CN117645422A - Cement production process based on zero outsourcing fossil energy and zero carbon emission of existing cement production line - Google Patents

Cement production process based on zero outsourcing fossil energy and zero carbon emission of existing cement production line Download PDF

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Publication number
CN117645422A
CN117645422A CN202311345856.8A CN202311345856A CN117645422A CN 117645422 A CN117645422 A CN 117645422A CN 202311345856 A CN202311345856 A CN 202311345856A CN 117645422 A CN117645422 A CN 117645422A
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cement production
enters
zero
gas
outsourcing
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赵琳
韩辉
彭学平
高伟强
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Tianjin Cement Industry Design and Research Institute Co Ltd
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Tianjin Cement Industry Design and Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/434—Preheating with addition of fuel, e.g. calcining
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02—Selection of the hardening environment
    • C04B40/0231—Carbon dioxide hardening
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting
    • C04B7/4407—Treatment or selection of the fuel therefor, e.g. use of hazardous waste as secondary fuel ; Use of particular energy sources, e.g. waste hot gases from other processes
    • C04B7/4438—Treatment or selection of the fuel therefor, e.g. use of hazardous waste as secondary fuel ; Use of particular energy sources, e.g. waste hot gases from other processes the fuel being introduced directly into the rotary kiln
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/48—Clinker treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
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Abstract

The invention relates to a cement production process with zero outsourcing fossil energy and zero carbon emission based on the existing cement production line, which is realized by equipment comprising a preheater system, a decomposing furnace, a rotary kiln, a separating module, a flow control module, heat exchange equipment, an electric/photocatalytic water splitting hydrogen production device, a catalytic conversion module, an ammonia catalytic decomposing device, a heater and a carbonization device; the cement production process of the invention fully utilizes the gas and heat generated in each step through the series of equipment, saves energy to the greatest extent, has almost no gas emission, and does not discharge CO in the whole process of cement production 2 Circulation or zero carbon emission is realized; all heat consumption in the cement production process comes from methane and liquid fuel generated by catalytic conversion, and part of carbon can realize internal circulation; because the pre-decomposition process is carried out by adopting oxy-fuel combustion in the first preheater system and N is adopted in the second preheater system 2 The heating performs a pre-decomposition process, so that almost no nitrogen oxides are generated.

Description

Cement production process based on zero outsourcing fossil energy and zero carbon emission of existing cement production line
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a cement production process with zero outsourcing fossil energy and zero carbon emission based on the existing cement production line.
Background
2, because the cement industry adopts calcium carbonate as a raw material, the discharged carbon source is from fuel combustion and limestone decomposition, and more carbon dioxide can be discharged than the steel industry and the thermal power industry; meanwhile, the smoke volume and CO in the cement industry are large 2 The low concentration presents greater difficulty for carbon capture.
For CO 2 The Chinese patent publication No. CN114739163A discloses a carbon dioxide enrichment system for cement industry and a process principle thereof, which not only realize enrichment of part of kiln tail flue gas carbon dioxide to greatly reduce the trapping and utilization cost of carbon dioxide, but also effectively reduce the negative influence on kiln systems, but also do not solve the problem of CO 2 Is a problem of purification and utilization; chinese patent publication No. CN114290504A discloses a process and a device for mineralizing and strengthening construction waste and mineralizing and curing concrete products by utilizing tail gas of a cement kiln, which are used for carrying out pressure swing adsorption on the tail gas of the cement kiln to improve CO 2 After concentration, the mixture is used for building rubbish reinforcement or concrete mineralization maintenance, but due to CO 2 The concentration is low, and the pressure swing adsorption purification cost is relatively high.
In summary, the existing cement industry is in CO 2 Emission reductionThere are also the following problems:
(1) CO in cement industry 2 The discharge amount is large, and the concentration is high;
(2)CO 2 the trapping and utilizing cost is high;
(3) The full-oxygen combustion adopts the air separation oxygen production technology, and a large amount of N is wasted in the discharge 2 ；
Thus, a CO suitable for the cement industry is sought 2 The technical route of emission reduction is urgent.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a cement production process based on zero outsourcing fossil energy and zero carbon emission of the existing cement production line, cement production can be carried out by adopting the process, the existing cement production equipment can be utilized for transformation, the outsourcing fossil energy is not needed in the production process, and CO is not generated 2 And the emission is realized, and the recycling of the system gas and heat is realized to the greatest extent.
The invention is realized in such a way that the cement production process based on zero outsourcing fossil energy and zero carbon emission of the existing cement production line is realized by the following equipment, wherein the process comprises a preheater system, a decomposing furnace, a rotary kiln, a separating module, a flow control module, heat exchange equipment, an electric/photolytic hydrogen production device, a catalytic conversion module, an ammonia catalytic decomposition device, a heater and a carbonization device;
the method comprises the following specific steps:
the main fuel of the decomposing furnace and the kiln head burner of the rotary kiln adopts CO 2 Hydrogenation synthesized CH 4 A gas; CH (CH) 4 And O generated by electrolysis/photolysis of water 2 After burning at the kiln head burner, the generated CO 2 And H 2 O enters a decomposing furnace after passing through a kiln tail smoke chamber; CH in decomposing furnace 4 And O 2 The combustion provides heat and generates CO at the same time 2 And H 2 O, a preheater system and a decomposing furnace for decomposing raw materials to generate CO 2 The burnt gas at the kiln head burner, the burnt gas in the decomposing furnace and the decomposed gas of the raw meal in the preheater system I are mixed and then enter the separating module I;
after passing through the first separation module, CO is added 2 And H 2 O separation; the vapor enters a first heat exchange device, is condensed into liquid water and then enters an electrolysis/photolysis water hydrogen production device; CO 2 The gas is divided into two paths by a second flow control module and enters a first catalytic conversion module and a second catalytic conversion module respectively;
liquid water is electrolyzed/electrolyzed to produce H by a hydrogen production device 2 And O 2 ；H 2 Entering a first catalytic conversion module; o (O) 2 As combustion-supporting gas, the combustion-supporting gas is divided into three paths by a first flow control module and respectively enters a kiln head burner, a decomposing furnace and an ammonia catalytic decomposing device;
CO entering catalytic conversion module one 2 And H 2 Generating H by reaction 2 O and CH 4 Then enters a second separation module to separate the water vapor and CH 4 Separating; the water vapor enters a second heat exchange device, is condensed into liquid water and then enters an electrolysis/photolysis water hydrogen production device; CH (CH) 4 The gas is divided into two paths by a flow control module III and respectively enters a kiln head burner and a decomposing furnace;
NH 3 enters a first heat exchange device, is preheated by the first heat exchange device, enters a second heat exchange device for preheating, enters an ammonia catalytic decomposition device with a catalytic reaction bed layer heated to a fixed temperature, and is decomposed to generate N 2 And H 2 Then enter a separation module III to make N 2 And H 2 Separating; h 2 Enters a second catalytic conversion module and is connected with CO 2 Generating liquid fuel through catalytic reaction; n (N) 2 Entering a heater;
the liquid fuel is divided into two paths, one path enters an ammonia catalytic decomposition device and O 2 The combustion reaction is used for heating a catalytic reaction bed layer in the ammonia catalytic decomposition device, and the gas CO after combustion 2 +H 2 O and NH 3 No contact is made in the catalytic reaction bed layer, and independent pipeline is used for heating, CO 2 +H 2 O enters a heater; the other path enters a kiln head burner and is used as CH 4 Supplementing fuel;
n in heater 2 +CO 2 +H 2 O enters a second preheater system for decomposing raw meal; raw material in the second preheater system is decomposed to produce CO 2 And after being mixed with the gas entering the second preheater system, the mixture enters a carbonization device for utilization.
Preferably, the catalyst filled in the catalytic conversion module I is a Ni-based or Ru-based catalyst, and the reaction temperature is 280-350 ℃; the catalyst filled in the second catalytic conversion module is a double-function catalyst, the double functions are a hydrogenation function and a carbon chain growth function, and the reaction temperature is 200-450 ℃.
Preferably, the catalyst filled in the ammonia catalytic decomposition device is a Ni-based or Co-based catalyst, and the reaction temperature is 600-850 ℃.
Preferably, the first separation module and the second separation module adopt ceramic membrane separation assemblies, and the third separation module adopts Pd separation membranes.
Preferably, the ammonia gas is subjected to heat exchange to 150-200 ℃ after passing through the first heat exchange device, is subjected to heat exchange to 250-300 ℃ after passing through the second heat exchange device, and then enters the ammonia catalytic decomposition device.
Preferably, the raw materials in the second preheater system are preheated and decomposed and then directly enter the rotary kiln, the raw materials in the first preheater system are preheated and then enter the decomposing furnace and then enter the rotary kiln, and a gas valve is arranged between the first preheater system and the second preheater system, so that gas between the first preheater system and the second preheater system does not circulate.
Preferably, N after passing through the third separation module 2 After passing through the heater, the temperature is heated to 850-900 ℃.
Preferably, the liquid fuel is an alkane, alkene, or alcohol compound.
Preferably, the carbonization device can be filled with low-calcium clinker autonomously produced by a cement plant, so that the high-performance auxiliary cementing material can be prepared after carbonization.
Preferably, the carbonization device can be filled with a concrete block precursor prepared from construction waste micropowder and other additives, so that the concrete block precursor can be carbonized and maintained to prepare the carbonized block.
The invention has the advantages and positive effects that:
(1) The whole process of the cement production process does not discharge CO 2 Realize circulation or zero carbon emission, and all heat consumption in the cement production processMethane and liquid fuel generated by self-catalytic conversion, and part of carbon can realize internal circulation;
(2) The invention fully utilizes the gas and heat generated in each step, saves energy to the greatest extent, and has almost no gas discharge;
(3) The invention adopts the total oxygen combustion to carry out the pre-decomposition process in the first preheater system and adopts N in the second preheater system to produce cement 2 The heating performs a pre-decomposition process, so that almost no nitrogen oxides are generated.
Drawings
Fig. 1 is a flow chart of a cement production process with zero outsourcing fossil energy and zero carbon emissions provided by an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "connected," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Examples
As shown in fig. 1, the invention provides a cement production process with zero outsourcing fossil energy and zero carbon emission based on the existing cement production line, which is realized by equipment comprising a preheater system, a decomposing furnace, a rotary kiln, a separating module, a flow control module, a heat exchange device, an electric/photolytic hydrogen production device, a catalytic conversion module, an ammonia catalytic decomposition device, a heater and a carbonization device.
The method comprises the following specific steps:
the main fuel of the decomposing furnace and the kiln head burner of the rotary kiln adopts CO 2 Hydrogenation synthesized CH 4 A gas; CH (CH) 4 And O generated by electrolysis/photolysis of water 2 After burning at the kiln head burner, the generated CO 2 And H 2 O enters a decomposing furnace after passing through a kiln tail smoke chamber; CH in decomposing furnace 4 And O 2 The combustion provides heat and generates CO at the same time 2 And H 2 O, a preheater system and a decomposing furnace for decomposing raw materials to generate CO 2 The gas after combustion at the kiln head burner, the gas after combustion in the decomposing furnace and the decomposing gas of the raw meal in the preheater system I are mixed and enter the separating module I, and the temperature of the mixed gas is about 260-350 ℃.
The first separation module is a ceramic membrane separation assembly, and CO is separated by the first separation module 2 And H 2 O separation; the vapor enters a first heat exchange device, is condensed into liquid water and then enters an electrolysis/photolysis water hydrogen production device; CO 2 The gas is divided into two paths by the second flow control module and enters the first catalytic conversion module and the second catalytic conversion module respectively.
The electrolytic/photolytic hydrogen production device needs to introduce a part of light energy or electric energy for supplementing, and the liquid water generates H through the electrolytic/photolytic hydrogen production device 2 And O 2 ；H 2 Entering a first catalytic conversion module; o (O) 2 As combustion-supporting gas, the combustion-supporting gas is divided into three paths by a first flow control module and respectively enters a kiln head burner, a decomposing furnace and an ammonia catalytic decomposing device.
The catalyst filled in the first catalytic conversion module is a Ni-based or Ru-based catalyst, the reaction temperature is 280-350 ℃, and CO entering the first catalytic conversion module 2 And H 2 Generating H by reaction 2 O and CH 4 Then enter a second separation module, wherein the second separation module adopts a ceramic membrane separation assembly to separate water vapor and CH 4 Separating; the water vapor enters a second heat exchange device, is condensed into liquid water and then enters an electrolysis/photolysis water hydrogen production device; CH (CH) 4 The gas is divided into two paths by a flow control module III and respectively enters a kiln head burner and a decomposing furnace.
NH 3 After entering the first heat exchange deviceHeat exchanging to 150-200 ℃, preheating by a first heat exchanging device, preheating by a second heat exchanging device, heat exchanging to 250-300 ℃, and then entering an ammonia catalytic decomposition device with a catalytic reaction bed layer heated to a fixed temperature to decompose and generate N 2 And H 2 Then enters a third separation module, wherein the third separation module adopts a Pd separation membrane to separate N 2 And H 2 Separating; the catalyst filled in the second catalytic conversion module is a double-function catalyst, the double functions are respectively a hydrogenation function and a carbon chain growth function, the reaction temperature is 200-450 ℃, and the reaction temperature is H 2 Enters a second catalytic conversion module and is connected with CO 2 Generating liquid fuel by catalytic reaction, wherein the liquid fuel is alkane, alkene and alcohol compounds; n (N) 2 And the mixture enters a heater, and the temperature is heated to 850-900 ℃.
The liquid fuel is divided into two paths, one path enters an ammonia catalytic decomposition device and O 2 The combustion reaction is used for heating a catalytic reaction bed layer in the ammonia catalytic decomposition device, a catalyst filled in the ammonia catalytic decomposition device is a Ni-based or Co-based catalyst, the reaction temperature is 600-850 ℃, and the burnt gas CO is 2 +H 2 O and NH 3 No contact is made in the catalytic reaction bed layer, and independent pipeline is used for heating, CO 2 +H 2 O enters a heater; another path of liquid fuel enters a kiln head burner and is used as CH 4 And (5) supplementing fuel.
N in heater 2 +CO 2 +H 2 O enters a second preheater system for decomposing raw meal; raw material in the second preheater system is decomposed to produce CO 2 And after being mixed with the gas entering the second preheater, the mixture enters a carbonization device for utilization. Wherein, the carbonization device can be filled with low-calcium clinker autonomously produced by a cement plant, so that the high-performance auxiliary cementing material can be prepared after carbonization. Or, the carbonization device can be provided with a concrete block precursor prepared from construction waste micropowder and other additives, so that the concrete block precursor can be carbonized and maintained to prepare the carbonized block.
Raw materials in the second preheater system are preheated and decomposed and then directly enter the rotary kiln, raw materials in the second preheater system are preheated and then enter the decomposing furnace and then enter the rotary kiln, and a gas valve is arranged between the first preheater system and the second preheater system outlet, so that gas between the first preheater system and the second preheater system is not circulated.
The following details the specific working procedure of the invention:
firstly, starting an electrolysis/photolysis water hydrogen production device, and introducing a certain amount of starting H into the device 2 O (l), a part of light energy or electric energy is needed to be introduced into the electrolysis/photolysis water hydrogen production device, and the electrolysis/photolysis water hydrogen production device generates O 2 And H 2 The method comprises the steps of carrying out a first treatment on the surface of the H produced 2 And a part of start-up CO 2 Introducing into a first catalytic conversion module, under the action of a catalyst, CO 2 And H 2 Reaction to generate CH 4 And H 2 O (g) enters a second separation module, and separated H 2 O (g) is condensed into H after passing through the second heat exchange equipment 2 O (l) then enters an electrolysis/photolysis water hydrogen production device to enter a circulation, and separated CH 4 And the waste gas enters a flow control module III and is divided into two paths, and the waste gas enters a kiln head burner and a decomposing furnace respectively.
O generated by electrolytic/photolytic hydrogen production device 2 The gas enters a first flow control module and is divided into three paths, wherein one path enters a kiln head burner and is communicated with CH 4 Post-mix combustion for providing heat for combustion in a kiln, CO produced after combustion 2 And H 2 O (g), after passing through a kiln tail smoke chamber, enters a decomposing furnace; meanwhile, the other path O in the first flow control module 2 And CH (CH) 4 After mixing, CO is generated by combustion in a decomposing furnace 2 And H 2 O (g) provides heat for decomposing biomass. The gas in the decomposing furnace enters a first separation module through a first preheater system, the temperature of the gas is about 260-350 ℃, and CO is obtained by separation 2 Enters a second flow control module to be separated to obtain H 2 O (g) enters the first heat exchange equipment and is condensed after passing through the first heat exchange equipment to obtain H 2 O (l) enters an electrolysis/photolysis water hydrogen production device. The other path O in the first flow control module 2 Enters an ammonia catalytic decomposition device.
CO 2 After entering the flow control module II, the flow control module II is divided into two paths, one path of CO 2 Introducing the first catalytic conversion module to replace the start CO 2 The method comprises the steps of carrying out a first treatment on the surface of the Another way CO 2 Leading to a second catalytic conversion module.
On another cycleIn ring systems, NH 3 The preheated NH passes through the first heat exchange device and the second heat exchange device in sequence 3 After passing through an ammonia catalytic decomposition device with a catalytic reaction bed layer heated to a fixed temperature, N is generated 2 And H 2 ，N 2 And H 2 Enters a separation module for separation, wherein N 2 Enters a heater H 2 Enters a second catalytic conversion module and CO therein 2 After mixing, synthesizing liquid fuel; part of liquid fuel enters a kiln head burner to supplement the combustion heat in the kiln, and the other part of liquid fuel enters an ammonia catalytic decomposition device to be used for ammonia catalytic decomposition to provide heat, and the liquid fuel and O 2 The combustion reaction is used for heating a catalytic reaction bed layer in the ammonia catalytic decomposition device, and the gas CO after combustion 2 +H 2 O and NH 3 No contact is made in the catalytic reaction bed layer, and independent pipeline is used for heating, CO 2 +H 2 O enters the heater and N enters the heater 2 After heating, the raw meal enters a second preheater system for decomposing the raw meal, and a second preheater system outlet N 2 And CO generated by decomposition of raw materials 2 Mixing and then feeding into a carbonization device for carbonizing concrete products or steel slag and the like. When the catalyst is used for carbonizing concrete products or steel slag, a part of pure oxygen is required to be introduced for supporting combustion, pure oxygen may come from an air separation oxygen generation system.
In summary, the whole process of the cement production process of the invention does not discharge CO 2 The invention fully utilizes the gas and heat generated in each step, saves energy to the greatest extent and has almost no gas discharge; all heat loss during cement production comes from methane and liquid fuel produced by catalytic conversion, and part of carbon can realize internal circulation.
The invention adopts the total oxygen combustion to carry out the pre-decomposition process in the first preheater system and adopts N in the second preheater system to produce cement 2 The heating performs a pre-decomposition process, so that almost no nitrogen oxides are generated.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments may be modified or some or all of the technical features may be replaced equivalently, and these modifications or replacements do not make the essence of the corresponding technical scheme deviate from the scope of the technical scheme of the embodiments of the present invention.

Claims (10)

1. The cement production process based on zero outsourcing fossil energy and zero carbon emission of the existing cement production line is realized by the following equipment, and comprises a preheater system, a decomposing furnace and a rotary kiln, and is characterized in that:
the device also comprises a separation module, a flow control module, heat exchange equipment, an electric/optical water splitting hydrogen production device, a catalytic conversion module, an ammonia catalytic decomposition device, a heater and a carbonization device;
the concrete steps of the cement production process are as follows:
the main fuel of the decomposing furnace and the kiln head burner of the rotary kiln adopts CO 2 Hydrogenation synthesized CH 4 A gas; CH (CH) 4 And O generated by electrolysis/photolysis of water 2 After burning at the kiln head burner, the generated CO 2 And H 2 O enters a decomposing furnace after passing through a kiln tail smoke chamber; CH in decomposing furnace 4 And O 2 The combustion provides heat and generates CO at the same time 2 And H 2 O, a preheater system and a decomposing furnace for decomposing raw materials to generate CO 2 The burnt gas at the kiln head burner, the burnt gas in the decomposing furnace and the decomposed gas of the raw meal in the preheater system I are mixed and then enter the separating module I;
after passing through the first separation module, CO is added 2 And H 2 O separation; the vapor enters a first heat exchange device, is condensed into liquid water and then enters an electrolysis/photolysis water hydrogen production device; CO 2 The gas is divided into two paths by a second flow control module and enters a first catalytic conversion module and a second catalytic conversion module respectively;
liquid water is electrolyzed/electrolyzed to produce H by a hydrogen production device 2 And O 2 ；H 2 Entering a first catalytic conversion module; o (O) 2 As combustion-supporting gas, the gas is divided into three paths by a first flow control module and respectively enters a kiln head for combustionA burner, a decomposing furnace and an ammonia catalytic decomposing device;
CO entering catalytic conversion module one 2 And H 2 Generating H by reaction 2 O and CH 4 Then enters a second separation module to separate the water vapor and CH 4 Separating; the water vapor enters a second heat exchange device, is condensed into liquid water and then enters an electrolysis/photolysis water hydrogen production device; CH (CH) 4 The gas is divided into two paths by a flow control module III and respectively enters a kiln head burner and a decomposing furnace;
NH 3 enters a first heat exchange device, is preheated by the first heat exchange device, enters a second heat exchange device for preheating, enters an ammonia catalytic decomposition device with a catalytic reaction bed layer heated to a fixed temperature, and is decomposed to generate N 2 And H 2 Then enter a separation module III to make N 2 And H 2 Separating; h 2 Enters a second catalytic conversion module and is connected with CO 2 Generating liquid fuel through catalytic reaction; n (N) 2 Entering a heater;
the liquid fuel is divided into two paths, one path enters an ammonia catalytic decomposition device and O 2 The combustion reaction is used for heating a catalytic reaction bed layer in the ammonia catalytic decomposition device, and the gas CO after combustion 2 +H 2 O and NH 3 No contact is made in the catalytic reaction bed layer, and independent pipeline is used for heating, CO 2 +H 2 O enters a heater; the other path enters a kiln head burner and is used as CH 4 Supplementing fuel;
n in heater 2 +CO 2 +H 2 O enters a second preheater system for decomposing raw meal; raw material in the second preheater system is decomposed to produce CO 2 And after being mixed with the gas entering the second preheater system, the mixture enters a carbonization device for utilization.
2. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: the catalyst filled in the first catalytic conversion module is a Ni-based or Ru-based catalyst, and the reaction temperature is 280-350 ℃; the catalyst filled in the second catalytic conversion module is a double-function catalyst, the double functions are a hydrogenation function and a carbon chain growth function, and the reaction temperature is 200-450 ℃.
3. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: the catalyst filled in the ammonia catalytic decomposition device is a Ni-based or Co-based catalyst, and the reaction temperature is 600-850 ℃.
4. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: the first separation module and the second separation module adopt ceramic membrane separation components, and the third separation module adopts Pd separation membranes.
5. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: the ammonia gas is subjected to heat exchange to 150-200 ℃ after passing through the first heat exchange device, is subjected to heat exchange to 250-300 ℃ after passing through the second heat exchange device, and then enters the ammonia catalytic decomposition device.
6. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: raw materials in the second preheater system are preheated and decomposed and then directly enter the rotary kiln, raw materials in the second preheater system are preheated and then enter the decomposing furnace and then enter the rotary kiln, and a gas valve is arranged between the first preheater system and the second preheater system outlet, so that gas between the first preheater system and the second preheater system is not circulated.
7. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: n after passing through the separation module III 2 After passing through the heater, the temperature is heated to 850-900 ℃.
8. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: the liquid fuel is alkane, alkene and alcohol compounds.
9. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: the carbonization device can be filled with low-calcium clinker autonomously produced by a cement plant, so that the high-performance auxiliary cementing material can be prepared after carbonization.
10. The cement production process based on zero outsourcing fossil energy and zero carbon emissions of existing cement production lines according to claim 1, characterized in that: the carbonization device can be filled with a concrete block precursor prepared from construction waste micropowder and other additives, so that the concrete block precursor can be prepared into carbonized blocks after carbonization and maintenance.
CN202311345856.8A 2023-10-17 2023-10-17 Cement production process based on zero outsourcing fossil energy and zero carbon emission of existing cement production line Pending CN117645422A (en)

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