CN107857238B - Poly-generation production system of metal magnesium and hydride thereof - Google Patents

Poly-generation production system of metal magnesium and hydride thereof Download PDF

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CN107857238B
CN107857238B CN201711133741.7A CN201711133741A CN107857238B CN 107857238 B CN107857238 B CN 107857238B CN 201711133741 A CN201711133741 A CN 201711133741A CN 107857238 B CN107857238 B CN 107857238B
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CN107857238A (en
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贾鹏
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Shanghai Covapor Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/10—Process efficiency

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Abstract

The invention relates to a poly-generation production system of metal magnesium and hydride thereof, which comprises a calcium carbide production device, a crystallization chamber, a magnesium refining and crushing device, a reaction pot, a magnesium hydroxide calcining furnace, a magnesium hydroxide container and an inert gas pipeline. The calcium carbide liquid outlet of the rotary kiln is connected to a calcium carbide liquid inlet of the reaction pot, the magnesium hydroxide container is connected to the magnesium hydroxide calcining furnace, a magnesium oxide outlet of the magnesium hydroxide calcining furnace is connected to a magnesium oxide inlet of the reaction pot, the inert gas pipeline is respectively connected to the magnesium oxide inlets of the magnesium hydroxide calcining furnace and the reaction pot, and the magnesium vapor outlet is connected to the crystallization chamber. The solid outlet of the crystallization chamber is connected to a magnesium metal container through a magnesium refining and crushing device, and the gas outlet is connected to an inert gas pipeline through a draught fan. The invention effectively utilizes the heat of each process, saves energy, protects environment, realizes the poly-generation of various products of metal magnesium, magnesium hydride, pure carbon maple energy and electric power, and has considerable economic benefit.

Description

Poly-generation production system of metal magnesium and hydride thereof
Technical Field
The invention belongs to the technical field of industrial furnaces, and relates to a poly-generation production system for metal magnesium and hydride thereof.
Background
Rotary kilns, also known as rotary kilns, are used in the metallurgical industry for the direct reduction of iron ores, the roasting of alumina minerals, the roasting of clay minerals, and the roasting, volatilization, segregation and drying of various bulk materials. The traditional industrial furnace calcines magnesium-containing raw materials and calcium-containing raw materials in a hearth oxidation environment to obtain magnesium oxide and calcium oxide products, waste heat cannot be effectively utilized, heat efficiency is low, and activity and quality of the products are poor.
The traditional magnesium metal is produced by a Pidgeon method, the required content of magnesium oxide raw materials is high, the production process is carried out under high vacuum, and the purity of a magnesium ingot product is low.
Disclosure of Invention
The invention aims to provide a poly-generation production system of metal magnesium and hydride thereof, which changes the traditional working mode of an industrial furnace, realizes the calcination, temperature control and slag discharge of materials and simultaneously gasifies the materials to obtain metal magnesium and hydride products thereof and can also produce pure carbon-maple energy, high-purity carbon dioxide and electric power products as byproducts.
The technical scheme of the invention is as follows: the poly-generation production system of metal magnesium and hydride thereof comprises a calcium carbide production device, wherein the calcium carbide production device is provided with a rotary kiln and a metal magnesium container. The system is provided with a crystallization chamber, a magnesium refining and crushing device, a reaction pot, a magnesium hydroxide calcining furnace, a magnesium hydroxide container and an inert gas pipeline, wherein the reaction pot comprises a pot body and a pot cover, the pot body is provided with a calcium carbide liquid inlet, a magnesium oxide inlet, a magnesium vapor outlet, a support lug, a clamping piece, a heating electrode and a heating coil, and the magnesium oxide inlet on the pot body is arranged at the bottom or the side or the top of the reaction pot. The calcium carbide liquid outlet of the rotary kiln is connected to a calcium carbide liquid inlet of the reaction pot, the magnesium hydroxide container is connected to the magnesium hydroxide calcining furnace, a magnesium oxide outlet of the magnesium hydroxide calcining furnace is connected to a magnesium oxide inlet of the reaction pot, the inert gas pipeline is respectively connected to a magnesium oxide outlet of the magnesium hydroxide calcining furnace and a magnesium oxide inlet of the reaction pot, and the magnesium steam outlet is connected to the crystallization chamber. The solid outlet of the crystallization chamber is connected to a magnesium metal container through a magnesium refining and crushing device, and the gas outlet is connected to an inert gas pipeline through a draught fan. The reaction pot is connected to a calcium carbide raw material preheater of the calcium carbide production device.
The calcium carbide production device comprises a calcium carbide raw material bin, a rotary kiln, waste heat power generation equipment, a Kohlepu unit, conversion separation equipment, carbon dioxide purification equipment, an hydrogen production unit, a metal magnesium container, harmful substance removal equipment, a metal magnesium hydride container, a raw material preheater and a carbon dioxide finished product tank. The rotary kiln is provided with a kiln body, a raw material inlet, a calcium carbide liquid outlet, a burner and a flue gas outlet, a seal box is arranged outside the kiln body, the burner is connected with a combustion-supporting gas pipeline and a fuel pipeline, the combustion-supporting gas of the burner is mixed gas, and the mixing ratio of oxygen to carbon dioxide is 0: 100: 0. The raw material storehouse of carbide is connected to the raw materials entry through raw materials preheater, and the flue gas export is connected to the transform splitter through raw materials preheater, waste heat power generation equipment, harmful substance desorption equipment and kohlip unit, and kohlip unit and waste heat power generation equipment circuit connection respectively to power transmission equipment. The outlet of the conversion separation equipment is divided into three paths, one path is connected to the hydrogen production unit, the other path is connected to the carbon dioxide purification equipment, and the other path is connected to the combustion-supporting gas pipeline and the fuel pipeline of the burner. The hydrogen production unit is provided with a metal magnesium inlet and a magnesium hydride outlet, the metal magnesium inlet is connected with a metal magnesium container, and the magnesium hydride outlet is connected with the metal magnesium hydride container. The carbon dioxide purification equipment is respectively connected to the combustion-supporting gas pipeline and the fuel pipeline of the carbon dioxide finished product tank and the burner. The conversion separation equipment is provided with a water filling port, and the magnesium hydroxide calcining furnace is connected to the conversion separation equipment through the water filling port and is used as part of reaction raw materials of the conversion separation equipment.
The system is provided with a maple energy preparation unit, the maple energy preparation unit is provided with a reaction product heat exchanger, a pulverizer, a separation device, carbon purification equipment and a pure maple energy storage bin, and one path of a reaction pot is connected with the reaction product heat exchanger, the pulverizer, the separation device, the carbon purification equipment and the pure maple energy storage bin in sequence. The other path of the reaction pot and the outlet at the bottom of the separation device are connected to a calcium carbide raw material preheater of the calcium carbide production device. The carbide apparatus for producing is equipped with functional gasifier and lime-ash cooler, and functional gasifier is equipped with nozzle, exhanst gas outlet and lime-ash export nozzle and combustion-supporting gas pipeline and fuel piping connection, and the combustion-supporting gas of nozzle (46) is the mist, and the exhanst gas outlet is connected with the kiln thorax entry linkage of rotary kiln, and the lime-ash export is connected to the lime-ash storehouse through the lime-ash cooler. The Kohler unit is respectively connected with the hydrogen production unit, the conversion separation equipment, the ash cooler, the crystallization pipe in the crystallization chamber and the reaction product heat exchanger in a circulating way through a circulating heat exchange medium pipeline.
The coanda unit includes an expander, a generator, a hydrogen heat compression device, and an intermediate reheater. The outlet of the expansion machine is connected to the inlet of the expansion machine through hydrogen heat compression equipment, the expansion machine is connected with a generator shaft, and the generator is connected with an external power system circuit. The hydrogen heat compression device is in a multi-stage cascade utilization mode, each cascade can be composed of a plurality of reaction beds, the operation mode of each reaction bed can adopt an internal metal hydride direct extraction and replacement mode, an indirect heat exchange mode, a heat carrier heating mode or an electric heating mode, the metal hydride in the reaction beds mainly takes rare earth as main material or other materials, and therefore hydrogen in the Koehumu unit enters an expander to do work after being heated and boosted by heat brought by a circulating heat exchange medium pipeline, and a generator is driven to generate electricity. The Koehringer's unit can also adopt a composite Koehringer's unit with a Rankine cycle and a compression-expansion combined cycle device, so that the overall efficiency of the system is further improved.
The hydrogen production unit comprises at least two hydrogen absorption reactors, a metal hydride replacing device, a metal magnesium container and a metal magnesium hydride container. The metal hydride outlet of the hydrogen absorption reactor is respectively connected with the metal magnesium container and the metal magnesium hydride container through a metal hydride replacing device, and the hydrogen absorption reactor is circularly connected with the Kohler unit through a circulating heat exchange medium pipeline to form a circulating loop. The metal hydride replacing device can adopt other methods of gravity conveying, mechanical conveying, pneumatic conveying, vacuum conveying, hydraulic conveying, electromagnetic conveying or the combination of the methods, thereby achieving the purpose of replacing corresponding materials and reliably realizing any method for replacing magnesium hydride and magnesium metal materials between the hydrogen absorption reactor and the magnesium metal container or between the magnesium hydride metal containers. The metal hydride replacing device can replace magnesium hydride and metal magnesium, magnesium hydride, magnesium hydroxide, magnesium hydride, magnesium oxide, a mixture of magnesium hydride, magnesium hydroxide and magnesium oxide, a mixture of metal magnesium, magnesium hydroxide, magnesium oxide and a mixture of metal magnesium, magnesium hydroxide and magnesium oxide, or a hydroxide or/and oxide of metal which is combined with hydrogen to form metal hydride or/and can react with water to release hydrogen or a mixture of the metal and other substances and the metal and other substances.
The lower part of the crystallization chamber is provided with a magnesium steam inlet, the upper part of the crystallization chamber is provided with an inert gas outlet, the crystallization chamber is provided with at least one crystallization pipe, and the crystallization pipe is inserted into the side wall of the crystallization chamber. The magnesium steam inlet is connected with the magnesium steam outlet of the reaction kettle, and the inert gas outlet is connected to the inert gas pipeline through the induced draft fan. It is permissible to use a magnesium-containing substance including calcined dolomite as a blowing-in magnesium-containing raw material in place of the magnesium oxide.
The magnesium hydride regenerating device comprises a calcium carbide production device, a crystallization chamber, a magnesium refining and crushing device, a reaction pot, a magnesium hydroxide calcining furnace, a magnesium hydroxide container and an inert gas pipeline. The calcium carbide production device comprises a calcium carbide raw material bin, a rotary kiln, waste heat power generation equipment, a Kohlepu unit, conversion separation equipment, carbon dioxide purification equipment, an hydrogen production unit, a metal magnesium container, harmful substance removal equipment, a metal magnesium hydride container, a raw material preheater and a carbon dioxide finished product tank. The rotary kiln is provided with a kiln body, a raw material inlet, a calcium carbide liquid outlet, a burner and a flue gas outlet, a seal box is arranged outside the kiln body, a fuel inlet of the burner is connected with a fuel pipeline, and a combustion-supporting gas inlet is connected with a combustion-supporting gas pipeline. The raw material storehouse of carbide is connected to the raw materials entry through raw materials preheater, and the exhanst gas outlet of rotary kiln passes through raw materials preheater, waste heat power generation equipment, harmful substance desorption equipment and kolepu unit and is connected to the transform splitter, and kolepu unit and waste heat power generation equipment power output cable are connected with the outside power transmission equipment of system. The outlet of the conversion separation equipment is divided into three paths, one path is connected to the hydrogen production unit, the other path is connected to the carbon dioxide purification equipment, and the other path is connected to the combustion-supporting gas pipeline and the fuel pipeline of the burner. The hydrogen production unit is provided with a metal magnesium inlet and a magnesium hydride outlet, the metal magnesium inlet is connected with a metal magnesium container, and the magnesium hydride outlet is connected with the metal magnesium hydride container. The Kohler unit is respectively connected with the conversion separation equipment, the hydrogen production unit and the crystallization pipe in the crystallization chamber through a circulating heat exchange medium pipeline. The calcium carbide liquid outlet of the rotary kiln is connected to a calcium carbide liquid inlet of the reaction pot, the magnesium hydroxide container is connected to the magnesium hydroxide calcining furnace, a magnesium oxide outlet of the magnesium hydroxide calcining furnace is connected to a magnesium oxide inlet of the reaction pot, the inert gas pipeline is respectively connected to a magnesium oxide outlet of the magnesium hydroxide calcining furnace and a magnesium oxide inlet of the reaction pot, and the magnesium steam outlet is connected to the crystallization chamber. The solid outlet of the crystallization chamber is connected to a magnesium metal container through a magnesium refining and crushing device, and the gas outlet is connected to an inert gas pipeline through a draught fan.
The circulating feed back of the rotary kiln enters the raw material preheater through a circulating feed inlet, exchanges heat with carbon monoxide tail gas generated in calcium carbide production and then is connected to a feed inlet, and a discharge port is connected to a reaction pot. And a carbon dioxide gas seal box is arranged outside the fish scale of the dynamic and static sealing element connected with the kiln head cover and the kiln tail cover, and the pressure of the seal box is higher than the kiln internal pressure of the rotary kiln, so that the gas in the rotary kiln is effectively isolated from the external air. The transformation separation equipment is provided with a hydrogen outlet and a carbon dioxide outlet, the hydrogen outlet is connected to the hydrogen production unit, and the carbon dioxide outlet is connected to the carbon dioxide purification equipment and the fuel pipeline inlet and the combustion-supporting gas pipeline of the burner. The outlet of the carbon dioxide purification equipment is connected to a carbon dioxide finished product tank. The Kohlepu unit is in circulating connection with the conversion separation equipment, the hydrogen production unit and the crystallization pipe in the crystallization chamber through a circulating heat exchange medium pipeline, and the Kohlepu unit and the conversion separation equipment are respectively connected to form a circulating loop so as to recover the waste heat of the equipment. The carbon monoxide in the conversion separation equipment reacts with the steam to generate chemical reaction heat released by carbon dioxide and hydrogen, and the magnesium metal in the hydrogen production unit absorbs the heat released by hydrogen and the heat released by magnesium condensation of a crystallization tube in the crystallization chamber. The circulating heat exchange medium of the circulating heat exchange medium pipeline connected with the Kohler unit is stable gas, liquid, solid medium or the mixture of the gas, the liquid and the solid medium. The circulating heat exchange medium of the circulating heat exchange medium pipeline is discharged from the Koehaipu unit, passes through the conversion separation equipment, the hydrogen production unit and the crystallization pipe in the crystallization chamber, recovers the waste heat of the equipment, and returns to the Koehaipu unit after heat exchange and temperature rise.
The magnesium hydride regeneration device uses oxygen, calcium-containing raw materials, pure carbon (maple energy) and magnesium hydroxide, the final products are magnesium hydride, carbon dioxide and electric power output, the pure carbon maple energy and pure oxygen are fed into a burner to be gasified to generate mixed gas mainly containing carbon monoxide, combustion-supporting gas of the burner is mixed gas, the mixing ratio of oxygen to carbon dioxide is 0: 100-. The gasification temperature is 1000-. The temperature of the calcined kiln tail flue gas is up to 500-2000 ℃, a flue gas outlet is connected with a Kohler unit through a raw material preheater, a waste heat power generation device and a harmful substance removal device, the flue gas outlet is connected with a transformation separation device after coming out of the Kohler unit, carbon dioxide separated from the transformation separation device is connected with a carbon dioxide purification device, one path of the purified carbon dioxide enters a finished product tank, the other path of the purified carbon dioxide is connected with a fuel pipeline and a combustion-supporting gas pipeline of a burner, and hydrogen separated from the transformation separation device enters a hydrogen production unit. The calcium carbide is discharged and then directly enters a reaction pot, magnesium hydroxide recycled from a magnesium hydride container after the magnesium hydride is used enters a magnesium hydroxide container, the magnesium hydroxide enters a magnesium hydroxide calcining furnace from the magnesium hydroxide container to be heated and calcined to generate magnesium oxide, byproduct steam enters a conversion separation device through a water inlet to be used as part of reaction raw materials of the conversion separation device, the magnesium oxide is brought into the reaction pot by circulating inert gas and is blown in from the bottom or the side part or the top of the reaction pot, the magnesium oxide and the liquid calcium carbide react at 2500 ℃, metal magnesium vapor, calcium-containing raw materials and carbon are generated, the reaction is an endothermic reaction, and heat is provided by the liquid calcium carbide and the solidification heat of the molten heat storage materials. Under the action of normal pressure or vacuum 0.01-100kPa (absolute pressure), the metal magnesium vapor and inert gas enter a crystallization chamber from an outlet at the top of a reaction pot, the magnesium vapor is condensed into a crude magnesium ingot in the crystallization chamber, and the inert gas is sucked by a draught fan for recycling. And (3) feeding the crude magnesium ingot into a magnesium refining and crushing device to produce high-purity metal magnesium powder, adding the high-purity metal magnesium powder into a metal magnesium container, adding the high-purity metal magnesium powder serving as self-use metal magnesium powder into an hydrogen production unit from the metal magnesium container, and reacting the high-purity metal magnesium powder with hydrogen to produce hydrogen product magnesium hydride. The crude magnesium ingot may be crushed without refining and then added to a magnesium metal container (15).
A plurality of reaction pots are arranged in parallel, the production is intermittent operation, firstly, liquid calcium carbide and heat storage materials are added into the reaction pots, pot covers are sealed, the heat storage materials and the calcium carbide are layered due to different specific gravities, the liquid calcium carbide floats upwards, and the heat storage materials sink. Introducing inert gas carrying magnesium oxide from the bottom, wherein the gas has stirring and floating functions, the carried magnesium oxide is firstly heated to 1000-2500 ℃ through a heat storage material layer, and after floating to a liquid calcium carbide layer, the preheated magnesium oxide reacts with the liquid calcium carbide to generate calcium-containing raw materials, carbon and metal magnesium vapor. Magnesium vapor is pumped out together with inert gas from a magnesium vapor outlet and enters a crystallization chamber, the magnesium vapor is condensed and solidified to form magnesium ingots, and the inert gas is recycled. When the heat accumulating material in the reactor is about to solidify, the magnesium oxide is stopped to be added, the magnesium oxide added is completely or basically reacted, magnesium oxide generated metal magnesium vapor enters the crystallization chamber to be recovered, reaction products remained in the reactor are condensed and contracted, the cover is opened to be poured out integrally, and the reaction products are recovered to the feed inlet of the rotary kiln with heat circulation. The heat storage material can be adopted or not according to the actual reaction requirement, and the adding amount can be more or less. Heating coils or heating electrodes can be used for auxiliary heating to provide reaction heat in the magnesium smelting process, so that the added magnesium oxide can be completely reacted as much as possible. The use of calcined dolomite as blowing raw material instead of magnesia was allowed.
The carbon-containing raw material used by the burner is pure carbon (maple energy), the whole production device has no pollutant emission, the whole device can be installed in a city or a sub-station of a hydrogen hydrogenation station and used as a regeneration device of magnesium hydride, and the discharge product of the reaction pot is not required to be separated and recycled. The sub-station of the hydrogen adding station provides magnesium hydride containers with protective gas for each hydrogen adding station base station and recovers the magnesium hydroxide containers filled with magnesium hydroxide. The heat of the whole device is fully recycled, the energy transportation cost is low, pure oxygen and maple energy are only needed to be transported, carbon dioxide is transported away, the production cost is reduced, and the device is environment-friendly.
The poly-generation production system of metal magnesium and hydride thereof of the invention generates mixed gas mainly comprising carbon monoxide by sending carbonaceous raw material and gasifying agent into a functional gasification furnace for gasification, heats and calcines the loaded calcium-containing raw material while gasifying, reacts the calcium-containing raw material with carbon at high temperature to generate calcium carbide, and further reacts the calcium carbide with magnesium oxide at high temperature to generate magnesium vapor, calcium oxide and carbon. The magnesium vapor enters the crystallization chamber, and the magnesium vapor is condensed in the crystallization chamber to form a magnesium ingot. The tail gas of the rotary kiln is subjected to conversion separation equipment to obtain hydrogen, and the hydrogen is sent to a hydrogen production device to react with the metal magnesium powder to produce a magnesium hydride product. And separating the solid product in the reaction kettle by a jigging separation device to obtain a pure carbon product (maple energy).
The invention adopts the functional gasification furnace to integrate a plurality of process flows of carbon gasification, material calcination, calcium carbide production, calcium carbide high-temperature reduction magnesium oxide and the like into one system to complete, thereby utilizing the heat generated in each process unit to the maximum extent and reducing the energy consumption of the magnesium metal production process. Meanwhile, poly-generation of various products of magnesium hydride, carbon dioxide and electric power is realized, the products are various and considerable in economy, and all carbon dioxide is recycled, so that the environmental pollution is reduced. The method adopts an oxygen heating method to produce calcium carbide, adopts a calcium carbide reduction method to produce metal magnesium, can use low-purity magnesium oxide raw materials, and produces high-purity magnesium powder by the production process under normal pressure or weak vacuum at high temperature.
Drawings
FIG. 1 is a schematic view of a polygeneration production apparatus for magnesium metal and its hydride of the present invention;
FIG. 2 is a schematic view of another embodiment of the present invention;
FIG. 3 is a schematic diagram of a Korlps unit according to the present invention;
FIG. 4 is a schematic diagram of an ampere hydrogen production plant of the present invention;
FIG. 5 is a schematic view of the structure of a reaction vessel according to the present invention;
FIG. 6 is a schematic view of the structure of a crystallization chamber;
wherein: 1-rotary kiln, 2-waste heat power generation equipment, 3-Kohlepu unit, 4-conversion separation equipment, 5-carbon dioxide purification equipment, 6-ampere hydrogen production unit, 7-separation device, 8-crystallization chamber, 9-magnesium refining and crushing device, 10-reaction pot, 11-magnesium oxide inlet, 12-circulating material inlet, 13-supplemented raw material inlet, 14-water filling port, 15-metal magnesium container, 16-inert gas pipeline, 17-crusher, 18-expander, 19-generator, 20-hydrogen thermal compression equipment, 21-intermediate reheater, 23-hydrogen absorption reactor, 24-metal hydride replacement device, 25-circulating heat exchange medium pipeline, 26-metal magnesium hydride container, 27-carbon purification equipment, 28-magnesium hydroxide calciner, 29-induced draft fan, 30-heating coil, 31-calcium carbide liquid inlet, 32-magnesium vapor outlet, 33-pot body, 34-raw material preheater, 35-functional gasification furnace, 36-heat insulation layer, 37-harmful substance removing device, 38-refractory brick, 39-liquid carbide layer, 40-liquid heat storage material layer, 41-magnesium hydroxide container, 42-pot cover, 43-lug, 44-clamping piece, 45-heating electrode, 46-burner, 47-ash cooler, 48-seal box, 49-carbon dioxide finished product tank, 50-heat storage material conveying pipeline, 51-reaction product heat exchanger, 52-magnesium steam inlet, 53-inert gas outlet and 54-crystallizing tube.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings. The scope of protection of the invention is not limited to the embodiments, and any modification made by those skilled in the art within the scope defined by the claims also falls within the scope of protection of the invention.
Example 1
The poly-generation production system of metal magnesium and hydride thereof is shown in figure 1 and comprises a calcium carbide production device, a crystallization chamber 8, a magnesium refining and crushing device 9, a maple energy preparation unit, a reaction pot 10, a magnesium hydroxide calcining furnace 28, a magnesium hydroxide container 41 and an inert gas pipeline 16. The calcium carbide production device comprises a calcium carbide raw material bin, a rotary kiln 1, a functional gasification furnace 35, an ash cooler 47, waste heat power generation equipment 2, a Kohlepu unit 3, conversion separation equipment 4, carbon dioxide purification equipment 5, a hydrogen production unit 6, a metal magnesium container 15, harmful substance removal equipment 37, a metal magnesium hydride container 26, a raw material preheater 34 and a carbon dioxide finished product tank 49. The rotary kiln is provided with a kiln body, a raw material inlet, a calcium carbide liquid outlet and a flue gas outlet, a sealing box 48 is arranged outside the kiln body, and the functional gasification furnace is provided with a burner 46, a flue gas outlet and an ash residue outlet. The burner fuel inlet of the functional gasification furnace 35 is connected with a fuel pipeline, the combustion-supporting gas inlet is connected with a combustion-supporting gas pipeline, the flue gas outlet is connected with the kiln chamber inlet of the rotary kiln, and the ash residue outlet is connected to an ash residue bin through an ash residue cooler. The raw material storehouse of carbide is connected to the raw materials entry through raw materials preheater, and the exhanst gas outlet of rotary kiln passes through raw materials preheater, waste heat power generation equipment, harmful substance desorption equipment and kolepu unit and is connected to the transform splitter, and kolepu unit and waste heat power generation equipment power output cable are connected with the outside power transmission equipment of system. The outlet of the conversion separation equipment 4 is divided into three paths, one path is connected to the hydrogen production unit, the other path is connected to the carbon dioxide purification equipment, the other path is connected to the combustion-supporting gas pipeline and the fuel pipeline of the burner, and the conversion separation equipment 4 is provided with a water filling port 14. The Kohlepu unit is respectively connected with the hydrogen production unit 6, the conversion separation equipment 4, the ash cooler 47, the crystallization pipe 54 in the crystallization chamber 8 and the reaction product heat exchanger 51 through a circulating heat exchange medium pipeline 25 to form a circulating loop, and the waste heat of the equipment is recovered: the magnesium metal in the hydrogen production unit 6 absorbs the heat released by hydrogen, the carbon monoxide in the conversion separation equipment 4 reacts with the water vapor to generate the chemical reaction heat released by carbon dioxide and hydrogen, the ash cooler 47 cools the condensation heat, the crystallization pipe 54 in the crystallization chamber 8 condenses the heat released by magnesium and the cooling heat of the residual calcium carbide and calcium oxide in the reaction product heat exchanger 51. The circulating heat exchange medium of the circulating heat exchange medium pipeline 25 connected with the Kohlepu unit adopts carbon dioxide. The low-temperature circulating heat exchange medium comes out from the Kohlegmap unit, passes through the hydrogen production unit 6, the conversion separation equipment 4, the ash cooler 47, the crystallization pipe 54 in the crystallization chamber 8 and the reaction product heat exchanger 51, recovers the waste heat of the equipment, and returns to the Kohlegmap unit after heat exchange and temperature rise.
The circulating feed back of the rotary kiln 1 enters the raw material preheater 34 through the circulating feed inlet 12 to exchange heat with carbon monoxide tail gas generated in calcium carbide production and then is connected to the feed inlet, and the discharge outlet is connected to the reaction pot 10. And a carbon dioxide gas seal box 48 is arranged outside the fish scale of the dynamic and static sealing element connected with the kiln head cover and the kiln tail cover, and the pressure of the seal box is higher than the kiln internal pressure of the rotary kiln, so that the gas in the rotary kiln is effectively isolated from the outside air. The conversion and separation equipment is provided with a hydrogen outlet and a carbon dioxide outlet, the hydrogen outlet is connected to the hydrogen production unit 6, and the carbon dioxide outlet is connected to the carbon dioxide purification equipment 5, a fuel conveying gas inlet of the burner and a combustion-supporting gas pipeline. The coke breeze line is connected to the fuel feed gas inlet of the combustion plant and the carbon dioxide purification plant outlet is connected to the food grade or industrial carbon dioxide product tank 49.
As shown in fig. 3, the kohlung unit 3 includes an expander 18, a generator 19, a hydrogen heat compression device 20, and an intermediate reheater 21, the expander outlet is connected to the expander inlet through the hydrogen heat compression device, the expander is connected to the generator shaft, and the generator is connected to the external power system circuit. The hydrogen is used as a working medium, reacts with rare earth metal at low temperature and low pressure in the hydrogen thermal compression equipment 20 to generate metal hydride, the metal hydride is heated to release high-temperature and high-pressure hydrogen to push an expansion machine to do work and generate power, the hydrogen is extracted in the expansion process and enters the intermediate reheater 21 to be heated to improve the working capacity of the hydrogen, and the low-temperature and low-pressure hydrogen which is discharged from the expansion machine and does work returns to the hydrogen thermal compression equipment 20 to be absorbed again for recycling. The hydrogen thermal compression apparatus 20 has six hydrogen thermal compression reactors, each of which alternately absorbs and discharges hydrogen. In actual production, the Kohlepu unit can be converted into various forms, such as a cascade utilization form or a form of additionally arranging an organic Rankine cycle low-temperature waste heat power generation device, and waste heat sources with various temperatures can be utilized. The cascade utilization mode means that the hydrogen thermal compression device 20 is provided with 18 metal hydride reaction beds, the metal hydride reaction beds absorb low-pressure hydrogen at low temperature and discharge high-pressure hydrogen at high temperature; the 18 metal hydride reaction beds are arranged into 3 stages, each stage is provided with 6 metal hydride reaction beds, the hydrogen discharge temperature of the upper metal hydride reaction bed is higher than the hydrogen discharge temperature of the lower metal hydride reaction bed, the hydrogen absorption temperature of the upper metal hydride reaction bed is also higher than the hydrogen absorption temperature of the lower metal hydride reaction bed, and the heat released when the upper metal hydride reaction bed absorbs hydrogen is supplied to the lower metal hydride reaction bed for use, so that the gradient utilization of the heat is realized; the expander 18 is a multistage expander, each stage is provided with an extraction port and an air inlet, and the extraction port of the previous stage is connected to the air inlet of the next stage through an intermediate reheater 21. The Koehaipu unit is additionally provided with an organic Rankine cycle low-temperature waste heat power generation device, so that the efficiency is further improved.
As shown in fig. 4, the hydrogen production unit includes at least two hydrogen absorption reactors 23, a metal hydride changing device 24, a magnesium metal container 15, and a magnesium metal hydride container 26. The magnesium metal container 15 is filled with high-purity magnesium metal powder with high-purity carbon dioxide shielding gas, a magnesium metal inlet is connected with the magnesium metal container, a magnesium metal hydride container 26 is filled with magnesium metal formed after hydrogen is absorbed by the magnesium metal, and also with high-purity carbon dioxide shielding gas, and a metal hydride outlet of the hydrogen absorption reactor 23 is respectively connected with the magnesium metal container 15 and the magnesium metal hydride container 26 through a metal hydride replacing device. The metal hydride replacing device 24 completes the material transfer process of the metal magnesium hydride formed after the metal magnesium powder in the metal magnesium container enters the hydrogen absorption reactor 23 and the metal magnesium hydride in the hydrogen absorption reactor 23 absorbs hydrogen into the metal magnesium hydride container through pneumatic, hydraulic or mechanical modes.
As shown in fig. 5, the reaction pot 10 includes a pot body 33 and a pot cover 42, and the reaction pot 10 is provided with a calcium carbide liquid inlet 31, a magnesium oxide inlet 11, a magnesium vapor outlet 32, a support lug 43, a clamping member 44 and a heating electrode 45. The interior of the pot body is built with refractory bricks 38 and an insulating layer 36, and the refractory bricks are made of zirconia. The reaction vessel 10 allows the provision of a heating coil 30 and a heating electrode 45 for auxiliary heating. The reaction vessel 10 is required to be tightly sealed. The calcium carbide liquid outlet of the rotary kiln is connected to a calcium carbide liquid inlet, the magnesium hydroxide container is connected to a magnesium oxide calcining furnace, a magnesium oxide outlet of the magnesium oxide calcining furnace is connected to a magnesium oxide inlet of the reaction pot, the inert gas pipeline 16 is respectively connected to the magnesium oxide calcining furnace and the magnesium oxide inlet of the reaction pot, and a magnesium steam outlet is connected to the crystallization chamber. The solid outlet of the crystallization chamber is connected to a magnesium metal container through a magnesium refining and crushing device, and the gas outlet is connected to an inert gas pipeline through an induced draft fan 29. And after the solid discharged from the reaction pot is poured out, the solid discharged from the reaction pot is sent to a maple energy preparation unit.
The maple energy preparation unit is equipped with reaction product heat exchanger 51, rubbing crusher 17, jigging separator, carbon purification equipment 27 and pure carbon maple energy warehouse, and the reaction pot is connected with reaction product heat exchanger, rubbing crusher, jigging separator, carbon purification equipment and pure carbon maple energy warehouse in proper order. The other path of the reaction pot and the outlet at the bottom of the jigging separation device are connected to a calcium carbide raw material preheater 34 of the calcium carbide production device. The Kohlepu unit is in circulation connection with the reaction product heat exchanger via a circulating heat exchange medium line 25.
As shown in FIG. 6, the crystallization chamber 8 is provided with a magnesium vapor inlet 52 at the lower part and an inert gas outlet 53 at the upper part, and is provided with 4 crystallization tubes 54 inserted into the side walls of the crystallization chamber. The magnesium steam inlet is connected with the magnesium steam outlet 32 of the reaction kettle 10, the inert gas outlet is connected with the inert gas pipeline 16 through the induced draft fan 29, and the crystallization pipe 54 is connected with the Korla unit 3 through the circulating heat exchange medium pipeline 25.
The heat-insulating layer is made of a fire-resistant and heat-insulating double-layer material, the pot body 33 is cast by cast iron, the refractory bricks 38 are made of a high-purity zirconia material and can resist the high temperature of 2300 ℃, the bearing material of the pot cover 42 is carbon steel and is made of heat-insulating and fire-resistant materials, and the liquid heat storage material layer is 75% of ferrotungsten.
The working process of the embodiment is as follows: the poly-generation production device of metal magnesium and hydride thereof uses raw materials of oxygen, coke powder, calcium oxide and magnesium oxide to produce calcium carbide, carbon dioxide, hydrogen, metal magnesium, pure carbon, magnesium hydride and electric power output, the coke powder and the pure oxygen are sent into a functional gasification furnace to be gasified to generate a mixed gas mainly containing carbon monoxide, combustion-supporting gas of a burner 46 is the mixed gas, the mixing ratio of the oxygen to the carbon dioxide is 99: 1, the coke powder is conveyed to the burner by carbon dioxide wind power to be subjected to functional gasification, the functional gasification is that the raw coke powder and a gasification agent pure oxygen are incompletely combusted in the functional gasification furnace 35 to generate carbon monoxide and a small amount of other gases, and part of the carbon dioxide gas can be added as a diluent during gasification; and realizes multiple functions of temperature control and slag discharge while finishing gasification. The gasification temperature is 2200 ℃, the calcium carbide is produced by entering the rotary kiln and heating the entering circulating feed back in a counter-current manner, the circulating feed back consists of the calcium carbide, calcium oxide and 75% ferrotungsten, and coke powder is added at the same time. The temperature of the calcined kiln tail flue gas is as high as 1500 ℃, a flue gas outlet is connected with a Kohler unit 3 through a raw material preheater 34, a waste heat power generation device 2 and a harmful substance removal device 37, the flue gas outlet is connected with a conversion separation device 4 after coming out of the Kohler unit 3, carbon dioxide separated from the conversion separation device 4 is connected with a carbon dioxide purification device 5, one path of the purified carbon dioxide enters a finished product tank, the other path of the purified carbon dioxide is connected with a fuel conveying gas inlet of a burner and a combustion-supporting gas pipeline, and hydrogen separated from the conversion separation device 4 enters an safety hydrogen production unit 6. The calcium carbide is discharged and then directly enters a reaction pot 10, magnesium hydroxide recycled from magnesium hydride in a magnesium hydride container 26 after use enters a magnesium hydroxide container 41, the magnesium hydroxide enters a magnesium hydroxide calcining furnace 28 from the magnesium hydroxide container 41 to be heated and calcined to generate magnesium oxide, byproduct steam enters a transformation separation device 4 through a water filling port 14 to be used as a partial reaction raw material of the transformation separation device 4, the magnesium oxide is brought into the reaction pot 10 by circulating inert gas and is blown in from the bottom or the side or the top of the reaction pot, the magnesium oxide and the liquid calcium carbide react at about 1950 ℃ to generate metal magnesium vapor, calcium oxide and carbon, the reaction is an endothermic reaction, and heat is provided by solidification heat of the liquid calcium carbide and 75% tungsten iron which is a molten heat storage material. Magnesium metal vapor and inert gas enter the crystallization chamber 8 from the top outlet of the reaction kettle 10 under the action of normal pressure or weak vacuum 90kPa (absolute pressure), the magnesium vapor is condensed into crude magnesium ingots in the crystallization chamber, the inert gas is sucked by the induced draft fan 29 for recycling, and the induced draft fan 29 can also be replaced by a vacuum pump. The crude magnesium ingot enters a magnesium refining and crushing device 9 to produce high-purity metal magnesium powder, the high-purity metal magnesium powder is added into a metal magnesium container 15, the high-purity metal magnesium powder is used as self-use metal magnesium powder, and the self-use metal magnesium powder is added into an ampere hydrogen production unit from the metal magnesium container 15 and reacts with hydrogen to produce an ampere hydrogen product, namely magnesium hydride.
A plurality of reactors are in parallel production and are in intermittent operation, firstly liquid calcium carbide and liquid ferrotungsten are added into a reactor, a pot cover is sealed, the ferrotungsten and the calcium carbide are layered due to different specific gravities, the liquid calcium carbide floats upwards, and the liquid ferrotungsten sinks. Introducing inert gas carrying magnesium oxide from the bottom, wherein the gas has stirring and floating functions, the carried magnesium oxide is firstly heated to 2000 ℃ through a liquid tungsten iron layer, and after floating to a liquid calcium carbide layer, the preheated magnesium oxide reacts with the liquid calcium carbide to generate calcium oxide, carbon and metal magnesium vapor. Magnesium vapor is pumped out together with inert gas from a magnesium vapor outlet 32 and enters a crystallization chamber 8, the magnesium vapor is condensed and solidified to form magnesium ingots, and the inert gas is recycled. When 75% of ferrotungsten in the reaction pot 10 tends to solidify, the magnesium oxide is stopped to be added, the magnesium oxide added is completely or basically reacted, magnesium vapor generated by the magnesium oxide enters the crystallization chamber 8 to be recovered, reaction products remained in the reaction pot are condensed and shrunk, the pot cover is opened to be wholly poured out, after primary separation, 75% of ferrotungsten is recycled to the feed inlet of the rotary kiln with heat circulation. The reaction product is subjected to heat exchange through a reaction product heat exchanger 51, then enters a crusher 17 to be crushed, is added into a jigging separation device, is subjected to jigging separation through a medium, is added into carbon purification equipment 27, and is further purified to obtain pure carbon clean energy maple energy with the impurity content of less than or equal to 0.03%. And (4) jigging the residual calcium carbide, the calcium oxide generated by the reaction and a small amount of impurity mixture, and returning the mixture to the rotary kiln raw material inlet for recycling. 75% ferrotungsten of the heat storage material can be adopted or not according to the actual needs of the reaction, and the addition amount can be more or less. Heating coils or heating electrodes can be used for auxiliary heating to provide reaction heat in the magnesium smelting process, so that the added magnesium oxide can be completely reacted as much as possible. The use of calcined dolomite as blowing raw material instead of magnesia was allowed.
Example 2
Another embodiment of the invention is shown in fig. 2, and comprises a calcium carbide production device, a crystallization chamber 8, a magnesium refining and crushing device 9, a reaction pot 10, a magnesium hydroxide calcining furnace 28, a magnesium hydroxide container 41 and an inert gas pipeline 16. The calcium carbide production device comprises a calcium carbide raw material bin, a rotary kiln 1, waste heat power generation equipment 2, a Kohlepu unit 3, conversion separation equipment 4, carbon dioxide purification equipment 5, a hydrogen production unit 6, a metal magnesium container 15, harmful substance removal equipment 37, a metal magnesium hydride container 26, a raw material preheater 34 and a carbon dioxide finished product tank 49. The rotary kiln is provided with a kiln body, a raw material inlet, a calcium carbide liquid outlet, a burner and a flue gas outlet, a seal box 48 is arranged outside the kiln body, a fuel inlet of the burner is connected with a fuel pipeline, and a combustion-supporting gas inlet is connected with a combustion-supporting gas pipeline. The raw material storehouse of carbide is connected to the raw materials entry through raw materials preheater, and the exhanst gas outlet of rotary kiln passes through raw materials preheater, waste heat power generation equipment, harmful substance desorption equipment and kolepu unit and is connected to the transform splitter, and kolepu unit and waste heat power generation equipment power output cable are connected with the outside power transmission equipment of system. The outlet of the conversion separation equipment 4 is divided into three paths, one path is connected to the hydrogen production unit, the other path is connected to the carbon dioxide purification equipment, and the other path is connected to the combustion-supporting gas pipeline and the fuel pipeline of the burner. The hydrogen production unit is provided with a metal magnesium inlet and a magnesium hydride outlet, the metal magnesium inlet is connected with a metal magnesium container, and the magnesium hydride outlet is connected with the metal magnesium hydride container. The Kohler unit is connected with the shift separation device 4, the Anhydrogen production unit 6 and the crystallization pipe 54 in the crystallization chamber 8 through the circulating heat exchange medium pipeline 25 respectively. The calcium carbide liquid outlet of the rotary kiln is connected to the calcium carbide liquid inlet of the reaction pot 10, the magnesium hydroxide container is connected to the magnesium hydroxide calcining furnace, the magnesium oxide outlet of the magnesium hydroxide calcining furnace is connected to the magnesium oxide inlet of the reaction pot, the inert gas pipeline 16 is respectively connected to the magnesium oxide outlet of the magnesium hydroxide calcining furnace and the magnesium oxide inlet of the reaction pot, and the magnesium vapor outlet is connected to the crystallization chamber. The solid outlet of the crystallization chamber is connected to a magnesium metal container through a magnesium refining and crushing device, and the gas outlet is connected to an inert gas pipeline through an induced draft fan 29.
The circulating feed back of the rotary kiln 1 enters the raw material preheater 34 through the circulating feed inlet 12 to exchange heat with carbon monoxide tail gas generated in calcium carbide production and then is connected to the feed inlet, and the discharge outlet is connected to the reaction pot 10. And a carbon dioxide gas seal box 48 is arranged outside the fish scale of the dynamic and static sealing element connected with the kiln head cover and the kiln tail cover, and the pressure of the seal box is higher than the kiln internal pressure of the rotary kiln, so that the gas in the rotary kiln is effectively isolated from the outside air. The conversion separation equipment is provided with a hydrogen outlet and a carbon dioxide outlet, the hydrogen outlet is connected to the hydrogen production unit 6, and the carbon dioxide outlet is connected to the carbon dioxide purification equipment 5 and a fuel pipeline and a combustion-supporting gas pipeline of the burner. The coke powder line is connected to the fuel line inlet of the combustion device and the carbon dioxide purification device outlet is connected to the food grade or industrial grade carbon dioxide product tank 49. The Kohlepu unit is circularly connected with the transformation separation equipment 4, the Anhydrogen production unit 6 and the crystallization pipe 54 in the crystallization chamber 8 through a circulating heat exchange medium pipeline 25, and is respectively connected to form a circulation loop and recover the waste heat of the equipment: the carbon monoxide in the shift separation device 4 reacts with the water vapor to generate the chemical reaction heat released by the carbon dioxide and the hydrogen, the heat released by the magnesium series metal absorbing the hydrogen in the hydrogen production unit 6 and the heat released by the magnesium condensation in the crystallization pipe 54 in the crystallization chamber 8. The circulating heat exchange medium of the circulating heat exchange medium pipeline 25 connected with the Kohlepu unit adopts carbon dioxide. The low-temperature circulating heat exchange medium comes out of the Koehaipu unit, passes through the transformation separation equipment 4, the hydrogen production unit 6 and the crystallization pipe 54 in the crystallization chamber 8, recovers the waste heat of the equipment, and returns to the Koehaipu unit after heat exchange and temperature rise. The other procedures were the same as in example 1.
The working process of the embodiment is as follows: a magnesium hydride regeneration device uses oxygen, calcium oxide, pure carbon (maple energy) and magnesium hydroxide, and the final product is magnesium hydride, carbon dioxide and electric power output, the pure maple energy and the pure oxygen produced in the embodiment 1 are fed into a burner 46 to be gasified to generate a mixed gas mainly containing carbon monoxide, the combustion-supporting gas of the burner 46 is the mixed gas, the mixing ratio of oxygen to carbon dioxide is 98: 2, the pure maple energy is conveyed to the burner by carbon dioxide wind power to be subjected to functional gasification, the functional gasification is that the raw pure maple energy and a gasifying agent pure oxygen are incompletely combusted in the burner 46 to generate carbon monoxide and a small amount of other gases, part of carbon dioxide gas can be added as a diluent during gasification, and multiple functions such as temperature control and the like are realized while the gasification is completed. The gasification temperature is 2300 ℃, the mixture enters a rotary kiln to perform counter-current heating and circulating feed back to produce the calcium carbide, the circulating feed back consists of the calcium carbide, calcium oxide, pure carbon and 75 percent ferrotungsten, and the maple energy is supplemented at the same time. The temperature of the calcined kiln tail flue gas is as high as 1500 ℃, a flue gas outlet is connected with a Kohleura unit 3 through a raw material preheater 34, a waste heat power generation device 2 and a harmful substance removal device 37, the flue gas is connected to a conversion separation device 4 after coming out of the Kohleura unit 3, carbon dioxide separated from the conversion separation device 4 is connected to a carbon dioxide purification device 5, one path of the purified carbon dioxide enters a finished product tank, the other path of the purified carbon dioxide is connected to a fuel pipeline inlet and a combustion-supporting gas pipeline of a burner, and hydrogen separated from the conversion separation device 4 enters an safety hydrogen production unit 6. The calcium carbide is discharged and then directly enters a reaction pot 10, magnesium hydroxide recycled from magnesium hydride in a magnesium hydride container 26 after use enters a magnesium hydroxide container 41, the magnesium hydroxide enters a magnesium hydroxide calcining furnace 28 from the magnesium hydroxide container 41 to be heated and calcined to generate magnesium oxide, byproduct steam enters a transformation separation device 4 through a water filling port 14 to be used as a partial reaction raw material of the transformation separation device 4, the magnesium oxide is brought into the reaction pot 10 by circulating inert gas and is blown in from the bottom or the side or the top of the reaction pot, the magnesium oxide and the liquid calcium carbide react at about 1950 ℃ to generate metal magnesium vapor, calcium oxide and carbon, the reaction is an endothermic reaction, and heat is provided by solidification heat of the liquid calcium carbide and 75% tungsten iron which is a molten heat storage material. Under the action of normal pressure or weak vacuum 95kPa, metal magnesium vapor and inert gas enter a crystallization chamber 8 from a top outlet of a reaction pot 10, the magnesium vapor is condensed into a crude magnesium ingot in the crystallization chamber, and the inert gas is pumped by a draught fan for recycling. The crude magnesium ingot enters a magnesium refining and crushing device 9 to produce high-purity metal magnesium powder, the high-purity metal magnesium powder is added into a metal magnesium container 15, the high-purity metal magnesium powder is used as self-use metal magnesium powder, and the self-use metal magnesium powder is added into an ampere hydrogen production unit from the metal magnesium container 15 and reacts with hydrogen to produce an ampere hydrogen product, namely magnesium hydride. The crude magnesium ingot may be simply crushed without refining and then added to the magnesium metal container 15.
A plurality of reaction pots are arranged in parallel, the production is intermittent operation, firstly, liquid calcium carbide and liquid ferrotungsten are added into the reaction pots, pot covers are sealed, the ferrotungsten and the calcium carbide are layered due to different specific gravities, the liquid calcium carbide floats upwards, and the liquid ferrotungsten sinks. Introducing inert gas carrying magnesium oxide from the bottom, wherein the gas has stirring and floating functions, the carried magnesium oxide is firstly heated to 2000 ℃ through a liquid tungsten iron layer, and after floating to a liquid calcium carbide layer, the preheated magnesium oxide reacts with the liquid calcium carbide to generate calcium oxide, carbon and metal magnesium vapor. Magnesium vapor is pumped out together with inert gas from a magnesium vapor outlet 32 and enters the crystallization chamber 8, the magnesium vapor is condensed and solidified to form magnesium ingots, and the inert gas is recycled. When 75% of ferrotungsten in the reaction kettle 10 tends to solidify, the magnesium oxide is stopped to be added, the magnesium oxide added is completely or basically reacted, magnesium vapor generated by the magnesium oxide enters the crystallization chamber 8 to be recovered, reaction products remained in the reaction kettle are condensed and shrunk, the kettle cover is opened to be poured out integrally, and the reaction products are recovered to the feed inlet of the rotary kiln with thermal cycle. 75% ferrotungsten of the heat storage material can be adopted or not according to the actual needs of the reaction, and the addition amount can be more or less. Heating coils or heating electrodes can be used for auxiliary heating to provide reaction heat in the magnesium smelting process, so that the added magnesium oxide can be completely reacted as much as possible. The use of calcined dolomite as blowing raw material instead of magnesia was allowed.
The present embodiment is different from embodiment 1 in that: the carbon-containing raw material used by the burner is pure carbon (maple energy), the whole production device has no pollutant emission, the whole device can be installed in a city or a sub-station of a hydrogen hydrogenation station and used as a regeneration device of magnesium hydride, and the discharge product of the reaction pot is not required to be subjected to jigging and recycled. The rest is the same as in example 1. The sub-station of the hydrogen adding station provides a magnesium hydride container added with carbon dioxide protective gas for each hydrogen adding station base station and recovers the magnesium hydroxide container. The heat of the whole device is fully recycled, the energy transportation cost is low, pure oxygen and maple energy are only needed to be transported, carbon dioxide is transported away, the production cost is reduced, and the device is environment-friendly.

Claims (7)

1. The utility model provides a many coproduction production system of metal magnesium and hydride thereof, includes carbide apparatus for producing, carbide apparatus for producing is equipped with rotary kiln (1) and metal magnesium container (15), characterized by: the system is provided with a crystallization chamber (8), a magnesium refining and crushing device (9), a reaction pot (10), a magnesium hydroxide calcining furnace (28), a magnesium hydroxide container (41) and an inert gas pipeline (16), wherein the reaction pot (10) comprises a pot body (33) and a pot cover (42), the pot body is provided with a calcium carbide liquid inlet (31), a magnesium oxide inlet (11), a magnesium steam outlet (32), a support lug (43), a clamping piece (44), a heating electrode (45) and a heating coil (30), and the magnesium oxide inlet (11) on the pot body is arranged at the bottom or the side or the top of the reaction pot; the calcium carbide liquid outlet of the rotary kiln is connected to a calcium carbide liquid inlet of the reaction pot, the magnesium hydroxide container is connected to the magnesium hydroxide calcining furnace, a magnesium oxide outlet of the magnesium hydroxide calcining furnace is connected to a magnesium oxide inlet of the reaction pot, the inert gas pipeline is respectively connected to the magnesium oxide outlet of the magnesium hydroxide calcining furnace and the magnesium oxide inlet of the reaction pot, and the magnesium vapor outlet is connected to the crystallization chamber; a solid outlet of the crystallization chamber is connected to a magnesium metal container through a magnesium refining and crushing device, and a gas outlet is connected to an inert gas pipeline through an induced draft fan (29); the reaction pot is connected to a calcium carbide raw material preheater (34) of the calcium carbide production device.
2. The poly-generation production system of metallic magnesium and its hydride as set forth in claim 1, wherein: the calcium carbide production device comprises a calcium carbide raw material bin, a rotary kiln (1), waste heat power generation equipment (2), a Kohlepu unit (3), conversion separation equipment (4), carbon dioxide purification equipment (5), a hydrogen adding production unit (6), a metal magnesium container (15), harmful substance removal equipment (37), a metal magnesium hydride container (26), a raw material preheater (34) and a carbon dioxide finished product tank (49); the rotary kiln is provided with a kiln body, a raw material inlet, a calcium carbide liquid outlet, a burner (46) and a flue gas outlet, a seal box (48) is arranged outside the kiln body, the burner (46) is connected with a combustion-supporting gas pipeline and a fuel pipeline, the combustion-supporting gas of the burner (46) is mixed gas, and the mixing ratio of oxygen to carbon dioxide is 0: 100-; the calcium carbide raw material bin is connected to a raw material inlet through a raw material preheater, the flue gas outlet is connected to a conversion separation device through the raw material preheater, waste heat power generation equipment, harmful substance removal equipment and a Kohlepu unit, and the Kohlepu unit and the waste heat power generation equipment are respectively connected to power transmission equipment through circuits; the outlet of the conversion separation equipment is divided into three paths, one path is connected to the hydrogen production unit, the other path is connected to the carbon dioxide purification equipment, and the other path is connected to a combustion-supporting gas pipeline and a fuel pipeline of the burner; the hydrogen production unit is provided with a metal magnesium inlet and a magnesium hydride outlet, the metal magnesium inlet is connected with a metal magnesium container, and the magnesium hydride outlet is connected with a metal magnesium hydride container; the carbon dioxide purification equipment is respectively connected to a carbon dioxide finished product tank (49) and a combustion-supporting gas pipeline and a fuel pipeline of the burner; the shift separation equipment is provided with a water filling port (14), and the magnesium hydroxide calcining furnace (28) is connected to the shift separation equipment through the water filling port and is used as part of reaction raw materials of the shift separation equipment;
the Kohler unit (3) comprises an expander (18), a generator (19), a hydrogen heat compression device (20) and an intermediate reheater (21); the expander outlet is connected to the expander inlet through a hydrogen thermal compression device, the expander is connected with a generator shaft, and the generator is connected with an external power system circuit; the hydrogen thermal compression device (20) adopts a multi-stage cascade utilization mode, and each cascade consists of one or more reaction beds; the operation mode of each reaction bed adopts an internal metal hydride direct extraction and replacement mode, or an indirect heat exchange mode, or a heat carrier heating mode or an electric heating mode, so that hydrogen in the Kohlehem pump unit enters an expansion machine (18) for acting after being heated and boosted by heat brought by a circulating heat exchange medium pipeline (25) to drive a generator (19) to generate electricity in the Kohlehem pump unit (3).
3. The poly-generation production system of metallic magnesium and its hydride as claimed in claim 2, wherein: the system is provided with a maple energy preparation unit, the maple energy preparation unit is provided with a reaction product heat exchanger (51), a pulverizer (17), a separation device (7), carbon purification equipment (27) and a pure carbon energy storage bin, and one path of the reaction pot is sequentially connected with the reaction product heat exchanger, the pulverizer, the separation device, the carbon purification equipment and the pure carbon energy storage bin; and the other path of the reaction pot and the outlet at the bottom of the separation device are connected to a calcium carbide raw material preheater (34) of the calcium carbide production device.
4. The poly-generation production system of metallic magnesium and its hydride as claimed in claim 3, wherein: the calcium carbide production device is provided with a functional gasification furnace (35) and an ash cooler (47), wherein the functional gasification furnace is provided with a burner (46), a flue gas outlet and an ash outlet; the burner is connected with a combustion-supporting gas pipeline and a fuel pipeline, combustion-supporting gas of the burner (46) is mixed gas, the flue gas outlet is connected with a kiln chamber inlet of the rotary kiln, and the ash residue outlet is connected to an ash residue bin through an ash residue cooler (47); the Kohlemp unit is respectively connected with the hydrogen production unit (6), the transformation separation equipment (4), the ash cooler (47), the crystallization pipe (54) in the crystallization chamber (8) and the reaction product heat exchanger (51) in a circulating way through a circulating heat exchange medium pipeline (25).
5. The poly-generation production system of metallic magnesium and its hydride as claimed in claim 2, wherein: the hydrogen production unit (6) comprises at least two hydrogen absorption reactors (23), a metal hydride replacing device (24), a metal magnesium container (15) and a metal magnesium hydride container (26); a metal hydride outlet of the hydrogen absorption reactor is respectively connected with a metal magnesium container and a metal magnesium hydride container through a metal hydride replacing device, and the hydrogen absorption reactor is circularly connected with the Korla unit (3) through a circulating heat exchange medium pipeline (25) to form a circulating loop; the metal hydride replacing device (24) adopts gravity conveying, mechanical conveying, pneumatic conveying, vacuum conveying, hydraulic conveying or electromagnetic conveying or the combination of the gravity conveying, the mechanical conveying, the pneumatic conveying, the vacuum conveying, the hydraulic conveying or the electromagnetic conveying, thereby achieving the purpose of replacing corresponding materials and reliably realizing any method for replacing materials of magnesium hydride and magnesium metal between the hydrogen absorption reactor (23) and the magnesium metal container (15) and between the magnesium metal hydride container (26); the metal hydride replacing device (24) is used for replacing magnesium hydride and magnesium metal, or replacing magnesium hydride and magnesium hydroxide, or replacing magnesium hydride and magnesium oxide, or replacing a mixture of magnesium hydride and magnesium hydroxide-magnesium oxide, or replacing magnesium metal and magnesium hydroxide, or replacing magnesium metal and magnesium oxide, or replacing a mixture of magnesium metal and magnesium hydroxide-magnesium oxide, or replacing hydroxides or/and oxides of metal which is combined with hydrogen to form metal hydride or/and can react with water to release hydrogen or mixture of the metal and other substances and the metal and other substances; it is permissible to use a magnesium-containing substance including calcined dolomite as a blowing-in magnesium-containing raw material in place of the magnesium oxide.
6. The poly-generation production system of metallic magnesium and its hydride as set forth in claim 1, wherein: the lower part of the crystallization chamber (8) is provided with a magnesium vapor inlet (52), the upper part of the crystallization chamber is provided with an inert gas outlet (53), the crystallization chamber is provided with at least one crystallization pipe (54), and the crystallization pipe is inserted into the side wall of the crystallization chamber; the magnesium vapor inlet (52) is connected with a magnesium vapor outlet (32) of the reaction kettle (10), and the inert gas outlet is connected to the inert gas pipeline (16) through an induced draft fan.
7. The poly-generation production system of metallic magnesium and its hydride as set forth in claim 1, wherein: the system also comprises a magnesium hydride regeneration device, wherein the magnesium hydride regeneration device comprises a calcium carbide production device, a crystallization chamber (8), a magnesium refining and crushing device (9), a reaction pot (10), a magnesium hydroxide calcining furnace (28), a magnesium hydroxide container (41) and an inert gas pipeline (16); the calcium carbide production device comprises a calcium carbide raw material bin, a rotary kiln (1), waste heat power generation equipment (2), a Kohlepu unit (3), conversion separation equipment (4), carbon dioxide purification equipment (5), a hydrogen production unit (6), a metal magnesium container (15), harmful substance removal equipment (37), a metal magnesium hydride container (26), a raw material preheater (34) and a carbon dioxide finished product tank (49); the rotary kiln is provided with a kiln body, a raw material inlet, a calcium carbide liquid outlet, a burner and a flue gas outlet, a seal box (48) is arranged outside the kiln body, a fuel inlet of the burner is connected with a fuel pipeline, and a combustion-supporting gas inlet is connected with a combustion-supporting gas pipeline; the calcium carbide raw material bin is connected to a raw material inlet through a raw material preheater, a flue gas outlet of the rotary kiln is connected to a conversion separation device through the raw material preheater, waste heat power generation equipment, harmful substance removal equipment and a Kohlepu unit, and the Kohlepu unit and a power output cable of the waste heat power generation equipment are connected with power transmission equipment outside the system; the outlet of the conversion separation equipment (4) is divided into three paths, one path is connected to the hydrogen production unit, the other path is connected to the carbon dioxide purification equipment, and the other path is connected to a combustion-supporting gas pipeline and a fuel pipeline of the burner; the hydrogen production unit is provided with a metal magnesium inlet and a magnesium hydride outlet, the metal magnesium inlet is connected with a metal magnesium container, and the magnesium hydride outlet is connected with the metal magnesium hydride container; the Kohleniu unit is respectively connected with the conversion separation equipment (4), the hydrogen production unit (6) and a crystallization pipe (54) in the crystallization chamber (8) through a circulating heat exchange medium pipeline (25); a calcium carbide liquid outlet of the rotary kiln is connected to a calcium carbide liquid inlet of the reaction pot (10), a magnesium hydroxide container is connected to the magnesium hydroxide calcining furnace, a magnesium oxide outlet of the magnesium hydroxide calcining furnace is connected to a magnesium oxide inlet of the reaction pot, an inert gas pipeline (16) is respectively connected to the magnesium oxide outlet of the magnesium hydroxide calcining furnace and the magnesium oxide inlet of the reaction pot, and a magnesium steam outlet is connected to the crystallization chamber;
a solid outlet of the crystallization chamber is connected to a magnesium metal container through a magnesium refining and crushing device, and a gas outlet is connected to an inert gas pipeline through an induced draft fan (29); circulating feed back of the rotary kiln (1) enters a raw material preheater (34) through a circulating material inlet (12) to exchange heat with carbon monoxide tail gas generated in calcium carbide production and then is connected to a feed inlet, and a discharge outlet is connected to a reaction pot (10); a carbon dioxide gas seal box (48) is arranged outside the fish scale of the dynamic and static sealing element connected with the kiln head cover and the kiln tail cover, and the pressure of the seal box is higher than the kiln internal pressure of the rotary kiln, so that the gas in the rotary kiln is effectively isolated from the outside air; the conversion separation equipment is provided with a hydrogen outlet and a carbon dioxide outlet, the hydrogen outlet is connected to the hydrogen production unit (6), and the carbon dioxide outlet is connected to the carbon dioxide purification equipment (5), a fuel pipeline inlet of the burner and a combustion-supporting gas pipeline; the outlet of the carbon dioxide purification equipment is connected to a carbon dioxide finished product tank (49); the Kohlepu unit is circularly connected with a conversion separation device (4), a hydrogen production unit (6) and a crystallization pipe (54) in a crystallization chamber (8) through a circulating heat exchange medium pipeline (25), and is respectively connected to form a circulation loop and recover the waste heat of the devices: the carbon monoxide in the conversion separation equipment (4) reacts with the steam to generate the chemical reaction heat released by the carbon dioxide and the hydrogen, the heat released by the magnesium metal absorbing the hydrogen in the hydrogen production unit (6) and the heat released by the magnesium condensation in the crystallization pipe (54) in the crystallization chamber (8); the circulating heat exchange medium of the circulating heat exchange medium pipeline (25) connected with the Kohleniu pump unit is stable gas, liquid, solid medium or the mixture of the gas, the liquid and the solid medium; the circulating heat exchange medium of the circulating heat exchange medium pipeline (25) is discharged from the Kohlepu unit, passes through the conversion separation equipment (4), the hydrogen production unit (6) and the crystallization pipe (54) in the crystallization chamber (8), recovers the waste heat of the equipment, and returns to the Kohlepu unit after heat exchange and temperature rise; the magnesium hydride regeneration device uses oxygen, calcium-containing raw materials, pure carbon and magnesium hydroxide, the final products are magnesium hydride, carbon dioxide and electric power output, pure carbon energy and pure oxygen are sent into a burner (46) to be gasified to generate mixed gas mainly containing carbon monoxide, combustion-supporting gas of the burner (46) is the mixed gas, the mixing ratio of oxygen to carbon dioxide is 0: 100-; the gasification temperature is 1000-; the temperature of the calcined kiln tail flue gas is up to 500-; the calcium carbide is discharged and then directly enters a reaction pot (10), magnesium hydroxide recycled after magnesium hydride in a metal magnesium hydride container (26) is used enters a magnesium hydroxide container (41), magnesium oxide is generated by heating and calcining the magnesium hydroxide in a magnesium hydroxide calcining furnace (28) from the magnesium hydroxide container (41), byproduct steam enters a conversion separation device (4) through a water filling port (14) and is used as a part of reaction raw materials of the conversion separation device (4), the magnesium oxide is brought into the reaction pot (10) by circulating inert gas and is blown in from the bottom or the side or the top of the reaction pot, the magnesium oxide and the liquid calcium carbide react at 2500 ℃ to generate metal magnesium vapor, calcium-containing raw materials and carbon, the reaction is an endothermic reaction, and heat is provided by solidification heat of the liquid calcium carbide and the molten heat storage materials; under the action of normal pressure or vacuum 0.01-100kPa, metal magnesium vapor and inert gas enter a crystallization chamber (8) from a top outlet of a reaction pot (10), the magnesium vapor is condensed into a crude magnesium ingot in the crystallization chamber, and the inert gas is sucked by a draught fan for recycling; the crude magnesium ingot enters a magnesium refining and crushing device (9) to produce high-purity metal magnesium powder, the high-purity metal magnesium powder is added into a metal magnesium container (15), the high-purity metal magnesium powder is used as self-use metal magnesium powder and is added into an ampere hydrogen production unit from the metal magnesium container (15), and the high-purity metal magnesium powder reacts with hydrogen to produce an ampere hydrogen product, namely magnesium hydride; after the crude magnesium ingot is refined or only crushed and not refined, the crude magnesium ingot is added into a magnesium metal container (15); the method comprises the following steps of (1) enabling a plurality of reaction pots to be arranged in parallel, wherein the production is intermittent operation, firstly adding liquid calcium carbide and a heat storage material into the reaction pots, sealing pot covers, layering the heat storage material and the calcium carbide due to different specific gravities, enabling the liquid calcium carbide to float upwards, and enabling the heat storage material to sink; introducing inert gas carrying magnesium oxide from the bottom, wherein the gas has stirring and floating functions, the carried magnesium oxide is firstly heated to 1000-2500 ℃ through a heat storage material layer, and after floating to a liquid calcium carbide layer, the preheated magnesium oxide reacts with the liquid calcium carbide to generate calcium-containing raw materials, carbon and metal magnesium vapor; magnesium vapor is pumped out together with inert gas from a magnesium vapor outlet (32) and enters a crystallization chamber (8), the magnesium vapor is condensed and solidified to form magnesium ingots, and the inert gas is recycled; when the heat storage material in the reaction pot (10) tends to be solidified, stopping adding magnesium oxide, completing the whole or basic reaction of the added magnesium oxide, recovering magnesium oxide generated metal magnesium vapor in the crystallization chamber (8), condensing and shrinking reaction products remained in the reaction pot, opening the pot cover to pour out the whole body, and recovering the heat circulation to the feed inlet of the rotary kiln; adopting or not adopting heat storage materials according to the actual needs of the reaction; the calcined dolomite is allowed to replace the magnesia and is used as a blowing raw material; the carbon-containing raw material used by the burner is pure carbon, the whole production device has no pollutant emission, the whole device is arranged in a city or a sub-station provided with a hydrogen hydrogenation station and is used as a regeneration device of magnesium hydride, and the discharged material product of the reaction pot is not required to be separated and recycled; the sub-station of the hydrogen adding station provides a metal magnesium hydride container with protective gas for each hydrogen adding station base station and recovers the magnesium hydroxide container filled with magnesium hydroxide; the heat of the whole device is fully recycled, the energy transportation cost is low, pure oxygen and pure carbon energy are only needed to be transported, carbon dioxide is transported away, the production cost is reduced, and the environment-friendly effect is achieved.
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