CN104004532A - Integrated refining system and process using oil shale retorting gas to produce hydrogen and upgrade - Google Patents

Abstract

The invention discloses an integrated refining system and process for producing hydrogen and upgrading oil shale dry distillation gas. The system includes an oil shale carbonization unit, a shale oil hydrotreating and upgrading unit, a methane steam reforming unit and a building material production unit; the methane steam reforming unit includes a steam reforming reactor, a CaO regenerative combustion furnace , Compression heat exchanger, steam reforming gas flash column and pressure swing adsorption unit. The present invention provides a hydrogen source for the hydrogenation and upgrading of shale oil by subjecting dry distillation gas to methane reforming reaction, and realizes the complementary utilization of hydrogen elements in dry distillation gas and shale oil. Rock combustion provides heat for the CaO regenerative combustion furnace to calcine CaCO ₃ , which improves the utilization efficiency of resources and energy. The invention can remarkably improve the economic benefits of the existing oil shale refining and upgrading process, improve the resource utilization rate of the process, and reduce the discharge of solid waste and industrial waste gas.

Description

An integrated refining system and process for hydrogen production and upgrading by oil shale retort gas

technical field

The invention belongs to the technical field of energy and chemical industry, and in particular relates to an integrated refining system and process for producing hydrogen and upgrading oil shale dry distillation gas.

Background technique

As the global oil demand continues to rise and the contradiction between oil supply and demand becomes increasingly severe, it is imperative to find alternative energy sources for oil. Oil shale is widely valued by countries all over the world because of its abundant reserves and feasibility of development and utilization. It is recognized as one of the most potential oil substitute resources. According to the latest statistics, converting the world's proven oil shale into 3 trillion barrels of shale oil is equivalent to 1.8 times the current proven crude oil reserves. my country not only has abundant oil shale reserves, but also has relatively shallow burial, which is conducive to the development and utilization of oil shale resources. Vigorously developing oil shale refining technology is conducive to alleviating the contradiction between the supply and demand of my country's oil resources and providing a feasible way to realize energy diversification.

A schematic flow chart of the traditional oil shale refining process is shown in Figure 1. The traditional oil shale refining process is mainly composed of an oil shale dry distillation unit 1 , a shale oil hydrotreating and upgrading unit 2 and a building material production unit 9 . After the oil shale is screened, it enters the oil shale retort unit. First, it undergoes retort reaction to generate shale oil, retort gas and semi-coke. The semi-coke enters the gasifier and undergoes gasification reaction under the action of air. Dry distillation furnace. The shale oil produced by the oil shale dry distillation unit enters the shale oil hydro-upgrading unit to produce naphtha, diesel oil and liquefied petroleum gas. The ash and debris shale produced by the oil shale dry distillation unit enters the building material production unit to obtain ceramsite and shale bricks.

The following problems exist in the traditional oil shale refining process: (1) The residual gas produced by the retort furnace has a low calorific value and can only be used as fuel for boilers or internal combustion engines instead of commercial gas, and its utilization value is not high; (2) Oil shale The clastic shale produced in the dry distillation process is not highly utilized, and about 25% of the clastic shale has a particle size of less than 10mm, which is discharged as waste and directly used for the production of building materials; (3) the current market price of hydrogen is relatively high, and the use of Purchasing hydrogen as a hydrogen source for shale oil hydrotreating and upgrading will undoubtedly increase the production cost of the process and reduce the economic benefits of the process.

Contents of the invention

In order to solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide an integrated refining system for hydrogen production and upgrading by oil shale retort gas.

Another object of the present invention is to provide an integrated refining process for producing hydrogen and upgrading oil shale dry distillation gas.

In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

An integrated refining system for hydrogen production and upgrading by oil shale dry distillation gas, the system includes an oil shale dry distillation unit, a shale oil hydrogenation upgrading unit, a building material production unit, and a methane steam reforming unit;

The oil shale retort unit is provided with an inlet leading into the oil shale raw material, and the shale oil outlet of the oil shale retort unit is directly connected with the shale oil raw material inlet of the shale oil hydrogenation and upgrading unit through a pipeline, and the oil shale retort unit The retort gas outlet of the shale retort unit is connected to the retort gas raw material inlet of the steam reforming reactor of the methane steam reforming unit through a pipeline, and the clastic shale outlet of the oil shale retort unit is connected to the methane steam reformer through a conveying device. The debris shale inlet of the CaO regenerative combustion furnace of the whole unit is connected, the ash outlet of the oil shale carbonization unit and the shale ash outlet of the methane steam reforming unit are all connected to the ash raw material inlet of the building material production unit through the conveying device The steam reforming reactor of the methane steam reforming unit is provided with an inlet for the steam feedstock, and the fresh hydrogen outlet of the methane steam reforming unit is connected with the fresh hydrogen feedstock of the shale oil hydrogenation upgrading unit through pipelines Ingress connection.

Preferably, the steam methane reforming unit comprises a steam reforming reactor, a CaO regeneration burner, a compression heat exchanger, a steam reforming gas flash tower, a pressure swing adsorption device and a separator;

The bottom of the steam reforming reactor is provided with a low-pressure steam inlet for feeding low-pressure steam and a retort gas raw material inlet for feeding retort gas; the retort gas outlet of the oil shale retort unit is directly connected to the bottom of the steam reforming reactor through a pipeline. The dry distillation gas raw material inlet is connected; the CaCO ₃ and CaO mixture outlet at the bottom of the steam reforming reactor is connected to the CaCO ₃ and CaO mixture inlet at the bottom of the CaO regenerative burner through a conveying device; the bottom of the CaO regenerative burner is provided with a shale The inlet of the debris, the outlet of the debris shale of the oil shale carbonization unit is connected with the inlet of the debris shale at the bottom of the CaO regenerative combustion furnace through a conveying device; The pump is directly connected to the CaO regenerative combustion furnace, and the CaO absorbent outlet at the bottom of the CaO regenerative combustion furnace is connected to the CaO absorbent inlet at the bottom of the steam reforming reactor through a conveying device; the steam reforming crude at the top of the steam reforming reactor The synthesis gas outlet is connected to the compressed gas inlet of the compression heat exchanger through a pipeline; the compressed gas outlet of the compression heat exchanger is connected to the flash steam synthesis gas inlet in the middle of the steam reforming gas flash tower through a pipeline; steam reforming The water vapor recombination gas outlet at the top of the gas flash tower is connected to the water vapor recombination gas inlet of the pressure swing adsorption device through the pipeline; The gas inlet is connected; the high-purity hydrogen outlet of the pressure swing adsorption device is connected to the high-purity hydrogen inlet of the separator through a pipeline; the fresh hydrogen outlet of the separator is connected to the fresh hydrogen inlet of the shale oil hydrogenation upgrading unit through a pipeline.

The CaO regenerative combustion furnace is also provided with a shale ash outlet, and the shale ash outlet of the CaO regenerative combustion furnace is connected with the ash raw material inlet of the building material production unit through a conveying device; There is a water outlet.

An integrated refining process for hydrogen production and upgrading by oil shale retort gas, comprising the following steps:

The crushed and screened oil shale is passed into the oil shale retort unit for retort reaction to obtain shale oil, retort gas, ash and unreactable clastic shale;

The dry distillation gas is passed into the steam reforming reactor of the methane steam reforming unit, and water vapor is introduced at the same time, and the dry distillation gas and water vapor are promoted by the CaO absorbent to perform the steam reforming reaction of methane and the water-gas shift reaction to obtain steam reforming Crude synthesis gas and CaCO ₃ and CaO mixture, steam reforming crude synthesis gas undergoes compression heat exchange and separation to obtain fresh hydrogen, unrecovered gas and hydrogen products, CaCO ₃ and CaO mixture enters CaO regenerative combustion of steam methane reforming unit furnace;

The clastic shale is sent to the CaO regenerative combustion furnace of the methane steam reforming unit, and air is introduced, and the unrecovered gas and clastic shale are burned under the atmosphere of air to calcinate the CaCO ₃ and CaO mixture to generate CaO absorbent and Shale ash and CaO absorbent enter the steam reforming reactor again for recycling;

Shale oil and fresh hydrogen enter the shale oil hydro-upgrading unit for hydrocracking reaction to produce upgraded oil;

Both the ash and shale ash are sent to the building material production unit to produce building material products.

The building material products include ceramsite and shale bricks, etc.

Preferably, the particle size of the crushed and screened oil shale is 10-75mm, and the dry distillation reaction conditions are 0.1MPa and 525°C.

Preferably, the molar ratio of the water vapor to the dry distillation gas is (0.3-0.8):1.0.

More preferably, the molar ratio of the water vapor and dry distillation gas is 1.31:1.00.

Preferably, the molar ratio of the CaO absorbent to the dry distillation gas is (0.3-0.8):1.0.

More preferably, the molar ratio of the CaO absorbent to the dry distillation gas is 0.5:1.0.

Preferably, the operating temperature of the steam reforming reactor is 600-700° C., and the pressure is 15-20 bar.

More preferably, the operating temperature of the steam reforming reactor is 650° C. and the pressure is 15 bar.

Preferably, the operating temperature of the CaO regenerative combustion furnace is 900-950° C., and the pressure is normal pressure.

More preferably, the operating temperature of the CaO regenerative combustion furnace is 900°C.

Preferably, the specific process of the steam methane reforming unit is as follows:

The retort gas is passed into the steam reforming reactor of the methane steam reforming unit, and at the same time, water vapor is passed into the steam reforming reactor and the retort gas undergoes methane steam reforming reaction and water-gas shift reaction. During the reforming reaction Using CaO absorbent to absorb CO ₂ to promote the steam reforming reaction of methane and the water gas shift reaction, the reaction in the steam reforming reactor produces steam reforming crude synthesis gas and a mixture of CaCO ₃ and CaO;

The steam reformed crude synthesis gas is compressed and exchanged by the compression heat exchanger to obtain the cooled steam reformed crude synthesis gas, and the cooled steam reformed crude synthesis gas enters the steam reformed gas flash tower, from the water Steam reforming gas flash tower top produces water vapor recombined into gas, and water is produced from the top of steam reforming gas flash tower; water vapor recombined into gas enters pressure swing adsorption device for separation to obtain high-purity hydrogen and unrecovered High-purity hydrogen is separated by a separator to obtain fresh hydrogen and hydrogen products required by the shale oil hydrogenation upgrading unit; the mixture of CaCO ₃ and CaO enters the CaO regenerative combustion furnace for calcination, and the regenerated CaO absorbent enters the water vapor again Reforming reactor recycling;

Detrital shale and unrecovered gas enter the CaO regenerative combustion furnace for combustion to calcine CaCO ₃ to generate CaO absorbent and shale ash, and the combustion reaction is carried out in an air atmosphere.

Preferably, the hydrocracking reaction temperature is 400°C, and the mass ratio of fresh hydrogen to shale oil is 0.03.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The present invention provides a hydrogen source for hydrogenation and upgrading of shale oil by subjecting retort gas to methane reforming reaction, realizes the complementary utilization of hydrogen elements of retort gas and shale oil, and avoids the direct combustion of retort gas to cause waste of resources. The present invention burns the detrital shale discarded by the oil shale carbonization unit to provide heat for the CaO regeneration combustion furnace to calcinate CaCO ₃ , thereby effectively improving the utilization efficiency of resources and energy.

(2) The present invention integrates the use of retort gas reforming to produce hydrogen with high economic value. On the one hand, it provides a hydrogen source for the shale oil hydrogenation upgrading unit, which reduces the production cost of the shale oil hydrogenation process; on the other hand, as a product output, it greatly increases the economic income of the oil shale processing industry. The investment profit rate of an integrated refining system for hydrogen production and upgrading of oil shale dry distillation gas has increased by 6.93% from the original 12.60% to 19.53%.

(3) The integrated refining system of the present invention effectively solves the problems of insufficient utilization of retort gas and clastic shale and high production cost of shale oil hydro-upgrading existing in the traditional oil shale refining process. By adopting the device and process of the present invention, the economic benefits of the existing oil shale refining and upgrading process can be significantly improved, the resource utilization rate of the process can be improved, and the discharge of solid waste and industrial waste gas can be reduced.

Description of drawings

Fig. 1 is a process schematic diagram of the existing oil shale refining process. Among them, 1 is the oil shale retort unit, 2 is the rock oil hydrogenation upgrading unit, 8 is the building material production unit; 3~7 and 9~11 are the logistics numbers, of which 3 is oil shale, 4 is retort gas, and 5 is shale Rock oil, 6 is hydrogen, 7 is upgraded oil, 9 is ash, 10 is clastic shale, and 11 is building materials.

Fig. 2 is a schematic diagram of an integrated refining system for hydrogen production and upgrading of oil shale dry distillation gas according to the present invention. Among them, 12 are methane steam reforming units. Among them, 13 is water vapor, 14 is air, 15 is shale ash, and 16 is fresh hydrogen. The rest of the numbers are the same as those in Figure 1 to represent the same operating units or streams.

Fig. 3 is a flow chart of the methane steam reforming unit process section of the integrated refining system of the present invention. Among them, 17 is a steam reforming reactor, 18 is a CaO regeneration burner, 21 is a compression heat exchanger, 23 is a steam reforming gas flash tower, 27 is a pressure swing adsorption device, and 30 is a separator; the rest are logistics Numbers, the same numbers as those in Figure 2 represent the same operating units or streams.

Detailed ways

The present invention will be further described in detail below with reference to the examples and drawings, but the implementation of the present invention is not limited thereto.

The process schematic diagram of the existing oil shale refining process is shown in Figure 1, wherein 1 is the oil shale carbonization unit, 2 is the rock oil hydrogenation upgrading unit, 8 is the building material production unit; 3-7 and 9-11 are Logistics number, where 3 is oil shale, 4 is retort gas, 5 is shale oil, 6 is hydrogen, 7 is upgraded oil, 9 is ash, 10 is clastic shale, and 11 is building materials .

The integrated refining system of the present invention using oil shale retort gas for hydrogen production and upgrading is specifically shown in Figure 2, including an oil shale retort unit 1, a shale oil hydrogenation upgrade unit 2, and a building material production unit 8, and also includes methane steam reforming unit 12;

The oil shale retort unit 1 is provided with an inlet leading into the oil shale raw material, and the shale oil outlet of the oil shale retort unit 1 is directly connected to the shale oil raw material inlet of the shale oil hydrogenation and upgrading unit 2 through a pipeline. Connection, the dry distillation gas outlet of the oil shale carbonization unit 1 is connected with the dry distillation gas raw material inlet of the steam reforming reactor of the methane steam reforming unit 12 through a pipeline, and the debris shale outlet of the oil shale carbonization unit 1 is conveyed The device is connected to the debris shale inlet of the CaO regenerative combustion furnace of the steam methane reforming unit 12, and the ash outlet of the oil shale carbonization unit 1 and the shale ash outlet of the steam methane reforming unit 12 both pass through the conveying device It is connected with the ash raw material inlet of the building material production unit 8; the steam reforming reactor of the steam methane reforming unit 12 is provided with an inlet leading into the steam raw material, and the fresh hydrogen outlet of the steam methane reforming unit 12 passes through a pipeline and The fresh hydrogen raw material inlet of the shale oil hydrotreating and upgrading unit 2 is connected.

The building material reforming unit 8 is also provided with a building material product outlet, the shale oil hydrotreating and upgrading unit 2 is also provided with an outlet for upgraded oil products, and the CaO regenerative combustion furnace of the methane steam reforming unit 12 is also provided with an air inlet entrance.

It can be seen that the integrated refining system process of the present invention using oil shale retort gas for hydrogen production and upgrading is different from the prior art shown in Figure 1 in that:

(1) In the system of the present invention, the dry distillation gas of the oil shale dry distillation unit 1 is used with the methane steam reforming unit 12 to produce hydrogen, and a part of the hydrogen produced is used as the hydrogen source of the shale oil hydrogenation upgrading unit 2, Another part is sold as products.

(2) In the system of the present invention, the clastic shale in the oil shale carbonization unit 1 is used to provide heat for calcining CaCO ₃ in the CaO regeneration burner in the steam methane reforming unit 12 .

In the above scheme, the specific process of the steam methane reforming unit 12 is shown in Figure 3:

The dry distillation gas 4 is passed into the steam reforming reactor 17 of the methane steam reforming unit, and at the same time, the steam 13 is passed into the steam reforming reactor 17 and the dry distillation gas 4 undergoes a methane steam reforming reaction and a water-gas shift reaction. During the reforming reaction, CaO absorbent is used to absorb CO ₂ to promote the steam reforming reaction of methane and the water gas shift reaction. The reaction in the steam reforming reactor 17 produces steam reforming crude synthesis gas 22 and CaCO ₃ and CaO mixture 19 ;

The steam reformed crude synthesis gas 22 is compressed and exchanged by the compression heat exchanger 21 to obtain the cooled steam reformed crude synthesis gas 24, and the cooled steam reformed crude synthesis gas 24 enters the steam reformed gas flash evaporation Tower 23, water vapor recombined into gas 26 is produced from the top of steam reforming gas flash tower 23, water 25 is produced from the top of steam reforming gas flash tower 23; water vapor recombined into gas 26 enters the pressure swing adsorption device 27 is separated to obtain high-purity hydrogen 29 and unrecovered gas 28; high-purity hydrogen 29 is separated by separator 30 to obtain fresh hydrogen 16 and hydrogen product 31 required by shale oil hydrogenation upgrading unit 2; CaCO ₃ and CaO mixture 19 enters the CaO regenerative combustion furnace 18 for calcination, and the regenerated CaO absorbent 20 enters the steam reforming reactor 17 for recycling;

Detrital shale 10 and unrecovered gas 28 enter the CaO regenerative combustion furnace 18 for combustion to calcine CaCO ₃ to generate CaO absorbent 20 and shale ash 15 , and the combustion reaction is carried out under the atmosphere of air 14 .

Example 1

The specific implementation of the integrated refining process for hydrogen production and upgrading of oil shale dry distillation gas in this embodiment is as follows:

The flow rate of raw material shale entering the process of the present invention is 300t/h, of which 225t/h enters the dry distillation furnace, and the flow rate of clastic shale is 75t/h. The circulation rate of CaO is 44.4t/h, and the flow rate of steam is 38.02t/h. The industrial analysis and elemental analysis of oil shale are shown in Table 1.

Table 1 Elemental analysis of industrial analysis of oil shale

The ar in the table indicates that the base is received.

The flow chart of the integrated refining process for hydrogen production and upgrading of oil shale dry distillation gas is shown in Figure 2 and Figure 3:

The integrated refining system includes an oil shale dry distillation unit 1, a shale oil hydro-upgrading unit 2, a methane steam reforming unit 12 and a building material production unit 8; wherein the methane steam reforming unit 12 includes a steam reforming reactor 17. CaO regenerative combustion furnace 18, compression heat exchanger 21, steam reforming gas flash tower 23, pressure swing adsorption device 27 and separator 30;

(1) The oil shale 3 with a particle size of 10-75mm after being crushed and screened is passed into the oil shale retort unit 1 to undergo a retort reaction under the conditions of 0.1MPa and 525°C to obtain shale oil 5, retort gas 4, cinder 9 and unreacted clastic shale 10;

(2) The retort gas 4 is passed into the steam reforming reactor 17 of the methane steam reforming unit 12, and the steam 13 is passed into the steam reforming reactor 17 and the retort gas 4 at 650° C. and a pressure of 15 bar. The steam reforming reaction of methane and the water-gas shift reaction occur under the conditions of the reforming reaction. During the reforming reaction, the CaO absorbent is used to absorb _CO2 to promote the steam reforming reaction of methane and the water-gas shift reaction. The reaction in the steam reforming reactor 17 produces water Steam reforming of raw synthesis gas 22 and CaCO ₃ and CaO mixture 19;

The steam reformed crude synthesis gas 22 is compressed and exchanged by the compression heat exchanger 21 to obtain the cooled steam reformed crude synthesis gas 24, and the cooled steam reformed crude synthesis gas 24 enters the steam reformed gas flash evaporation Tower 23, from the top of the steam reforming gas flash tower 23, water vapor is recombined into gas 26, and the hydrogen content is increased to 43%, and water 25 is produced from the top of the steam reforming gas flash tower 23; The gas 26 enters the pressure swing adsorption device 27 for separation to obtain high-purity hydrogen gas 29 with a purity of 99.95% and unrecovered gas 28; the high-purity hydrogen gas 29 is separated by a separator 30 to obtain fresh Hydrogen gas 16 and high-purity hydrogen gas 31 as products; CaCO ₃ and CaO mixture 19 enter the CaO regenerative combustion furnace 18 for calcination, the calcination temperature is 900°C, regenerated CaO absorbent 20 enters the steam reforming reactor 17 again, and recycles ;

Detrital shale 10 and unrecovered gas 28 enter the CaO regenerative combustion furnace 18 for combustion to calcine CaCO ₃ to generate CaO absorbent 20 and shale ash 15, and the combustion reaction is carried out under the atmosphere of air 14;

(3) Put the shale oil 5 and fresh hydrogen 16 into the shale oil hydro-upgrading unit 2 to carry out hydrocracking reaction at 400°C to generate the upgraded oil 7; the fresh hydrogen 16 and the shale oil 5 The mass ratio is 0.03;

(4) Both the ash 9 and the shale ash 15 are sent to the building material production unit 8 to produce the building material product 11 .

The oil shale dry distillation process, the shale oil hydrogenation upgrading process and the building material production process are the same as the prior art.

Finally, the investment profit rate of the integrated refining system for hydrogen production and upgrading of oil shale dry distillation gas in this embodiment has increased by 6.93% from 12.60% of the existing oil shale refining system to 19.53%; the energy efficiency has increased from the current The 26.21% of the oil shale refining system increased by 3.12% to 29.33%.

Example 2

The specific implementation of the integrated refining process for hydrogen production and upgrading of oil shale dry distillation gas in this embodiment is as follows:

The flow rate of raw material shale entering the process of the present invention is 400t/h, of which 300t/h enters the carbonization furnace, and the flow rate of clastic shale is 100t/h. The circulation rate of CaO is 60.5t/h, and the flow rate of steam is 55.75t/h. The industrial analysis and elemental analysis of oil shale are shown in Table 2.

Table 2 Elemental analysis of industrial analysis of oil shale

The ar in the table indicates that the base is received.

The flow chart of the integrated refining process for hydrogen production and upgrading of oil shale dry distillation gas is shown in Figure 2 and Figure 3:

The integrated refining system includes an oil shale dry distillation unit 1, a shale oil hydro-upgrading unit 2, a methane steam reforming unit 12 and a building material production unit 8; wherein the methane steam reforming unit 12 includes a steam reforming reactor 17. CaO regenerative combustion furnace 18, compression heat exchanger 21, steam reforming gas flash tower 23, pressure swing adsorption device 27 and separator 30;

(1) The oil shale 3 with a particle size of 10-75mm after being crushed and screened is passed into the oil shale retort unit 1 to undergo a retort reaction under the conditions of 0.1MPa and 525°C to obtain shale oil 5, retort gas 4, cinder 9 and unreacted clastic shale 10;

(2) The retort gas 4 is passed into the steam reforming reactor 17 of the methane steam reforming unit 12, and the steam 13 is passed into the steam reforming reactor 17 and the retort gas 4 at 700° C. and a pressure of 20 bar. The steam reforming reaction of methane and the water-gas shift reaction occur under the conditions of the reforming reaction. During the reforming reaction, the CaO absorbent is used to absorb _CO2 to promote the steam reforming reaction of methane and the water-gas shift reaction. The reaction in the steam reforming reactor 17 produces water Steam reforming of raw synthesis gas 22 and CaCO ₃ and CaO mixture 19;

The steam reformed crude synthesis gas 22 is compressed and exchanged by the compression heat exchanger 21 to obtain the cooled steam reformed crude synthesis gas 24, and the cooled steam reformed crude synthesis gas 24 enters the steam reformed gas flash evaporation Tower 23, from the top of the steam reforming gas flash tower 23, water vapor is recombined into gas 26, and the hydrogen content is increased to 43%, and water 25 is produced from the top of the steam reforming gas flash tower 23; The gas 26 enters the pressure swing adsorption device 27 for separation to obtain high-purity hydrogen gas 29 with a purity of 99.95% and unrecovered gas 28; the high-purity hydrogen gas 29 is separated by a separator 30 to obtain fresh Hydrogen gas 16 and high-purity hydrogen gas 31 as a product; CaCO ₃ and CaO mixture 19 enters the CaO regeneration combustion furnace 18 for calcination, the calcination temperature is 950°C, regenerates CaO absorbent 20 and enters the steam reforming reactor 17 again for recycling ;

Detrital shale 10 and unrecovered gas 28 enter the CaO regenerative combustion furnace 18 for combustion to calcine CaCO ₃ to generate CaO absorbent 20 and shale ash 15, and the combustion reaction is carried out under the atmosphere of air 14;

(3) Put the shale oil 5 and fresh hydrogen 16 into the shale oil hydro-upgrading unit 2 to carry out hydrocracking reaction at 400°C to generate the upgraded oil 7; the fresh hydrogen 16 and the shale oil 5 The mass ratio is 0.03;

(4) Both the ash 9 and the shale ash 15 are sent to the building material production unit 8 to produce the building material product 11 .

The oil shale dry distillation process, the shale oil hydrogenation upgrading process and the building material production process are the same as the prior art.

Finally, the investment profit rate of the integrated refining system for hydrogen production and upgrading of oil shale dry distillation gas in this embodiment has increased by 6.47% from 12.60% of the existing oil shale refining system to 19.07%; the energy efficiency has increased from the current The 26.21% of oil shale refining systems increased by 3.03% to 29.24%.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (10)

1. An integrated refining system for hydrogen production and upgrading by oil shale retort gas, comprising an oil shale retort unit, a shale oil hydrogenation upgrade unit and a building material production unit, characterized in that the system also includes methane steam reforming unit; The oil shale retort unit is provided with an inlet leading into the oil shale raw material, and the shale oil outlet of the oil shale retort unit is directly connected with the shale oil raw material inlet of the shale oil hydrogenation and upgrading unit through a pipeline, and the oil shale retort unit The retort gas outlet of the shale retort unit is connected to the retort gas raw material inlet of the steam reforming reactor of the methane steam reforming unit through a pipeline, and the clastic shale outlet of the oil shale retort unit is connected to the methane steam reformer through a conveying device. The debris shale inlet of the CaO regenerative combustion furnace of the whole unit is connected, the ash outlet of the oil shale carbonization unit and the shale ash outlet of the methane steam reforming unit are all connected to the ash raw material inlet of the building material production unit through the conveying device The steam reforming reactor of the methane steam reforming unit is provided with an inlet for the steam feedstock, and the fresh hydrogen outlet of the methane steam reforming unit is connected with the fresh hydrogen feedstock of the shale oil hydrogenation upgrading unit through pipelines Ingress connection. 2. The integrated refining system according to claim 1, wherein the steam methane reforming unit comprises a steam reforming reactor, a CaO regeneration burner, a compression heat exchanger, a steam reforming gas flash Distillation columns, pressure swing adsorption units and separators; The steam reforming reactor is provided with a low-pressure steam inlet leading into low-pressure steam and a retort gas raw material inlet leading into retort gas; the retort gas outlet of the oil shale retort unit is directly connected to the retort gas outlet of the steam reforming reactor through a pipeline. The gas raw material inlet is connected; the CaCO ₃ and CaO mixture outlet of the steam reforming reactor is connected with the CaCO ₃ and CaO mixture inlet of the CaO regenerative burner through a conveying device; the CaO regenerative burner is provided with an inlet for shale debris, The clastic shale outlet of the oil shale carbonization unit is connected with the clastic shale inlet of the CaO regenerative combustion furnace through a conveying device; the CaO regenerative combustion furnace is also provided with an air inlet, and the CaO absorbent outlet of the CaO regenerative combustion furnace The conveying device is connected to the CaO absorbent inlet of the steam reforming reactor; the steam reforming crude synthesis gas outlet of the steam reforming reactor is connected to the compressed gas inlet of the compression heat exchanger through a pipeline; the compression of the compression heat exchanger The gas outlet is connected to the flash steam synthesis gas inlet of the steam reforming gas flash tower through a pipeline; Integrate into the gas inlet connection; the unrecovered gas outlet of the pressure swing adsorption unit is connected to the unrecovered gas inlet of the CaO regeneration burner through a pipeline; the high-purity hydrogen outlet of the pressure swing adsorption unit is connected to the high-purity hydrogen inlet of the separator through a pipeline; The fresh hydrogen outlet of the separator is connected with the fresh hydrogen inlet of the shale oil hydro-upgrading unit through a pipeline. 3. An integrated refining process for hydrogen production and upgrading with oil shale retort gas, characterized in that it comprises the following steps: The crushed and screened oil shale is passed into the oil shale retort unit for retort reaction to obtain shale oil, retort gas, ash and unreactable clastic shale; The retort gas is passed into the steam reforming reactor of the steam methane reforming unit, and water vapor is fed at the same time, and the steam reforming reaction of methane and the water gas shift reaction are promoted by the CaO absorbent to obtain the steam reforming crude synthesis gas And CaCO ₃ and CaO mixture, the steam reforming raw synthesis gas is separated to obtain fresh hydrogen, unrecovered gas and hydrogen products, and the CaCO ₃ and CaO mixture enters the CaO regenerative combustion furnace of the steam methane reforming unit; The clastic shale is sent to the CaO regenerative combustion furnace of the methane steam reforming unit, and air is introduced, and the unrecovered gas and clastic shale are burned under the atmosphere of air to calcinate the CaCO ₃ and CaO mixture to generate CaO absorbent and Shale ash and CaO absorbent enter the steam reforming reactor again for recycling; Shale oil and fresh hydrogen enter the shale oil hydro-upgrading unit for hydrocracking reaction to produce upgraded oil; Both ash and shale ash are sent to the building material production unit to produce building material products. 4. The integrated refining process according to claim 3, characterized in that the particle size of the crushed and screened oil shale is 10-75mm, and the dry distillation reaction conditions are 0.1MPa and 525°C. 5. The integrated refining process according to claim 3, characterized in that the molar ratio of the water vapor to the retort gas is (0.3-0.8): 1.0; the molar ratio of the CaO absorbent to the retort gas is ( 0.3～0.8): 1.0. 6. The integrated refining process according to claim 5, characterized in that the molar ratio of the water vapor to the dry distillation gas is 1.31:1.00; the molar ratio of the CaO absorbent to the dry distillation gas is 0.5:1.0. 7. The integrated refining process according to claim 3, characterized in that the operating temperature of the steam reforming reactor is 600-700° C., and the pressure is 15-20 bar. 8. The integrated refining process according to claim 3, characterized in that the operating temperature of the CaO regenerative combustion furnace is 900-950°C, and the pressure is normal pressure. 9. The integrated refining process according to claim 3, characterized in that, the specific process of the steam methane reforming unit is as follows: The retort gas is passed into the steam reforming reactor of the methane steam reforming unit, and at the same time, water vapor is passed into the steam reforming reactor and the retort gas undergoes methane steam reforming reaction and water-gas shift reaction. During the reforming reaction CaO absorbent is used to absorb _CO2 to promote the steam reforming reaction of methane and the water gas shift reaction, and the reaction in the steam reforming reactor produces steam reformed crude synthesis gas and a mixture of CaCO ₃ and CaO; steam reformed crude synthesis gas After being compressed and exchanged by the compression heat exchanger, it enters the steam reforming gas flash tower, and the water vapor is produced from the top of the steam reforming gas flash tower to be recombined into gas, and the water is produced from the bottom of the steam reforming gas flash tower; The steam recombined gas enters the pressure swing adsorption device for separation to obtain high-purity hydrogen and unrecovered gas; the high-purity hydrogen is separated by a separator to obtain fresh hydrogen and hydrogen products required for shale oil hydrogenation and upgrading; CaCO ₃ and The CaO mixture enters the CaO regeneration burner for calcination, and the regenerated CaO absorbent enters the steam reforming reactor for recycling; Detrital shale and unrecovered gas enter the CaO regenerative combustion furnace for combustion to calcine CaCO ₃ to generate CaO absorbent and shale ash, and the combustion reaction is carried out in an air atmosphere. 10. The integrated refining process according to claim 3, characterized in that the hydrocracking reaction temperature is 400°C, and the mass ratio of fresh hydrogen entering the hydro-upgrading unit to shale oil is 0.03.