CN112279277A - System and method for high-end resource utilization of flue gas desulfurization by magnesium method - Google Patents

System and method for high-end resource utilization of flue gas desulfurization by magnesium method Download PDF

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CN112279277A
CN112279277A CN202011341636.4A CN202011341636A CN112279277A CN 112279277 A CN112279277 A CN 112279277A CN 202011341636 A CN202011341636 A CN 202011341636A CN 112279277 A CN112279277 A CN 112279277A
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magnesium
ammonium
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crystallization
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彭振超
韩默先
郭清
韩硕怀
刘艳霞
刘志斌
王勇跃
李增杰
赵柏然
彭跃
韩冰
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Xingtai Runtian Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/06—Preparation of sulfates by double decomposition
    • C01D5/10—Preparation of sulfates by double decomposition with sulfates of magnesium, calcium, strontium, or barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/22—Preparation in the form of granules, pieces, or other shaped products
    • C01D3/24—Influencing the crystallisation process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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Abstract

A system and a method for high-end resource utilization of flue gas magnesium desulphurization belong to the technical field of atmospheric pollution treatment. The method for forming a perfect system by introducing potassium chloride and soda ash in the conversion of the desulfurization solution simplifies and optimizes the process, improves the operability and controllability, improves the conversion rate and efficiency, further reduces the energy consumption, enables the quality and the level of the product to be greatly improved when the soda ash replaces the soda ash, and also greatly improves the profit margin when the product is converted and upgraded. Provides reliable, effective and favorable technical basis for realizing the discharge of waste residue, waste water and zero waste, and changes waste into valuable, and has extremely high development prospect and economic and social benefits.

Description

System and method for high-end resource utilization of flue gas desulfurization by magnesium method
Technical Field
The invention belongs to the technical field of atmospheric pollution treatment, and particularly relates to a system and a method for high-end resource utilization of coal-fired flue gas by magnesium desulfurization.
Background
The applicant filed a patent application, patent acceptance number 202011185828.0, to the patent office of the national intellectual property office on 27/10/2020 for a flue gas magnesium desulfurization resource utilization system and method.
The method is based on flue gas magnesium desulphurization, takes the high value-added resource transfer of desulphurization solution magnesium sulfate as a main line, selectively obtains partial high-quality magnesium sulfate series products, and sequentially performs double decomposition of potassium chloride and magnesium sulfate to obtain a potassium sulfate target and a magnesium chloride transition substance; the intervention lime reacts with the magnesium chloride transition substance to obtain a magnesium hydroxide target substance and a calcium chloride transition substance; the intervention natural alkali reacts with calcium chloride transition substance to obtain calcium carbonate target substance and sodium chloride transition substance; evaporating and crystallizing the mixed solution of the sodium chloride transition substance to obtain a sodium chloride target substance and an ammonium-based filtrate transition substance; evaporating and crystallizing the ammonium-based filtrate transition substance to finally obtain a solid ammonium-based fertilizer; the system condensate water is used for preparing potassium chloride; washing water for washing the magnesium hydroxide is used for lime digestion; washing water for washing calcium carbonate is used for dissolving trona; when the purified flue gas is discharged after reaching the standard, all substances entering the system are orderly extracted from waste to valuable and from inferior to superior in a resource manner, so that the discharge of waste residues, waste water and zero is fundamentally realized, the large problems of solid waste disposal and groundwater pollution caused by soluble salt in the prior art are thoroughly solved, and the influence on environmental hazard is eliminated.
Although the invention aims to convert the desulfurization liquid of magnesium desulfurization into resources, and forms a complete system process chain by intervening potassium chloride, lime and trona, thereby obtaining products with high added values, such as potassium sulfate, magnesium hydroxide, calcium carbonate, sodium chloride, ammonium fertilizer and the like with commercial values and market demands, and also thoroughly solving the problem of solid waste disposal while realizing the discharge of waste residue, waste water and zero, the invention also has the problem of over-dependence on trona resource, and once the problems of depletion of trona resource, quality reduction, increase of harmful impurities and the like occur, the process operation is limited, the cost is increased and the product quality is even influenced.
Therefore, it is necessary to further develop the idea based on the above technical advantages, and make the technical level of the flue gas magnesium desulphurization resource utilization system and method be new on the premise of improving the quality of raw materials and improving the grade of the produced products.
Disclosure of Invention
The invention aims to provide a system and a method for high-end resource utilization of flue gas magnesium desulphurization, which enable a desulphurization product magnesium sulfate to be converted according to a complete process chain, and obtain various chemical products with excellent commodity properties, high commercial value and great market demands.
The method is based on flue gas magnesium desulphurization, takes the resource transfer of the desulphurization solution magnesium sulfate to high added value as a main line, and sequentially intervenes in double decomposition reaction of potassium chloride and the desulphurization solution magnesium sulfate to obtain a potassium sulfate target and a magnesium chloride transition solution except selectively obtaining part of high-quality magnesium sulfate series products; introducing soda ash and a magnesium chloride transition solution to react to obtain a magnesium carbonate transition filter material and a sodium chloride transition solution, wherein the magnesium carbonate transition filter material is subjected to heat conversion, drying and crushing, drying and calcining and crushing, and drying, calcining and electric melting respectively to obtain light magnesium carbonate, silicon steel-grade magnesium oxide and high-purity electric melting magnesite target products; evaporating and crystallizing the sodium chloride transition solution to obtain a sodium chloride target substance and an ammonium group transition filtrate; evaporating and crystallizing the ammonium-based transition filtrate to finally obtain a solid ammonium-based fertilizer; the system condensate water is used for preparing potassium chloride and washing a magnesium carbonate transition filter material; washing water (liquid) for washing the magnesium carbonate transition filter material is used for dissolving soda ash or/and digesting magnesium oxide to prepare magnesium hydroxide slurry (slurry); when the purified flue gas is discharged after reaching the standard, all substances entering the system are orderly extracted from waste to valuable and from inferior to superior in a resource manner, so that the discharge of waste residues, waste water and zero is fundamentally realized, the large problems of solid waste disposal and groundwater pollution caused by soluble salt in the prior art are thoroughly solved, and the influence on environmental hazard is eliminated.
In order to achieve the purpose, the invention provides a system for high-end resource utilization of flue gas magnesium desulphurization, which is formed by sequentially associating a plurality of chemical engineering units and comprises the following components:
p1: sequentially formed from Mg (OH)2Slurrying unit, magnesium desulfurization unit and MgSO4Evaporative crystallization Unit, MgSO4Centrifugal separation Unit, MgSO4Composition of drying Unit MgSO4A series product preparation subsystem;
p2: sequentially dissolved by KCLDecomposition unit, double salt evaporation crystallization unit, K2SO4Centrifugal separation Unit, K2SO4Drying Unit composition K2SO4Preparing a subsystem;
p4: the NaCL preparation subsystem is composed of a NaCL evaporation crystallization unit, a NaCL centrifugal separation unit and a NaCL drying unit in sequence;
p5: an ammonium-based fertilizer preparation subsystem is sequentially composed of an ammonium salt mixed solution evaporation crystallization unit, an ammonium salt mixed crystallization centrifugal separation unit and an ammonium salt mixed crystallization drying unit;
characterized in that, the system also includes:
p3: sequentially comprises a soda ash dissolving and purifying unit and MgCO precipitation3Unit, MgCO3The light magnesium carbonate 4MgCO is composed of a filtering and washing unit, three parallel thermal conversion-drying and crushing combined units, a drying-calcining and crushing combined unit and a drying-calcining-electric melting combined unit3Mg(OH)24H2A preparation subsystem of O, silicon steel grade magnesia MgO and high-purity fused magnesia (the fused magnesia preparation subsystem is called for short);
P6；MgSO4the (NH) content of the centrifugal separation unit4)2SO4、NH4NO3MgSO (2) of4The filtrate outlet is connected with the feed inlet of the double decomposition unit; k2SO4MgCL for centrifugal separation units2Transition filtrate outlet and precipitated MgCO3The feed inlets of the units are connected; MgCO3The output port of the NaCL transition filtrate of the filtering and washing unit is connected with the feed port of the NaCL evaporative crystallization unit, MgCO3MgCO as part of a filtration and washing unit3The output end of the transition filter material is connected with the feed inlet of the heat conversion-drying and crushing combined unit, and MgCO is used3Two-part MgCO of a filtration and washing unit3The output end of the transition filter material is connected with the feed inlet of the drying-calcining-crushing combined unit, and MgCO is used for filtering the waste water3Three parts of MgCO in filtering and washing unit3The output end of the transition filter material is connected with the feed inlet of the drying calcination-electric melting combined unit, and MgCO is used for filtering the air3The outlet of the washing liquid (water) of the filtering and washing unit is respectively connected with the inlet of the soda dissolving and purifying unit or/and Mg (OH)2The feed inlets of the slurry melting units are connected; KCL (KCL), (NH) containing NaCL centrifugal separation unit4)2SO4、NH4NO3An ammonium-based transition filtrate output port of a small amount of sodium chloride is connected with a feed inlet of an ammonium salt mixed solution evaporation crystallization unit; the filtrate (mother liquor) outlet of the ammonium salt mixed crystallization centrifugal separation unit is connected with the feed inlet of the ammonium salt mixed liquor evaporation crystallization unit; the output ports of the condensed water collecting systems of all the evaporation and drying units are respectively connected with the feed port of the potassium chloride dissolving unit or/and the MgCO3The feed inlets of the filtering and washing units are connected.
The invention aims to provide a system for high-end resource utilization of flue gas magnesium desulphurization, which reasonably converts the magnesium sulfate of a desulphurization solution into various products with commercial values and market demands, so that a main task of a magnesium sulfate series product preparation subsystem is not or not to obtain the magnesium sulfate series products as much as possible, but to crystallize out part of magnesium sulfate in the desulphurization solution on the basis of ensuring the quality of the magnesium sulfate products, so that ammonium nitrate, ammonium sulfate and other ammonium salt impurities generated in the desulphurization solution in the process of denitration and desulphurization are continuously retained in a transition solution (mixed solution) in an ionic state, are continuously enriched in a subsequent process, and are finally evaporated, crystallized and dried into a valuable solid ammonium-based fertilizer.
Generally, the lower the proportion of magnesium sulfate crystallized from the magnesium sulfate as a desulfurized liquid, the more the purity of the magnesium sulfate can be ensured without being affected by other impurities. Generally, the crystallization rate is controlled to be lower than 50%, so that the magnesium sulfate can meet the agricultural grade standard requirements, and the quality requirements of industrial grade magnesium sulfate products can be basically met by controlling the crystallization rate to be lower than 30%. Under special conditions, based on the market price, market capacity and product management aspects of magnesium sulfate series products, the desulfurized liquid magnesium sulfate can be completely converted into other products with higher added values except magnesium sulfate, namely, a desulfurized magnesium sulfate solution outlet is directly connected with a feed inlet of a double decomposition unit, the work of magnesium sulfate evaporative crystallization, magnesium sulfate centrifugal separation and magnesium sulfate drying units is closed, and even the units are eliminated in product design schemes.
In order to achieve the aim, the invention provides a high-end resource utilization method for flue gas magnesium desulphurization, which is formed by sequentially associating a plurality of chemical unit operations and is characterized in that:
step S1: performing magnesium desulfurization, preparing magnesium hydroxide slurry from magnesium oxide and/or magnesium hydroxide by using washing water for washing a magnesium carbonate transition filter material, conveying the magnesium hydroxide slurry to a desulfurization unit for magnesium desulfurization, emptying clean flue gas, crystallizing and separating desulfurized liquid after moderate evaporation and concentration, wherein filtrate is magnesium sulfate mixed liquid containing ammonium sulfate and ammonium nitrate for later use, and drying the filter material to obtain a magnesium sulfate heptahydrate, magnesium sulfate monohydrate and anhydrous magnesium sulfate series product;
step S2: performing double decomposition reaction of potassium chloride and sulfate, dissolving the potassium chloride with the system condensed water, performing double decomposition reaction with the magnesium sulfate in the filtrate subjected to evaporation crystallization separation in the step S1, performing evaporation crystallization separation to obtain a filtrate which is a magnesium chloride transition solution containing ammonium sulfate, ammonium nitrate and potassium chloride for later use, and drying the filter material to obtain potassium sulfate;
step S3: precipitating soda ash and magnesium chloride transition solution, adjusting soda ash into slurry with washing water (liquid) for washing magnesium carbonate transition filter material, purifying and refining, reacting with magnesium chloride transition solution in the filtrate of step S2 to precipitate magnesium carbonate, filtering, separating and washing to obtain filtrate as sodium chloride transition solution containing ammonium sulfate, ammonium nitrate and potassium chloride, returning the washing water to the step to dissolve soda ash or returning to step S1 to prepare magnesium hydroxide slurry, wherein the filter material is magnesium carbonate transition filter material, and part of MgCO is part of magnesium carbonate transition filter material3The transition filter material is processed by hot transformation-dried and crushed magnesium salt to obtain a light magnesium carbonate product 4MgCO3Mg(OH)24H2O, two-part MgCO3The transition filter material is processed by dried, calcined and crushed magnesium salt to obtain silicon steel grade magnesium oxide MgO, and the third part of the magnesium oxide MgO is MgCO3The transition filter material is processed by magnesium salt of drying, calcining and electric melting combination to obtain high-purity electric melting magnesia MgO;
step S4: performing a concentration and crystallization process of a sodium chloride transition solution, wherein the filtrate obtained in the step S3 is the sodium chloride transition solution containing ammonium sulfate, ammonium nitrate and potassium chloride, after evaporation, crystallization and separation, the filtrate is a mixed solution (ammonium-based transition filtrate) containing ammonium sulfate, ammonium nitrate, potassium chloride and a small amount of sodium chloride for later use, and the filter material is dried to obtain a sodium chloride product;
step S5: and (4) implementing an amino chemical fertilizer recovery process, wherein after the ammonium-based transition filtrate obtained in the step S4 passes through the processes from the step S1 to the step S4, the concentrations of ammonium sulfate, ammonium nitrate and potassium chloride are continuously enriched, further evaporation, crystallization and separation are implemented in the step, a filter material is dried to obtain a solid ammonium-based chemical fertilizer containing potassium chloride, ammonium sulfate and ammonium nitrate, and the filtrate (mother liquor) returns to repeat evaporation, crystallization and separation, and is finally completely converted into the ammonium-based chemical fertilizer.
Compared with the prior art, the invention has the beneficial effects that:
the invention not only replaces the trona with wide source and stable quality with the trona with the prior art to achieve the aim of high added value conversion of the desulfurization solution resource of magnesium desulfurization, but also simplifies and optimizes the process, improves the operability control, improves the conversion rate and efficiency, further reduces the energy consumption, improves the quality and the hierarchy of the product while replacing the trona with the trona, and greatly improves the profit margin while converting and upgrading the product. Provides reliable, effective and favorable technical basis for realizing the discharge of waste residue, waste water and zero waste, and changes waste into valuable, and has extremely high development prospect and economic and social benefits.
Drawings
The invention is further described below with reference to the accompanying drawings and embodiments, it is obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings can be obtained by those skilled in the art without inventive effort.
FIG. 1 shows a system for high-end resource utilization of flue gas desulfurization by magnesium method provided by the invention
Detailed Description
Example 1: as can be seen from fig. 1, the invention provides a system for high-end resource utilization of flue gas magnesium desulphurization, which is composed of a plurality of chemical engineering units in sequence, and comprises:
p1: sequentially formed from Mg (OH)2Slurrying unit, magnesium desulfurization unit and MgSO4Evaporative crystallization Unit, MgSO4Centrifugal separation Unit, MgSO4Composition of drying Unit MgSO4A series product preparation subsystem;
p2: sequentially comprises a KCL dissolving unit, a double decomposition unit, a double salt evaporation crystallization unit and K2SO4Centrifugal separation Unit, K2SO4Drying Unit composition K2SO4Preparing a subsystem;
p4: the NaCL preparation subsystem is composed of a NaCL evaporation crystallization unit, a NaCL centrifugal separation unit and a NaCL drying unit in sequence;
p5: an ammonium-based fertilizer preparation subsystem is sequentially composed of an ammonium salt mixed solution evaporation crystallization unit, an ammonium salt mixed crystallization centrifugal separation unit and an ammonium salt mixed crystallization drying unit;
it is characterized by also comprising
P3: sequentially comprises a soda ash dissolving and purifying unit and MgCO precipitation3Unit, MgCO3The light magnesium carbonate 4MgCO is composed of a filtering and washing unit, three parallel thermal conversion-drying and crushing combined units, a drying-calcining and crushing combined unit and a drying-calcining-electric melting combined unit3Mg(OH)2H2A preparation subsystem of O, silicon steel grade magnesia MgO and high-purity fused magnesia (the fused magnesia preparation subsystem is called for short);
P6；MgSO4the (NH) content of the centrifugal separation unit4)2SO4、NH4NO3MgSO (2) of4The filtrate outlet is connected with the feed inlet of the double decomposition unit; k2SO4MgCL for centrifugal separation units2Filtrate outlet and precipitated MgCO3The feed inlets of the units are connected; MgCO3The NaCL transition filtrate outlet of the filtering and washing unit is connected with the feed inlet of the NaCL evaporative crystallization unit, and MgCO is used for removing the impurities3MgCO as part of a filtration and washing unit3The output end of the transition filter material is connected with the feed inlet of the heat conversion-drying and crushing combined unit, and MgCO is used3Two-part MgCO of a filtration and washing unit3Transition filter materialThe output end is connected with the feed inlet of the drying-calcining-crushing combined unit, and MgCO is added3Three parts of MgCO in filtering and washing unit3The output end of the transition filter material is connected with the feed inlet of the drying calcination-electric melting combined unit, and MgCO is used for filtering the air3The outlet of the washing water of the filtering and washing unit is respectively connected with the inlet of the soda dissolving and purifying unit or/and Mg (OH)2The feed inlets of the slurry melting units are connected; the centrifugal separation unit of NaCL contains KCL, (NH4)2SO4、NH4NO3An ammonium-based transition filtrate output port of a small amount of sodium chloride is connected with a feed inlet of an ammonium salt mixed solution evaporation crystallization unit; the filtrate (mother liquor) outlet of the ammonium salt mixed crystallization centrifugal separation unit is connected with the feed inlet of the ammonium salt mixed liquor evaporation crystallization unit; the output ports of the condensed water collecting system of all the evaporation and drying units are respectively connected with MgCO3The washing water feed inlet of the filtration washing unit or/and the potassium chloride dissolving unit feed inlet are/is connected.
System runtime
P1 in Mg (OH)2Adding desulfurizing agent MgO into the slurrying unit, and using MgCO3Filtering the washing water (liquid) of the washing unit to Mg (OH)2Refining the slurry (slurry) into desulfurized slurry, delivering to a magnesium desulfurization unit for wet desulfurization, and converting the desulfurized slurry into MgSO (MgSO) after cyclic desulfurization of the desulfurizer4The desulfurization completion liquid or desulfurization liquid as main component is purified and then introduced into MgSO4Evaporating and crystallizing unit, evaporating and concentrating according to magnesium sulfate crystallization rate lower than 50%, crystallizing and separating, and then passing through MgSO4Solid-liquid separation is carried out by a centrifugal separation unit, and the obtained filter material is MgSO4.7H2Crystallizing with O, filtering with MgSO4Mainly contains (NH)4)2SO4、NH4NO3The filter material can be selectively dried into MgSO4.7H2O、MgSO4.H2O or MgSO4Completion of MgSO1Preparing a subsystem task for a series of products;
adding KCL into the KCL dissolving unit for dissolving P2, dissolving with condensed water collected by the system, refining, and sending to the metathesis unit and P1 subsystem for obtaining MgSO4Mainly contains (NH)4)2SO4、NH4NO3Reacting the mixed solution of soluble inorganic salt impurity components, delivering the reaction solution to a double salt evaporation crystallization unit for concentration, cooling and crystallization, and then performing K crystallization2SO4Solid-liquid separation is carried out by a centrifugal separation unit, and the filtrate is MgCL2Mainly comprises KCL, (NH4)2SO4、NH4NO3MgCL of2The transition solution is ready for use, and the filter material is K2SO4Crystallization is sent K2SO4Drying Unit completion K2SO4And preparing a subsystem task.
P3 soda ash is added into soda ash dissolving and purifying unit, MgCO is washed3After the washing water of the filter material is dissolved and purified, MgCO is precipitated3Unit and MgCL2MgCO is carried out by transition solution3Precipitation reaction, MgCO after the reaction is finished3The filtering and washing unit is used for filtering and washing, and the filtrate mainly contains NaCL and KCL (NH4)2SO4、NH4NO3The NaCL transition solution is ready for use, and the filter material is MgCO3Transition filter material, a part of MgCO3The output end of the transition filter material is connected with the feed inlet of the heat conversion-drying and crushing combined unit for obtaining light magnesium carbonate and two parts of MgCO3The output end of the transition filter material is connected with the feed inlet of the drying-calcining-crushing combined unit for obtaining silicon steel grade magnesium oxide, and the third part of MgCO3The output end of the transition filter material is connected with the feed inlet of the drying calcination-electric smelting combined unit for obtaining high-purity electric smelting magnesite, MgCO3The washing liquid outlet of the filtering and washing unit is respectively connected with the feed inlet of the soda dissolution and purification unit and is used for dissolving soda or/and Mg (OH)2The feed inlet of the slurry melting unit is connected with the slurry inlet used for Mg (OH)2Slurrying, thereby completing the task of the subsystem for preparing the fused magnesia;
p4 transferring the NaCL transition solution to NaCL mixed solution evaporation crystallization unit for concentration and crystallization, and performing solid-liquid separation by NaCL centrifugal separation unit to obtain filtrate containing KCL (KCL), (NH4)2SO4、NH4NO3And a small amount of ammonium-based transition filtrate (mixed solution) of NaCL for standby, wherein the filter material is NaCL, and the NaCL preparation subsystem task is completed by drying through a NaCL drying unit;
p5, sending the ammonium transition filtrate to an ammonium salt mixed solution evaporation crystallization unit for concentration and crystallization, passing through an ammonium salt mixed crystallization centrifugal separation unit, returning the filtrate which is a mother solution which is not completely crystallized to the ammonium salt mixed solution evaporation crystallization unit of the subsystem for concentration and crystallization; the filter material is ammonium salt mixed crystals, and the ammonium salt mixed crystals are dried by an ammonium salt mixed crystal drying unit to complete the task of the ammonium-based fertilizer preparation subsystem.
Embodiment 2 is to achieve the above object, and the present invention provides a method for high-end resource utilization of flue gas desulfurization by magnesium method, which is composed of several chemical unit operations in sequence, and is characterized in that:
step S1: performing magnesium desulfurization, preparing magnesium hydroxide slurry from magnesium oxide and/or magnesium hydroxide by using washing water for washing a magnesium carbonate transition filter material, delivering the magnesium hydroxide slurry to a desulfurization unit for magnesium desulfurization, exhausting clean flue gas, evaporating and concentrating desulfurization liquid according to the condition that the crystallization rate of magnesium sulfate is lower than 20 percent of the total content, performing crystallization separation, and obtaining filtrate which is magnesium sulfate mixed liquid containing ammonium sulfate and ammonium nitrate for later use, and drying the filter material to obtain magnesium sulfate monohydrate;
step S2: performing double decomposition reaction of potassium chloride and sulfate, dissolving the potassium chloride with the system condensed water, performing double decomposition reaction with the magnesium sulfate in the filtrate subjected to evaporation crystallization separation in the step S1, performing evaporation crystallization separation to obtain a filtrate which is a magnesium chloride transition solution containing ammonium sulfate, ammonium nitrate and potassium chloride for later use, and drying the filter material to obtain potassium sulfate;
step S3: precipitating soda ash and magnesium chloride transition solution, adjusting soda ash into slurry with washing solution for washing magnesium carbonate transition filter material, purifying and refining, reacting with magnesium chloride transition solution in the filtrate obtained in step S2 to precipitate magnesium carbonate, filtering, separating and washing to obtain filtrate as sodium chloride transition solution containing ammonium sulfate, ammonium nitrate and potassium chloride, returning the washing solution to the step to dissolve soda ash, wherein the filter material is magnesium carbonate transition filter material, and part of MgCO is part of MgCO transition filter material3The transition filter material is processed by hot transformation-dried and crushed magnesium salt to obtain a light magnesium carbonate product 4MgCO3Mg(OH)24H2O, two-part MgCO3The transition filter material is processed by dried, calcined and crushed magnesium salt to obtain silicon steel grade magnesium oxide MgO, and the third part of the magnesium oxide MgO is MgCO3Transition filter material warpProcessing the magnesium salt by drying, calcining and electric melting to obtain high-purity electric melting magnesia MgO;
step S4: performing a concentration and crystallization process of a sodium chloride transition solution, wherein the filtrate obtained in the step S3 is the sodium chloride transition solution containing ammonium sulfate, ammonium nitrate and potassium chloride, after evaporation, crystallization and separation, the filtrate is an ammonium-based transition filtrate (mixed solution) containing ammonium sulfate, ammonium nitrate, potassium chloride and a small amount of sodium chloride for later use, and the filter material is dried to obtain a sodium chloride product;
step S5: and (4) implementing an amino chemical fertilizer recovery process, wherein after the ammonium-based transition filtrate obtained in the step S4 passes through the processes from the step S1 to the step S4, the concentrations of ammonium sulfate, ammonium nitrate and potassium chloride are continuously enriched, further evaporation, crystallization and separation are implemented in the step, a filter material is dried to obtain a solid ammonium-based chemical fertilizer containing potassium chloride, ammonium sulfate and ammonium nitrate, and the filtrate is returned for repeated evaporation, crystallization and separation, and finally is completely converted into the ammonium-based chemical fertilizer.

Claims (3)

1.一种烟气镁法脱硫高端资源化利用的系统，由若干化工单元按照依次关联组成，包括：1. A system for high-end resource utilization of flue gas magnesium desulfurization, which is composed of several chemical units in sequence, including: P1：依次由Mg(OH)2化浆单元、镁法脱硫单元、MgSO4蒸发结晶单元、MgSO4离心分离单元、MgSO4干燥单元组成MgSO4系列产品制取子系统；P1: The MgSO 4 series product preparation subsystem is composed of Mg(OH) 2 slurry unit, magnesium method desulfurization unit, MgSO 4 evaporative crystallization unit, MgSO 4 centrifugal separation unit, and MgSO 4 drying unit in turn; P2：依次由KCL溶解单元、复分解单元、复盐蒸发结晶单元、K2SO4离心分离单元、K2SO4干燥单元组成K2SO4制取子系统；P2: The K 2 SO 4 preparation subsystem is sequentially composed of a KCL dissolving unit, a double decomposition unit, a double salt evaporation and crystallization unit, a K 2 SO 4 centrifugal separation unit, and a K 2 SO 4 drying unit; P4：依次由NaCL蒸发结晶单元、NaCL离心分离单元、NaCL干燥单元组成NaCL制取子系统；P4: The NaCL preparation subsystem is composed of a NaCL evaporation and crystallization unit, a NaCL centrifugal separation unit, and a NaCL drying unit in turn; P5：依次由铵盐混合液蒸发结晶单元、铵盐混合结晶离心分离单元、铵盐混合结晶干燥单元组成铵基化肥制取子系统；P5: The ammonium-based fertilizer preparation subsystem is sequentially composed of the ammonium salt mixed liquid evaporation and crystallization unit, the ammonium salt mixed crystallization centrifugal separation unit, and the ammonium salt mixed crystallization drying unit; 其特征在于，该系统还包括It is characterized in that the system also includes P3：依次由纯碱溶解净化单元、沉淀MgCO3单元、MgCO3过滤洗涤单元以及三个并联的热转型-干燥粉碎组合单元、干燥-煅烧粉碎组合单元、干燥煅烧-电熔组合单元组成轻质碳酸镁4MgCO3Mg(OH)24H2O、硅钢级氧化镁MgO、高纯电熔镁砂制取子系统(简称电熔镁砂制取子系统)；P3: Light carbonic acid is composed of a soda ash dissolution and purification unit, a precipitation MgCO 3 unit, a MgCO 3 filtration and washing unit, and three parallel thermal transformation-drying and pulverizing combined units, drying-calcining and pulverizing combined units, and drying and calcining-electromelting combined units. Magnesium 4MgCO 3 Mg(OH) 2 4H 2 O, silicon steel grade magnesium oxide MgO, high-purity fused magnesia production subsystem (referred to as fused magnesia production subsystem); P6；MgSO4离心分离单元之含有(NH4)2SO4、NH4NO3的MgSO4滤液输出口与复分解单元之进料口连接；K2SO4离心分离单元之MgCL2过渡滤液输出口与沉淀MgCO3单元之进料口连接；MgCO3过滤洗涤单元之NaCL过渡滤液之输出口与NaCL蒸发结晶单元之进料口连接，MgCO3过滤洗涤单元之一部分MgCO3过渡滤料输出端与热转型-干燥粉碎组合单元进料口连接，MgCO3过滤洗涤单元之二部分MgCO3过渡滤料输出端与干燥-煅烧粉碎组合单元进料口连接，MgCO3过滤洗涤单元之三部分MgCO3过渡滤料输出端与干燥煅烧-电熔组合单元进料口连接，MgCO3过滤洗涤单元之洗涤液输出口分别与纯碱溶解净化单元进料口或者/和Mg(OH)2化浆单元之进料口连接；NaCL离心分离单元之含有KCL、(NH4)2SO4、NH4NO3和少量氯化钠的铵基过渡滤液输出口与铵盐混合液蒸发结晶单元进料口连接；铵盐混合结晶离心分离单元滤液输出口与铵盐混合液蒸发结晶单元之进料口连接；所有蒸发、干燥单元之冷凝水汇集系统其输出口分别与氯化钾溶解单元进料口或者/和MgCO3过滤洗涤单元之进料口连接。P6; the MgSO 4 filtrate output port containing (NH 4 ) 2 SO 4 and NH 4 NO 3 of the MgSO 4 centrifugal separation unit is connected to the feed port of the metathesis unit; the MgCL 2 transition filtrate output port of the K 2 SO 4 centrifugal separation unit It is connected with the feed port of the precipitation MgCO 3 unit; the output port of the NaCL transition filtrate of the MgCO 3 filtration and washing unit is connected to the feed port of the NaCL evaporation and crystallization unit, and the output end of a part of the MgCO 3 filtration and washing unit of the transition filter material is connected with the heat The transformation-drying and pulverizing unit is connected to the feed port, and the output end of the second part of the MgCO 3 filtration and washing unit is connected to the feed port of the drying-calcining and pulverizing unit, and the third part of the MgCO 3 filtration and washing unit is MgCO 3 transition filtration The material output end is connected with the feed port of the drying calcination-electrofusion combined unit, and the washing liquid output port of the MgCO 3 filtration and washing unit is respectively connected with the feed port of the soda ash dissolution purification unit or/and the feed port of the Mg(OH) 2 slurry unit. Connection; the ammonium transition filtrate output port of the NaCL centrifugal separation unit containing KCL, (NH 4 ) 2 SO 4 , NH 4 NO 3 and a small amount of sodium chloride is connected to the feed port of the ammonium salt mixed liquid evaporation and crystallization unit; ammonium salt mixing The filtrate output port of the crystallization centrifugal separation unit is connected with the feed port of the ammonium salt mixed liquid evaporation and crystallization unit; the output ports of the condensed water collection systems of all evaporation and drying units are respectively connected with the feed port of the potassium chloride dissolving unit or/and MgCO 3 filtration The feed port of the washing unit is connected. 2.一种烟气镁法脱硫高端资源化利用的方法，由若干化工单元操作依次关联组成，其特征在于：2. A method for high-end resource utilization of flue gas magnesium desulfurization, which is formed by sequentially correlating several chemical unit operations, and is characterized in that: 步骤S1：实施镁法脱硫，氧化镁和/或氢氧化镁用洗涤碳酸镁过渡滤料的洗涤水调制成氢氧化镁料浆，送脱硫单元镁法脱硫，净烟气排空，脱硫液经适度蒸发浓缩后结晶分离，滤液为含有硫酸铵、硝酸铵的硫酸镁混合液待用，滤料经干燥获得七水硫酸镁、一水硫酸镁和无水硫酸镁系列产品；Step S1: implement magnesium desulfurization, magnesium oxide and/or magnesium hydroxide are prepared into magnesium hydroxide slurry with the washing water of the magnesium carbonate transition filter material, and sent to the desulfurization unit for magnesium desulfurization, the clean flue gas is emptied, and the desulfurization liquid is passed through. After moderate evaporation and concentration, crystallization is separated, and the filtrate is a magnesium sulfate mixed solution containing ammonium sulfate and ammonium nitrate for later use, and the filter material is dried to obtain magnesium sulfate heptahydrate, magnesium sulfate monohydrate and anhydrous magnesium sulfate series products; 步骤S2：实施氯化钾与硫酸盐的复分解反应，氯化钾用系统冷凝水溶解后，与步骤S1蒸发结晶分离后滤液中的硫酸镁发生复分解反应，经蒸发结晶分离后，滤液为含有硫酸铵、硝酸铵、氯化钾的氯化镁过渡溶液待用，滤料经干燥得到硫酸钾；Step S2: implement the metathesis reaction of potassium chloride and sulfate, after the potassium chloride is dissolved in the system condensed water, metathesis reaction occurs with the magnesium sulfate in the filtrate after the evaporative crystallization separation in step S1, and after the evaporative crystallization separation, the filtrate contains sulfuric acid. The magnesium chloride transition solution of ammonium, ammonium nitrate and potassium chloride is for use, and the filter material is dried to obtain potassium sulfate; 步骤S3：实施纯碱与氯化镁过渡溶液的沉淀反应，纯碱用洗涤碳酸镁过渡滤料的洗涤液调解成料浆，净化精制后与步骤S2滤液中的氯化镁过渡溶液反应沉淀出碳酸镁，经过滤分离洗涤后，滤液为含有硫酸铵、硝酸铵、氯化钾的氯化钠过渡溶液待用，洗涤水返回本步骤溶解纯碱或者返回步骤S1调制氢氧化镁料浆，滤料为碳酸镁过渡滤料，之一部分MgCO3过渡滤料经热转型-干燥粉碎的镁盐加工后获得轻质碳酸镁产品4MgCO3Mg(OH)24H2O，之二部分MgCO3过渡滤料经干燥-煅烧粉碎的镁盐加工后获得硅钢级氧化镁MgO，之三部分MgCO3过渡滤料经干燥煅烧-电熔组合的镁盐加工后获得高纯电熔镁砂MgO；Step S3: carry out the precipitation reaction of soda ash and magnesium chloride transition solution, soda ash is adjusted into slurry with the washing solution of washing magnesium carbonate transition filter material, after purification and purification, it reacts with the magnesium chloride transition solution in step S2 filtrate to precipitate magnesium carbonate, and is separated by filtration After washing, the filtrate is a transitional sodium chloride solution containing ammonium sulfate, ammonium nitrate and potassium chloride for use, and the washing water returns to this step to dissolve soda ash or returns to step S1 to prepare magnesium hydroxide slurry, and the filter material is magnesium carbonate transitional filtration. One part of MgCO 3 transition filter material is processed by thermal transformation-drying and pulverized magnesium salt to obtain light magnesium carbonate product 4MgCO 3 Mg(OH) 2 4H 2 O, and the other part of MgCO 3 transition filter material is dried-calcined and pulverized Silicon steel grade magnesia MgO is obtained after the magnesium salt processing, and high-purity fused magnesia MgO is obtained after the three -part MgCO transition filter material is processed by drying and calcining-electrofusion combined magnesium salt; 步骤S4：实施氯化钠过渡溶液的浓缩结晶过程，步骤S3获得的滤液为含有硫酸铵、硝酸铵、氯化钾的氯化钠过渡溶液，经蒸发结晶分离后，滤液为含有硫酸铵、硝酸铵、氯化钾和少量氯化钠的铵基过渡滤液待用，滤料经干燥获得氯化钠产品；Step S4: carrying out the concentration and crystallization process of the sodium chloride transition solution, the filtrate obtained in step S3 is a sodium chloride transition solution containing ammonium sulfate, ammonium nitrate and potassium chloride, and after separation by evaporative crystallization, the filtrate contains ammonium sulfate, nitric acid Ammonium-based transition filtrate of ammonium, potassium chloride and a small amount of sodium chloride is for use, and the filter material is dried to obtain sodium chloride product; 步骤S5：实施氨基化肥回收过程，步骤S4获得的铵基过渡滤液，经步骤S1至步骤S4的过程后，其硫酸铵、硝酸铵和氯化钾的浓度不断得到富集，在本步骤实施进一步的蒸发结晶分离，滤料经干燥获得含有氯化钾、硫酸铵、硝酸铵的固态铵基化肥，滤液返回重复蒸发结晶分离，最终全部转变成铵基化肥。Step S5: implementing the amino fertilizer recovery process, the ammonium-based transition filtrate obtained in step S4, after the process from step S1 to step S4, the concentration of ammonium sulfate, ammonium nitrate and potassium chloride is continuously enriched, and further implementation is carried out in this step. The filtrate is separated by evaporation and crystallization, and the filter material is dried to obtain solid ammonium-based fertilizers containing potassium chloride, ammonium sulfate, and ammonium nitrate. 3.根据权利要求2所述的方法，其特征在于：步骤S1所述的脱硫液经适度蒸发浓缩后结晶分离为脱硫液按照硫酸镁结晶率低于总含量50％进行蒸发浓缩后结晶分离。3. The method according to claim 2, characterized in that: the desulfurization liquid described in step S1 is appropriately evaporated and concentrated and then crystallization is separated into the desulfurization liquid according to the magnesium sulfate crystallization rate lower than the total content of 50%, and the crystallization separation is carried out after evaporation and concentration.
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