CN104004532A - Integrated refining system and process using oil shale retorting gas to produce hydrogen and upgrade - Google Patents
Integrated refining system and process using oil shale retorting gas to produce hydrogen and upgrade Download PDFInfo
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Abstract
The invention discloses an integrated refining system and process using an oil shale retorting gas to produce hydrogen and upgrade. The system comprises an oil shale destructive distillation unit, a shale oil hydrogenation and upgrading unit, a methane vapor reforming unit and a building material production unit, wherein the methane vapor reforming unit comprises a vapor reforming reactor, a CaO regenerative combustion furnace, a compression heat exchanger, a vapor reforming gas flash-evaporation tower and a transformation adsorption device. According to the system and process disclosed by the invention, methane reforming reaction is carried out onto the destructive distillation gas, a hydrogen source is provided for shale oil hydrogenation and upgrading, complementary utilization of the destructive distillation gas and the shale oil hydrogen element is realized, and waste fragment shale of the oil shale destructive distillation unit is combusted to provide heat for roasting CaCO3 in the CaO regenerative combustion furnace, so that utilization efficiency of resources and energy resources is improved. According to the system and process disclosed by the invention, economic benefits of the existing oil shale oil-refining and upgrading processes can be remarkably improved, resource utilization rate of the process is increased, and emission of solid waste and an industrial waste gas is reduced.
Description
Technical field
The invention belongs to the energy and chemical technology field, be specifically related to a kind of integrated refining system and technique with oil shale distillation gas hydrogen manufacturing upgrading.
Background technology
Along with global demand of petroleum constantly rises, contradiction between oil supply and demand is increasingly serious, and search for oil substitute energy is imperative.Resinous shale is abundant with its reserves, develops and has feasibility, is subject to the extensive attention of countries in the world, is acknowledged as one of oil replacement resource of tool potentiality.According to recent statistics, convert the explored resinous shale in the whole world to 3,000,000,000,000 barrels of shale oil, be equivalent to current 1.8 times of having verified crude oil 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, for realizing energy diversification, provide practicable approach.
The general flow chart of traditional oils shale refining process is shown in Fig. 1.Traditional oils shale refining process is mainly by oil shale distillation unit 1, and hydrogenation of shale oil upgrading unit 2 and production of construction materials unit 9 form.Resinous shale enters oil shale distillation unit after screening, first through dry distillation reactor, generates shale oil, carbonization gas and semicoke, and semicoke enters vapourizing furnace generating gasification reaction under the effect of air, and the gaseous mixture of generation returns to gas retort.The shale oil that oil shale distillation unit generates enters hydrogenation of shale oil upgrading unit and generates petroleum naphtha, diesel oil and liquefied petroleum gas (LPG).The lime-ash that oil shale distillation unit produces and chip shale enter production of construction materials unit and obtain haydite and shale brick.
There is following problem in tradition oil-shale eduction process: the residual gas calorific value that (1) gas retort produces is low, can only can not be used as business coal gas as boiler or automotive fuel, and utility value is not high; (2) the chip shale that oil shale distillation process produces utilizes degree not high, has the particle diameter of the chip shale of 25% left and right to be less than 10mm, as waste discharge, is directly used in production building material product; (3) hydrogen market value is higher at present, adopts outsourcing hydrogen to carry out hydrogenation of shale oil upgrading as hydrogen source, can improve undoubtedly the production cost of process, reduces the economic benefit of process.
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 integrated refining system with oil shale distillation gas hydrogen manufacturing upgrading.
Another object of the present invention is to provide a kind of integrated refining process with oil shale distillation gas hydrogen manufacturing upgrading.
For achieving the above object, the present invention adopts following technical scheme:
With an integrated refining system for oil shale distillation gas hydrogen manufacturing upgrading, described system comprises oil shale distillation unit, hydrogenation of shale oil upgrading unit and production of construction materials unit, also comprises methane vapor reforming unit;
Described oil shale distillation unit is provided with the entrance that passes into resinous shale raw material, the shale oil outlet of oil shale distillation unit is directly connected with the shale oil feed(raw material)inlet of hydrogenation of shale oil upgrading unit by pipeline, the carbonization gas outlet of oil shale distillation unit is connected with the carbonization gas feed(raw material)inlet of the steam reforming reaction device of methane vapor reforming unit by pipeline, the chip shale outlet of oil shale distillation unit is connected with the chip shale entrance of the CaO regenerative combustion stove of methane vapor reforming unit by e Foerderanlage, the lime-ash outlet of oil shale distillation unit and the shale lime-ash outlet of methane vapor reforming unit are all connected with the lime-ash feed(raw material)inlet of production of construction materials unit by e Foerderanlage, the steam reforming reaction device of methane vapor reforming unit is provided with the entrance that passes into water vapour raw material, and the fresh hydrogen outlet of methane vapor reforming unit is connected with the fresh hydrogen feed(raw material)inlet of hydrogenation of shale oil upgrading unit by pipeline.
Preferably, described methane vapor reforming unit comprises steam reforming reaction device, CaO regenerative combustion stove, compression interchanger, steam reforming gas flashing tower, pressure-swing absorption apparatus and separator;
Described steam reforming reaction device bottom is provided with the low-pressure steam entrance that passes into low-pressure steam and the carbonization gas feed(raw material)inlet that passes into carbonization gas; The carbonization gas outlet of oil shale distillation unit is directly connected with the carbonization gas feed(raw material)inlet of steam reforming reaction device bottom by pipeline; The CaCO of steam reforming reaction device bottom
3with CaO mixture outlet by the CaCO of e Foerderanlage and CaO regenerative combustion furnace bottom
3be connected with CaO mixture inlet; CaO regenerative combustion furnace bottom is provided with the entrance that passes into shale chip, and the chip shale outlet of oil shale distillation unit is connected with the chip shale entrance of CaO regenerative combustion furnace bottom by e Foerderanlage; CaO regenerative combustion furnace bottom is also provided with the entrance that passes into air, air directly passes into CaO regenerative combustion stove by compression pump, and the CaO absorption agent outlet of CaO regenerative combustion furnace bottom is connected with the CaO absorption agent entrance of steam reforming reaction device bottom by e Foerderanlage; The steam reforming crude synthesis gas outlet at steam reforming reaction device top is connected with the compressed gas entrance of compression interchanger by pipeline; The compressed gas outlet of compression interchanger is connected with the flash distillation water vapour synthetic gas entrance at steam reforming gas flashing tower middle part by pipeline; The steam reforming syngas outlet at steam reforming gas flashing tower top is connected with the steam reforming synthetic gas entrance of pressure-swing absorption apparatus by pipeline; The gas outlet of not reclaiming of pressure-swing absorption apparatus is connected with the not recovery gas entrance of CaO regenerative combustion furnace roof portion by pipeline; The high-purity hydrogen outlet of pressure-swing absorption apparatus is connected with the high-purity hydrogen entrance of separator by pipeline; The fresh hydrogen outlet of separator is connected with the fresh hydrogen entrance of hydrogenation of shale oil upgrading unit by pipeline.
CaO regenerative combustion stove is also provided with the outlet of shale lime-ash, and the shale lime-ash outlet of CaO regenerative combustion stove is connected with the lime-ash feed(raw material)inlet of production of construction materials unit by e Foerderanlage; The bottom of steam reforming gas flashing tower is also provided with water out.
An integrated refining process with oil shale distillation gas hydrogen manufacturing upgrading, comprises the following steps:
Resinous shale after crushing and screening passes into the chip shale that dry distillation reactor obtains shale oil, carbonization gas, lime-ash and can not react occurs in oil shale distillation unit;
Carbonization gas passes into the steam reforming reaction device of methane vapor reforming unit, passes into water vapour simultaneously, and carbonization gas and water vapour is methane-steam reforming and water gas shift reaction under CaO absorption agent promotes, obtains steam reforming crude synthesis gas and CaCO
3with CaO mixture, the compressed heat exchange of steam reforming crude synthesis gas with separatedly obtain fresh hydrogen, do not reclaim gas and hydrogen product, CaCO
3enter the CaO regenerative combustion stove of methane vapor reforming unit with CaO mixture;
Chip shale is sent into the CaO regenerative combustion stove of methane vapor reforming unit, and passes into air, does not reclaim gas and chip shale and under the atmosphere of air, burns with calcining CaCO
3with CaO mixture, generate CaO absorption agent and shale lime-ash, CaO absorption agent enters the recycle of steam reforming reaction device again;
Shale oil and fresh hydrogen enter hydrogenation of shale oil upgrading unit and carry out hydrocracking reaction, generate the oil product after upgrading;
Lime-ash and shale lime-ash are all sent into production of construction materials unit to be produced and obtains building material product.
Described building material product comprises haydite and shale brick etc.
Preferably, the resinous shale particle diameter after described crushing and screening is 10～75mm, and the condition of dry distillation reactor is 0.1MPa, 525 ℃.
Preferably, the mol ratio of described water vapour and carbonization gas is (0.3～0.8): 1.0.
Preferred, the mol ratio of described water vapour and carbonization gas is 1.31:1.00.
Preferably, the mol ratio of described CaO absorption agent and carbonization gas is (0.3～0.8): 1.0.
Preferred, the mol ratio of described CaO absorption agent and carbonization gas is 0.5:1.0.
Preferably, the service temperature of described steam reforming reaction device is 600～700 ℃, and pressure is 15～20bar.
Preferred, the service temperature of described steam reforming reaction device is 650 ℃, and pressure is 15bar.
Preferably, the service temperature of described CaO regenerative combustion stove is 900～950 ℃, and pressure is normal pressure.
Preferred, the service temperature of described CaO regenerative combustion stove is 900 ℃.
Preferably, the specific embodiment of described methane vapor reforming unit is as follows:
Carbonization gas passes into the steam reforming reaction device of methane vapor reforming unit, water vapour is passed into steam reforming reaction device and carbonization gas generation methane-steam reforming and water gas shift reaction simultaneously, in reforming reaction process, adopt CaO absorption agent to absorb CO
2promote methane-steam reforming and water gas shift reaction, in steam reforming reaction device, reaction produces steam reforming crude synthesis gas and CaCO
3with CaO mixture;
After the compressed interchanger compression of steam reforming crude synthesis gas heat exchange, obtain cooled steam reforming crude synthesis gas, cooled steam reforming crude synthesis gas enters steam reforming gas flashing tower, from steam reforming gas flashing tower top recovered water steam reforming synthetic gas, from steam reforming gas flashing tower top recovered water; Steam reforming synthetic gas enters pressure-swing absorption apparatus to carry out obtaining high-purity hydrogen and not reclaiming gas after separation; High-purity hydrogen obtains hydrogenation of shale oil upgrading unit required fresh hydrogen and hydrogen product through separator separation; CaCO
3enter CaO regenerative combustion stove with CaO mixture and calcine, the CaO absorption agent regenerating enters the recycle of steam reforming reaction device again;
Chip shale with do not reclaim gas and enter CaO regenerative combustion stove and burn to calcine CaCO
3generate CaO absorption agent and shale lime-ash, combustion reactions is carried out under the atmosphere of air.
Preferably, described hydrocracking reaction temperature is 400 ℃, and the mass ratio of fresh hydrogen and shale oil is 0.03.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention, by carbonization gas is carried out to methane reforming reaction, for hydrogenation of shale oil upgrading provides hydrogen source, has realized the complementation utilization of carbonization gas and shale oil protium, has avoided the wasting of resources that the direct burning of carbonization gas is caused.The present invention, by the discarded chip shale in oil shale distillation unit is burnt, is CaO regenerative combustion stove calcining CaCO
3heat is provided, effectively raises the utilising efficiency of resource and the energy.
(2) the integrated use carbonization gas of the present invention is reformed and is produced the hydrogen of high economic worth.For hydrogenation of shale oil upgrading unit provides hydrogen source, reduced the production cost of hydrogenation of shale oil process on the one hand; As output of products, greatly improved the income of resinous shale processing industry on the other hand.A kind of return on investment (ROI) of integrated refining system of oil shale distillation gas hydrogen manufacturing upgrading has improved 6.93% from original 12.60%, has reached 19.53%.
(3) integrated refining system of the present invention has solved carbonization gas and the underutilization of chip shale and the too high problem of hydrogenation of shale oil upgrading production cost existing in traditional oil-shale eduction process effectively.Adopt device of the present invention and technique, can significantly improve the economic benefit of existing oil shale oil-refining and upgrading process thereof, improve the resource utilization of process, reduced the discharge of solid waste and industrial gaseous waste.
Accompanying drawing explanation
Fig. 1 is the process schematic representation of existing oil-shale eduction process.Wherein 1 is oil shale distillation unit, 2 rock oil hydrogenation upgrading unit, and 8 is production of construction materials unit; 3～7 and 9～11 is logistics numbering, and wherein 3 is resinous shale, and 4 is carbonization gas, and 5 is shale oil, and 6 is hydrogen, and 7 is the oil product after upgrading, and 9 is lime-ash, and 10 is chip shale, and 11 is building material product.
Fig. 2 is that the present invention is with the integrated refining system schematic of oil shale distillation gas hydrogen manufacturing upgrading.Wherein 12 is methane vapor reforming unit.Wherein 13 is water vapour, and 14 is air, and 15 is shale lime-ash, and 16 is fresh hydrogen.Operating unit or logistics that all the other numberings are identical with same reference numeral in Fig. 1.
Fig. 3 is the methane vapor reforming cell process workshop section schema of the integrated refining system of the present invention.Wherein 17 is steam reforming reaction device, and 18 is CaO regenerative combustion stove, and 21 is compression interchanger, and 23 is steam reforming gas flashing tower, and 27 is pressure-swing absorption apparatus, and 30 is separator; All the other,, for logistics numbering, number operating unit or the logistics identical with same reference numeral in Fig. 2.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
As shown in Figure 1, wherein 1 is oil shale distillation unit to the process schematic representation of existing oil-shale eduction process, 2 rock oil hydrogenation upgrading unit, and 8 is production of construction materials unit; 3～7 and 9～11 is logistics numbering, and wherein 3 is resinous shale, and 4 is carbonization gas, and 5 is shale oil, and 6 is hydrogen, and 7 is the oil product after upgrading, and 9 is lime-ash, and 10 is chip shale, and 11 is building material product.
The present invention with the integrated refining system of oil shale distillation gas hydrogen manufacturing upgrading specifically as shown in Figure 2, comprises oil shale distillation unit 1, hydrogenation of shale oil upgrading unit 2 and production of construction materials unit 8, also comprises methane vapor reforming unit 12;
Described oil shale distillation unit 1 is provided with the entrance that passes into resinous shale raw material, the shale oil outlet of oil shale distillation unit 1 is directly connected with the shale oil feed(raw material)inlet of hydrogenation of shale oil upgrading unit 2 by pipeline, the carbonization gas outlet of oil shale distillation unit 1 is connected with the carbonization gas feed(raw material)inlet of the steam reforming reaction device of methane vapor reforming unit 12 by pipeline, the chip shale outlet of oil shale distillation unit 1 is connected with the chip shale entrance of the CaO regenerative combustion stove of methane vapor reforming unit 12 by e Foerderanlage, the lime-ash outlet of oil shale distillation unit 1 and the shale lime-ash outlet of methane vapor reforming unit 12 are all connected with the lime-ash feed(raw material)inlet of production of construction materials unit 8 by e Foerderanlage, the steam reforming reaction device of methane vapor reforming unit 12 is provided with the entrance that passes into water vapour raw material, and the fresh hydrogen outlet of methane vapor reforming unit 12 is connected with the fresh hydrogen feed(raw material)inlet of hydrogenation of shale oil upgrading unit 2 by pipeline.
Building materials reformer unit 8 is also provided with building material product outlet, and hydrogenation of shale oil upgrading unit 2 is also provided with the oil product outlet after upgrading, and the CaO regenerative combustion stove of methane vapor reforming unit 12 is also provided with the entrance that passes into air.
Visible, of the present inventionly with the integrated refining system process of oil shale distillation gas hydrogen manufacturing upgrading and the difference of the prior art shown in Fig. 1, be:
(1) in system of the present invention, the carbonization gas of oil shale distillation unit 1 is used and methane vapor reforming unit 12 hydrogen makings, and a hydrogen part for generation is as the hydrogen source of hydrogenation of shale oil upgrading unit 2, and another part is as production marketing.
(2), in system of the present invention, the chip shale of oil shale distillation unit 1 is used to CaO regenerative combustion stove calcining CaCO in methane vapor reforming unit 12
3heat is provided.
In such scheme, the specific embodiment of described methane vapor reforming unit 12 as shown in Figure 3:
Carbonization gas 4 passes into the steam reforming reaction device 17 of methane vapor reforming unit, water vapour 13 is passed into steam reforming reaction device 17 simultaneously, with carbonization gas 4, methane-steam reforming and water gas shift reaction occur, in reforming reaction process, adopt CaO absorption agent to absorb CO
2promote methane-steam reforming and water gas shift reaction, in steam reforming reaction device 17, reaction produces steam reforming crude synthesis gas 22 and CaCO
3with CaO mixture 19;
After the compressed interchanger 21 compression heat exchange of steam reforming crude synthesis gas 22, obtain cooled steam reforming crude synthesis gas 24, cooled steam reforming crude synthesis gas 24 enters steam reforming gas flashing tower 23, from steam reforming gas flashing tower 23 top recovered water steam reforming synthetic gas 26, from steam reforming gas flashing tower 23 top recovered waters 25; Steam reforming synthetic gas 26 enters pressure-swing absorption apparatus 27 to carry out obtaining high-purity hydrogen 29 and not reclaiming gas 28 after separation; High-purity hydrogen 29 obtains the required fresh hydrogen 16 in hydrogenation of shale oil upgrading unit 2 and hydrogen product 31 through separator 30 separation; CaCO
3enter CaO regenerative combustion stove 18 with CaO mixture 19 and calcine, the CaO absorption agent 20 regenerating enters 17 recycles of steam reforming reaction device again;
Chip shale 10 with do not reclaim gas 28 and enter CaO regenerative combustion stove 18 and burn to calcine CaCO
3generate CaO absorption agent 20 and shale lime-ash 15, combustion reactions is carried out under the atmosphere of air 14.
Embodiment 1
Specifically being implemented as follows of the integrated refining process of the oil shale distillation gas hydrogen manufacturing upgrading of the present embodiment:
The raw material shale flow that enters technique of the present invention is 300t/h, and that wherein enter gas retort is 225t/h, and chip shale flow is 75t/h.The internal circulating load of CaO is 44.4t/h, and the flow of steam is 38.02t/h.The technical analysis of resinous shale and ultimate analysis are in Table 1.
The technical analysis ultimate analysis of table 1 resinous shale
In table, ar represents as received basis.
The schema of the integrated refining process of oil shale distillation gas hydrogen manufacturing upgrading is as shown in Figures 2 and 3:
Integrated refining system comprises oil shale distillation unit 1, hydrogenation of shale oil upgrading unit 2, methane vapor reforming unit 12 and production of construction materials unit 8; Wherein methane vapor reforming unit 12 comprises steam reforming reaction device 17, CaO regenerative combustion stove 18, compression interchanger 21, steam reforming gas flashing tower 23, pressure-swing absorption apparatus 27 and separator 30;
(1) resinous shale 3 that particle diameter is 10～75mm after crushing and screening passes in oil shale distillation unit 1 under 0.1MPa, the condition of 525 ℃ the chip shale 10 that dry distillation reactor obtains shale oil 5, carbonization gas 4, lime-ash 9 and can not react occurs;
(2) carbonization gas 4 passes into the steam reforming reaction device 17 of methane vapor reforming unit 12, under the condition that water vapour 13 to be passed into steam reforming reaction device 17 and carbonization gas 4 be 15bar at 650 ℃, pressure simultaneously, there is methane-steam reforming and water gas shift reaction, in reforming reaction process, adopt CaO absorption agent to absorb CO
2promote methane-steam reforming and water gas shift reaction, in steam reforming reaction device 17, reaction produces steam reforming crude synthesis gas 22 and CaCO
3with CaO mixture 19;
After the compressed interchanger 21 compression heat exchange of steam reforming crude synthesis gas 22, obtain cooled steam reforming crude synthesis gas 24, cooled steam reforming crude synthesis gas 24 enters steam reforming gas flashing tower 23, from steam reforming gas flashing tower 23 top recovered water steam reforming synthetic gas 26, hydrogen content rises to 43%, from steam reforming gas flashing tower 23 top recovered waters 25; Steam reforming synthetic gas 26 enters pressure-swing absorption apparatus 27 to carry out obtaining purity after separation being 99.95% high-purity hydrogen 29 and not reclaiming gas 28; High-purity hydrogen 29 obtains the required fresh hydrogen 16 in hydrogenation of shale oil upgrading unit 2 and as the high-purity hydrogen 31 of product through separator 30 separation; CaCO
3enter CaO regenerative combustion stove 18 with CaO mixture 19 and calcine, calcining temperature is 900 ℃, regenerates CaO absorption agent 20 and again enters steam reforming reaction device 17, recycle;
Chip shale 10 with do not reclaim gas 28 and enter CaO regenerative combustion stove 18 and burn to calcine CaCO
3generate CaO absorption agent 20 and shale lime-ash 15, combustion reactions is carried out under the atmosphere of air 14;
(3) shale oil 5 and fresh hydrogen 16 are entered to hydrogenation of shale oil upgrading unit 2 and at 400 ℃, carry out hydrocracking reaction, generate the oil product 7 after upgrading; Fresh hydrogen 16 is 0.03 with the mass ratio of shale oil 5;
(4) lime-ash 9 and shale lime-ash 15 are all sent into production of construction materials unit 8 production building material products 11.
Wherein oil shale distillation process, hydrogenation of shale oil upgrading process and production of construction materials process are same as the prior art.
Finally, the return on investment (ROI) of the integrated refining system of the oil shale distillation gas hydrogen manufacturing upgrading of the present embodiment has improved 6.93% from 12.60% of existing resinous shale refining system, has reached 19.53%; Energy efficiency has improved 3.12% from 26.21% of existing resinous shale refining system, has reached 29.33%.
Embodiment 2
Specifically being implemented as follows of the integrated refining process of the oil shale distillation gas hydrogen manufacturing upgrading of the present embodiment:
The raw material shale flow that enters technique of the present invention is 400t/h, and that wherein enter gas retort is 300t/h, and chip shale flow is 100t/h.The internal circulating load of CaO is 60.5t/h, and the flow of steam is 55.75t/h.The technical analysis of resinous shale and ultimate analysis are in Table 2.
The technical analysis ultimate analysis of table 2 resinous shale
In table, ar represents as received basis.
The schema of the integrated refining process of oil shale distillation gas hydrogen manufacturing upgrading is as shown in Figures 2 and 3:
Integrated refining system comprises oil shale distillation unit 1, hydrogenation of shale oil upgrading unit 2, methane vapor reforming unit 12 and production of construction materials unit 8; Wherein methane vapor reforming unit 12 comprises steam reforming reaction device 17, CaO regenerative combustion stove 18, compression interchanger 21, steam reforming gas flashing tower 23, pressure-swing absorption apparatus 27 and separator 30;
(1) resinous shale 3 that particle diameter is 10～75mm after crushing and screening passes in oil shale distillation unit 1 under 0.1MPa, the condition of 525 ℃ the chip shale 10 that dry distillation reactor obtains shale oil 5, carbonization gas 4, lime-ash 9 and can not react occurs;
(2) carbonization gas 4 passes into the steam reforming reaction device 17 of methane vapor reforming unit 12, under the condition that water vapour 13 to be passed into steam reforming reaction device 17 and carbonization gas 4 be 20bar at 700 ℃, pressure simultaneously, there is methane-steam reforming and water gas shift reaction, in reforming reaction process, adopt CaO absorption agent to absorb CO
2promote methane-steam reforming and water gas shift reaction, in steam reforming reaction device 17, reaction produces steam reforming crude synthesis gas 22 and CaCO
3with CaO mixture 19;
After the compressed interchanger 21 compression heat exchange of steam reforming crude synthesis gas 22, obtain cooled steam reforming crude synthesis gas 24, cooled steam reforming crude synthesis gas 24 enters steam reforming gas flashing tower 23, from steam reforming gas flashing tower 23 top recovered water steam reforming synthetic gas 26, hydrogen content rises to 43%, from steam reforming gas flashing tower 23 top recovered waters 25; Steam reforming synthetic gas 26 enters pressure-swing absorption apparatus 27 to carry out obtaining purity after separation being 99.95% high-purity hydrogen 29 and not reclaiming gas 28; High-purity hydrogen 29 obtains the required fresh hydrogen 16 in hydrogenation of shale oil upgrading unit 2 and as the high-purity hydrogen 31 of product through separator 30 separation; CaCO
3enter CaO regenerative combustion stove 18 with CaO mixture 19 and calcine, calcining temperature is 950 ℃, regenerates CaO absorption agent 20 and again enters steam reforming reaction device 17, recycle;
Chip shale 10 with do not reclaim gas 28 and enter CaO regenerative combustion stove 18 and burn to calcine CaCO
3generate CaO absorption agent 20 and shale lime-ash 15, combustion reactions is carried out under the atmosphere of air 14;
(3) shale oil 5 and fresh hydrogen 16 are entered to hydrogenation of shale oil upgrading unit 2 and at 400 ℃, carry out hydrocracking reaction, generate the oil product 7 after upgrading; Fresh hydrogen 16 is 0.03 with the mass ratio of shale oil 5;
(4) lime-ash 9 and shale lime-ash 15 are all sent into production of construction materials unit 8 production building material products 11.
Wherein oil shale distillation process, hydrogenation of shale oil upgrading process and production of construction materials process are same as the prior art.
Finally, the return on investment (ROI) of the integrated refining system of the oil shale distillation gas hydrogen manufacturing upgrading of the present embodiment has improved 6.47% from 12.60% of existing resinous shale refining system, has reached 19.07%; Energy efficiency has improved 3.03% from 26.21% of existing resinous shale refining system, has reached 29.24%.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. with an integrated refining system for oil shale distillation gas hydrogen manufacturing upgrading, comprise oil shale distillation unit, hydrogenation of shale oil upgrading unit and production of construction materials unit, it is characterized in that, described system also comprises methane vapor reforming unit;
Described oil shale distillation unit is provided with the entrance that passes into resinous shale raw material, the shale oil outlet of oil shale distillation unit is directly connected with the shale oil feed(raw material)inlet of hydrogenation of shale oil upgrading unit by pipeline, the carbonization gas outlet of oil shale distillation unit is connected with the carbonization gas feed(raw material)inlet of the steam reforming reaction device of methane vapor reforming unit by pipeline, the chip shale outlet of oil shale distillation unit is connected with the chip shale entrance of the CaO regenerative combustion stove of methane vapor reforming unit by e Foerderanlage, the lime-ash outlet of oil shale distillation unit and the shale lime-ash outlet of methane vapor reforming unit are all connected with the lime-ash feed(raw material)inlet of production of construction materials unit by e Foerderanlage, the steam reforming reaction device of methane vapor reforming unit is provided with the entrance that passes into water vapour raw material, and the fresh hydrogen outlet of methane vapor reforming unit is connected with the fresh hydrogen feed(raw material)inlet of hydrogenation of shale oil upgrading unit by pipeline.
2. integrated refining system according to claim 1, it is characterized in that, described methane vapor reforming unit comprises steam reforming reaction device, CaO regenerative combustion stove, compression interchanger, steam reforming gas flashing tower, pressure-swing absorption apparatus and separator;
Described steam reforming reaction device is provided with the low-pressure steam entrance that passes into low-pressure steam and the carbonization gas feed(raw material)inlet that passes into carbonization gas; The carbonization gas outlet of oil shale distillation unit is directly connected with the carbonization gas feed(raw material)inlet of steam reforming reaction device by pipeline; The CaCO of steam reforming reaction device
3with CaO mixture outlet by the CaCO of e Foerderanlage and CaO regenerative combustion stove
3be connected with CaO mixture inlet; CaO regenerative combustion stove is provided with the entrance that passes into shale chip, and the chip shale outlet of oil shale distillation unit is connected with the chip shale entrance of CaO regenerative combustion stove by e Foerderanlage; CaO regenerative combustion stove is also provided with the entrance that passes into air, and the CaO absorption agent outlet of CaO regenerative combustion stove is connected with the CaO absorption agent entrance of steam reforming reaction device by e Foerderanlage; The steam reforming crude synthesis gas outlet of steam reforming reaction device is connected with the compressed gas entrance of compression interchanger by pipeline; The compressed gas outlet of compression interchanger is connected with the flash distillation water vapour synthetic gas entrance of steam reforming gas flashing tower by pipeline; The steam reforming of steam reforming gas flashing tower is integrated gas outlet and is connected with the steam reforming synthetic gas entrance of pressure-swing absorption apparatus by pipeline; The gas outlet of not reclaiming of pressure-swing absorption apparatus is connected with the not recovery gas entrance of CaO regenerative combustion stove by pipeline; The high-purity hydrogen outlet of pressure-swing absorption apparatus is connected with the high-purity hydrogen entrance of separator by pipeline; The fresh hydrogen outlet of separator is connected with the fresh hydrogen entrance of hydrogenation of shale oil upgrading unit by pipeline.
3. with an integrated refining process for oil shale distillation gas hydrogen manufacturing upgrading, it is characterized in that, comprise the following steps:
Resinous shale after crushing and screening passes into the chip shale that dry distillation reactor obtains shale oil, carbonization gas, lime-ash and can not react occurs in oil shale distillation unit;
Carbonization gas passes into the steam reforming reaction device of methane vapor reforming unit, passes into water vapour simultaneously, and the two is methane-steam reforming and water gas shift reaction under CaO absorption agent promotes, obtains steam reforming crude synthesis gas and CaCO
3with CaO mixture, steam reforming crude synthesis gas is isolated to fresh hydrogen, does not reclaim gas and hydrogen product, CaCO
3enter the CaO regenerative combustion stove of methane vapor reforming unit with CaO mixture;
Chip shale is sent into the CaO regenerative combustion stove of methane vapor reforming unit, and passes into air, does not reclaim gas and chip shale and under the atmosphere of air, burns with calcining CaCO
3with CaO mixture, generate CaO absorption agent and shale lime-ash, CaO absorption agent enters the recycle of steam reforming reaction device again;
Shale oil and fresh hydrogen enter hydrogenation of shale oil upgrading unit and carry out hydrocracking reaction, generate the oil product after upgrading;
Lime-ash and shale lime-ash are all sent into production of construction materials unit and are produced building material product.
4. integrated refining process according to claim 3, is characterized in that, the resinous shale particle diameter after described crushing and screening is 10～75mm, and the condition of dry distillation reactor is 0.1MPa, 525 ℃.
5. integrated refining process according to claim 3, is characterized in that, the mol ratio of described water vapour and carbonization gas is (0.3～0.8): 1.0; The mol ratio of described CaO absorption agent and carbonization gas is (0.3～0.8): 1.0.
6. integrated refining process according to claim 5, is characterized in that, the mol ratio of described water vapour and carbonization gas is 1.31:1.00; The mol ratio of described CaO absorption agent and carbonization gas is 0.5:1.0.
7. integrated refining process according to claim 3, is characterized in that, the service temperature of described steam reforming reaction device is 600～700 ℃, and pressure is 15～20bar.
8. integrated refining process according to claim 3, is characterized in that, the service temperature of described CaO regenerative combustion stove is 900～950 ℃, and pressure is normal pressure.
9. integrated refining process according to claim 3, is characterized in that, the specific embodiment of described methane vapor reforming unit is as follows:
Carbonization gas passes into the steam reforming reaction device of methane vapor reforming unit, water vapour is passed into steam reforming reaction device and carbonization gas generation methane-steam reforming and water gas shift reaction simultaneously, in reforming reaction process, adopt CaO absorption agent to absorb CO
2promote methane-steam reforming and water gas shift reaction, in steam reforming reaction device, reaction produces steam reforming crude synthesis gas and CaCO
3with CaO mixture; After the compressed interchanger compression of steam reforming crude synthesis gas heat exchange, enter steam reforming gas flashing tower, from steam reforming gas flashing tower top recovered water steam reforming synthetic gas, from steam reforming gas flashing tower bottom recovered water;
Steam reforming synthetic gas enters pressure-swing absorption apparatus to carry out obtaining high-purity hydrogen and not reclaiming gas after separation; High-purity hydrogen obtains the required fresh hydrogen of hydrogenation of shale oil upgrading and hydrogen product through separator separation; CaCO
3enter CaO regenerative combustion stove with CaO mixture and calcine, the CaO absorption agent regenerating enters the recycle of steam reforming reaction device again;
Chip shale with do not reclaim gas and enter CaO regenerative combustion stove and burn to calcine CaCO
3generate CaO absorption agent and shale lime-ash, combustion reactions is carried out under the atmosphere of air.
10. integrated refining process according to claim 3, is characterized in that, described hydrocracking reaction temperature is 400 ℃, enters the fresh hydrogen of hydrogenation upgrading unit and the mass ratio of shale oil is 0.03.
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Application publication date: 20140827 |