CN213668635U

CN213668635U - Coproduction device for producing folic acid, gypsum, desulfurizer and/or denitrifier

Info

Publication number: CN213668635U
Application number: CN202021321548.3U
Authority: CN
Inventors: 尹标林; 尹跳; 张同生; 荣丰葶; 黄光浩; 敖卿硕
Original assignee: Guangdong Zhongzhong Biotechnology Co ltd
Current assignee: Guangdong Zhongzhong Biotechnology Co ltd
Priority date: 2020-07-07
Filing date: 2020-07-07
Publication date: 2021-07-13
Anticipated expiration: 2030-07-07

Abstract

The utility model relates to a coproduction device of production folic acid, gypsum, desulfurizer and/or denitration agent. The co-production apparatus comprises: 1) a plant for producing folic acid; 2) a plant for producing gypsum; 3) a device for producing a desulfurizing agent; and/or 4) an apparatus for producing a denitration agent.

Description

Coproduction device for producing folic acid, gypsum, desulfurizer and/or denitrifier

Technical Field

The utility model relates to a medicine field, especially a coproduction device of production folic acid, gypsum, desulfurizer and/or denitration agent.

Background

Folic acid (folate), also known as vitamin B9 or pteroylglutamic acid, has the following structural formula:

the deficiency of folic acid can lead to anemia, neural tube malformation, megaloblastic anemia, cleft lip and palate, depression, etc. Therefore, supplementation is often clinically recommended to effectively avoid a variety of diseases. Folic acid can also be used as food additive and livestock feed additive. At present, the total annual production amount of folic acid in the global range is about 2000 tons, wherein 10 percent of folic acid is medicinal folic acid, and 90 percent of folic acid is used for food additives, livestock feed additives and the like. The health care function of folic acid is gradually recognized by people, and folic acid health care products are more and more popular with consumers. This has led to a continuous increase in the market demand for folic acid, with annual demand growth rates projected to be 5% to 8%.

An exemplary method of producing folic acid includes: 1)2,4, 5-triamino-6-hydroxypyrimidine, N- (4-aminobenzoyl) -L-glutamic acid and alpha, beta-dibromopropionaldehyde are prepared into a folic acid crude product, and the folic acid containing two molecular crystal water is obtained by refining the crude product; 2) reacting 1,1,3, 3-tetramethoxy-2-propanol or 2-hydroxypropanedialdehyde with N- (4-aminobenzoyl) -L-glutamic acid to obtain corresponding diimine, and reacting with 2,4, 5-triamino-6-hydroxypyrimidine in the presence of sulfite to obtain folic acid; and 3) reacting 2,4, 5-triamino-6-hydroxypyrimidine, 1, 3-trichloroacetone and N- (4-aminobenzoyl) -L-glutamic acid to prepare a crude folic acid product, and performing acid refining and alkali refining on the crude folic acid product to obtain a pure folic acid product (CN 101182323A; CN 102558180A; 511-512 parts of China journal of medical industry 2014,45 (6); hebei Industrial science 2010,27(5), 309-. The raw materials of the method 1), namely alpha and beta-dibromopropionaldehyde, are unstable, have high price and contain harmful bromine elements, so that the method is gradually eliminated. The raw material 1,1,3, 3-tetramethoxy-2-propanol or 2-hydroxypropanedialdehyde of the method 2) is expensive and difficult to prepare, which makes the method difficult to industrially produce. Method 3) is the mainstream method for producing folic acid currently used in industry.

An exemplary synthetic route for method 3) is shown below:

the disadvantage of process 3) is that the solubility of 2,4, 5-triamino-6-hydroxypyrimidine in water is very low, only a small proportion is dissolved in water and the majority is still present in solid form. As the reaction proceeds, the starting 2,4, 5-triamino-6-hydroxypyrimidine gradually dissolves. However, the folic acid which is a product generated at the same time is not easily dissolved in water and is precipitated in the form of solid. This results in the possibility of solid particles of folic acid encapsulating unreacted 2,4, 5-triamino-6-hydroxypyrimidine. The coated 2,4, 5-triamino-6-hydroxypyrimidine cannot continue to react. This results in a lower yield of the process. The overall yield of the process is about 50-70%. In addition, the amount of waste water produced by the process is large. About 100 tons of wastewater are generated per 1 ton of folic acid produced in industry. There have been methods for treating folic acid waste water, such as treating waste water by adsorption and decolorization with a resin, but the method consumes a high cost of resin and the salt content in the aqueous solution is increasing with continuous recycling (CN 101323614).

SUMMERY OF THE UTILITY MODEL

The utility model discloses a new installation of resource cyclic utilization's angle development. The utility model relates to a coproduction device of folic acid, gypsum, desulfurizer and/or denitration agent.

As is well known in the art, the folic acid production wastewater comprises wastewater generated in each stage of folic acid production, such as crude wastewater, acid refining wastewater and alkali refining wastewater. The utility model discloses deposit the sulfate radical ion in folic acid waste water with the form of calcium sulfate (gypsum). The precipitated solid is used as modified gypsum for brick and tile batching, cement stirring coagulant and ground cement mixture. The utility model discloses the discovery, folic acid waste water still can be used to produce desulfurization water agent. The desulfurization water agent can realize improved desulfurization efficiency. The desulfurization water agent is particularly advantageous for removing sulfur oxides (SOx) in flue gas (such as flue gas of a novel dry cement kiln or flue gas of a brick kiln). In addition, folic acid waste water can also be used for producing denitration aqua. The aqueous denitration agent is particularly advantageous for removing nitrogen oxides (NOx) in flue gas (such as flue gas of a novel dry cement kiln or flue gas of a tile kiln). The folic acid production wastewater described herein includes wastewater produced in each stage of folic acid production, such as crude wastewater, acid refining wastewater, alkali refining wastewater, or a combination thereof; also comprises liquid obtained after the folic acid production wastewater is further treated, such as liquid after gypsum is separated.

In one aspect, the present invention relates to the following sections.

Folic acid production section

The folic acid production section comprises the steps of:

a) and (3) crude product production: reacting 2,4, 5-triamino-6-hydroxypyrimidine or a salt thereof, 1, 3-trihaloacetone and N- (4-aminobenzoyl) -L-glutamic acid in a reactor to generate folic acid, and separating by filtering (such as pressure filtration) to obtain a folic acid crude product and a crude product wastewater;

b) acid refining: adding the folic acid crude product into an acidic aqueous solution to obtain an acidic aqueous solution containing folic acid, adding water into the acidic aqueous solution containing folic acid to separate out acid-refined folic acid from the solution, and filtering and separating to obtain acid-refined folic acid and acid-refined wastewater.

c) Alkali refining: adding the folic acid refined by acid into an alkaline aqueous solution to obtain an alkaline aqueous solution containing folic acid, adding activated carbon or diatomite into the alkaline aqueous solution containing folic acid to perform adsorption decoloration, filtering and collecting filtrate, adjusting the pH value of the filtrate to acidity (preferably pH is 2-5) by acid to separate folic acid refined by alkali from the filtrate, and filtering and separating to obtain folic acid refined by alkali and alkali refined wastewater.

The salt of 2,4, 5-triamino-6-hydroxypyrimidine in the above step a may be 2,4, 5-triamino-6-hydroxypyrimidine sulfate, 2,4, 5-triamino-6-hydroxypyrimidine hydrochloride, 2,4, 5-triamino-6-hydroxypyrimidine nitrate, 2,4, 5-triamino-6-hydroxypyrimidine phosphate, or a combination thereof. The 1,1, 3-trihaloacetone can be 1,1, 3-trichloroacetone, 1, 3-tribromoacetone, or a combination thereof. Step a may employ water, alcohol, or a combination thereof as a solvent. The alcohol comprises methanol, ethanol, ethylene glycol, glycerol, or a combination thereof. If water and alcohol are used as the solvent, the water and alcohol may be mixed in any ratio. When an alcohol solvent is used, the resulting waste stream is still referred to herein as waste water. When the wastewater herein contains an alcohol, the wastewater can still be used to produce gypsum, a water-based desulfurization agent, or a water-based denitrification agent according to the methods herein. In some embodiments, a reducing agent such as sodium metabisulfite may be added to avoid oxidation of the 2,4, 5-triamino-6-hydroxypyrimidine or its salt before and during the reaction.

The acidic aqueous solution of step b comprises an aqueous solution comprising sulfuric acid.

The basic aqueous solution of step c comprises an aqueous solution comprising sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, or a combination thereof.

Desulfurizing agent production section

And (2) compounding the folic acid production wastewater (crude product wastewater, acid refining wastewater, alkali refining wastewater or a combination thereof) with a desulfurization compound agent comprising sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide or a combination thereof to obtain the desulfurization aqueous solution. The volume-weight ratio of the folic acid production wastewater to the desulfurization mixture is 100: 1-100: 20.

In another aspect, the present invention relates to the following sections.

Folic acid production section

The folic acid production section comprises the steps of:

Denitration water agent production section

And compounding the folic acid production wastewater (crude wastewater, acid refined wastewater, alkali refined wastewater or a combination thereof) with a denitration compound agent comprising urea, ammonia water or a combination thereof to obtain the novel dry-process cement kiln flue gas denitration aqueous solution. The volume-weight ratio of the folic acid production wastewater to the denitration mixture is 100: 1-100: 20.

In another aspect, the present invention relates to the following sections.

Folic acid production section

The folic acid production section comprises the steps of:

The salt of 2,4, 5-triamino-6-hydroxypyrimidine in the above step a may be 2,4, 5-triamino-6-hydroxypyrimidine sulfate, 2,4, 5-triamino-6-hydroxypyrimidine hydrochloride, 2,4, 5-triamino-6-hydroxypyrimidine nitrate, 2,4, 5-triamino-6-hydroxypyrimidine phosphate, or a combination thereof. The 1,1, 3-trihaloacetone can be 1,1, 3-trichloroacetone, 1, 3-tribromoacetone, or a combination thereof. Step a may employ water, alcohol, or a combination thereof as a solvent. The alcohol comprises methanol, ethanol, ethylene glycol, glycerol, or a combination thereof. If water and alcohol are used as the solvent, the water and alcohol may be mixed in any ratio. When an alcohol solvent is used, the resulting waste stream is still referred to herein as waste water. When the wastewater contains alcohol, the wastewater can still be used for producing gypsum, a water desulfurization agent and a water denitration agent according to the method. In some embodiments, a reducing agent such as sodium metabisulfite may be added to avoid oxidation of the 2,4, 5-triamino-6-hydroxypyrimidine or its salt before and during the reaction.

Gypsum production section

Contacting the crude wastewater, acid refining wastewater, and/or alkali refining wastewater with calcium oxide, calcium carbonate, calcium hydroxide, or a combination thereof to obtain a slurry. The slurry pH is adjusted to alkaline to precipitate solids (the component is calcium sulfate, i.e. gypsum). Isolating the solid. The solids are subjected to optional washing, dewatering and drying steps to obtain a gypsum product. Collecting the liquid after separating the gypsum. The separation comprises pressure filtration.

The calcium oxide, calcium carbonate, or calcium hydroxide may be in various forms such as solids, solutions, emulsions, suspensions, slurries, and the like.

The liquid after gypsum separation can be used for producing a desulfurization water agent.

Desulfurizing agent production section

And (3) compounding the folic acid production wastewater (crude product wastewater, acid refining wastewater, alkali refining wastewater, liquid after gypsum separation or a combination thereof) with a desulfurization compound agent comprising sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide or a combination thereof to obtain a desulfurization aqueous solution. The volume-weight ratio of the folic acid production wastewater to the desulfurization mixture is 100: 1-100: 20.

In another aspect, the present invention relates to the following sections.

Folic acid production section

The folic acid production section comprises the steps of:

Gypsum production section

The liquid after gypsum separation can be used for producing a denitration water agent.

Denitration water agent production section

And compounding the folic acid production wastewater (crude product wastewater, acid refined wastewater, alkali refined wastewater, liquid after gypsum separation or a combination thereof) with a denitration compound agent comprising urea, ammonia water or a combination thereof to obtain the novel dry-process cement kiln flue gas denitration aqueous solution. The volume-weight ratio of the folic acid production wastewater to the denitration mixture is 100: 1-100: 20.

In a more preferred aspect, the present invention relates to the following production sections.

Folic acid production section

The folate production segment described herein comprises the following steps:

Gypsum production section

Contacting the crude wastewater, acid refining wastewater, and/or alkali refining wastewater described herein with calcium oxide, calcium carbonate, calcium hydroxide, or a combination thereof to obtain a slurry. The slurry pH is adjusted to alkaline to precipitate solids (the component is calcium sulfate, i.e. gypsum). Isolating the solid. The solids are subjected to optional washing, dewatering and drying steps to obtain a gypsum product. Collecting the liquid after separating the gypsum. The separation comprises pressure filtration.

The liquid after gypsum separation can be used for producing a desulfurization water agent and/or a denitration water agent.

Desulfurizing agent production section

And (2) compounding a part of the folic acid production wastewater (crude product wastewater, acid refined wastewater, alkali refined wastewater, liquid after gypsum separation or a combination thereof) with a desulfurization compound agent comprising sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide or a combination thereof to obtain the novel dry-process cement kiln flue gas desulfurization aqueous solution. The volume-weight ratio of the folic acid production wastewater to the desulfurization mixture is 100: 1-100: 20.

Denitration water agent production section

And compounding the other part of the folic acid production wastewater (crude wastewater, acid refined wastewater, alkali refined wastewater, liquid after gypsum separation or a combination thereof) with a denitration compound agent comprising urea, ammonia water or a combination thereof to obtain the novel dry-process cement kiln flue gas denitration water aqua. The volume-weight ratio of the folic acid production wastewater to the denitration mixture is 100: 1-100: 20.

In one aspect, this document relates to a co-production plant for producing folic acid, gypsum, a desulfurizing agent, and a denitrating agent, comprising:

1) an apparatus for producing folic acid, the apparatus comprising the following units:

a) a crude folic acid production unit, which comprises a folic acid production module and a folic acid separation module,

the folic acid production module is used for reacting 2,4, 5-triamino-6-hydroxypyrimidine or salt thereof, 1, 3-trihaloacetone and N- (4-aminobenzoyl) -L-glutamic acid to generate a folic acid crude product;

the folic acid separation module is used for separating folic acid to provide crude folic acid and crude folic acid wastewater;

b) an acid refining unit including an acid dissolving module and a folic acid separating module,

the acid dissolving module is used for mixing the crude folic acid and the acid aqueous solution to provide the acid aqueous solution containing folic acid,

the folic acid separation module is used for separating the folic acid refined by acid to provide folic acid refined by acid and acid refined wastewater;

c) an alkali refining unit comprising an alkali dissolution module and a folic acid separation module;

the alkaline solubilization module for mixing the acid refined folic acid and an alkaline aqueous solution to provide an alkaline aqueous solution containing folic acid,

the folic acid separation module is used for separating the folic acid refined by alkali so as to provide the folic acid refined by alkali and the alkali refined wastewater;

2) an apparatus for producing gypsum comprising a gypsum production unit, a gypsum separation unit, and a gypsum refining unit,

the gypsum production unit includes a mixing module and a precipitation module,

the mixing module is used for mixing the crude product wastewater, the acid refining wastewater and/or the alkali refining wastewater with calcium oxide, calcium carbonate, calcium hydroxide or the combination thereof to obtain slurry,

the precipitation module is used for adjusting the pH value of the slurry by providing materials to precipitate gypsum from the slurry;

the gypsum separation unit is used for separating the gypsum to provide gypsum and liquid after the gypsum is separated;

the gypsum refining unit is used for carrying out refining treatment including dehydration and drying on the gypsum to provide refined gypsum;

3) the equipment for producing the desulfurizer comprises a desulfurizer mixing module,

the desulfurizer mixing module is used for mixing a part of the liquid after gypsum separation with a desulfurization mixture agent comprising sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide or a mixture of two or more of the sodium carbonate, the sodium bicarbonate, the sodium hydroxide, the potassium carbonate, the potassium bicarbonate and the potassium hydroxide to provide a desulfurizer; and

4) the equipment for producing the denitrifier comprises a denitrifier mixing module,

the denitration agent mixing module is used for mixing the other part of the liquid after the gypsum is separated with a denitration compound agent comprising urea, ammonia water or a mixture of urea and ammonia water to provide a denitration agent.

In a preferred embodiment, the apparatus for producing folic acid further comprises a storage unit for storing the crude wastewater, the acid purification wastewater, the alkali purification wastewater, or a mixture thereof.

In one aspect, this document relates to a co-production plant for producing folic acid, gypsum, and a desulfurizing agent, comprising:

the gypsum production unit includes a mixing module and a precipitation module,

the gypsum refining unit is used for carrying out refining treatment including dehydration and drying on the gypsum to provide refined gypsum; and

the desulfurizer mixing module is used for mixing the liquid after gypsum separation with a desulfurization mixture agent comprising sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide or a mixture of two or more of the foregoing to provide a desulfurizer.

In one aspect, this document relates to a co-production plant for producing folic acid, gypsum, a denitrifier, comprising:

the gypsum production unit includes a mixing module and a precipitation module,

3) the equipment for producing the denitrifier comprises a denitrifier mixing module,

the denitration agent mixing module is used for mixing the liquid after the gypsum is separated with a denitration compound agent comprising urea, ammonia water or a mixture of urea and ammonia water to provide a denitration agent.

In one aspect, this document relates to a co-production plant for producing folic acid, a desulfurizing agent, and a denitrating agent, comprising:

2) the equipment for producing the desulfurizer comprises a desulfurizer mixing module,

the desulfurizer mixing module is used for mixing a part of the crude wastewater, the acid refining wastewater and/or the alkali refining wastewater with a desulfurization mixture agent comprising sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide or a mixture of two or more of the foregoing to provide a desulfurizer; and

the denitrifier mixing module is used for mixing the other part of the crude wastewater, the acid refining wastewater and/or the alkali refining wastewater with a denitrifier compound agent comprising urea, ammonia water or a mixture thereof so as to provide a denitrifier.

In one aspect, this document relates to a co-production apparatus for producing folic acid and a desulfurizing agent, comprising:

the folic acid separation module is used for separating the folic acid refined by alkali so as to provide the folic acid refined by alkali and the alkali refined wastewater; and

the desulfurizer mixing module is used for mixing a part of the crude wastewater, the acid refining wastewater and/or the alkali refining wastewater with a desulfurization mixture comprising sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide or a mixture of two or more of the foregoing to provide a desulfurizer.

In one aspect, this document relates to a co-production plant for producing folic acid and a denitrifier, comprising:

2) the equipment for producing the denitrifier comprises a denitrifier mixing module,

In one embodiment, the folic acid production module in the crude folic acid production unit comprises a reactor with a corrosion resistant liner. The dissolving modules of the acid refining unit and the alkali refining unit comprise a container with a stirring device, and the container preferably comprises a corrosion-resistant lining. The mixing module of the gypsum production unit comprises a vessel with stirring means, which preferably comprises a corrosion-resistant lining. The desulfurizer mixing module comprises a vessel with a stirring device, preferably comprising a corrosion-resistant liner. The denitrifier mixing module comprises a vessel with stirring means, which preferably comprises a corrosion-resistant lining. In any of the preceding embodiments, the corrosion resistant inner liner comprises a polytetrafluoroethylene, titanium alloy, ceramic, glass, enamel, or the like inner liner. The various devices, units, modules described herein may be integrated into one reactor/vessel as desired.

The volume-weight ratio of the folic acid production wastewater to the denitration compound agent is the ratio of the amount of folic acid wastewater in liters to the amount of the denitration compound agent in kilograms. The volume to weight ratio may be in the range of 100:1 to 100:20, or any ratio or combination thereof, for example 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100: 20.

The volume-weight ratio of the folic acid production wastewater to the desulfurization compound agent refers to the ratio of the amount of the folic acid wastewater in liters to the amount of the desulfurization compound agent in kilograms. The volume to weight ratio may be in the range of 100:1 to 100:20, or any ratio or combination thereof, for example 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100: 20.

In the gypsum production section described herein, the gypsum is subjected to separation (e.g., filter-press separation, filter separation) and optionally a water wash step, with the liquids after gypsum separation including both the direct filtrate and the subsequent water wash. In some embodiments herein, the post-gypsum separation liquid and the post-gypsum separation filtrate can be used interchangeably.

The crude product wastewater refers to any wastewater generated in the crude product production link.

The acid refining wastewater refers to any wastewater generated in the acid refining link.

The alkali refining wastewater refers to any wastewater generated in the alkali refining link.

The desulfurization water agent can improve desulfurization efficiency. The desulfurization water agent can be sprayed by a spray gun, and is convenient to use. The aqueous denitration agent can also achieve good denitration efficiency. The denitration water agent can be sprayed by a spray gun, and is convenient to use.

The desulfurization water agent described herein may also be combined with further known catalysts, desulfurization agents. The further desulfurization catalyst comprises a catalyst comprising iron, manganese, vanadium, titanium, cerium, molybdenum, lithium, or a combination thereof. The further desulfurization catalyst may be a metallurgical slag containing iron, manganese, vanadium, titanium, cerium, molybdenum, lithium, or combinations thereof, or a commercially available catalyst. In one embodiment, the further catalyst comprises titanium dioxide, cerium dioxide, manganese dioxide, vanadium pentoxide, lithium hydroxide, and the like. The further desulfurizing agent comprises calcium hydroxide, calcium oxide, magnesium oxide, iron oxide and the like.

Possible chemical reactions involved in the desulfurization described herein are as follows:

2NaOH+SO₂→Na₂SO₃+H₂O

Na₂SO₃+SO₂+H₂O→2NaHSO₃

Na₂SO₃+1/2O₂→Na₂SO₄

NaHSO₃+1/2O₂→NaHSO₄

Ca(OH)₂+Na₂SO₃→2NaOH+CaSO₃

Ca(OH)₂+2NaHSO₃→Na₂SO₃+CaSO₃+2H₂O

2NaOH+SO₃→Na₂SO₄+H₂O

2KOH+SO₃→K₂SO₄+H₂O

Ca(OH)₂+Na₂SO₄→2NaOH+CaSO₄

CaO+SO₃→CaSO₄

Ca(OH)₂+SO₃→CaSO₄+H₂O

MgO+H₂O→Mg(OH)₂

Mg(OH)₂+SO₃→MgSO₄+H₂O

Fe₂O₃+3SO₃→Fe₂(SO₄)₃

possible chemical reactions involved in the denitrification described herein are as follows:

organic carbon denitration:

CxHyOz→(x-z)C+z CO+y/2H₂

2H₂+2NO→N₂+2H₂O

2NOx+x C→N₂+x CO₂

2NOx+2x C→N₂+2x CO

2NOx+2x CO→N₂+2x CO₂

organic amine denitration:

CxHyOzN_m→(x-z)C+z CO+(y-3)/2H₂+NH₃

2H₂+2NO→N₂+2H₂O

2NOx+x C→N₂+x CO₂

2NOx+2x C→N₂+2x CO

2NOx+2x CO→N₂+2x CO₂

4NO+4NH₃+O₂→4N₂+6H₂O

2NO₂+4NH₃+O₂→3N₂+6H₂O

the novel dry cement production method is a modern cement production method taking suspension preheating and kiln outside decomposition technologies as the core, and is a cement production method generally adopted in China. The apparatus used in the new dry cement production process typically includes components such as rotary kilns, decomposers, etc. The production line of the novel dry-method cement kiln is very large in size, and sulfur and nitrogen containing pollutants can be generated in a plurality of devices or production links. Therefore, the flue gas of the novel dry-method cement kiln needs to be subjected to desulfurization and denitration treatment so as to meet the emission environment-friendly requirement.

And a desulfurization water agent and a denitration water agent can be applied to the position between the outlet of the decomposing furnace and the inlet of the lowest stage cyclone. The position between the outlet of the decomposing furnace and the inlet of the lowest stage cyclone can be the descending part of the connecting air pipe between the outlet of the decomposing furnace and the lowest stage cyclone. The position between the outlet of the decomposing furnace and the inlet of the lowest stage cyclone can also be the inlet part of the lowest stage cyclone. The lowest stage of cyclone is the lowest stage of cyclone from bottom to top in the first stage or the multi-stage cyclones. For example, the lowest stage cyclone of the five-stage cyclone is a C5 cyclone, the lowest stage cyclone of the six-stage cyclone is a C6 cyclone, and so on. The decomposing furnace is connected with the lowest stage cyclone cylinder through a connecting air pipe. The connecting air pipe can be in any shape determined according to actual conditions. Typically, the connecting duct comprises an ascending portion and a descending portion. And the ascending part of the connecting air pipe is connected with the outlet of the decomposing furnace and used for leading out gas. The downstream part of the connecting air pipe is connected with the upstream part and the inlet of the lowest stage of cyclone and is used for guiding gas into the cyclone. The ascending portion and the descending portion are intended to indicate that gas flows first through the ascending portion and then through the descending portion, and are not intended to define the gas flow direction in other meanings. In one embodiment, the connecting duct is curved, having a shape with a middle portion higher than one or both of the ends, such as an inverted U-shape or an n-shape. In this case, the upward flow portion also means a portion where the gas travels upward, and the downward flow portion also means a portion where the gas travels downward. The furnace outlet is also referred to herein as the burnout zone. Or a desulfurization water agent and a denitration water agent can be applied to the connecting air pipes between the air ducts of all stages.

The desulfurization water agent can also be applied to a connecting air pipe between a three-stage cyclone and a two-stage cyclone or a connecting air pipe between the two-stage cyclone and the one-stage cyclone.

The aqueous desulfurization agent described herein may be combined with further desulfurization powder, which may be added, for example, at the chute between the raw meal homogenizing silo and the kiln inlet elevator. The desulfurization powder can also be directly added into a kiln elevator. Desulfurization as used herein refers to the removal of Sulfur Oxides (SO) from flue gases_x)。

The utility model discloses denitration water agent can be applyed in the blast connection pipe department between the export of dore furnace or dore furnace to five-stage cyclone entry. Denitration as used herein refers to the removal of Nitrogen Oxides (NO) from flue gas_X)。

When the composite material is used for a brick kiln, a desulfurization water agent and a denitration water agent can be applied to a flue of the brick kiln.

The "position" described herein refers to a position where the desulfurization water agent and the denitration water agent are applied, and may be used interchangeably with the "spraying position".

In one embodiment of the present invention, the desulfurization water agent and the denitration water agent are applied by spray guns (such as single-fluid spray guns or two-fluid spray guns). In one embodiment of the present invention, a two-fluid spray gun is used to atomize the aqueous denitration agent into droplets of <10 μm, from which the aqueous denitration agent is sprayed. In the utility model, the operations of spraying, throwing, spraying, applying and adding can be interchanged.

In one embodiment, the present invention may utilize multiple/multiple layer lances at the injection site. The utility model discloses a multilayer spray gun overall arrangement (the preferred certain angle that staggers between each layer spray gun) forms the full coverage, evenly spouts and adds, improves the utilization efficiency of desulfurization water agent, denitration water agent.

The denitration water agent is used in an amount of 0.01 to 0.8 wt% (e.g., 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 wt%) of the feeding amount of the cement raw material. The utility model discloses flue gas denitration efficiency that realizes can reach more than 70%, for example 71%, 72%, 73%, 74%, 75%.

The utility model discloses in, denitration efficiency ═ 100% in the background concentration before (the denitration before the background concentration-after-denitration emission concentration)/denitration before.

The desulfurization water agent is used in an amount of 0.01 to 1.0 wt% (e.g., 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 wt%) based on the feeding amount of the cement raw material. The flue gas desulfurization efficiency of the utility model can reach more than 90%, for example 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%.

The utility model discloses in, desulfurization efficiency ═ background concentration before the desulfurization-emission concentration behind the desulfurization)/background concentration before the desulfurization 100%.

Also provided herein is a method for co-producing folic acid, gypsum, an aqueous desulfurization agent, and/or an aqueous denitration agent, the method comprising a combination of two or more of the foregoing folic acid production section, gypsum production section, aqueous desulfurization agent production section, and/or aqueous denitration agent production section.

Unless otherwise specified, percentages, ratios, proportions, amounts, or parts of the present invention are by weight. The concentration of the utility model is weight concentration.

The temperature unit "degree" of the utility model refers to degree centigrade.

The desulfurization water agent and/or the denitration water agent refer to the desulfurizer and/or the denitration agent in a liquid state prepared according to the utility model.

For the additionally added desulfurizing agent/denitrifying agent, it is referred to herein as desulfurizing powder/denitrifying powder if it is in a powdery state, and also referred to as desulfurizing water agent/denitrifying water agent if it is also in a liquid state.

In this context, filtrate and slurry may be used interchangeably. The term filtrate or slurry is non-limiting and is intended to indicate that reference herein is made to a liquid and not to limit the actual state of the liquid.

Drawings

FIG. 1: the present invention is one non-limiting exemplary embodiment.

Description of the reference numerals

1. Equipment for producing folic acid

2. Apparatus for producing gypsum

3. Equipment for producing desulfurizing agent

4. A equipment for producing denitrifier

Detailed Description

For a better understanding of the present invention, the contents of the present invention will be further described below with reference to the following examples, but the present invention is not limited to the following examples. The experimental operations described in the following examples are all routine operations unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.

Example 1

1) Folic acid production section

a) And (3) crude product production: in a reaction kettle with a stirring device and a polytetrafluoroethylene lining, 20 liters of water and N- (4-aminobenzoyl) -L-glutamic acid (1.33 kg) are mixed, heated to 60 ℃ for dissolution, and then cooled to 40-42 ℃. Sodium metabisulfite (0.95 kg) was added with stirring before no precipitate appeared and dissolved. 1,1, 3-trichloroacetone (1.21 kg) was added thereto, and the reaction was continued with stirring for 0.5 hour, and then 2,4, 5-triamino-6-hydroxypyrimidine sulfate (1.195 kg) was added thereto and the reaction was continued at 38 ℃ for 0.5 hour. And then maintaining the pH value to be 2.5-3.0 by using a 10% sodium carbonate solution until the pH value is stabilized at 3.5. Then, the reaction solution was cooled to room temperature after 1 hour of heat preservation, and the reaction solution was filtered, and the filter cake was washed with water (5 liters) and then dried by suction to obtain 2.0 kg of a crude folic acid product with a yield of 91%. The filtrate was collected as crude wastewater.

b) Acid refining: adding the folic acid crude product into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding 10 liters of 25 percent sulfuric acid aqueous solution, and stirring until the folic acid crude product is dissolved. Then pouring the mixture into 120 liters of 35 ℃ water to immediately separate out light yellow solid, stirring the solution for about 10min at 35 ℃ until the solution becomes turbid, completely crystallizing, standing, performing suction filtration, washing a filter cake with distilled water, and performing suction drying to obtain 1.8 kg of acid refined folic acid. And collecting the filtrate as acid refining wastewater.

c) Alkali refining: adding the acid refined folic acid into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding distilled water with the weight about 10 times of the wet weight of the acid refined product, heating to 80 ℃, stirring, adjusting the pH of the solution to 9-9.5 by using a 10% sodium hydroxide aqueous solution, stirring until the solution is completely dissolved, adding active carbon (the weight is 0.22% of the ratio of the acid refined folic acid to the acid refined folic acid), carrying out heat preservation and decolorization, carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate to 2.5-3 by using 30% sulfuric acid at 80 ℃, carrying out heat preservation for 10 minutes, carrying out suction filtration while the solution is hot, washing a filter cake to be neutral by using cold water, and carrying out low-temperature drying to obtain 1.53. Collecting the filtrate as alkali refining wastewater.

2) Gypsum production section

And (3) combining the crude wastewater, the acid refined wastewater and the alkali refined wastewater to obtain 82 liters of mixed liquor, adding the mixed liquor into a reaction tank with a stirring device and a polytetrafluoroethylene lining, adding calcium oxide solid to adjust the pH value to 10, filtering insoluble substances, washing the insoluble substances with water, and drying the insoluble substances to obtain 6.5 kilograms of solid. The detection shows that the purity of the calcium sulfate is more than 95%. The resulting gypsum-separated filtrate, which contained N- (4-aminobenzoyl) -L-glutamic acid and 2,4, 5-triamino-6-hydroxypyrimidine, had a volume of 125 liters, a Chemical Oxygen Demand (COD) of 28420, and an ammonia nitrogen content of 138mg/L, was combined.

And equally dividing the filtrate after gypsum separation into two parts. One part is used for producing a desulfurization water agent, and the other part is used for producing a denitration water agent.

3) Desulfurizing agent production section

Adding 62.5 liters of filtrate after gypsum separation into a reaction tank with a stirring device and a polytetrafluoroethylene lining, then adding 1.5 kilograms of sodium carbonate solid, and stirring and mixing to obtain the desulfurization water agent.

4) Denitration water agent production section

Adding 62.5 liters of filtrate after gypsum separation into a reaction tank with a stirring device and a polytetrafluoroethylene lining, then adding 6 kilograms of urea, and stirring and mixing to obtain the denitration aqueous solution.

Example 2

1) Folic acid production section

a) And (3) crude product production: in a reaction kettle with a stirring device and a polytetrafluoroethylene lining, 20 liters of water and N- (4-aminobenzoyl) -L-glutamic acid (1.33 kg) are mixed, heated to 60 ℃ for dissolution, and then cooled to 40-42 ℃. Sodium metabisulfite (0.95 kg) was added with stirring before no precipitate appeared and dissolved. 1,1, 3-trichloroacetone (1.21 kg) was added thereto, and the reaction was continued with stirring for 0.5 hour, and then 2,4, 5-triamino-6-hydroxypyrimidine sulfate (1.195 kg) was added thereto and the reaction was continued at 38 ℃ for 0.5 hour. And then maintaining the pH value to be 2.5-3.0 by using a 10% sodium carbonate solution until the pH value is stabilized at 3.5. Then, the temperature was maintained for 1 hour, the reaction solution was cooled to room temperature, filtered, and the filter cake was washed with water (5L) and then dried to obtain 2.02 kg of crude folic acid in 92% yield. The filtrate was collected as crude wastewater.

b) Acid refining: adding the folic acid crude product into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding 10 liters of 25 percent sulfuric acid aqueous solution, and stirring until the folic acid crude product is dissolved. Pouring into 120 liters of 35 ℃ water, immediately precipitating light yellow solid, enabling the solution to become turbid, stirring for about 10min at 35 ℃, completely crystallizing, standing, carrying out suction filtration, washing a filter cake with distilled water, and draining to obtain 1.81 kg of acid refined folic acid. And collecting the filtrate as acid refining wastewater.

c) Alkali refining: adding the acid refined folic acid into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding distilled water with the weight about 10 times of the wet weight of the acid refined product, heating to 80 ℃, stirring, adjusting the pH of the solution to 9-9.5 by using a 10% sodium hydroxide aqueous solution, stirring until the solution is completely dissolved, adding active carbon (the weight is 0.22% of the ratio of the acid refined folic acid to the acid refined folic acid), carrying out heat preservation and decolorization, carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate to 2.5-3 by using 30% sulfuric acid at 80 ℃, carrying out heat preservation for 10 minutes, carrying out suction filtration while the solution is hot, washing a filter cake to be neutral by using cold water, and carrying out low-temperature drying to obtain 1.54. Collecting the filtrate as alkali refining wastewater.

2) Gypsum production section

Mixing the crude wastewater, acid refined wastewater and alkali refined wastewater to obtain 89L mixed solution, adding into a reaction tank with stirring device and polytetrafluoroethylene lining, and adding lime milk (Ca (OH)₂) After adjusting to pH 10, the insoluble matter was filtered, washed with water, and dried to obtain 6.8 kg of a solid. The detection shows that the purity of the calcium sulfate is more than 95%. The resulting gypsum-separated filtrate, which contained N- (4-aminobenzoyl) -L-glutamic acid and 2,4, 5-triamino-6-hydroxypyrimidine, had a volume of 146 liters, a COD of 27666, and an ammonia nitrogen content of 145mg/L, was combined.

3) Desulfurizing agent production section

Adding 73 liters of filtrate after gypsum separation into a reaction tank with a stirring device and a polytetrafluoroethylene lining, then adding 2 kilograms of sodium carbonate solid, and stirring and mixing to obtain the desulfurization water agent.

4) Denitration water agent production section

Adding 73 liters of filtrate after gypsum separation into a reaction tank with a stirring device and a polytetrafluoroethylene lining, then adding 2 kilograms of urea, and stirring and mixing to obtain the denitration aqueous solution.

Example 3

1) Folic acid production section

a) And (3) crude product production: in a reaction kettle with a stirring device and a polytetrafluoroethylene lining, 20 liters of water and N- (4-aminobenzoyl) -L-glutamic acid (1.33 kg) are mixed, heated to 60 ℃ for dissolution, then cooled to 40-42 ℃, and sodium metabisulfite (0.95 kg) is added for dissolution under stirring before precipitates are not generated. 1,1, 3-trichloroacetone (1.01 kg) was added, the reaction was continued for 0.5 hour with stirring, and then 2,4, 5-triamino-6-hydroxypyrimidine hydrochloride (1.186 kg) was added and the reaction was continued at 38 ℃ for 0.5 hour. And (3) maintaining the pH to be 2.5-3.0 by using a 10% sodium carbonate solution until the pH is stabilized at 3.5, preserving the temperature for 1 hour, cooling the reaction solution to room temperature, carrying out suction filtration, washing a filter cake by using water (5 liters), and carrying out suction drying to obtain 1.96 kg of crude folic acid product with the yield of 89%. The filtrate was collected as crude wastewater.

b) Acid refining: adding the folic acid crude product into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding 10 liters of 25 percent sulfuric acid aqueous solution, and stirring until the folic acid crude product is dissolved. Pouring into 120 liters of 35 ℃ water, immediately precipitating light yellow solid, enabling the solution to become turbid, stirring for about 10min at 35 ℃, completely crystallizing, standing, carrying out suction filtration, washing a filter cake with distilled water, and draining to obtain 1.76 kg of acid refined folic acid. And collecting the filtrate as acid refining wastewater.

c) Alkali refining: adding the acid refined folic acid into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding distilled water with the weight about 10 times of the wet weight of the acid refined product, heating to 80 ℃, stirring, adjusting the pH of the solution to 9-9.5 by using a 10% sodium hydroxide aqueous solution, stirring until the solution is completely dissolved, adding active carbon (the weight is 0.22% of the ratio of the acid refined folic acid to the acid refined folic acid), carrying out heat preservation and decolorization, carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate to 2.5-3 by using 30% sulfuric acid at 80 ℃, carrying out heat preservation for 10 minutes, carrying out suction filtration while the solution is hot, washing a filter cake to be neutral by using cold water, and carrying out low-temperature drying to obtain 1.5. Collecting the filtrate as alkali refining wastewater.

2) Gypsum production section

Mixing the crude wastewater, acid refined wastewater and alkali refined wastewater to obtain 93L mixed solution, adding into a reaction tank with stirring device and polytetrafluoroethylene lining, and adding lime milk (Ca (OH)₂) After adjusting to pH 10, the insoluble matter was filtered, washed with water, and dried to obtain 6.4 kg of a solid. The detection shows that the purity of the calcium sulfate is more than 95%. Combining the resulting gypsum-separated filtrate comprising N- (4-aminobenzoyl) -L-glutamic acid and 2,4, 5-triamino-6-Hydroxypyrimidine, 155L in volume, 29574 in COD and 462mg/L in ammonia nitrogen content.

3) Desulfurizing agent production section

77.5 liters of filtrate after gypsum separation is added into a reaction tank with a stirring device and a polytetrafluoroethylene lining, then 2 kilograms of sodium carbonate solid is added, and the mixture is stirred and mixed to obtain the desulfurization water agent.

4) Denitration water agent production section

77.5 liters of filtrate after gypsum separation is added into a reaction tank with a stirring device and a polytetrafluoroethylene lining, and then 1.9 kilograms of urea is added, stirred and mixed to obtain the denitration aqueous solution.

Example 4

1) Folic acid production section

a) And (3) crude product production: in a reaction kettle with a stirring device and a polytetrafluoroethylene lining, 20 liters of water and N- (4-aminobenzoyl) -L-glutamic acid (1.33 kg) are mixed, heated to 60 ℃ for dissolution, then cooled to 40-42 ℃, and sodium metabisulfite (0.95 kg) is added for dissolution under stirring before precipitates are not generated. Adding 1,1, 3-trichloroacetone (1.01 kg), continuously stirring and continuously reacting for 0.5 hour, then adding 2,4, 5-triamino-6-hydroxypyrimidine nitrate (1.22 kg) and reacting for 0.5 hour at 38 ℃, starting to maintain the pH at 2.5-3.0 by using a 10% sodium carbonate solution until the pH is stabilized at 3.5, starting to keep the temperature for 1 hour, cooling the reaction solution to room temperature, performing suction filtration, washing a filter cake by using water (5 liters), and performing suction filtration to obtain 1.94 kg of crude folic acid, wherein the yield is 88%. The filtrate was collected as crude wastewater.

b) Acid refining:

adding the folic acid crude product into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding 10 liters of 25 percent sulfuric acid aqueous solution, stirring until the folic acid crude product is dissolved, pouring the solution into 120 liters of 35 ℃ water, immediately separating out light yellow solid, stirring for about 10min at 35 ℃ until the solution becomes turbid, completely crystallizing, standing, performing suction filtration, washing a filter cake with distilled water, and performing suction drying to obtain 1.65 kg of acid refined folic acid. And collecting the filtrate as acid refining wastewater.

c) Alkali refining: adding the acid refined folic acid into a reaction kettle with a stirring device and a polytetrafluoroethylene lining, adding distilled water with the weight about 10 times of the wet weight of the acid refined product, heating to 80 ℃, stirring, adjusting the pH of the solution to 9-9.5 by using a 10% sodium hydroxide aqueous solution, stirring until the solution is completely dissolved, adding active carbon (the weight is 0.22% of the ratio of the acid refined folic acid to the acid refined folic acid), carrying out heat preservation and decolorization, carrying out suction filtration while the solution is hot, adjusting the pH of the filtrate to 2.5-3 by using 30% sulfuric acid at 80 ℃, carrying out heat preservation for 10 minutes, carrying out suction filtration while the solution is hot, washing a filter cake to be neutral by using cold water, and carrying out low-temperature drying to obtain 1.32. Collecting the filtrate as alkali refining wastewater.

2) Gypsum production section

Mixing the crude wastewater, acid refined wastewater and alkali refined wastewater to obtain 96L of mixed solution, adding into a reaction tank with stirring device and polytetrafluoroethylene lining, and adding lime milk (Ca (OH)₂) After adjusting to pH 10, the insoluble matter was filtered, washed with water, and dried to obtain 6.7 kg of a solid. The detection shows that the purity of the calcium sulfate is more than 95%. The resulting gypsum-separated filtrate, which contained N- (4-aminobenzoyl) -L-glutamic acid and 2,4, 5-triamino-6-hydroxypyrimidine in a volume of 164 liters, a COD of 29686, and an ammonia nitrogen content of 398mg/L, was combined.

3) Desulfurizing agent production section

And (2) adding 82 liters of filtrate after gypsum separation into a reaction tank with a stirring device and a polytetrafluoroethylene lining, then adding 2 kilograms of sodium carbonate solid, and stirring and mixing to obtain the desulfurization water agent.

4) Denitration water agent production section

And adding 82 liters of filtrate after gypsum separation into a reaction tank with a stirring device and a polytetrafluoroethylene lining, then adding 2 kilograms of urea, and stirring and mixing to obtain the denitration aqueous solution.

Desulfurization and desulfurization in the following examplesThe nitrate tests were all carried out on the same 5000t/d novel dry cement production line located in the Guangdong. The same batch of raw materials and the same production process parameters were used. Therefore, SO in the flue gas before desulfurization and denitration₂The concentration and the NOx concentration are substantially the same.

Example 5: removing sulfur in flue gas

This example was carried out on a 5000t/d new dry cement line located in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. The desulfurization water agent produced in example 1 was sprayed through 4 spray guns disposed at 90 ° intervals on the same plane at the connecting air duct between the secondary cyclone and the primary cyclone, and atomized into a mist by high-pressure air<Droplets of 10 μm or less. The spraying amount of the desulfurizing agent is 1200L/h (about 0.3 percent of the feeding amount of the cement raw material), and the SO in the flue gas is obtained after 20 minutes₂The concentration can be stabilized at 100mg/m³And the cement kiln flue gas desulfurization efficiency is 91%.

Example 6: removing sulfur in flue gas

This example was carried out on a 5000t/d new dry cement line located in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. The aqueous desulfurization agent produced in example 2 was used. Spraying a desulfurization water agent at the position of a connecting air pipe between the secondary cyclone and the primary cyclone through 4 spray guns which are arranged on the same plane at intervals of 90 degrees, and atomizing the desulfurization water agent into powder by using high-pressure air<Droplets of 10 μm or less. The spraying amount of the desulfurizing agent is 1200L/h (about 0.3 percent of the feeding amount of the cement raw material), and the SO in the flue gas is obtained after 20 minutes₂The concentration can be stabilized at 80mg/m³And the cement kiln flue gas desulfurization efficiency is 93 percent.

Example 7: removing sulfur in flue gas

This example was carried out on a 5000t/d new dry cement line located in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. The aqueous desulfurization agent produced in example 3 was used. Spraying a desulfurization water agent at the connecting air pipe between the secondary cyclone and the primary cyclone through 4 spray guns arranged on the same plane at intervals of 90 degrees, and utilizing high-pressure air to spray the desulfurization water agentAtomization into<Droplets of 10 μm or less. The spraying amount of the desulfurizing agent is 1200L/h (about 0.3 percent of the feeding amount of the cement raw material), and the SO in the flue gas is obtained after 20 minutes₂The concentration can be stabilized at 90mg/m³And the cement kiln flue gas desulfurization efficiency is 91%.

Comparative example 8

This comparative example was carried out on a 5000t/d new dry cement line located in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. A commercial ammonia-and alkali-containing desulfurization water agent (ammonia 10 wt% and sodium carbonate 5 wt%) was used as a comparative desulfurization water agent. Spraying comparative desulfurization water agent on the connecting air pipe between the secondary cyclone and the primary cyclone through 4 spray guns arranged on the same plane at intervals of 90 degrees, and atomizing the desulfurization water agent into<Droplets of 10 μm or less. The injection amount of the desulfurization water agent is 1200L/h (about 0.3 percent of the feeding amount of the cement raw material), and the SO in the flue gas is obtained after 20 minutes₂The concentration can be stabilized at 300mg/m³And the cement kiln flue gas desulfurization efficiency is 73%.

Comparative example 9

The comparative example was carried out on a 5000t/d new dry cement production line located in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. A desulfurization water agent containing organic amine and sodium carbonate is used as a comparative desulfurization water agent, and the composition of the desulfurization water agent is 20 wt% of ethylenediamine and 5 wt% of sodium carbonate. Spraying comparative desulfurization water agent on the connecting air pipe between the secondary cyclone and the primary cyclone through 4 spray guns arranged on the same plane at intervals of 90 degrees, and atomizing the desulfurization water agent into<Droplets of 10 μm or less. The injection amount of the desulfurization water agent is 1200L/h (about 0.3 percent of the feeding amount of the cement raw material), and the SO in the flue gas is obtained after 20 minutes₂The concentration can be stabilized at 250mg/m³And the cement kiln flue gas desulfurization efficiency is 77%.

Example 10: removing nitrogen oxides (NOx) in flue gas

This example was carried out on a 5000t/d new dry cement line located in the Guangdong. The actual monitoring of the concentration of NOx in the flue gas is 800mg/m³. The aqueous denitration agent produced in example 2 was used. Spraying denitration water agent on the outlet of the decomposing furnace through 4 spray guns arranged on the same plane at intervals of 90 degrees, and utilizing high-pressure airAtomizing denitration water into<Droplets of 10 μm or less. The spraying amount of the denitration water agent is 800L/h (about 0.2 percent of the feeding amount of the cement raw material), and the concentration of NOx in the flue gas can be stabilized at 240mg/m after 10 minutes³And the cement kiln flue gas denitration efficiency is 70%.

Example 11: removing nitrogen oxides (NOx) in flue gas

This example was carried out on a 5000t/d new dry cement line located in the Guangdong. The actual monitoring of the concentration of NOx in the flue gas is 800mg/m³. The aqueous denitration agent produced in example 3 was used. Spraying denitration water agent at outlet of decomposing furnace through 4 spray guns arranged on same plane at intervals of 90 degrees, and atomizing denitration water agent into denitration water agent by using high-pressure air<Droplets of 10 μm or less. The spraying amount of the denitration water agent is 800L/h (about 0.2 percent of the feeding amount of the cement raw material), and the concentration of NOx in the flue gas can be stabilized at 230mg/m after 10 minutes³And the cement kiln flue gas denitration efficiency is 71%.

Example 12: removing nitrogen oxides (NOx) in flue gas

The embodiment is carried out on a 5000t/d novel dry method cement production line positioned in Guangdong, and the actual monitoring of the concentration of NOx in flue gas is 800mg/m³. The aqueous denitration agent produced in example 4 was used. Spraying 4 spray guns arranged at intervals of 90 degrees on the same plane at the outlet of the decomposing furnace with denitration water agent, and atomizing the denitration water agent into denitration water agent by using high-pressure air<Droplets of 10 μm or less. The spraying amount of the denitration water agent is 800L/h (about 0.2 percent of the feeding amount of the cement raw material), and the concentration of NOx in the flue gas can be stabilized at 220mg/m after 10 minutes³And the cement kiln flue gas denitration efficiency is 73%.

Comparative example 13

This comparative example was carried out on a 5000t/d new dry cement line located in the Guangdong. The actual monitoring of the concentration of NOx in the flue gas is 800mg/m³. A commercially available aqueous denitration agent was used: 20% wt ammonia water as a comparative denitration water agent. Spraying contrast denitration water agent on the outlet of the decomposing furnace through 4 spray guns arranged on the same plane at intervals of 90 degrees, and atomizing the denitration water agent into denitration water agent by utilizing high-pressure air<Droplets of 10 μm or less. Compared with the denitration water agent with the spraying amount of 800L/h (about 0.2 percent of the feeding amount of the cement raw material), the concentration of NOx in the flue gas can be stabilized at 250mg/m after 10 minutes³Cement ofThe denitration efficiency of the kiln flue gas is 69%.

Comparative example 14

This comparative example was carried out on a 5000t/d new dry cement line located in the Guangdong. The actual monitoring of the concentration of NOx in the flue gas is 800mg/m³. The urea-containing aqueous denitration agent was used as a comparative aqueous denitration agent and consisted of a 30% wt urea solution. Spraying contrast denitration water agent on the outlet of the decomposing furnace through 4 spray guns arranged on the same plane at intervals of 90 degrees, and atomizing the denitration water agent into denitration water agent by utilizing high-pressure air<Droplets of 10 μm or less. Compared with the denitration water agent spraying amount of 800L/h (about 0.2% of the cement raw material feeding amount), the concentration of NOx in the flue gas can be stabilized at 300mg/m after 10 minutes³And the cement kiln flue gas denitration efficiency is 62.5%.

Example 15: removing sulfur in flue gas

This example was carried out on a 5000t/d new dry cement line located in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. The aqueous desulfurization agent produced in example 2 was used. Spraying a desulfurization water agent at the position of a connecting air pipe between the secondary cyclone and the primary cyclone through 4 spray guns which are arranged on the same plane at intervals of 90 degrees, and atomizing the desulfurization water agent into powder by using high-pressure air<Droplets of 10 μm or less. The spraying amount of the desulfurization water agent is 1200L/h (about 0.3 percent of the feeding amount of cement raw meal). And adding desulfurization powder to the kiln elevator, wherein the desulfurization powder comprises the following components: 80 wt% calcium hydroxide +20 wt% manganese dioxide. The addition amount of the desulfurization powder was 0.5 ton/hr (about 0.12% of the raw cement material feed amount)

SO in flue gas after 20 minutes₂The concentration can be stabilized at 50mg/m³And the cement kiln flue gas desulfurization efficiency is 95%.

Comparative example 16

The method is carried out on a 5000t/d novel dry cement production line in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. A desulfurization water agent containing organic amine and sodium carbonate is used as a comparative desulfurization water agent, and the composition of the desulfurization water agent is 20 wt% of ethylenediamine and 5 wt% of sodium carbonate. Spraying contrast desulfurizing water agent on the connecting air pipe between the secondary cyclone and the primary cyclone through 4 spray guns arranged on the same plane at intervals of 90 degrees, and utilizing high-pressure airThe gas atomizes the desulfurizing water agent into<Droplets of 10 μm or less. The spraying amount of the comparative desulfurization water agent is 1200L/h (about 0.3 percent of the feeding amount of cement raw meal). And adding desulfurization powder to the kiln elevator, wherein the desulfurization powder comprises the following components: 80 wt% calcium hydroxide +20 wt% manganese dioxide. The addition amount of the desulfurization powder was 0.5 ton/hr (about 0.12% of the raw cement material feed amount)

SO in flue gas after 20 minutes₂The concentration can be stabilized at 120mg/m³And the cement kiln flue gas desulfurization efficiency is 89%.

Comparative example 17

This comparative example was carried out on a 5000t/d new dry cement line located in the Guangdong. SO in flue gas₂The actual concentration monitoring is 1100mg/m³. A commercial ammonia-and alkali-containing desulfurization water agent (ammonia 10 wt% and sodium carbonate 5 wt%) was used as a comparative desulfurization water agent. Spraying comparative desulfurization water agent on the connecting air pipe between the secondary cyclone and the primary cyclone through 4 spray guns arranged on the same plane at intervals of 90 degrees, and atomizing the desulfurization water agent into<Droplets of 10 μm or less. The spraying amount of the comparative desulfurization water agent is 1200L/h (about 0.3 percent of the feeding amount of cement raw meal). And adding desulfurization powder to the kiln elevator, wherein the desulfurization powder comprises the following components: 80 wt% calcium hydroxide +20 wt% manganese dioxide. The addition amount of the desulfurization powder was 0.5 ton/hr (about 0.12% of the raw cement material feed amount)

SO in flue gas after 20 minutes₂The concentration can be stabilized at 150mg/m³And the cement kiln flue gas desulfurization efficiency is 86%.

The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting in any way the application. Any simple modification, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention all fall within the scope of the technical solution of the present invention.

Claims

1. The utility model provides a coproduction device of production folic acid, gypsum, desulfurizer and denitrifier which characterized in that includes:

the gypsum production unit includes a mixing module and a precipitation module,

2. The co-production plant according to claim 1, wherein the plant for producing folic acid further comprises a storage unit for storing crude wastewater, acid refined wastewater, alkali refined wastewater, or a mixture thereof.

3. A co-production device for producing folic acid, gypsum and a desulfurizing agent is characterized by comprising:

the gypsum production unit includes a mixing module and a precipitation module,

4. The co-production plant according to claim 3, wherein the plant for producing folic acid further comprises a storage unit for storing crude wastewater, acid refined wastewater, alkali refined wastewater, or a mixture thereof.

5. The utility model provides a coproduction device of production folic acid, gypsum, denitrifier which characterized in that includes:

the gypsum production unit includes a mixing module and a precipitation module,

6. The co-production plant according to claim 5, wherein the plant for producing folic acid further comprises a storage unit for storing crude wastewater, acid refined wastewater, alkali refined wastewater, or a mixture thereof.

7. A coproduction device for producing folic acid, a desulfurizer and a denitrifier is characterized by comprising:

8. The co-production plant according to claim 7, wherein the plant for producing folic acid further comprises a storage unit for storing crude wastewater, acid refined wastewater, alkali refined wastewater, or a mixture thereof.

9. A coproduction device for producing folic acid and a desulfurizer is characterized by comprising:

10. The co-production plant according to claim 9, wherein the plant for producing folic acid further comprises a storage unit for storing crude wastewater, acid refined wastewater, alkali refined wastewater, or a mixture thereof.

11. A coproduction device for producing folic acid and a denitration agent is characterized by comprising:

12. The co-production plant according to claim 11, wherein the plant for producing folic acid further comprises a storage unit for storing crude wastewater, acid refined wastewater, alkali refined wastewater, or a mixture thereof.