CN104152166B - A kind of oil shale oil-refining integrated association hydrogen production from coal gasification utilization system and technique - Google Patents
A kind of oil shale oil-refining integrated association hydrogen production from coal gasification utilization system and technique Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 185
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000004058 oil shale Substances 0.000 title claims abstract description 130
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- 239000003034 coal gas Substances 0.000 claims description 66
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- 150000002431 hydrogen Chemical class 0.000 claims description 51
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- 210000000952 spleen Anatomy 0.000 claims description 28
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- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000003763 carbonization Methods 0.000 claims description 16
- 239000000498 cooling water Substances 0.000 claims description 14
- 238000009825 accumulation Methods 0.000 claims description 13
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- 238000004148 unit process Methods 0.000 claims description 11
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- 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
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Abstract
The invention discloses a kind of oil shale oil-refining integrated association hydrogen production from coal gasification utilization system and technique. Described system comprises the oil shale retorting unit, shale oil gas separative element, hydrogenation of shale oil upgrading unit and the separator that connect successively, also comprises combustion furnace, coal supercritical water gasification unit, heat exchanger, hydrogen purification unit and production of construction materials unit. The present invention provides heat by chip shale discarded oil shale retorting 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 invention belongs to the energy and chemical technology field, be specifically related to the integrated association coal gas of a kind of oil shale oil-refiningChange hydrogen manufacturing utilization system and technique.
Background technology
Along with Chinese society and rapid economic development, energy demand is increased day by day. For reducing Imported oilDependence, the energy strategy that China just actively implements diversification continues supply to ensure the energy. Oil shale is onePlanting sedimentary rock, have the skeleton of inorganic mineral, and contain SOLID ORGANIC matter, is the combustion of low heat value solid fossilMaterial. 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 476Hundred million tons, far above 2,200,000,000 tons of crude oil proved reserves. China not only oil shale reserves is abundant, and bury more shallow,All be conducive to the exploitation of oil shale resources. Greatly develop oil shale oil-refining technology and be conducive to alleviate China's stoneOil resource supply and demand contradiction, provides practicable approach for realizing energy diversification.
The domestic technology of utilizing to oil shale is mainly destructive distillation oil refining technology at present. By underground mining or outdoorThe oil shale that exploitation obtains, through broken, screening, under the condition of isolated air, is heated to uniform temperature modelEnclose, a series of physical-chemical reaction occurs, finally generate shale oil, coal gas and semicoke etc. This technology veryLess broken shale and the higher solid waste such as semicoke and lime-ash of calorific value are used. This has just caused energy moneyThe problems such as a large amount of wastes in source and economic benefit are poor. For example, after oil shale pyrolysis oil refining or burning, form greatlyAmount lime-ash (accounting for the 60-80% of oil shale processes amount) is piled up and is taken a large amount of soils nearby; Water for a long time through rainwaterDrench, the many harmful substances that retain in lime-ash enter water system and soil with rainwater, cause its severe contamination straightConnect influence ecological environment; The a lot of thin dirt containing in lime-ash, enters atmospheric environment, causes PM to pollute, shadowRing the healthy of resident.
How further to improve oil shale oil-refining process economy performance, become " the bottle of oil shale processing industryNeck ". The shale oil that oil shale retorting at present obtains is mainly used in the low side primary fuels such as boiler oil, containsThe non-hydrocarbons organic compounds such as many unsaturated hydro carbons and sulphur, nitrogen, oxygen, these impurity very easily cause colloid in oilChange is many, reduces oily stability, and impurity burning simultaneously also can produce a large amount of pernicious gas contaminated environment. ThereforeShale oil needs deep processing to remove impurity, as generated fuel oil and other chemicals. To hydrogenation of shale oil processingBe one compared with mature technology, day by day come into one's own containing the oil-shale eduction process of hydrogenation upgrading. Showing of this processIntention as shown in Figure 1. But this process one-time investment is large, equipment needed thereby expense and operating cost are also very high,Cause domestic deep processing of shale oil rate very low. In addition, the hydrogen market price is higher at present, ifAdopt outsourcing hydrogen as hydrogen source, can improve undoubtedly the production cost of process, reduce the economic benefit of process.
Shale ore is normal and coal mine associated, and conventionally containing a large amount of cheap brown coal, so the association of employing oil shaleCoal resources can ensure that hydrogen feedstock coal source is sufficient. For example,, at the western opencut order of Fushun Mine Administration of ChinaFront yearly productive capacity is 7,000,000 tons, oil shale, 2,600,000 tons, coal; East opencut planning scale is a year produce oil page1,190 ten thousand tons, rock, 800,000 tons, coal. But traditional coal process for making hydrogen flow process, comprises air separation unit, coal gasification listUnit, gas purification unit, converter unit and psa unit. There is many subject matter, as gasificationProduct is rich carbon gas, and hydrogen content is lower; Environmental pollution is serious; For the high coal of moisture, enterRow pretreatment; Gasify bulky, system complex, the problem that investment cost is too high.
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of oil pageRock is refined oil integrated association hydrogen production from coal gasification utilization system.
Another object of the present invention is to provide a kind of oil shale oil-refining integrated association hydrogen production from coal gasification comprehensive utilizationTechnique.
For achieving the above object, the present invention 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 successively and connectingThe oil shale retorting unit, shale oil gas separative element, hydrogenation of shale oil upgrading unit and the separator that connect, alsoComprise combustion furnace, coal supercritical water gasification unit, heat exchanger, hydrogen purification unit and production of construction materials unit;
Described oil shale retorting unit is provided with the entrance that passes into oil shale raw material, the oil gas of oil shale retorting unitMixture outlet is connected with the gas mixture feed(raw material)inlet of shale oil gas separative element by pipeline; ShaleThe shale oil of Oil-gas Separation unit exports by the shale oil feed(raw material)inlet of pipeline and hydrogenation of shale oil upgrading unitBe connected, the circulating gas outlet of shale oil gas separative element is carried by the heat of pipeline and oil shale retorting unitBody feed(raw material)inlet is connected; The thick oil product of rock oil hydrogenation upgrading unit exports by the thick oil of pipeline and separatorProduct feed(raw material)inlet is connected;
The hydrogen outlet of separator is divided into two passages, and a passage is by pipeline and hydrogenation of shale oil upgrading listThe circulating hydrogen entrance of unit 3 connects, and another passage speeds to exit for discharge;
The chip shale outlet of oil shale retorting unit and the residual gas outlet of shale oil gas separative elementBe connected with the fuel inlet of combustion furnace by pipeline respectively, the shale lime-ash outlet of combustion furnace is dry with oil shaleThe lime-ash that heats up in a steamer unit is connected with the lime-ash feed(raw material)inlet of production of construction materials unit by pipeline after exporting and mixing, combustionThe combustion heat that burns stove generation provides coal supply supercritical water gasification unit;
Described coal supercritical water gasification unit is provided with water-coal-slurry feed(raw material)inlet, the closing of coal supercritical water gasification unitBecome gas outlet to be connected with the high-temperature gas entrance of heat exchanger by pipeline; The normal temperature syngas outlet of heat exchanger is logicalPiping is connected with the hydrogen feed entrance of hydrogen purification unit; The hydrogen outlet of hydrogen purification unit divides twoPassage, a passage is connected with the fresh hydrogen entrance of shale hydrogenation upgrading unit by pipeline, another passageAs the outlet of product hydrogen; After mixing with fresh water entrance, passes through the circulating water outlet of hydrogen purification unit pipeRoad is connected with the cooling water inlet of heat exchanger; The supercritical water of heat exchanger exports by pipeline and coal supercritical waterThe supercritical water entrance of gasification unit connects.
Preferably, described oil shale retorting unit includes oil shale preheater, drier, retort section,One point of gas-solid is from device, the first cooler, scrubbing tower, the second cooler, gas-liquid separator and separator; ItsMiddle retort section comprises dry distillation reactor device, gasification reactor, the second gas-solid separator, heat exchanger and accumulation of heat reactionDevice;
Described preheater is provided with oil shale feed(raw material)inlet, and preheater, drier and dry distillation reactor device pass through pipelineConnect successively; Dry distillation reactor device is provided with the oil shale entrance that removes surface water, the air-fuel mixture of dry distillation reactor deviceOutlet is connected with the gas mixture entrance of the first gas-solid separator by pipeline, the first gas-solid separatorThe mixture flow export of oily is the mixture inflow entrance phase with the high temperature oily of the first cooler by pipelineConnect the mixture outlet of shale oil and carbonization gas and scrubbing tower mixture after the condensation separation of the first coolerInflow entrance is connected, and the washing gas exit of scrubbing tower is divided into two passages, respectively by pipeline and second coldBut the washing gas entry of device and gas-liquid separator is connected, and the cooled washing coal gas of the second cooler goes outMouth is connected with the logistics entrance of separator by pipeline;
Gasification reactor is provided with saturated air entrance, and the solid material inlet of gasification reactor is by pipeline andThe solid material outlet of one gas-solid separator is connected, and the gas-solid mixture flow export of gasification reactor is by pipeRoad is connected with the gas-solid mixture inflow entrance of the second gas-solid separator; The gasification gas of the second gas-solid separator goes outMouth is divided into two passages, and a passage is directly connected with the gasifying gas entrance of dry distillation reactor device by pipeline, anotherThe Heating Cyclic gas exit of one passage and heat exchanger is former by the heat carrier of pipeline and dry distillation reactor device after mixingMaterial entrance is connected;
The purification gas exit of separator is divided into two passages, and a passage is clean by pipeline and accumulation of heat reactorChange gas entry and be connected, another passage is connected with the fuel inlet of combustion furnace by pipeline; Accumulation of heat reactionDevice is provided with air intake, and the combustion reaction gas of accumulation of heat reactor exports by the combustion reaction of pipeline and heat exchangerGas entrance is connected, and the gas entry after the purification of heat exchanger is after by the purification of pipeline and gas-liquid separatorGas exit is connected.
Preferred, the outlet of the washing gas exit of described scrubbing tower, the gasification gas of the second gas-solid separator andThe purification gas exit of separator is divided into two passages by current divider, current divider, coal gas current divider respectively;Coal gas after one of them passage of gasification gas outlet and the heating of heat exchanger of described the second gas-solid separator goes outMouth mixes by concetrated pipe; Scrubbing tower, gas-liquid separator and separator are provided with shale oil outlet, three respectivelyThe shale oil of individual outlet mixes by mixing arrangement.
In such scheme, described coal gas current divider is fluid shunting device, for according to Heating Cyclic coal gasThe size adjustment split ratio of required thermic load, regulates and enters the coal gas amount of gas retort accumulation of heat reactor and enterThe coal gas amount of combustion furnace.
Preferably, described hydrogenation of shale oil upgrading unit comprise heating furnace, A reactor, second reactor,Heat exchanger, hp flash drum, fractionating column and compressor;
Heating furnace is provided with entrance, the shale oil of heating furnace and the logistics of hydrogen of shale oil and hydrogen mixture streamAfter outlet mixes with the outlet of the residual hydrocracking product of A reactor, then by pipeline and second order reactionThe logistics entrance of device is connected, the hydrorefined products export of oil shale of second reactor by pipeline with changeThe hydrorefined product inlet of oil shale of hot device is connected, the hydrogenation of shale oil gas product of heat exchanger, productOil is connected with the mixture inflow entrance of hp flash drum by pipeline with the mixture flow export of unreacting hydrogenConnect, the hydrogenated products outlet of hp flash drum is connected with the logistics entrance of fractionating column by pipeline, and high pressure dodgesThe hydrogen outlet of steaming pot is divided into two passages, and a 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, a passage passes through pipelineMix with shale oil, after the circulation residual oil outlet of another passage and fractionating column bottom mixes, then by pipeline andThe heat exchange logistics entrance of heat exchanger connects, and the heat exchange logistics outlet of heat exchanger is by pipeline and A reactorLogistics entrance is connected.
Preferred, the hydrogen outlet of hp flash drum is divided into two passages by hydrogen current divider.
In such scheme, described hydrogen current divider is fluid shunting device, for according to compression power consumption and hydrogenElement efficiency regulates split ratio, reduces discharge capacity and can improve protium efficiency, but can improve process energyConsumption, need to be optimized and could determine best split ratio.
Preferably, described coal supercritical water gasification unit comprise combustion furnace, coal supercritical water gasification reactor,Heat exchanger; Described hydrogen purification unit comprises that preheater, high-pressure separator, pressure-swing absorption apparatus and low pressure dividesFrom device;
Preheater is provided with water-coal-slurry entrance, and the water-coal-slurry of preheater exports by pipeline and coal supercritical water gasificationThe water-coal-slurry entrance of reactor is connected, and the gasification furnace of coal supercritical water gasification reactor is worked off one's feeling vent one's spleen to export and passed throughPipeline and the gasification furnace of the heat exchanger entrance of working off one's feeling vent one's spleen is connected, and the cool gasification outlet of still gas outlet of heat exchanger is logicalPiping is connected with the gas feed of high-pressure separator, and pipeline is passed through in the hydrogen-rich gas outlet of high-pressure separatorBe connected with the hydrogen-rich gas entrance of pressure-swing absorption apparatus, the gas-liquid mixture outlet of high-pressure separator is by pipeRoad is connected with the gas-liquid mixture entrance of low pressure separator, the circulating water outlet of low pressure separator and fresh waterEntrance is connected with the cooling water inlet of heat exchanger by feed pump after mixing, the supercritical water outlet of heat exchangerBe connected with the supercritical water entrance of coal supercritical water gasification reactor by pipeline; Coal supercritical water gasification is anti-Answer required thermic load in device gasification reaction process to provide by combustion furnace.
On the flue gas outlet pipeline of combustion furnace, can also be provided with heat recovery boiler.
The integrated association hydrogen production from coal gasification of a kind of oil shale oil-refining comprehensive utilization process, comprises the following steps:
Oil shale after crushing and screening passes into oil shale retorting unit generation dry distillation reactor and obtains air-fuel mixtureThing, lime-ash and unreacted chip shale, pass into shale oil gas separative element by the gas mixture obtaining and divideFrom obtaining circulating gas, shale oil and residual gas;
Wherein circulating gas returns to oil shale retorting unit process, and shale oil enters hydrogenation of shale oil upgrading unitThe mixture that obtains hydrogenation of shale oil gas product, product oil and unreacting hydrogen, mixture divides by separatorFrom obtaining unreacting hydrogen and product oil and gas product, gained unreacting hydrogen is divided into two parts, oneDivide and return to hydrogenation of shale oil upgrading unit process, a part is directly discharged;
Chip shale and residual gas pass into combustion furnace burning, obtain flue 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 water-coal-slurry preheating, pass into the unit process of coal supercritical water gasification, obtain gasification furnace and work off one's feeling vent one's spleen, wherein anti-The combustion heat of answering required heat to be produced by combustion furnace provides; Gained gasification furnace is worked off one's feeling vent one's spleen after heat exchanger heat exchangeObtain cooled gasification furnace and work off one's feeling vent one's spleen, cooled gasification furnace is worked off one's feeling vent one's spleen and is entered hydrogen purification unit process and obtainTo hydrogen, waste gas and recirculated water; Wherein a part for hydrogen passes into hydrogenation of shale oil upgrading as fresh hydrogenUnit process, another part, as product hydrogen, passes into and changes as cooling water after recirculated water mixes with fresh waterHot device heat exchange obtains supercritical water and passes into the unit process of coal supercritical water gasification.
Preferably, described oil shale particle diameter after crushing and screening is 8～75mm; Described oil shale retorting unitThe temperature of middle dry distillation reactor is 500～600 DEG C, pressure 0.1MPa.
Preferred, described reaction temperature is 525 DEG C.
Preferably, the reaction temperature 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 water-coal-slurry adopted is the brown coal of oil shale association.
In such scheme, in oil shale charging, particle diameter enters oil shale retorting list at the oil shale of 8～75mm scopeUnit, the shale that particle diameter is less than 8mm enters combustion furnace with the residual gas that oil shale retorting process produces,For the reaction of coal supercritical water gasification provides heat; The hydrogen part being obtained by coal supercritical water gasification unit is doneFor the hydrogen source of hydrogenation of shale oil upgrading, reduce the production cost of hydrogenation of shale oil upgrading unit, in addition a partHydrogen export as gas product, improve the income of process; Coal supercritical water gasification unit separator dividesFrom after the water circulation that obtains use, after mixing with fresh water, enter heat exchanger.
Preferred, in the charging of described oil shale retorting unit, the mass ratio of dry air and steam is1.05～1.20。
Preferred, the mass ratio of described dry air and steam is 1.13.
Preferably, the reaction temperature 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, operating temperature is 500～650 DEG C, and pressure is23～27MPa; The operating temperature of high-pressure separator is 25 DEG C, and pressure is 23～27MPa; Low pressure separatorOperating temperature be 25 DEG C, pressure is 0.1MPa.
More preferably 24MPa of described high-pressure separator press operation pressure.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) to be that coal is super by chip shale discarded oil shale retorting unit and unnecessary residual gas face in the present inventionBoundary's water gasification reaction provides heat, has saved and has maintained coal supercritical water gasification reaction consumption higher thermal value and Gao JingThe coal resources that Ji is worth. In existing oil shale distillation process, in most of situation, the shale to chip does not enterRow utilizes, and unnecessary coal gas is used for the lower power generation process (being generally 28～36%) of energy efficiency, and at thisIn invention, chip shale has all been utilized, and unnecessary coal gas is as the raw material of combustion process, burnsEfficiency is conventionally more than 85%.
(2) brown coal of the integrated use shale ore of the present invention association are produced the hydrogen of high economic worth. Be on the one handHydrogenation of shale oil upgrading unit provides stable hydrogen source, has reduced the production cost of hydrogenation of shale oil process; AnotherAspect, as output of products, has greatly improved the income of oil shale processing industry. A kind of oil shale refiningThe income of the integrated association hydrogen production from coal gasification comprehensive utilization of oil process has improved compared with the simple refining process of oil shaleApproximately 37%, and total investment expenses and total cost of production have approximately improved 15% and 18%.
(3) the present invention adopt coal supercritical water gasification technology for hydrogenation of shale oil upgrading unit provide stable,Enough, cheap hydrogen. Effectively solve existing scheme, comprised that residual gas pressure swing adsorption hydrogen production existsThe problem of amounts of hydrogen deficiency; There is the unsettled problem of hydrogen source in the hydrogen manufacturing of coal bed gas methane; Tradition hydrogen production from coal gasificationComplex structure, the problem that investment cost is large.
(4) oil shale accounts for 60～80% of oil shale processes amount through the lime-ash of burning or retort process generation,In existing technique most of as solid waste discharge in environment, severe contamination environment. ThisBright this solid waste is used, when having optimized resource distribution, has also improved the economy effect of processBenefit.
Brief description of the drawings
Fig. 1 is the process schematic representation of current oil-shale eduction process. Wherein 1 is oil shale retorting unit, and 2 areShale oil gas separative element, 3 is hydrogenation of shale oil upgrading unit, 4 is separator; 5～17 is logistics numbering,Wherein 5 is oil shale, and 6 is gas mixture, and 7 is chip shale, and 8 is lime-ash, and 9 is circulating gas,10 is shale oil, and 11 is residual gas, and 12 is fresh hydrogen, and 13 is hydrogenation of shale oil gas product, productThe mixture of oil and unreacting hydrogen, 14 is circulating hydrogen, and 15 is product oil and gas product, and 16 is unreactedHydrogen, 17 is the venting of speeding.
Fig. 2 is the technique of the integrated association hydrogen production from coal gasification comprehensive utilization of a kind of oil shale oil-refining of the present invention processSchematic diagram. Wherein 18 is combustion furnace, and 19 is coal supercritical water gasification unit, and 20 is heat exchanger, and 21 is hydrogenGas purifier units, 22 is production of construction materials unit; 23～37 is logistics numbering, and wherein 23 is water-coal-slurry, and 24 areThe combustion heat, 25 work off one's feeling vent one's spleen for gasification furnace, and 26 is fresh water, and 27 is cooling water, and 28 is supercritical water, 29For cooled gasification furnace is worked off one's feeling vent one's spleen, 30 is waste gas, and 31 is hydrogen, 32, and be recirculated water, 33 is product hydrogenGas, 34 is shale lime-ash, and 35 is flue gas, and 36 is lime-ash logistics, and 37 is building material product. All the other numberingsThe operating unit identical with same reference numeral in Fig. 1 or logistics.
Fig. 3 is the process chart of oil shale retorting process. Wherein 84 is preheater, and 85 is drier, 86For dry distillation reactor device, 87 is the first gas-solid separator, and 88 is gasification reactor, and 89 is the second gas-solid separator,90 is current divider, and 91 is concetrated pipe, and 92 is the first cooler, and 93 is scrubbing tower, and 95 is the second cooler,96 is gas-liquid separator, and 97 is separator, and 98 is mixing arrangement, and 99 is current divider, and 100 is heat exchanger,101 is accumulation of heat reactor; 38-62 is logistics numbering, and wherein 38 is the oil shale after preheating, and 39 for removingThe oil shale of surface water, 40 for removing water, and 41 is gasifying gas, and 42 is the mixture of shale oil and carbonization gas,43 is the solids stream of inorganic mineral and semicoke etc., and 44 is the mixing of shale oil and carbonization gas after condensation separationThing, 45 is washing coal gas, and 46 for separating latter part of shale oil and impurity, and 47 and 48 is washing coal gas,49 is cooled washing coal gas, and 50 for purifying coal gas, and 51 is shale oil, and 52 is the coal gas after purifying,53 is shale oil, and 54 is coal gas after purifying, and 55 is air, and 56 is combustion reaction gas, and 57 is Heating CyclicCoal gas, 58 is flue gas, and 59 is gasifying gas, and 60 is gasifying gas, and 61 is gasifying gas, inorganic ore depositThe mixture of material and lime-ash, 62 is saturated air. All the other numbering with Fig. 1 in same reference numeral phase jljlStream.
Fig. 4 is the technological process of hydrogenation of shale oil upgrading unit. Wherein 102 is heating furnace, and 103 is that one-level is anti-Answer device, 104 is second reactor, and 105 is heat exchanger, and 106 is high-pressure separator, and 107 is fractionating column,108 is compressor, and 109 is current divider; 63-77 is logistics numbering, and wherein 63 is that shale oil and hydrogen mixLogistics, 64 is the product of residual hydrocracking, and 65 for mixing logistics, and 66 is the hydrorefined product of oil shale,67 is the logistics after heat exchange, and 68 is circulation residual oil, and 69 is hydrogenated products, and 70 is dry gas, and 71 is liquefaction stoneOil gas, 72 is naphtha, and 73 is diesel oil, and 74 is the circulating hydrogen after compression, the 75th, mixed hydrogen, 76With 77 be hydrogen. All the other number logistics identical with same reference numeral in Fig. 1.
Fig. 5 is the process chart of coal supercritical water gasification unit. 110 is heat recovery boiler, and 111 is pre-Hot device, 112 is high-pressure separator, and 113 is pressure-swing absorption apparatus, and 114 is low pressure separator, and 115 is chargingPump, 116 is coal supercritical water gasification reactor. 78-83 is logistics numbering, and wherein 78 is air, and 79 areHot flue gases, 80 is the water-coal-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.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but enforcement side of the present inventionFormula is not limited to this.
As shown in Figure 1, wherein 1 is oil shale to the process schematic representation of oil-shale eduction process of the prior artDestructive distillation unit, 2 is shale oil gas separative element, and 3 is hydrogenation of shale oil upgrading unit, and 4 is separator; 5～17For logistics numbering, wherein 5 is oil shale, and 6 is gas mixture, and 8 is lime-ash, and 7 is chip shale, 9For circulating gas, 10 is shale oil, and 11 is residual gas, and 12 is fresh hydrogen, and 13 is hydrogenation of shale oilThe mixture of gas product, product oil and unreacting hydrogen, 14 is circulating hydrogen, 15 is product oil and gas product,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 present invention utilization system, as shown in Figure 2,Described system comprises the oil shale retorting unit 1, shale oil gas separative element 2, the hydrogenation of shale oil that connect successivelyUpgrading unit 3 and separator 4, also comprise combustion furnace 18, coal supercritical water gasification unit 19, heat exchanger 20,Hydrogen purification unit 21 and production of construction materials unit 22;
Described oil shale retorting unit 1 is provided with the entrance that passes into oil shale raw material, oil shale retorting unit 1Gas mixture outlet is connected with the gas mixture feed(raw material)inlet of shale oil gas separative element 2 by pipeline;The shale oil of shale oil gas separative element 2 exports by the shale oil of pipeline and hydrogenation of shale oil upgrading unit 3Feed(raw material)inlet is connected, and the circulating gas of shale oil gas separative element 2 exports by pipeline and oil shale retortingThe heat carrier feed(raw material)inlet of unit 1 is connected; Pipeline is passed through in the thick oil product outlet of rock oil hydrogenation upgrading unit 3Be connected with the thick oil product feed(raw material)inlet of separator 4;
The hydrogen outlet of separator 4 is divided into two passages, and a passage is by pipeline and hydrogenation of shale oil upgradingThe circulating hydrogen entrance of unit 3 connects, and another passage speeds to exit for discharge;
The chip shale outlet of oil shale retorting unit 1 and the residual gas of shale oil gas separative element 2Outlet is connected with the fuel inlet of combustion furnace 18 by pipeline respectively, the shale lime-ash outlet of combustion furnace 18After mixing with the lime-ash outlet of oil shale retorting unit 1 by the lime-ash raw material of pipeline and production of construction materials unit 22Entrance is connected, and the combustion heat that combustion furnace 18 produces provides coal supply supercritical water gasification unit 19;
Described coal supercritical water gasification unit 19 is provided with water-coal-slurry feed(raw material)inlet, coal supercritical water gasification unit 19Syngas outlet be connected with the high-temperature gas entrance of heat exchanger 20 by pipeline; The normal temperature of heat exchanger 20 closesBecome gas outlet to be connected with the hydrogen feed entrance of hydrogen purification unit 21 by pipeline; Hydrogen purification unit 21Hydrogen outlet divide two passages, a passage is by the fresh hydrogen of pipeline and shale hydrogenation upgrading unit 3Entrance connects, and another passage is as the outlet of product hydrogen; The circulating water outlet of hydrogen purification unit 21 is with newFresh water inlet is connected with the cooling water inlet of heat exchanger 20 by pipeline after mixing; Heat exchanger 20 overcriticalWater out is connected with the supercritical water entrance of coal supercritical water gasification unit 19 by pipeline.
From Fig. 1 and Fig. 2, the present invention is by chip shale discarded oil shale retorting unit and unnecessary remainingRemaining coal gas provides heat for coal supercritical water gasification reacts, and has saved and has maintained coal supercritical water gasification reaction consumptionThe coal resources of higher thermal value and high economic worth.
The present invention also provides one to realize the integrated association hydrogen production from coal gasification comprehensive utilization of above-mentioned oil shale oil-refining systemThe technique of system, comprises the following steps:
Oil shale 5 after crushing and screening passes into oil shale retorting unit 1 and dry distillation reactor occurs to obtain oil gas mixedCompound 6, lime-ash 8 and unreacted chip shale 7, pass into shale oil gas by the gas mixture obtaining 6 and divideSeparate and obtain circulating gas 9, shale oil 10 and residual gas 11 from unit 2;
Wherein circulating gas 9 returns to oil shale retorting unit 1 and reacts, and shale oil 10 enters hydrogenation of shale oil and carriesMatter unit 3 obtains the mixture 13 of hydrogenation of shale oil gas product, product oil and unreacting hydrogen, mixture 13Separate and obtain unreacting hydrogen 16 and product oil and gas product 15, gained unreacting hydrogen by separator16 are divided into two parts part returns to hydrogenation of shale oil upgrading unit 3 and reacts, and a part is directly discharged;
Chip shale 7 and residual gas 11 pass into combustion furnace 18 and burn, and obtain flue gas 35, shale lime-ash34 and the combustion heat 24; The mixed lime-ash logistics 36 of lime-ash 8 and shale lime-ash 34 passes into production of construction materials unit22 produce building material product 37;
After water-coal-slurry 23 preheatings, pass into coal supercritical water gasification unit 19 and react, obtain gasification 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 combustion furnace provides; Gained gasification furnace 25 warps of working off one's feeling vent one's spleenAfter heat exchanger 20 heat exchange, obtain cooled gasification furnace and work off one's feeling vent one's spleen 29, cooled gasification furnace is worked off one's feeling vent one's spleen and 29 is enteredEnter 21 reactions of hydrogen purification unit and obtain hydrogen 31, waste gas 30 and recirculated water 32; Wherein one of hydrogen 31Part passes into hydrogenation of shale oil upgrading unit 3 as fresh hydrogen 12 and reacts, and another part is as product hydrogen33, after recirculated water 32 mixes with fresh water 26, pass into heat exchanger 20 heat exchange as cooling water 27 and obtain super facingBoundary's water 28 also passes into coal supercritical water gasification unit 19 and reacts. Waste gas 30 directly discharges.
In above-mentioned technique in oil shale retorting unit 1 reaction detailed process as shown in Figure 3:
Oil shale 5 after crushing and screening is through preheater 84 preheatings, the oil shale 38 drying devices after preheating85 remove after outside water 40, and the oil shale 39 that removes surface water enters dry distillation reactor device 86, carries out destructive distillation anti-Should generate the mixing logistics 6 containing shale oil, carbonization gas and semicoke; Mix logistics 6 through the first gas-solid separator87 are separated into mixture 42 and the solids stream 43 of shale oil and carbonization gas;
The mixture 42 of shale oil and carbonization gas is shale after the cooling condensation separation obtaining of the first cooler 92The mixture 44 of oil and carbonization gas enters scrubbing tower 93 and washs, and obtains separating rear portion shale oil and impurity46 with washing coal gas 45, washing coal gas 45 be divided into two bursts of logistics by current divider 94, be respectively washing coal gas 47With washing coal gas 48, washing coal gas 48 enters gas-liquid separator 96 and obtains the coal gas after shale oil 53 and purification52, the coal gas 52 after purification enters heat exchanger 100; Washing coal gas 47 obtains cooling through the second cooler 95After washing coal gas 49, cooled washing coal gas 49 enters and obtains shale oil 51 after separator 97 and purifyRear coal gas 50, coal gas 50 coal gas 54 and residual gas 11 after coal gas current divider 99 is divided into purification after purifyingTwo parts, after purifying, coal gas 54 enters after accumulation of heat reactor 101 mixes with air 55 and burns, thenThe combustion reaction gas 56 obtaining passes into heat exchanger 100 and the coal gas 52 after purifying is heated to 500～600 DEG C,Obtain circulating gas 57 and flue gas 58 after heating, residual gas 11 enters combustion furnace 18;
Solids stream 43 enters gasification reactor 88 and mixes generating gasification reaction with saturated air 62, reactTo the mixing logistics 61 of gasifying gas, inorganic mineral and lime-ash enter the second gas-solid separator 89 and removeLime-ash 8 obtains gasifying gas 60 after (also comprising the solid matters such as semicoke), and the gasifying gas 60 obtaining is through dividingStream device 90 is divided into gasifying gas 41 and gasifying gas 59 two parts, and it is anti-that gasifying gas 41 directly passes into destructive distillationAnswer device 86, for retort section provides heat, the circulating gas 57 after gasifying gas 59 and heating is through concetrated pipe 91After mixing, obtain circulating gas 9, 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 arrangement 98 mixes.
Described in above-mentioned technique in the charging of the gasification reactor of oil shale retorting unit, air and steamMass ratio is 1.05～1.20. Preferred, the mass ratio of described air and steam 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:
Circulating hydrogen 74 after the fresh hydrogen 12 that make-up hydrogen compressor comes and recycle gas compressor 108 compressions is mixedHydrogen 75 after closing is divided into hydrogen 77 and hydrogen 76 two parts, and shale oil 10 enters and adds together with hydrogen 77Hot stove 102 heats, and obtains shale oil and hydrogen mixture stream 63, and it is 63 same that shale oil and hydrogen mixture flowThe mixed mixing logistics 65 of product 64 of the residual hydrocracking of stage reactor 103 enters second reactor104 carry out the refining reactions such as desulfurization, denitrogenation, concurrent first portion cracking reaction, and second reactor 104 obtainsThe hydrorefined product 66 of oil shale obtains containing hydrogenation of shale oil gas product, product after heat exchanger 105 heat exchangeThe mixture 13 of product oil and unreacting hydrogen, mixture 13 enters high-pressure separator 106 and obtains unreacting hydrogen16 and hydrogenated products 69, unreacting hydrogen 16 is divided into most of hydrogen 14 and little portion through hydrogen current divider 109Divide hydrogen 17, most of hydrogen 14 enters recycle gas compressor 108 and recycles, and fraction hydrogen 17 is doneExit for speeding and directly discharge; Hydrogenated products 69 through fractionating column 107 obtain dry gas 70, liquefied petroleum gas 71,Naphtha 72, diesel oil 73 and unconverted circulation residual oil 68, circulation residual oil 68 is taken out at the bottom of by fractionating column 107 towersGo out, after mixing with hydrogen 76, enter heat exchanger 105 and changed with hydrorefined product 66 heat exchange of oil shaleLogistics 67 after heat, 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 reaction temperature of second reactor are350～400 DEG C, pressure is 15.7MPa; The mass ratio of fresh hydrogen and shale oil is 0.03～0.04. More excellentChoosing, the reaction temperature of described A reactor is 385 DEG C; The reaction temperature of described second reactor is 390℃。
The detailed process of reacting in coal supercritical water gasification unit described in above-mentioned technique and hydrogen purification unit asShown in Fig. 5:
Through preheater, 111 heating obtain the water-coal-slurry 80 after preheating, the water-coal-slurry after preheating to water-coal-slurry 2380 enter coal supercritical water gasification reactor 116 reacts with supercritical water 28 generating gasification and obtains gasification furnace outletGas 25, gasification furnace is worked off one's feeling vent one's spleen and 25 after heat exchanger 20 heat exchange, is obtained cooled gasification furnace and work off one's feeling vent one's spleen 29; ColdBut the gasification furnace after 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 low pressure and dividesObtain waste gas 30 and recirculated water 32 from device 114, recirculated water 32 and the mixed water 83 of fresh water 26 are through enteringMaterial pump 115 enters heat exchanger 20 as cooling water 27, and 25 heat exchange of working off one's feeling vent one's spleen of cooling water 27 and gasification furnace obtainSupercritical water 28, supercritical water 28 enters the 116 generating gasification reactions of coal supercritical water gasification reactor; Gasification24 of the combustions heat required in course of reaction provide by combustion furnace 18;
The chip shale 7 of described oil shale retorting unit and residual gas 11 are all crossed fuel inlet and are passed into combustion furnace18 as fuel, produces the combustion heat 24, shale lime-ash 34 and hot flue gases 79, hot cigarette with air 78 burningsFlue gas 35 after road gas 79 must be lowered the temperature after heat recovery boiler 110; Hydrogenation of shale oil upgrading unit newThe hydrogen 31 that fresh hydrogen is produced by coal supercritical water gasification unit provides.
In above-mentioned technique, the lime-ash 8 that described oil shale retorting unit produces and coal supercritical water gasification unit produceRaw shale lime-ash 34, all passes into production of construction materials unit 22.
In described coal supercritical gasification reaction member, the operating temperature of gasification reactor is 500～650 DEG C, pressureBe 23～27MPa; The operating temperature of high-pressure separator is 25 DEG C, and pressure is 23～27MPa; Low pressure separatesThe operating temperature of device is 25 DEG C, and pressure is 0.1MPa. Described high-pressure separator press operation pressure more preferably24MPa。
Embodiment 1
Specifically being implemented as follows of the oil shale of the present embodiment and association coal comprehensive utilization process thereof:
The raw material shale flow that enters technique of the present invention is 322.5t/h, and that wherein enter gas retort is 275t/h,Chip shale flow is 47.5t/h. Gas retort gasification section steam is 1.13 with air quality ratio. Entering of brown coalMaterial amount is 33.91t/h. The Industrial Analysis of oil shale and brown coal and elementary analysis are in table 1. Oil shale oil-refining is integratedThe process chart of association hydrogen production from coal gasification comprehensive utilization process is shown in Fig. 2.
The Industrial Analysis elementary analysis of table 1 oil shale and brown coal
(M in table, FC, V, and A represents respectively the content of moisture in oil shale, fixed carbon, volatile matter and ash, and ar represents As-received, wt representsMass fraction)
Oil shale retorting process is as shown in Figure 3:
After crushing and screening, the oil shale 5 of particle diameter 8～75mm is through preheater 84 preheatings, the oil shale after preheating38 drying devices 85 remove after outside water 40, and the oil shale 39 that removes surface water enters dry distillation reactor device 86,At 0.1MPa, 525 DEG C, carry out dry distillation reactor and generate the mixing logistics 6 containing shale oil, carbonization gas and semicoke;Mix logistics 6 is separated into shale oil and carbonization gas mixture 42 and solids through the first gas-solid separator 87Stream 43;
The mixture 42 of shale oil and carbonization gas is shale after the cooling condensation separation obtaining of the first cooler 92The mixture 44 of oil and carbonization gas enters scrubbing tower 93 and washs, and obtains separating rear portion shale oil and impurity46 with washing coal gas 45, washing coal gas 45 be divided into two bursts of logistics by current divider 94, be respectively washing coal gas 47With washing coal gas 48, washing coal gas 48 enters gas-liquid separator 96 and obtains the coal gas after shale oil 53 and purification52, the coal gas 52 after purification enters heat exchanger 100; Washing coal gas 47 obtains cooling through the second cooler 95After washing coal gas 49, cooled washing coal gas 49 enters and obtains shale oil 51 after separator 97 and purifyRear coal gas 50, coal gas 50 coal gas 54 and residual gas 11 after coal gas current divider 99 is divided into purification after purifyingTwo parts, after purifying, coal gas 54 enters after accumulation of heat reactor 101 mixes with air 55 and burns, thenThe combustion reaction gas 56 obtaining passes into heat exchanger 100 and the coal gas 52 after purifying is heated to 550 DEG C, obtainsCirculating gas 57 after heating and flue gas 58, residual gas 11 enters combustion furnace 18;
Solids stream 43 enters 88 and 85 DEG C of saturated airs 62 of gasification reactor and is blended in 0.1MPa, 850 DEG CLower generating gasification reaction, the mixing logistics 61 of gasifying gas, inorganic mineral and lime-ash that reaction obtains entersThe second gas-solid separator 89 obtains gasifying gas 60 after removing lime-ash 8 (also comprising the solid matters such as semicoke),The gasifying gas 60 obtaining is divided into gasifying gas 41 and gasifying gas 59 two parts through current divider 90, gasificationGas 41 directly passes into dry distillation reactor device 86, for retort section provides heat, after gasifying gas 59 and heatingCirculating gas 57 obtains circulating gas 9 after concetrated pipe 91 mixes, and circulating gas 9 passes into dry distillation reactor device86, for retort section provides heat;
Shale oil 46, shale oil 53 and shale oil 51 obtain shale oil 10 after mixing arrangement 98 mixes.
Hydrogenation of shale oil upgrading process is as shown in Figure 4:
Circulating hydrogen 74 after the fresh hydrogen 12 that make-up hydrogen compressor comes and recycle gas compressor 108 compressions is mixedHydrogen 75 after closing is divided into hydrogen 77 and hydrogen 76 two parts, and shale oil 10 enters and adds together with hydrogen 77Hot stove 102 heats, and obtains shale oil and hydrogen mixture stream 63, and it is 63 same that shale oil and hydrogen mixture flowAfter mixing, the product 64 of the residual hydrocracking of stage reactor 103 enters second reactor 104 at 380 DEG C of barsUnder part, carry out the refining reactions such as desulfurization, denitrogenation, concurrent first portion cracking reaction, second reactor 104 obtainsThe hydrorefined product 66 of oil shale after heat exchanger 105 heat exchange, obtain containing hydrogenation of shale oil gas product,The mixture 13 of product oil and unreacting hydrogen, mixture 13 enters high-pressure separator 106 and obtains unreacted hydrogenGas 16 and hydrogenated products 69, unreacting hydrogen 16 is divided into most of hydrogen 14 and little through hydrogen current divider 109Hydrogen partial 17, most of hydrogen 14 enters recycle gas compressor 108 and recycles, fraction hydrogen 17Exit as speeding and directly discharge; Hydrogenated products 69 through fractionating column 107 obtain dry gas 70, liquefied petroleum gas 71,Naphtha 72, diesel oil 73 and unconverted circulation residual oil 68, circulation residual oil 68 is taken out at the bottom of by fractionating column 107 towersGo out, after mixing with hydrogen 76, enter heat exchanger 105 and changed with hydrorefined product 66 heat exchange of oil shaleLogistics 67 after heat, it is to enter under 380 DEG C of conditions in temperature that the logistics 67 after heat exchange enters A reactor 103Row hydrocracking reaction. 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 water-coal-slurry 80 after preheating, the water-coal-slurry after preheating to water-coal-slurry 2380 enter coal supercritical water gasification reactor 116 reacts with supercritical water 28 generating gasification and obtains gasification furnace outlet(water-coal-slurry 80 after preheating and supercritical water 28 are from the Lower Half of coal supercritical water gasification reactor 19 for gas 25Divide and pass into, gasification furnace works off one's feeling vent one's spleen 25 from the extraction of reactor the first half), reaction temperature is 600 DEG C, pressure is25MPa, gasification furnace is worked off one's feeling vent one's spleen and 25 after heat exchanger 20 heat exchange, is obtained cooled gasification furnace and work off one's feeling vent one's spleen 29;Cooled gasification 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 mixture82; Hydrogen-rich gas 81 enters pressure-swing absorption apparatus 113, obtains hydrogen 31; Gas-liquid mixture 82 enters lowPress separator 114 to obtain waste gas 30 and recirculated water 32, recirculated water 32 and the mixed water 83 of fresh water 26Enter heat exchanger 20 through feed pump 115 as cooling water 27,25 heat exchange of working off one's feeling vent one's spleen of cooling water 27 and gasification furnaceObtain supercritical water 28, 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 are by combustion furnace 18 burn chip shale 7 and residual gas11 provide.
Existing oil-shale eduction process mainly comprises above-mentioned oil shale retorting process and hydrogenation of shale oil process,To 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 efficiencyCan be increased to respectively 33.88% and 22.72% with profit-investment ratio, the lime-ash that process produces nearly all obtains effectivelyUtilize. Compare existing oil-shale eduction process, energy efficiency and profit-investment ratio have improved respectively compared with process7.97% and 9.87%.
Embodiment 2
Specifically being implemented as follows of the oil shale of the present embodiment and association coal comprehensive utilization process thereof:
The raw material shale flow that enters technique of the present invention is 375t/h, and that wherein enter gas retort is 300t/h,Chip shale flow is 75t/h. Gas retort gasification section steam is 1.20 with air quality ratio. The charging of brown coalAmount is 48.36t/h. The Industrial Analysis of oil shale and brown coal and elementary analysis are in table 2. The integrated companion of oil shale oil-refiningThe process chart of soft coal gasification hydrogen-producing comprehensive utilization process is shown in Fig. 2.
The Industrial Analysis elementary analysis of table 2 oil shale and brown coal
(M in table, FC, V, and A represents respectively the content of moisture in oil shale, fixed carbon, volatile matter and ash, and ar represents As-received, wt representsMass fraction)
Oil shale retorting process is as shown in Figure 3:
After crushing and screening, the oil shale 5 of particle diameter 8～75mm is through preheater 84 preheatings, the oil shale after preheating38 drying devices 85 remove after outside water 40, and the oil shale 39 that removes surface water enters dry distillation reactor device 86,At 0.1MPa, 600 DEG C, carry out dry distillation reactor and generate the mixing logistics 6 containing shale oil, carbonization gas and semicoke;Mix logistics 6 is separated into shale oil and carbonization gas mixture 42 and solids through the first gas-solid separator 87Stream 43;
The mixture 42 of shale oil and carbonization gas is shale after the cooling condensation separation obtaining of the first cooler 92The mixture 44 of oil and carbonization gas enters scrubbing tower 93 and washs, and obtains separating rear portion shale oil and impurity46 with washing coal gas 45, washing coal gas 45 be divided into two bursts of logistics by current divider 94, be respectively washing coal gas 47With washing coal gas 48, washing coal gas 48 enters gas-liquid separator 96 and obtains the coal gas after shale oil 53 and purification52, the coal gas 52 after purification enters heat exchanger 100; Washing coal gas 47 obtains cooling through the second cooler 95After washing coal gas 49, cooled washing coal gas 49 enters and obtains shale oil 51 after separator 97 and purifyRear coal gas 50, coal gas 50 coal gas 54 and residual gas 11 after coal gas current divider 99 is divided into purification after purifyingTwo parts, after purifying, coal gas 54 enters after accumulation of heat reactor 101 mixes with air 55 and burns, thenThe combustion reaction gas 56 obtaining passes into heat exchanger 100 and the coal gas 52 after purifying is heated to 600 DEG C, obtainsCirculating gas 57 after heating and flue gas 58, residual gas 11 enters combustion furnace 18;
Solids stream 43 enters 88 and 85 DEG C of saturated airs 62 of gasification reactor and is blended in 0.1MPa, 900 DEG CLower generating gasification reaction, the mixing logistics 61 of gasifying gas, inorganic mineral and lime-ash that reaction obtains entersThe second gas-solid separator 89 obtains gasifying gas 60 after removing lime-ash 8 (also comprising the solid matters such as semicoke),The gasifying gas 60 obtaining is divided into gasifying gas 41 and gasifying gas 59 two parts through current divider 90, gasificationGas 41 directly passes into dry distillation reactor device 86, for retort section provides heat, after gasifying gas 59 and heatingCirculating gas 57 obtains circulating gas 9 after concetrated pipe 91 mixes, and circulating gas 9 passes into dry distillation reactor device86, for retort section provides heat;
Shale oil 46, shale oil 53 and shale oil 51 obtain shale oil 10 after mixing arrangement 98 mixes.
Hydrogenation of shale oil upgrading process is as shown in Figure 4:
Circulating hydrogen 74 after the fresh hydrogen 12 that make-up hydrogen compressor comes and recycle gas compressor 108 compressions is mixedHydrogen 75 after closing is divided into hydrogen 77 and hydrogen 76 two parts, and shale oil 10 enters and adds together with hydrogen 77Hot stove 102 heats, and obtains shale oil and hydrogen mixture stream 63, and it is 63 same that shale oil and hydrogen mixture flowAfter mixing, the product 64 of the residual hydrocracking of stage reactor 103 enters second reactor 104 at 400 DEG C of barsUnder part, carry out the refining reactions such as desulfurization, denitrogenation, concurrent first portion cracking reaction, second reactor 104 obtainsThe hydrorefined product 66 of oil shale after heat exchanger 105 heat exchange, obtain containing hydrogenation of shale oil gas product,The mixture 13 of product oil and unreacting hydrogen, mixture 13 enters high-pressure separator 106 and obtains unreacted hydrogenGas 16 and hydrogenated products 69, unreacting hydrogen 16 is divided into most of hydrogen 14 and little through hydrogen current divider 109Hydrogen partial 17, most of hydrogen 14 enters recycle gas compressor 108 and recycles, fraction hydrogen 17Exit as speeding and directly discharge; Hydrogenated products 69 through fractionating column 107 obtain dry gas 70, liquefied petroleum gas 71,Naphtha 72, diesel oil 73 and unconverted circulation residual oil 68, circulation residual oil 68 is taken out at the bottom of by fractionating column 107 towersGo out, after mixing with hydrogen 76, enter heat exchanger 105 and changed with hydrorefined product 66 heat exchange of oil shaleLogistics 67 after heat, it is to enter under 380 DEG C of conditions in temperature that the logistics 67 after heat exchange enters A reactor 103Row hydrocracking reaction. 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 water-coal-slurry 80 after preheating, the water-coal-slurry after preheating to water-coal-slurry 2380 enter coal supercritical water gasification reactor 116 reacts with supercritical water 28 generating gasification and obtains gasification furnace outletGas 25, reaction temperature is 650 DEG C, and pressure is 27MPa, and gasification furnace works off one's feeling vent one's spleen 25 through heat exchanger 20 heat exchangeAfter obtain cooled gasification furnace and work off one's feeling vent one's spleen 29; Cooled gasification furnace is worked off one's feeling vent one's spleen and 29 is entered high-pressure separator112 obtain hydrogen-rich gas 81 and gas-liquid mixture 82; Hydrogen-rich gas 81 enters pressure-swing absorption apparatus 113,To hydrogen 31; Gas-liquid mixture 82 enters low pressure separator 114 and obtains waste gas 30 and recirculated water 32, circulationWater 32 enters heat exchanger 20 through feed pump 115 as cooling water 27 with the mixed water 83 of fresh water 26,25 heat exchange of working off one's feeling vent one's spleen of cooling water 27 and gasification furnace obtain supercritical water 28, and it is overcritical that supercritical water 28 enters coalThe 116 generating gasification reactions of water gasification reactor; 24 of the combustions heat required in gasification reaction process pass through burningBurn chip shale 7 and residual gas 11 of stove 18 provides.
Existing oil-shale eduction process mainly comprises above-mentioned oil shale retorting process and hydrogenation of shale oil process,To 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 efficiencyCan be increased to respectively 34.20% and 22.95% with profit-investment ratio, the lime-ash that process produces nearly all obtains effectivelyUtilize. Compare existing oil-shale eduction process, energy efficiency and profit-investment ratio have improved 8.29% and 8.50%.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not subject to above-mentioned realityExecute routine restriction, other any do not deviate from the change done under Spirit Essence of the present invention and principle, modification,Substitute, combine, simplify, all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. the integrated association hydrogen production from coal gasification of an oil shale oil-refining utilization system, comprises the oil connecting successivelyShale retorting unit, shale oil gas separative element, hydrogenation of shale oil upgrading unit and separator, its feature existsIn, described system also comprises combustion furnace, coal supercritical water gasification unit, First Heat Exchanger, hydrogen purification listUnit and production of construction materials unit;
Described oil shale retorting unit is provided with the entrance that passes into oil shale raw material, the oil gas of oil shale retorting unitMixture outlet is connected with the gas mixture feed(raw material)inlet of shale oil gas separative element by pipeline; ShaleThe shale oil of Oil-gas Separation unit exports by the shale oil feed(raw material)inlet of pipeline and hydrogenation of shale oil upgrading unitBe connected, the circulating gas outlet of shale oil gas separative element is carried by the heat of pipeline and oil shale retorting unitBody feed(raw material)inlet is connected; The thick oil product outlet of hydrogenation of shale oil upgrading unit is thick by pipeline and separatorOil product feed(raw material)inlet is connected;
The hydrogen outlet of separator is divided into two passages, and a passage is by pipeline and hydrogenation of shale oil upgrading listThe circulating hydrogen entrance of unit connects, and another passage speeds to exit for discharge;
The chip shale outlet of oil shale retorting unit and the residual gas outlet of shale oil gas separative elementBe connected with the fuel inlet of combustion furnace by pipeline respectively, the shale lime-ash outlet of combustion furnace is dry with oil shaleThe lime-ash that heats up in a steamer unit is connected with the lime-ash feed(raw material)inlet of production of construction materials unit by pipeline after exporting and mixing, combustionThe combustion heat that burns stove generation provides coal supply supercritical water gasification unit;
Described coal supercritical water gasification unit is provided with water-coal-slurry feed(raw material)inlet, the closing of coal supercritical water gasification unitBecome gas outlet to be connected with the high-temperature gas entrance of First Heat Exchanger by pipeline; The normal temperature of First Heat Exchanger is syntheticGas outlet is connected with the hydrogen feed entrance of hydrogen purification unit by pipeline; The hydrogen of hydrogen purification unit goes outMouth point two passages, a passage is connected with the fresh hydrogen entrance of shale hydrogenation upgrading unit by pipeline,Another passage is as product hydrogen outlet; After the circulating water outlet of hydrogen purification unit mixes with fresh water entranceBe connected with the cooling water inlet of First Heat Exchanger by pipeline; The supercritical water outlet of First Heat Exchanger is by pipeRoad is connected with the supercritical water entrance of coal supercritical water gasification unit.
2. system according to claim 1, is characterized in that, described oil shale retorting unit includesOil shale preheater, drier, retort section, the first gas-solid separator, the first cooler, scrubbing tower,Two coolers, gas-liquid separator and separator; Wherein retort section comprise dry distillation reactor device, gasification reactor,The second gas-solid separator, the second heat exchanger and accumulation of heat reactor;
Described preheater is provided with oil shale feed(raw material)inlet, and preheater, drier and dry distillation reactor device pass through pipelineConnect successively; Dry distillation reactor device is provided with the oil shale entrance that removes surface water, the air-fuel mixture of dry distillation reactor deviceOutlet is connected with the gas mixture entrance of the first gas-solid separator by pipeline, the first gas-solid separatorThe mixture flow export of oily is the mixture inflow entrance phase with the high temperature oily of the first cooler by pipelineConnect the mixture outlet of shale oil and carbonization gas and scrubbing tower mixture after the condensation separation of the first coolerInflow entrance is connected, and the washing gas exit of scrubbing tower is divided into two passages, respectively by pipeline and second coldBut the washing gas entry of device and gas-liquid separator is connected, and the cooled washing coal gas of the second cooler goes outMouth is connected with the logistics entrance of separator by pipeline;
Gasification reactor is provided with saturated air entrance, and the solid material inlet of gasification reactor is by pipeline andThe solid material outlet of one gas-solid separator is connected, and the gas-solid mixture flow export of gasification reactor is by pipeRoad is connected with the gas-solid mixture inflow entrance of the second gas-solid separator; The gasification gas of the second gas-solid separator goes outMouth is divided into two passages, and a passage is directly connected with the gasifying gas entrance of dry distillation reactor device by pipeline, anotherThe Heating Cyclic gas exit of one passage and the second heat exchanger carries by the heat of pipeline and dry distillation reactor device after mixingBody feed(raw material)inlet is connected;
The purification gas exit of separator is divided into two passages, and a passage is clean by pipeline and accumulation of heat reactorChange gas entry and be connected, another passage is connected with the fuel inlet of combustion furnace by pipeline; Accumulation of heat reactionDevice is provided with air intake, and the combustion reaction gas of accumulation of heat reactor exports by the burning of pipeline and the second heat exchangerReaction gas entrance is connected, and the gas entry after the purification of the second heat exchanger is by pipeline and gas-liquid separatorGas exit after purification is connected.
3. system according to claim 1, is characterized in that, described hydrogenation of shale oil upgrading unit bagDraw together heating furnace, A reactor, second reactor, the 3rd heat exchanger, hp flash drum, fractionating column and pressureContracting machine;
Heating furnace is provided with entrance, the shale oil of heating furnace and the logistics of hydrogen of shale oil and hydrogen mixture streamAfter outlet mixes with the outlet of the residual hydrocracking product of A reactor by pipeline, then by pipeline andSecond reactor logistics entrance is connected, and the hydrorefined products export of oil shale of second reactor is by pipeRoad is connected with the hydrorefined product inlet of oil shale of the 3rd heat exchanger, and the shale oil of the 3rd heat exchanger addsThe mixture flow export of hydrogen production gas, product oil and unreacting hydrogen mixes by pipeline and hp flash drumLogistics entrance is connected, and the hydrogenated products outlet of hp flash drum is the logistics entrance phase with fractionating column by pipelineConnect, the hydrogen outlet of hp flash drum is divided into two passages, and a passage is by the hydrogen of pipeline and compressorEntrance is connected, and another passage directly discharge speeds to exit;
The hydrogen outlet of compressor is divided into two passages after mixing with fresh hydrogen entrance, a passage passes through pipelineMix with shale oil, after the circulation residual oil outlet of another passage and fractionating column bottom mixes, then by pipeline andThe heat exchange logistics entrance of the 3rd heat exchanger connects, and the heat exchange logistics of the 3rd heat exchanger exports by pipeline and one-levelThe logistics entrance of reactor is connected.
4. system according to claim 1, is characterized in that, described coal supercritical water gasification unit bagContaining coal supercritical water gasification reactor, preheater; Described hydrogen purification unit comprises high-pressure separator, transformationAdsorbent equipment and low pressure separator;
Preheater is provided with water-coal-slurry entrance, and the water-coal-slurry of preheater exports by pipeline and coal supercritical water gasificationThe water-coal-slurry entrance of reactor is connected, and the gasification furnace of coal supercritical water gasification reactor is worked off one's feeling vent one's spleen to export and passed throughPipeline and the gasification furnace of the First Heat Exchanger entrance of working off one's feeling vent one's spleen is connected, the cool gasification outlet of still of First Heat ExchangerGas outlet is connected with the gas feed of high-pressure separator by pipeline, the hydrogen-rich gas outlet of high-pressure separatorBe connected with the hydrogen-rich gas entrance of pressure-swing absorption apparatus by pipeline, the gas-liquid mixture of high-pressure separator goes outMouth is connected with the gas-liquid mixture entrance of low pressure separator by pipeline, the circulating water outlet of low pressure separatorAfter mixing with fresh water entrance, be connected with the cooling water inlet of First Heat Exchanger by feed pump, the first heat exchangeThe supercritical water outlet of device is connected with the supercritical water entrance of coal supercritical water gasification reactor by pipeline.
5. the integrated association hydrogen production from coal gasification of an oil shale oil-refining comprehensive utilization process, is characterized in that, comprisesFollowing steps:
Oil shale after crushing and screening passes into oil shale retorting unit generation dry distillation reactor and obtains air-fuel mixtureThing, lime-ash and unreacted chip shale, pass into shale oil gas separative element by the gas mixture obtaining and divideFrom obtaining circulating gas, shale oil and residual gas;
Wherein circulating gas returns to oil shale retorting unit process, and shale oil enters hydrogenation of shale oil upgrading unitThe mixture that obtains hydrogenation of shale oil gas product, product oil and unreacting hydrogen, mixture divides by separatorFrom obtaining unreacting hydrogen and product oil and gas product, a gained unreacting hydrogen part is returned to shale oilHydrogenation upgrading unit process, a part is directly discharged;
Chip shale and residual gas pass into combustion furnace burning, obtain flue 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 water-coal-slurry preheating, pass into the unit process of coal supercritical water gasification, obtain gasification furnace and work off one's feeling vent one's spleen, wherein anti-The combustion heat of answering required heat to be produced by combustion furnace provides; Gained gasification furnace is worked off one's feeling vent one's spleen after heat exchanger is coolingEnter hydrogen purification unit process and obtain hydrogen, waste gas and recirculated water; Wherein a part for hydrogen is as freshHydrogen passes into hydrogenation of shale oil upgrading unit process, and recirculated water passes into heat exchanger heat exchange and obtains after mixing with fresh waterTo supercritical water and pass into the unit process of coal supercritical water gasification.
6. technique according to claim 5, is characterized in that, described oil shale after crushing and screeningParticle diameter is 8～75mm; In described oil shale retorting unit, the temperature of dry distillation reactor is 500～600 DEG C, pressure0.1MPa。
7. technique according to claim 5, is characterized in that, described hydrogenation of shale oil upgrading unitReaction temperature is 350～400 DEG C, and pressure is 15.7MPa.
8. technique according to claim 5, is characterized in that, the charging of described oil shale retorting unitIn, the mass ratio of dry air and steam is 1.05～1.20.
9. technique according to claim 5, is characterized in that, described hydrogenation of shale oil upgrading unitReaction temperature is 350～400 DEG C, and pressure is 15.7MPa; The mass ratio of fresh hydrogen and shale oil is0.03～0.04。
10. technique according to claim 5, is characterized in that, described coal supercritical water gasification reactionThe operating temperature of unit is 500～650 DEG C, and pressure is 23～27MPa; The operating temperature of high-pressure separator is25 DEG C, pressure is 23～27MPa; The operating temperature of low pressure separator is 25 DEG C, and pressure is 0.1MPa.
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| 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 |
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