CN105859592A - Method for recycling coproduct hydrochloric acid in ADC (azodicarbonamide) foaming agent preparation process - Google Patents
Method for recycling coproduct hydrochloric acid in ADC (azodicarbonamide) foaming agent preparation process Download PDFInfo
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- CN105859592A CN105859592A CN201610460101.6A CN201610460101A CN105859592A CN 105859592 A CN105859592 A CN 105859592A CN 201610460101 A CN201610460101 A CN 201610460101A CN 105859592 A CN105859592 A CN 105859592A
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- hydrazine hydrate
- hydrochloric acid
- foaming agent
- solution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/20—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group the two nitrogen atoms of the functional groups being doubly-bound to each other, e.g. azoformamide
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
Abstract
The invention discloses a method for recycling a coproduct hydrochloric acid in an ADC (azodicarbonamide) foaming agent preparation process. The method comprises the following steps: S1. pretreatment of crude hydrazine hydrate; S2. pretreatment of coproduct hydrochloric acid; S3. neutralizing treatment of primary hydrazine hydrate solution; S4. desalting treatment of secondary hydrazine hydrate solution; S5. preparation of biurea; and S6. preparation of ADC foaming agent. The coproduct hydrochloric acid produced in the step S6 is recycled, and treated by the step S2 to form hydrogen chloride gas; and the hydrogen chloride gas is introduced into the hydrazine hydrate solution in the step S3 to remove abundant sodium carbonate in the hydrazine hydrate solution, thereby implementing the cyclic utilization on the coproduct hydrochloric acid. The method solves the problem of the disposition of the coproduct hydrochloric acid, and avoids the environmental pollution caused by the hydrochloric acid. The sodium carbonate in the hydrazine hydrate solution is treated, and the formed main waste sodium chloride can be discharged to the salt field, so that the ADC foaming agent preparation process is more environment-friendly. The hydrogen chloride treatment technique is simple, and has the advantages of low energy consumption and obvious economic benefits.
Description
Technical field
The present invention relates to producing of ADC foaming agent, be specifically related to a kind of ADC foaming agent and produced
The method in journey, by-product hydrochloric acid recycled.
Background technology
China is hydrazine hydrate production big country, and the 70% of general hydrazine hydrate yield is used to produce ADC
Foaming agent, so China is also the big producing country of ADC foaming agent.
The preparation method of China's hydrazine hydrate is generally urea method.Chemical equation is:
NH2CONH2+NaClO+NaOH→N2H4·H2O+NaCl+Na2CO3,
Urea method can produce substantial amounts of sodium chloride and sodium carbonate by-product during producing hydrazine hydrate,
Therefore the hydrazine hydrate generated is thick hydrazine hydrate.
During being produced ADC foaming agent by hydrazine hydrate, need to make before hydrazine hydrate generation condensation reaction
Thick hydrazine hydrate is converted into essence hydrazine hydrate, so first needing at the thick hydrazine hydrate to urea method generation
Reason, processing procedure need to first pass through pretreatment and is reduced to from about 142g/L by the content of sodium carbonate
The common processing method of sodium carbonate of about 85g/L, remaining about 85g/L be with 98% dense
Sulphuric acid neutralizes, and to remove most sodium carbonate, but it is secondary to generate again sodium sulfate in hydrazine hydrate
Product, therefore still need to continue sodium sulfate byproduct is realized remove impurity, this kind of method dedoping step loaded down with trivial details and
Effect is not thorough, and this is a problem present in ADC foaming agent producing process.
Additionally, there is another problem in ADC foaming agent producing process, use di-
During urea produces ADC foaming agent, first hydrazine hydrate need to generate biruea with urea condensation,
Produced by biruea the most again and obtain ADC foaming agent.Biruea produces the equation of ADC foaming agent
Formula is: NH2CONHCONH2+Cl2→NH2CON=NCONH2+ 2HCl,
The principal product of this reaction is azodicarbonamide, i.e. ADC foaming agent, and by-product is hydrochloric acid,
The processing mode of by-product hydrochloric acid typically used by this part hydrochloric acid through filtration, purification, add pyrolysis
Analysis, freezing except water, except delivering to the PVC device unstripped gas as PVC after water, but in present stage
Conventionally produced in, PVC technique typically matches with chloralkali process, and it is useless that himself produces
Acid has been difficult to process, so without reapplying produced salt in ADC foaming agent producing process
Acid, and during processing the hydrochloric acid that ADC foaming agent produces, the processing procedure consumption of hydrochloric acid
Can be higher, the input cost of unit is the highest, the chlorination to participating in reaction of the PVC device
The prescription of hydrogen is the highest, and hydrogen chloride resolution gas, in order to meet high-quality requirement, first needs to use
Carbon steel filter carries out filtration, purification operation to hydrochloric acid, and the hydrochloric acid after filtration is delivered to resolve again
Tower resolves to hydrogen chloride gas, and analytically in tower, the hydrogen chloride gas of output also needs to continue to use freezing
The operations such as remove impurity, operation is loaded down with trivial details, and real process is difficult to.
Summary of the invention
It is an object of the invention to provide by-product hydrochloric acid in a kind of ADC foaming agent producing process to reclaim
The method utilized, is used for solving in existing ADC foaming agent producing process, it is difficult to thick hydrazine hydrate
In sodium carbonate realize remove impurity, simultaneously also with hydrochloric acid in the ADC foaming agent ultimately generated
Generate, the problem how hydrochloric acid of this generation utilizes.
To achieve these goals, the present invention provides following technical scheme:
A kind of method that in ADC foaming agent producing process, by-product hydrochloric acid recycles, including:
Pre-treatment step S1 of thick hydrazine hydrate: thick hydrazine hydrate is realized pretreatment operation, so that thick water
Closing the carbonate content in hydrazine and be down to 80～90g/L, after thick hydrazine hydrate separates, gained liquid phase is primary
Hydrazine hydrate solution；
Pre-treatment step S2 of by-product hydrochloric acid: by the by-product hydrochloric acid in ADC foaming agent producing process
After filtering out containing a small amount of biruea and ADC, it is preheated to 60～70 DEG C, is then sent to hydrochloric acid
Analytic Tower resolves, to obtain hydrogen chloride gas；
Neutralisation treatment step S3 of primary hydrazine hydrate solution: the hydrogen chloride gas obtained through step S2
It is passed through in the primary hydrazine hydrate solution after step S1 processes, makes hydrogen chloride gas and primary hydrazine hydrate
Sodium carbonate in solution occurs to neutralize reaction, to remove the part carbonic acid in primary hydrazine hydrate solution
Sodium, obtains two grades of hydrazine hydrate solutions that carbonate content is 5～10g/L；
The desalination of two grades of hydrazine hydrate solutions processes step S4: to the two grades of hydrations prepared through step S3
Hydrazine solution is evaporated operation, the sodium chloride that will separate out from two grades of hydrazine hydrate solutions in evaporation process
Crystal isolates two grades of hydrazine hydrate systems, to obtain the essence hydration that concentration of hydrazine hydrate is 55～65g/L
Hydrazine solution；
The forming steps S5 of biruea: the smart hydrazine hydrate solution after step S4 processes is anti-with carbamide
Product biruea should be prepared；
The forming steps S6 of ADC foaming agent: produce, through step S5, the biruea obtained anti-with chlorine
Should generate ADC foaming agent and by-product hydrochloric acid, by-product hydrochloric acid reclaims and continues to use step S2 to process also
It is applied in the subsequent step of step S2.
Preferably, the process in step S2 filtered hydrochloric acid uses carbon steel filter to realize.
Preferably, formed during in step S2, the warm-up operation of hydrochloric acid uses thick hydrazine hydrate preparation process
Hydrothermal solution or step S4 in two grades of hydrazine hydrate solutions during evaporation operation realize heat supply.
Preferably, in step S3, hydrogen chloride gas is passed through primary hydrazine hydrate solution generation and neutralizes reaction
Time, the temperature of primary hydrazine hydrate solution controls to be 75～80 DEG C.
Preferably, the carbon dioxide generated with reaction in step S3 uses blower fan to pump, chilled,
Water cooling and except after water conservancy project sequence, delivering to utilize in the carbonation process of ammonia-soda process preparing soda.
Preferably, step S5 uses acid system to produce with hydrazine hydrate and carbamide for raw material and obtain di-
Urea.
Compared to prior art, by-product hydrochloric acid in ADC foaming agent producing process of the present invention
The method recycled has the advantage that in the ADC foaming agent producing process that the present invention provides
The method that by-product hydrochloric acid recycles, passes through the by-product hydrochloric acid in ADC foaming agent producing process
Form hydrogen chloride gas after process, be passed through in hydrazine hydrate solution, a large amount of to remove in hydrazine hydrate solution
Sodium carbonate so that in the producing process of ADC foaming agent formed main garbage be chlorination
Sodium, has not only processed the whereabouts problem of by-product hydrochloric acid, it is to avoid it is to environment, and
Sodium carbonate in hydrazine hydrate solution is achieved process, and the sodium chloride garbage of formation can drain into salt
Field, therefore, the pollution in the producing process of ADC foaming agent is fallen below minimum by the present invention, makes
Obtain the producing process more environmental protection of ADC foaming agent.Meanwhile, the work of by-product hydrochloric acid in the present invention
With being to remove the sodium carbonate in hydrazine hydrate solution, therefore the purity requirement to hydrogen chloride is the highest, hydrogen chloride
Process technique simply efficient, consume energy low, carry out as PVC unstripped gas compared to traditional approach
Application cost is lower, remarkable in economical benefits.
Accompanying drawing explanation
By reading the detailed description of hereafter preferred implementation, various other advantage and benefit pair
Will be clear from understanding in those of ordinary skill in the art.Accompanying drawing is only used for illustrating preferred implementation
Purpose, and be not considered as limitation of the present invention.In the accompanying drawings:
Fig. 1 shows salt in the ADC foaming agent producing process of a kind of preferred implementation of the present invention
The flow chart of acid recovery Application way.
Detailed description of the invention
The invention provides many applicable creative concepts, this creativeness concept can substantial amounts of body
Now in concrete context.In the specific embodiment described in following embodiments of the present invention
It is only used as the exemplary illustration of the detailed description of the invention of the present invention, and does not constitute the scope of the invention
Limit.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment one
Referring to Fig. 1, the present embodiment provides by-product hydrochloric acid in a kind of ADC foaming agent producing process to return
Receive the method utilized, including:
Pre-treatment step S1 of thick hydrazine hydrate: in the present embodiment, uses urea method to make the thick of formation
In hydrazine hydrate solution, the content of sodium carbonate is 142g/L, and thick hydrazine hydrate is realized pretreatment operation, with
Making the carbonate content in thick hydrazine hydrate be down to 80～90g/L, after thick hydrazine hydrate separates, gained liquid phase is
For primary hydrazine hydrate solution.Above-mentioned pretreatment operation can be freezing method or reaction method, the tool of freezing method
Body operating process carries out cooling process for using low-temperature receiver to thick hydrazine hydrate solution so that it is be cooled to
Between-2～0 DEG C, so that the partial sodium carbonate in thick hydrazine hydrate solution forms washing soda crystallization,
To the thick hydrazine hydrate solid-liquid separation after chilled process, thus isolate washing soda crystal,
To liquid phase be the primary hydrazine hydrate solution that carbonate content is 80～90g/L.Reaction method can be adopted
With generating the chloride of precipitation, such as magnesium chloride, calcium chloride etc., according to thick hydrazine hydrate with sodium carbonate
The content of middle sodium carbonate and the volume of thick hydrazine hydrate calculate the amount of the required reactant used, sodium carbonate
Operating by solid-liquid separation with warp after reactant reaction, it is molten that isolated liquid phase is primary hydrazine hydrate
Liquid, certainly, it is possible to use the mode adding hydrogen chloride in thick hydrazine hydrate solution so that be slightly hydrated
In hydrazine, the content of sodium carbonate reduces between 80～90g/L.
In the present embodiment, thick hydrazine hydrate solution uses the glycol water of room temperature recirculated water and-15 DEG C
It is cooled down step by step so that thick hydrazine hydrate solution self is cooled to 0 DEG C, in the cooling of thick hydrazine hydrate
During, partial sodium carbonate forms washing soda crystallization, by centrifugally operated to chilled process
After thick hydrazine hydrate process, to isolate washing soda crystal, the liquid phase obtained is carbon
Acid sodium content is the primary hydrazine hydrate solution of 85g/L.
Pre-treatment step S2 of by-product hydrochloric acid: by the by-product hydrochloric acid in ADC foaming agent producing process
Carry out filtering, preheat and resolving, to obtain hydrogen chloride gas.Above-mentioned filtration treatment uses carbon steel
Filter realizes.Carbon steel filter refers to use carbon steel to make the filter formed, carbon
Element steel is that phosphorus content is less than 1.35%, miscellaneous except the silicon within ferrum, carbon and limitation, manganese, phosphorus, sulfur etc.
Outside matter, without the steel of other alloying elements.When using carbon steel that by-product hydrochloric acid is filtered, first
First need carbon steel filter is carried out pretreatment, alpha-cellulose and water for industrial use are stirred, so
Circulation operation is played by the alpha-cellulose even application of water mixing on carbon steel filter afterwards, i.e. by pump
Complete the pretreatment of carbon steel filter.In the filter tank of carbon steel filter by hydrochloric acid and α-
Cellulose stirs, consumption according to ADC foaming agent institute output every 7.18 tons of by-product hydrochloric acids with
The alpha-cellulose of 0.09 kilogram mixes.Alpha-cellulose, also known as alpha cellulose, is by D-pyrans
A kind of homogeneous macromolecule that type glucosyl group is formed by connecting with Isosorbide-5-Nitrae-β glycosidic bond each other, is filtering
During application the main pipeline of carbon steel filter can be played filtrating aid function, because its fiber is tough,
Therefore the drainage layer formed should not peel off and chap.The by-product hydrochloric acid that ADC foaming agent is produced is
The hydrochloric acid of 12%～15%, after carbon steel filter process, can remove the di-of 1um～15um
Urea and ADC impurity.Hydrochloric acid after filtration uses the pre-heat treatment again so that its temperature is 60～70 DEG C,
The steam that this pre-heat treatment produces during using step S4 evaporation operation realizes heat supply, this enforcement
In example, after the preheated process of hydrochloric acid, temperature rises to 65 DEG C.Hydrochloric acid after preheating sends into resolving hydrochloric acid tower
In carry out dissection process so that hydrochloric acid be converted into hydrogen chloride gas output, obtained hydrogen chloride gas
Body is to be the hydrogen chloride gas of 99.0% containing a small amount of water and content.Analytic Tower is large-scale leaching workshop
One of key equipment of exhaust gas recovery system technique, hydrochloric acid is input in Analytic Tower to be steamed by air stripping
The mode that evaporates and export hydrogen chloride gas, air stripping, also known as parsing, is a kind of to separate liquid phase mixture
Operation, with a kind of gas by liquid mixture to be separated, thus carries volatile component
Out, the traditional handicraft resolving to chemical industry of hydrochloric acid, it is well known to those skilled in the art,
Therefore be not described in detail in this.
Neutralisation treatment step S3 of primary hydrazine hydrate solution: the chlorination that will obtain through the process of step S2
Hydrogen is passed through in the primary hydrazine hydrate solution that the process of step S1 obtains so that hydrogen chloride gas
Occurring to neutralize reaction with the sodium carbonate in primary hydrazine hydrate solution, reaction equation is:
2HCl+Na2CO3→2NaCl+H2O+CO2↑.By a large amount of sodium carbonate in primary hydrazine hydrate solution
It is converted into sodium chloride, thus obtains two grades of hydrazine hydrate solutions that carbonate content is 5～10g/L.This
In embodiment, in primary hydrazine hydrate solution, the content of sodium carbonate is 85g/L, according to by primary hydrazine hydrate
The content of the sodium carbonate in solution is reduced to 10g/L and calculates, according to reaction equation, and the most every thousand
Gram primary hydrazine hydrate need to be passed through hydrogen chloride 51.6kg.According to the feed rate of primary hydrazine hydrate, pass through
Regulate and keep the input rate of hydrogen chloride, make the addition of hydrogen chloride according to the primary hydration added
Sodium carbonate and the mass ratio of the hydrogen chloride of addition in hydrazine solution are that 1.45:1 is passed through.
It should be noted that during being passed through hydrogen chloride gas in primary hydrazine hydrate solution,
The temperature of primary hydrazine hydrate solution controls to be between 75～80 DEG C, to ensure in the process, primary
The reaction of hydrazine hydrate solution and hydrogen chloride gas is to neutralize reaction, if primary hydrazine hydrate solution
Temperature is less than design temperature, then hydrazine hydrate and hydrochloric acid can be caused to generate hydrazine hydrochloride, be unfavorable for that the later stage is anti-
The carrying out answered.
Neutralizing the carbon dioxide produced during reaction is carried out uses blower fan to pump, chilled, water
Cooling and dewatering process are transported in the carbonation process of ammonia-soda process preparing soda carry out after processing
Utilize.Carbonation process refers to NaCl+NH in ammonia-soda process preparing soda3+CO2+H2O
→NaHCO3+NH4The step of Cl.Decrease the discharge of waste gas in the present embodiment processing technology.
In the present embodiment in two grades of hydrazine hydrate solutions that the process of step S3 obtains the content of sodium carbonate
For 8.3g/L.
The desalination of two grades of hydrazine hydrate solutions processes step S4: to the two grades of hydrations prepared through step S3
Hydrazine solution uses evaporation operation to process, and during evaporation process, continuous sample analysis
The content of hydrazine hydrate in liquid phase, during until the concentration of hydrazine hydrate is between 55～65g/L in liquid phase,
Stop evaporation operation.During evaporation process, sodium chloride present in two grades of hydrazine hydrate solutions
Reach saturation, can separate out with the form of crystallization, can carry when sodium chloride crystal separates out a small amount of
Crystals of sodium carbonate, use centrifuge to process, the Crystallization Separation that can separate out, the liquid of centrifugal gained
Being essence hydrazine hydrate solution mutually, the concentration of gained essence hydrazine hydrate solution is 60g/L.
The forming steps S5 of biruea: with the smart hydrazine hydrate solution after step S4 processes and carbamide
Solution and hydrochloric acid or sulphuric acid react as raw material, use acid system to produce and obtain biruea, this
Acid in embodiment is preferably hydrochloric acid, to avoid sulfate radical to enter in reaction system.But due to 36%
Concentrated hydrochloric acid participates in reaction can dilute the concentration of hydrazine hydrate, and concentrated sulphuric acid concentration can reach 98%, no
Can dilute hydrazine hydrate, the consumption of sulphuric acid is typically at 1.6～1.7 ton/ton ADC, before the present invention
Sequence operates, and sulfuric acid dosage can be reduced to 0.3～0.6 ton, selects hydrochloric acid or sulphuric acid to participate in producing reaction
Can adjust according to producing reality.That selects hydrochloric acid participation biruea in the present embodiment produces reaction,
Reaction equation is: N2H4·H2O+2H2NCONH2+2HCl→H2NCONHHNCONH2
+2NH4Cl+H2O
In this step, the producing process of biruea uses classical acid legal system and takes the process of biruea,
This reparation technology is well known to those skilled in the art, therefore does not repeats them here.
The forming steps S6 of ADC foaming agent: to react prepared biruea and chlorine in step S5
Solid/liquid/gas reactions generates ADC foaming agent and by-product hydrochloric acid, and reaction equation is:
H2NCONHHNCONH2+Cl2→H2NCON=NCONH2+2HCl
Using biruea and chlorine reaction to generate ADC foaming agent is the popular response of this area, for
As it is known to those skilled in the art that therefore do not repeat them here.
Gained by-product hydrochloric acid reclaims and continues to use step S2 to carry out processing and apply the reaction follow-up
During, producing one ton of ADC foaming agent has 0.6～0.63 ton of by-product hydrogen chloride, about can consume carbon
0.91 ton of sodium of acid, if by-product hydrochloric acid is too much, then during ADC foaming agent subsequent production, can
Using intermediate product biruea as production marketing, to reduce the yield of by-product hydrochloric acid, or may be used without
With unnecessary by-product hydrochloric acid in the crystals of sodium carbonate separated out during Freeze crystallization, to reduce salt
The discharge of acid, it is achieved the output of hydrochloric acid balances with using.
Embodiment two
Referring to Fig. 1, the present embodiment provides by-product hydrochloric acid in a kind of ADC foaming agent producing process to return
Receive the method utilized, including:
Pre-treatment step S1 of thick hydrazine hydrate: in the present embodiment, uses urea method to make the thick of formation
In hydrazine hydrate solution, the content of sodium carbonate is 142g/L, thick hydrazine hydrate solution use room temperature recirculated water and
It is cooled down by the glycol water of-15 DEG C step by step so that thick hydrazine hydrate self is cooled to-1 DEG C,
In the temperature-fall period of thick hydrazine hydrate, partial sodium carbonate forms washing soda crystallization, by centrifugal behaviour
The thick hydrazine hydrate after chilled process of opposing processes, to isolate washing soda crystal,
To the primary hydrazine hydrate solution that carbonate content is 90g/L；
Pre-treatment step S2 of by-product hydrochloric acid: by the by-product hydrochloric acid in ADC foaming agent producing process
Carrying out filtering, preheat and resolving, to obtain hydrogen chloride gas, above-mentioned filtration treatment uses carbon steel
Filter realizes.When using carbon steel that by-product hydrochloric acid is filtered, first need carbon steel is filtered
Device carries out pretreatment, alpha-cellulose and water for industrial use is stirred, and then beats circulation behaviour by pump
Make the alpha-cellulose even application of water mixing on carbon steel filter, i.e. complete carbon steel filter
Pretreatment.Hydrochloric acid and alpha-cellulose are stirred by the filter tank of carbon steel filter, uses
Measure the every 7.18 tons of by-product hydrochloric acids according to ADC foaming agent institute output and the alpha-cellulose of 0.09 kilogram
Mix.The by-product hydrochloric acid that ADC foaming agent is produced is the hydrochloric acid of 12%～15%, via
After carbon steel filter process, biruea and the ADC impurity of 1um～15um can be removed.Filter
After hydrochloric acid use the pre-heat treatment again so that its temperature is 60～70 DEG C, this pre-heat treatment use thick water
Close the steam produced in hydrazine preparation process and carry out heat supply, temperature after the preheated process of hydrochloric acid in the present embodiment
Degree rises to 70 DEG C.Hydrochloric acid after preheating is sent in resolving hydrochloric acid tower and is carried out dissection process, so that salt
Acid is converted into hydrogen chloride gas output, and obtained hydrogen chloride gas is for containing a small amount of water and content to be
The hydrogen chloride gas of 99.3%.
Neutralisation treatment step S3 of primary hydrazine hydrate solution: the chlorination that will obtain through the process of step S2
Hydrogen is passed through in the primary hydrazine hydrate solution that the process of step S1 obtains, leading to of hydrogen chloride gas
Entering speed according to the mass ratio of the sodium carbonate in primary hydrazine hydrate solution and hydrogen chloride is that 1.45:1 comes
Set.Hydrogen chloride gas and the sodium carbonate in primary hydrazine hydrate solution is made reaction to occur to neutralize, instead
The equation is answered to be: 2HCl+Na2CO3→2NaCl+H2O+CO2↑.Big by primary hydrazine hydrate
Amount sodium carbonate is converted into sodium chloride, thus obtains two grades of hydrazine hydrates that carbonate content is 5～10g/L
Solution.It should be noted that during being passed through hydrogen chloride gas in primary hydrazine hydrate solution,
The temperature of primary hydrazine hydrate solution controls to be between 75～80 DEG C, to ensure in the process, primary
The reaction of hydrazine hydrate solution and hydrogen chloride gas is to neutralize reaction.
Neutralizing the carbon dioxide produced during reaction is carried out uses blower fan to pump, chilled, water
Cooling and dewatering process are transported in the carbonation process of ammonia-soda process preparing soda after processing realize
Utilize.Carbonation process refers to reaction equation in ammonia-soda process preparing soda
NaCl+NH3+CO2+H2O→NaHCO3+NH4The step of Cl.Decrease the present embodiment and make work
The discharge of waste gas in skill.
In the present embodiment in two grades of hydrazine hydrate solutions that the process of step S3 obtains the content of sodium carbonate
For 9.8g/L.
The desalination of two grades of hydrazine hydrate solutions processes step S4: to the two grades of hydrations prepared through step S3
Hydrazine solution uses evaporation operation to process, and during evaporation process, continuous sample analysis
The content of hydrazine hydrate in liquid phase, during until the concentration of hydrazine hydrate is between 55～65g/L in liquid phase,
Stop evaporation operation.During evaporation process, sodium chloride present in two grades of hydrazine hydrate solutions
Reach saturation, can separate out with the form of crystallization, can carry when sodium chloride crystal separates out a small amount of
Crystals of sodium carbonate, use centrifuge to process, the Crystallization Separation that can separate out, the liquid of centrifugal gained
Being essence hydrazine hydrate solution mutually, the concentration of gained essence hydrazine hydrate solution is 65g/L.
The forming steps S5 of biruea: with the smart hydrazine hydrate solution after step S4 processes and carbamide
Solution and hydrochloric acid or sulphuric acid react as raw material, use acid system to produce and obtain biruea, this
Sulphuric acid is selected in acid in embodiment.Reaction equation is: N2H4·H2O+2H2NCONH2+
H2SO4→H2NCONHHNCONH2+(NH4)2SO4+H2O。
The forming steps S6 of ADC foaming agent: to react prepared biruea and chlorine in step S5
Solid/liquid/gas reactions generates ADC foaming agent and by-product hydrochloric acid, and reaction equation is:
H2NCONHHNCONH2+Cl2→H2NCON=NCONH2+2HCl
Gained by-product hydrochloric acid reclaims and continues to use step S2 to carry out processing and apply the reaction follow-up
During, to constitute, by-product hydrochloric acid is recycled.
Embodiment three
Referring to Fig. 1, the present embodiment provides by-product hydrochloric acid in a kind of ADC foaming agent producing process to return
Receive the method utilized, including:
Pre-treatment step S1 of thick hydrazine hydrate: in the present embodiment, uses urea method to make the thick of formation
In hydrazine hydrate solution, the content of sodium carbonate is 142g/L, thick hydrazine hydrate solution use room temperature recirculated water and
It is cooled down by the glycol water of-15 DEG C step by step so that thick hydrazine hydrate self is cooled to-2 DEG C,
In the temperature-fall period of thick hydrazine hydrate, partial sodium carbonate forms washing soda crystallization, by centrifugal behaviour
The thick hydrazine hydrate after chilled process of opposing processes, to isolate washing soda crystal,
To the primary hydrazine hydrate solution that carbonate content is 80g/L；
Pre-treatment step S2 of by-product hydrochloric acid: by the by-product hydrochloric acid in ADC foaming agent producing process
Carrying out filtering, preheat and resolving, to obtain hydrogen chloride gas, above-mentioned filtration treatment uses carbon steel
Filter realizes.When using carbon steel that by-product hydrochloric acid is filtered, first need carbon steel is filtered
Device carries out pretreatment, alpha-cellulose and water for industrial use is stirred, and then beats circulation behaviour by pump
Make the alpha-cellulose even application of water mixing on carbon steel filter, i.e. complete carbon steel filter
Pretreatment.Hydrochloric acid and alpha-cellulose are stirred by the filter tank of carbon steel filter, uses
Measure the every 7.18 tons of by-product hydrochloric acids according to ADC foaming agent institute output and the alpha-cellulose of 0.09 kilogram
Mix.The by-product hydrochloric acid that ADC foaming agent is produced is the hydrochloric acid of 12%～15%, via
After carbon steel filter process, biruea and the ADC impurity of 1um～15um can be removed.Filter
After hydrochloric acid use the pre-heat treatment again so that its temperature is 60～70 DEG C, this pre-heat treatment use thick water
Close the hydrothermal solution produced in hydrazine preparation process and carry out heat supply, temperature after the preheated process of hydrochloric acid in the present embodiment
Degree rises to 60 DEG C.Hydrochloric acid after preheating is sent in resolving hydrochloric acid tower and is carried out dissection process, so that salt
Acid is converted into hydrogen chloride gas output, and obtained hydrogen chloride gas is for containing a small amount of water and content to be
The hydrogen chloride gas of 99.4%.
Neutralisation treatment step S3 of primary hydrazine hydrate solution: the chlorination that will obtain through the process of step S2
Hydrogen is passed through in the primary hydrazine hydrate solution that the process of step S1 obtains, leading to of hydrogen chloride gas
Entering speed according to the mass ratio of the sodium carbonate in primary hydrazine hydrate solution and hydrogen chloride is that 1.45:1 comes
Set.Hydrogen chloride gas and the sodium carbonate in primary hydrazine hydrate solution is made reaction to occur to neutralize, instead
The equation is answered to be: 2HCl+Na2CO3→2NaCl+H2O+CO2↑.Big by primary hydrazine hydrate
Amount sodium carbonate is converted into sodium chloride, thus obtains two grades of hydrazine hydrates that carbonate content is 5～10g/L
Solution.It should be noted that during being passed through hydrogen chloride gas in primary hydrazine hydrate solution,
The temperature of primary hydrazine hydrate solution controls to be between 75～80 DEG C, to ensure in the process, primary
The reaction of hydrazine hydrate solution and hydrogen chloride gas is to neutralize reaction.
Neutralizing the carbon dioxide produced during reaction is carried out uses blower fan to pump, chilled, water
Cooling and dewatering process are transported in the carbonation process of ammonia-soda process preparing soda after processing realize
Utilize.Carbonation process refers to reaction equation in ammonia-soda process preparing soda
NaCl+NH3+CO2+H2O→NaHCO3+NH4The step of Cl.Decrease the present embodiment and make work
The discharge of waste gas in skill.
In the present embodiment in two grades of hydrazine hydrate solutions that the process of step S3 obtains the content of sodium carbonate
For 5.0g/L.
The desalination of two grades of hydrazine hydrate solutions processes step S4: to the two grades of hydrations prepared through step S3
Hydrazine solution uses evaporation operation to process, and during evaporation process, continuous sample analysis
The content of hydrazine hydrate in liquid phase, during until the concentration of hydrazine hydrate is between 55～65g/L in liquid phase,
Stop evaporation operation.During evaporation process, sodium chloride present in two grades of hydrazine hydrate solutions
Reach saturation, can separate out with the form of crystallization, can carry when sodium chloride crystal separates out a small amount of
Crystals of sodium carbonate, use centrifuge to process, the Crystallization Separation that can separate out, the liquid of centrifugal gained
Being essence hydrazine hydrate solution mutually, the concentration of gained essence hydrazine hydrate solution is 55g/L.
The forming steps S5 of biruea: with the smart hydrazine hydrate solution after step S4 processes and carbamide
Solution and hydrochloric acid or sulphuric acid react as raw material, use acid system to produce and obtain biruea, this
Acid in embodiment selects hydrochloric acid.Reaction equation is: N2H4·H2O+2H2NCONH2+2HCl
→H2NCONHHNCONH2+2NH4Cl+H2O。
The forming steps S6 of ADC foaming agent: to react prepared biruea and chlorine in step S5
Solid/liquid/gas reactions generates ADC foaming agent and by-product hydrochloric acid, and reaction equation is:
H2NCONHHNCONH2+Cl2→H2NCON=NCONH2+2HCl
Gained by-product hydrochloric acid reclaims and continues to use step S2 to carry out processing and apply the reaction follow-up
During, to constitute, by-product hydrochloric acid is recycled.
In the ADC foaming agent producing process provided in embodiment one～embodiment three, by-product hydrochloric acid returns
Receive the method utilized, it is achieved that by-product hydrochloric acid is recycled, and make to foam at ADC
The main garbage formed in the producing process of agent is sodium chloride, has not only processed going of by-product hydrochloric acid
To problem, it is to avoid it is to environment, and realizes the sodium carbonate in hydrazine hydrate solution
Processing, the sodium chloride garbage of formation can drain into salt pan, and therefore, ADC is foamed by the present invention
Pollution in the producing process of agent falls below minimum so that the producing process of ADC foaming agent is more
Environmental protection.Meanwhile, the effect of by-product hydrochloric acid in the present invention is to remove the sodium carbonate in hydrazine hydrate solution,
Therefore purity requirement to hydrogen chloride is the highest, the process technique of hydrogen chloride is simply efficient, consumes energy low, phase
Lower than carrying out application cost in traditional approach as PVC unstripped gas, remarkable in economical benefits.
It should be noted that above-described embodiment the present invention will be described rather than carries out the present invention
Limit, and those skilled in the art can set without departing from the scope of the appended claims
Count out alternative embodiment.In the claims, any reference marks between bracket should not will be located in
It is configured to limitations on claims.Word " comprises " not exclude the presence of and does not arranges in the claims
Element or step.
Claims (6)
1. the method that in ADC foaming agent producing process, by-product hydrochloric acid recycles, its feature exists
In, including:
Pre-treatment step S1 of thick hydrazine hydrate: thick hydrazine hydrate is realized pretreatment, so that thick hydrazine hydrate
In liquid phase, the content of sodium carbonate is down to 80～90g/L, and after thick hydrazine hydrate separates, gained liquid phase is primary
Hydrazine hydrate solution；
Pre-treatment step S2 of by-product hydrochloric acid: by the by-product hydrochloric acid in ADC foaming agent producing process
Filter out containing biruea and ADC after, be preheated to 60～70 DEG C, be then sent to resolving hydrochloric acid
Tower resolves, to obtain hydrogen chloride gas；
Neutralisation treatment step S3 of primary hydrazine hydrate solution: the hydrogen chloride gas obtained through step S2
It is passed through in the primary hydrazine hydrate solution after step S1 processes, makes hydrogen chloride gas and primary hydrazine hydrate
Sodium carbonate in solution occurs to neutralize reaction, to remove the part carbonic acid in primary hydrazine hydrate solution
Sodium, obtains two grades of hydrazine hydrate solutions that carbonate content is 5～10g/L；
The desalination of two grades of hydrazine hydrate solutions processes step S4: through two grades of hydrazine hydrates that step S3 is prepared
Solution is evaporated operation, by brilliant for the sodium chloride separated out from two grades of hydrazine hydrate solutions in evaporation process
Body isolates two grades of hydrazine hydrate solution systems, to obtain the smart water that concentration of hydrazine hydrate is 55～65g/L
Close hydrazine solution；
The forming steps S5 of biruea: the smart hydrazine hydrate solution after step S4 processes is anti-with carbamide
Product biruea should be prepared；
The forming steps S6 of ADC foaming agent: produce, through step S5, the biruea obtained anti-with chlorine
Should generate ADC foaming agent and by-product hydrochloric acid, by-product hydrochloric acid reclaims and continues to use step S2 to process also
It is applied in the subsequent process steps of step S2.
In ADC foaming agent producing process the most according to claim 1, by-product hydrochloric acid recycles
Method, it is characterised in that in step S2 to hydrochloric acid filter process use carbon steel filter
Realize.
In ADC foaming agent producing process the most according to claim 1, by-product hydrochloric acid recycles
Method, it is characterised in that in step S2 hydrochloric acid warm-up operation use thick hydrazine hydrate prepared
The hydrothermal solution or the steam that produce in journey or during step S4 evaporation operation realize heat supply.
In ADC foaming agent producing process the most according to claim 1, by-product hydrochloric acid recycles
Method, it is characterised in that in step S3, hydrogen chloride gas is passed through primary hydrazine hydrate solution and occurs
When neutralizing reaction, the temperature of primary hydrazine hydrate solution controls to be 75～80 DEG C.
In ADC foaming agent producing process the most according to claim 1, by-product hydrochloric acid recycles
Method, it is characterised in that in step S3 and reaction generate carbon dioxide use blower fan pump,
Chilled, water cooling and except water conservancy project sequence after, deliver to the carbonation process of ammonia-soda process preparing soda is carried out
Utilize.
In ADC foaming agent producing process the most according to claim 1, by-product hydrochloric acid recycles
Method, it is characterised in that step S5 uses acid system to produce with hydrazine hydrate and carbamide for raw material
Obtain biruea.
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| CN111499546A (en) * | 2020-04-07 | 2020-08-07 | 青海盐湖工业股份有限公司 | Method and system for producing biurea by acid method |
| CN114890919A (en) * | 2022-06-01 | 2022-08-12 | 宁夏日盛高新产业股份有限公司 | Production method of ADC foaming agent |
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| CN101219974A (en) * | 2008-01-22 | 2008-07-16 | 浙江海虹控股集团有限公司 | Method for recovery utilization of mother solution hydrochloric acid for ADC foaming agent production |
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| CN111499546A (en) * | 2020-04-07 | 2020-08-07 | 青海盐湖工业股份有限公司 | Method and system for producing biurea by acid method |
| CN114890919A (en) * | 2022-06-01 | 2022-08-12 | 宁夏日盛高新产业股份有限公司 | Production method of ADC foaming agent |
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