, for retort section provides heat,
Shale oil 46, shale oil 53 and shale oil 51 obtain shale oil 10 after mixing device 98 mixes.
Hydrogenation of shale oil upgrading process is as shown in Figure 4:
The mixed hydrogen 75 of circulating hydrogen 74 after the fresh hydrogen 12 that make-up hydrogen compressor comes and recycle gas compressor 108 compressions is divided into hydrogen 77 and hydrogen 76 two portions, shale oil 10 enters process furnace 102 and heats together with hydrogen 77, obtain shale oil and hydrogen mixture stream 63, shale oil enters second reactor 104 after mixing with the product 64 of hydrogen mixture stream 63 residual hydrocrackings with A reactor 103 and carry out desulfurization under 380 DEG C of condition, the refining reactions such as denitrogenation, concurrent first portion cracking reaction, the hydrorefined product 66 of resinous shale that second reactor 104 obtains obtains containing hydrogenation of shale oil gas product after interchanger 105 heat exchange, the mixture 13 of product oil and unreacting hydrogen, mixture 13 enters high-pressure separator 106 and obtains unreacting hydrogen 16 and hydrogenated products 69, unreacting hydrogen 16 is divided into most of hydrogen 14 and small portion hydrogen 17 through hydrogen splitter 109, most of hydrogen 14 enters recycle gas compressor 108 and recycles, small portion hydrogen 17 is as speeding to exit directly discharge, hydrogenated products 69 obtain dry gas 70, liquefied petroleum gas (LPG) 71, petroleum naphtha 72, diesel oil 73 and unconverted circulation residual oil 68 through separation column 107, circulation residual oil 68 is extracted out at the bottom of by separation column 107 towers, after mixing with hydrogen 76, enter interchanger 105 and obtain the logistics 67 after heat exchange with hydrorefined product 66 heat exchange of resinous shale, it is to carry out hydrocracking reaction under 380 DEG C of conditions in temperature that the logistics 67 after heat exchange enters A reactor 103.In this process, fresh hydrogen and shale oil mass ratio are 0.035.
In coal supercritical water gasification unit and hydrogen purification unit, react specifically as shown in Figure 5:
Through preheater, 111 heating obtain the coal water slurry 80 after preheating to coal water slurry 23, coal water slurry 80 after preheating enters coal supercritical water gasification reactor 116 and reacts with supercritical water 28 generating gasification and obtain vapourizing furnace and work off one's feeling vent one's spleen 25 (coal water slurry 80 after preheating and supercritical water 28 pass into from lower part of coal supercritical water gasification reactor 19, vapourizing furnace works off one's feeling vent one's spleen 25 from the extraction of reactor upper part), temperature of reaction is 600 DEG C, pressure is 25MPa, and vapourizing furnace is worked off one's feeling vent one's spleen and 25 after interchanger 20 heat exchange, obtained cooled vapourizing furnace and work off one's feeling vent one's spleen 29; Cooled vapourizing furnace is worked off one's feeling vent one's spleen and 29 is entered high-pressure separator 112 and obtain hydrogen-rich gas 81 and gas-liquid mixture 82; Hydrogen-rich gas 81 enters pressure-swing absorption apparatus 113, obtains hydrogen 31; Gas-liquid mixture 82 enters light pressure separator 114 and obtains waste gas 30 and recirculated water 32, recirculated water 32 enters interchanger 20 through fresh feed pump 115 as water coolant 27 with the mixed water 83 of fresh water 26,25 heat exchange of working off one's feeling vent one's spleen of water coolant 27 and vapourizing furnace obtain supercritical water 28, and supercritical water 28 enters the 116 generating gasification reactions of coal supercritical water gasification reactor; In gasification reaction process, 24 of the required combustions heat provide by burn chip shale 7 and residual gas 11 of roasting kiln 18.
Existing oil-shale eduction process mainly comprises above-mentioned oil shale distillation process and hydrogenation of shale oil process, will no longer this repeat to set forth.
Finally, the integrated association hydrogen production from coal gasification comprehensive utilization of the present embodiment oil shale oil-refining process, energy efficiency and return on investment (ROI) can be increased to respectively 33.88% and 22.72%, and the lime-ash that process produces is nearly all utilized effectively.Compare existing oil-shale eduction process, energy efficiency and return on investment (ROI) have improved respectively 7.97% and 9.87% compared with process.
Embodiment 2
Specifically being implemented as follows of the resinous shale of the present embodiment and association coal comprehensive utilization process thereof:
The raw material shale flow that enters the utility model technique is 375t/h, and that wherein enter gas retort is 300t/h, and chip shale flow is 75t/h.Gas retort gasification section water vapour is 1.20 with Air quality ratio.The inlet amount of brown coal is 48.36t/h.The technical analysis of resinous shale and brown coal and ultimate analysis are in table 1.The process flow sheet of the integrated association hydrogen production from coal gasification comprehensive utilization of oil shale oil-refining process is shown in Fig. 2.
The technical analysis ultimate analysis of table 1 resinous shale and brown coal
(M in table, FC, V, and A represents respectively the content of moisture in resinous shale, fixed carbon, volatile matter and ash, ar represents as received basis, wt represents massfraction)
Oil shale distillation process is as shown in Figure 3:
After crushing and screening, the resinous shale 5 of particle diameter 8～75mm is through preheater 84 preheatings, resinous shale 38 drying devices 85 after preheating remove after outside water 40, the resinous shale 39 that removes surface water enters dry distillation reactor device 86, carries out dry distillation reactor and generate the mixture flow 6 containing shale oil, carbonization gas and semicoke at 0.1MPa, 600 DEG C; Mixture flow 6 is separated into mixture 42 and the solids stream 43 of shale oil and carbonization gas through the first gas-solid separator 87;
The mixture 42 of shale oil and carbonization gas mixture 44 of shale oil and carbonization gas after the cooling condensation separation obtaining of the first water cooler 92 enters washing tower 93 and washs, obtain separating rear portion shale oil and impurity 46 and washing coal gas 45, washing coal gas 45 is divided into two bursts of logistics by splitter 94, be respectively washing coal gas 47 and washing coal gas 48, washing coal gas 48 enters gas-liquid separator 96 and obtains the coal gas 52 after shale oil 53 and purification, and the coal gas 52 after purification enters interchanger 100; Washing coal gas 47 obtains cooled washing coal gas 49 through the second water cooler 95, cooled washing coal gas 49 obtains shale oil 51 and purifies rear coal gas 50 after entering separator 97, coal gas 50 coal gas 54 and residual gas 11 two portions after coal gas splitter 99 is divided into purification after purifying, after purifying, coal gas 54 enters after accumulation of heat reactor 101 mixes with air 55 and burns, then the combustion reactions gas 56 obtaining passes into interchanger 100 and the coal gas 52 after purifying is heated to 600 DEG C, obtain circulating gas 57 and stack gas 58 after heating, residual gas 11 enters roasting kiln 18;
Solids stream 43 enters 88 and 85 DEG C of saturated airs 62 of gasifying reactor and is blended in 0.1MPa, generating gasification reaction at 900 DEG C, the gasifying gas that reaction obtains, the mixture flow 61 of inorganic mineral and lime-ash enters after the second gas-solid separator 89 is removed lime-ash 8 (also comprising the solid matters such as semicoke) and obtains gasifying gas 60, the gasifying gas 60 obtaining is divided into gasifying gas 41 and gasifying gas 59 two portions through splitter 90, gasifying gas 41 directly passes into dry distillation reactor device 86, for retort section provides heat, gasifying gas 59 obtains circulating gas 9 with the circulating gas 57 after heating after collecting tubule 91 mixes, circulating gas 9 passes into dry distillation reactor device 86, for retort section provides heat,
Shale oil 46, shale oil 53 and shale oil 51 obtain shale oil 10 after mixing device 98 mixes.
Hydrogenation of shale oil upgrading process is as shown in Figure 4:
The mixed hydrogen 75 of circulating hydrogen 74 after the fresh hydrogen 12 that make-up hydrogen compressor comes and recycle gas compressor 108 compressions is divided into hydrogen 77 and hydrogen 76 two portions, shale oil 10 enters process furnace 102 and heats together with hydrogen 77, obtain shale oil and hydrogen mixture stream 63, shale oil enters second reactor 104 after mixing with the product 64 of hydrogen mixture stream 63 residual hydrocrackings with A reactor 103 and carry out desulfurization under 400 DEG C of condition, the refining reactions such as denitrogenation, concurrent first portion cracking reaction, the hydrorefined product 66 of resinous shale that second reactor 104 obtains obtains containing hydrogenation of shale oil gas product after interchanger 105 heat exchange, the mixture 13 of product oil and unreacting hydrogen, mixture 13 enters high-pressure separator 106 and obtains unreacting hydrogen 16 and hydrogenated products 69, unreacting hydrogen 16 is divided into most of hydrogen 14 and small portion hydrogen 17 through hydrogen splitter 109, most of hydrogen 14 enters recycle gas compressor 108 and recycles, small portion hydrogen 17 is as speeding to exit directly discharge, hydrogenated products 69 obtain dry gas 70, liquefied petroleum gas (LPG) 71, petroleum naphtha 72, diesel oil 73 and unconverted circulation residual oil 68 through separation column 107, circulation residual oil 68 is extracted out at the bottom of by separation column 107 towers, after mixing with hydrogen 76, enter interchanger 105 and obtain the logistics 67 after heat exchange with hydrorefined product 66 heat exchange of resinous shale, it is to carry out hydrocracking reaction under 380 DEG C of conditions in temperature that the logistics 67 after heat exchange enters A reactor 103.In this process, fresh hydrogen and shale oil mass ratio are 0.035.
In coal supercritical water gasification unit and hydrogen purification unit, react specifically as shown in Figure 5:
Through preheater, 111 heating obtain the coal water slurry 80 after preheating to coal water slurry 23, coal water slurry 80 after preheating enters coal supercritical water gasification reactor 116 and reacts with supercritical water 28 generating gasification and obtain vapourizing furnace and work off one's feeling vent one's spleen 25, temperature of reaction is 650 DEG C, pressure is 27MPa, and vapourizing furnace is worked off one's feeling vent one's spleen and 25 after interchanger 20 heat exchange, obtained cooled vapourizing furnace and work off one's feeling vent one's spleen 29; Cooled vapourizing furnace is worked off one's feeling vent one's spleen and 29 is entered high-pressure separator 112 and obtain hydrogen-rich gas 81 and gas-liquid mixture 82; Hydrogen-rich gas 81 enters pressure-swing absorption apparatus 113, obtains hydrogen 31; Gas-liquid mixture 82 enters light pressure separator 114 and obtains waste gas 30 and recirculated water 32, recirculated water 32 enters interchanger 20 through fresh feed pump 115 as water coolant 27 with the mixed water 83 of fresh water 26,25 heat exchange of working off one's feeling vent one's spleen of water coolant 27 and vapourizing furnace obtain supercritical water 28, and supercritical water 28 enters the 116 generating gasification reactions of coal supercritical water gasification reactor; In gasification reaction process, 24 of the required combustions heat provide by burn chip shale 7 and residual gas 11 of roasting kiln 18.
Existing oil-shale eduction process mainly comprises above-mentioned oil shale distillation process and hydrogenation of shale oil process, will no longer this repeat to set forth.
Finally, the integrated association hydrogen production from coal gasification comprehensive utilization of the present embodiment oil shale oil-refining process, energy efficiency and return on investment (ROI) can be increased to respectively 34.20% and 22.95%, and the lime-ash that process produces is nearly all utilized effectively.Compare existing oil-shale eduction process, energy efficiency and return on investment (ROI) have improved 8.29% and 8.50%.
Above-described embodiment is preferably embodiment of the utility model; but embodiment of the present utility model is not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present utility model and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection domain of the present utility model.
Claims (4)
1. the integrated association hydrogen production from coal gasification of an oil shale oil-refining utilization system, comprise the oil shale distillation unit, shale oil gas separating unit, hydrogenation of shale oil upgrading unit and the separator that connect successively, it is characterized in that, described system also comprises roasting kiln, coal supercritical water gasification unit, interchanger, hydrogen purification unit and production of construction materials unit;
Described oil shale distillation unit is provided with the entrance that passes into resinous shale raw material, and the gas-oil mixture outlet of oil shale distillation unit is connected with the gas-oil mixture feed(raw material)inlet of shale oil gas separating unit by pipeline; The shale oil outlet of shale oil gas separating unit is connected with the shale oil feed(raw material)inlet of hydrogenation of shale oil upgrading unit by pipeline, and the circulating gas outlet of shale oil gas separating unit is connected with the thermal barrier feed(raw material)inlet of oil shale distillation unit by pipeline; The thick oil product outlet of rock oil hydrogenation upgrading unit is connected with the thick oil product feed(raw material)inlet of separator by pipeline;
The hydrogen outlet of separator is divided into two passages, and a passage is connected with the circulating hydrogen entrance of hydrogenation of shale oil upgrading unit by pipeline, and another passage speeds to exit for discharge;
The chip shale outlet of oil shale distillation unit and the residual gas outlet of shale oil gas separating unit are connected with the fuel inlet of roasting kiln by pipeline respectively, the shale lime-ash outlet of roasting kiln is connected with the lime-ash feed(raw material)inlet of production of construction materials unit by pipeline after mixing with the lime-ash outlet of oil shale distillation unit, and the combustion heat that roasting kiln produces provides coal supply supercritical water gasification unit;
Described coal supercritical water gasification unit is provided with coal water slurry feed(raw material)inlet, and the syngas outlet of coal supercritical water gasification unit is connected with the high-temperature gas entrance of interchanger by pipeline; The normal temperature syngas outlet of interchanger is connected with the hydrogen feed entrance of hydrogen purification unit by pipeline; The hydrogen outlet of hydrogen purification unit divides two passages, and a passage is connected with the fresh hydrogen entrance of shale hydrogenation upgrading unit by pipeline, and another passage is as product hydrogen outlet; The circulating water outlet of hydrogen purification unit is connected with the cooling water inlet of interchanger by pipeline after mixing with fresh water entrance; The supercritical water outlet of interchanger is connected with the supercritical water entrance of coal supercritical water gasification unit by pipeline.
2. system according to claim 1, is characterized in that, described oil shale distillation unit includes resinous shale preheater, moisture eliminator, retort section, first point of gas-solid from device, the first water cooler, washing tower, the second water cooler, gas-liquid separator and separator; Wherein retort section comprises dry distillation reactor device, gasifying reactor, the second gas-solid separator, interchanger and accumulation of heat reactor;
Described preheater is provided with resinous shale feed(raw material)inlet, and preheater, moisture eliminator and dry distillation reactor device are connected successively by pipeline, dry distillation reactor device is provided with the resinous shale entrance that removes surface water, the air-fuel mixture outlet of dry distillation reactor device is connected with the gas-oil mixture entrance of the first gas-solid separator by pipeline, the mixture flow outlet of the oily of the first gas-solid separator is connected with the mixture flow entrance of the high temperature oily of the first water cooler by pipeline, after the condensation separation of the first water cooler, the mixture outlet of shale oil and carbonization gas is connected with washing tower mixture flow entrance, the washing gas exit of washing tower is divided into two passages, be connected with the washing gas entry of the second water cooler and gas-liquid separator by pipeline respectively, the cooled washing gas exit of the second water cooler is connected with the logistics entrance of separator by pipeline,
Gasifying reactor is provided with saturated air entrance, the solid material inlet of gasifying reactor is connected with the solid materials outlet of the first gas-solid separator by pipeline, and the gas-solid mixture spout of gasifying reactor is connected with the gas-solid mixture influx of the second gas-solid separator by pipeline; The gasification gas outlet of the second gas-solid separator is divided into two passages, one passage is directly connected with the gasifying gas entrance of dry distillation reactor device by pipeline, and the heating cycle gas exit of another passage and interchanger is connected with the thermal barrier feed(raw material)inlet of dry distillation reactor device by pipeline after mixing;
The purification gas exit of separator is divided into two passages, and a passage is connected with the purification gas entry of accumulation of heat reactor by pipeline, and another passage is connected with the fuel inlet of roasting kiln by pipeline; Accumulation of heat reactor is provided with gas inlet, and the outlet of the combustion reactions gas of accumulation of heat reactor is connected with the combustion reactions gas entrance of interchanger by pipeline, and the gas exit of the gas entry after the purification of interchanger after by the purification of pipeline and gas-liquid separator is connected.
3. system according to claim 1, is characterized in that, described hydrogenation of shale oil upgrading unit comprises process furnace, A reactor, second reactor, interchanger, hp flash drum, separation column and compressor;
Process furnace is provided with the entrance of shale oil and hydrogen mixture stream, after the shale oil of process furnace and the logistics of hydrogen outlet mix with the outlet of the residual hydrocracking product of A reactor by pipeline, be connected with second reactor logistics entrance by pipeline again, the hydrorefined products export of resinous shale of second reactor is connected with the hydrorefined product inlet of resinous shale of interchanger by pipeline, the hydrogenation of shale oil gas product of interchanger, the mixture flow outlet of product oil and unreacting hydrogen is connected with the mixture flow entrance of hp flash drum by pipeline, the hydrogenated products outlet of hp flash drum is connected with the logistics entrance of separation column by pipeline, the hydrogen outlet of hp flash drum is divided into two passages, one passage is connected with the hydrogen inlet of compressor by pipeline, another passage directly discharge speeds to exit,
The hydrogen outlet of compressor is divided into two passages after mixing with fresh hydrogen entrance, one passage mixes with shale oil by pipeline, after another passage mixes with the circulation residual oil outlet of separation column bottom, be connected with the heat exchange logistics entrance of interchanger by pipeline, the heat exchange logistics outlet of interchanger is connected with the logistics entrance of A reactor by pipeline again.
4. system according to claim 1, is characterized in that, described coal supercritical water gasification unit comprises roasting kiln, coal supercritical water gasification reactor, interchanger; Described hydrogen purification unit comprises preheater, high-pressure separator, pressure-swing absorption apparatus and light pressure separator;
Preheater is provided with coal water slurry entrance, the coal water slurry outlet of preheater is connected with the coal water slurry entrance of coal supercritical water gasification reactor by pipeline, the outlet of working off one's feeling vent one's spleen of the vapourizing furnace of coal supercritical water gasification reactor is connected by pipeline and the vapourizing furnace of the interchanger entrance of working off one's feeling vent one's spleen, the cool gasification outlet of still gas outlet of interchanger is connected with the gas feed of high-pressure separator by pipeline, the hydrogen-rich gas outlet of high-pressure separator is connected with the hydrogen-rich gas entrance of pressure-swing absorption apparatus by pipeline, the gas-liquid mixture outlet of high-pressure separator is connected with the gas-liquid mixture entrance of light pressure separator by pipeline, the circulating water outlet of light pressure separator is connected with the cooling water inlet of interchanger by fresh feed pump after mixing with fresh water entrance, the supercritical water outlet of interchanger is connected with the supercritical water entrance of coal supercritical water gasification reactor by pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420310615.XU CN203938647U (en) | 2014-06-11 | 2014-06-11 | The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420310615.XU CN203938647U (en) | 2014-06-11 | 2014-06-11 | The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN203938647U true CN203938647U (en) | 2014-11-12 |
Family
ID=51857979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201420310615.XU Withdrawn - After Issue CN203938647U (en) | 2014-06-11 | 2014-06-11 | The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN203938647U (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152166A (en) * | 2014-06-11 | 2014-11-19 | 华南理工大学 | Comprehensive utilization system and process for hydrogen production by gasification of oil shale refining integrated associated coal |
| CN104386648A (en) * | 2014-11-17 | 2015-03-04 | 华南理工大学 | Solid heat transfer oil shale refinement/retort gas hydrogen production integrated system and technique |
| CN105664668A (en) * | 2016-03-31 | 2016-06-15 | 四川天采科技有限责任公司 | Method for recovering hydrocarbons from polyolefin tail gas by full-temperature pressure swing adsorption |
| CN109401784A (en) * | 2018-12-13 | 2019-03-01 | 上海博申工程技术有限公司 | A kind of method of comprehensive utilization and device of heavy poor oil and oil shale |
-
2014
- 2014-06-11 CN CN201420310615.XU patent/CN203938647U/en not_active Withdrawn - After Issue
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152166A (en) * | 2014-06-11 | 2014-11-19 | 华南理工大学 | Comprehensive utilization system and process for hydrogen production by gasification of oil shale refining integrated associated coal |
| CN104152166B (en) * | 2014-06-11 | 2016-05-04 | 华南理工大学 | A kind of oil shale oil-refining integrated association hydrogen production from coal gasification utilization system and technique |
| CN104386648A (en) * | 2014-11-17 | 2015-03-04 | 华南理工大学 | Solid heat transfer oil shale refinement/retort gas hydrogen production integrated system and technique |
| CN104386648B (en) * | 2014-11-17 | 2017-02-22 | 华南理工大学 | Solid heat transfer oil shale refinement/retort gas hydrogen production integrated system and technique |
| CN105664668A (en) * | 2016-03-31 | 2016-06-15 | 四川天采科技有限责任公司 | Method for recovering hydrocarbons from polyolefin tail gas by full-temperature pressure swing adsorption |
| CN105664668B (en) * | 2016-03-31 | 2018-01-02 | 四川天采科技有限责任公司 | A kind of method of complete warm journey pressure-variable adsorption recovery polyolefin tail hydro carbons |
| CN109401784A (en) * | 2018-12-13 | 2019-03-01 | 上海博申工程技术有限公司 | A kind of method of comprehensive utilization and device of heavy poor oil and oil shale |
| CN109401784B (en) * | 2018-12-13 | 2023-10-20 | 上海博申工程技术有限公司 | Comprehensive utilization method of heavy inferior oil and oil shale |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104152166B (en) | A kind of oil shale oil-refining integrated association hydrogen production from coal gasification utilization system and technique | |
| CN101717656B (en) | Grading liquefaction method for solid fuel containing carbon and three-phase suspension bed reactor for same | |
| CN103160296B (en) | Pyrolysis gasification coupling integrated poly-generation system and process for coal chemical industry | |
| CN102849676B (en) | High-temperature water vapor pyrolysis-cracking-gasification device and method for solid fuel | |
| CN101649233B (en) | Isothermal methanation process and device for the preparation of synthetic natural gas | |
| CN101538473B (en) | Incoherence or weak caking coal deep processing method | |
| CN104593037B (en) | A kind of method of combined type coal hydrogenation oil refining reactor and oil refining | |
| CN105154121A (en) | Low-rank coal gradation usage poly-generation system and method | |
| CN101328415A (en) | Piston type fluidized bed low temperature dry distillation technological process | |
| CN203938647U (en) | The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining utilization system | |
| CN101250419B (en) | Low-temperature dry distillation process with coal gas internal heat | |
| CN101818073A (en) | Dry distillation and semicoke incineration integrated system for oil shale | |
| CN102295941B (en) | Combined system of oil shale bubble column dry distillation and semicoke circulating fluidized bed combustion | |
| Ni et al. | Research on coal staged conversion poly-generation system based on fluidized bed | |
| CN205133505U (en) | Low order coal grading utilizes many cogeneration system | |
| CN204125164U (en) | A kind of oil shale distillation chemistry chain hydrogen manufacturing combined generating system | |
| CN204589076U (en) | The resinous shale utilization system of a kind of coupled gas and solid thermal carriers | |
| CN104004532A (en) | Integrated refining system and process using oil shale retorting gas to produce hydrogen and upgrade | |
| CN203159536U (en) | Coal chemical industry pyrolysis and gasification coupling integrated poly-generation system | |
| CN102504850B (en) | Oil sand solid hot carrier low-temperature dry distillation process | |
| CN102161900A (en) | Device and method for extracting oil from blocky oil shale with high efficiency | |
| CN105087035A (en) | Method and device for preparing clean fuel oil by pyrolyzing oil sand | |
| CN203938646U (en) | A kind of integrated refining system with oil shale distillation gas hydrogen manufacturing upgrading | |
| Proshunin et al. | Underground gasification of coal and lignite | |
| CN105176552A (en) | Novel gas heat carrier retorting and gas power generation integrated device and technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20141112 Effective date of abandoning: 20160504 |
|
| C25 | Abandonment of patent right or utility model to avoid double patenting |