CN208898517U - A kind of no CO2The ammonia preparation facilities of discharge - Google Patents
A kind of no CO2The ammonia preparation facilities of discharge Download PDFInfo
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Abstract
The utility model belongs to a kind of no CO2The ammonia preparation facilities of discharge；Including electrolytic cell, anode slot and cathode can are equipped in electrolytic cell, it is equipped with anode stub and reactant gas delivery path road in anode slot, is equipped with cathode bar in cathode can, power supply is equipped between anode stub and cathode bar, the bottom of cathode can is connected by pipeline with reacting furnace, the bottom of reacting furnace is equipped with nitrogen gas delivery-line, and the top of reacting furnace is connected with hydrolytic tank, and hydrolytic tank is connected with centrifuge, centrifuge outlet at bottom is connected with drying system, and the bottom of drying system is equipped with metal hydroxides pipeline；, technical flow design simple with structure does not consume fossil energy directly rationally, or not without CO2The advantages of reactant discharge, used can be recycled effectively, can react under normal pressure and reduce energy consumption.
Description
Technical field
The utility model belongs to ammonia preparation technical field, and in particular to a kind of no CO2The ammonia preparation facilities of discharge.
Background technique
Ammonia provides required nitrogen for crop growth, is the chemical fertilizer such as urea, ammonium hydrogen carbonate, ammonium chloride ammonium sulfate
Basic chemical raw materials, while ammonia also reaches its maturity as the industrial applications of fuel and energy-accumulating medium.Its demand must be with it
The expansion of application field is continuously increased, and global ammonia production capacity in 2016 is about 1.8 hundred million tons according to statistics, and China's ammonia production capacity is close to 70,000,000
Ton.
Industrial at present that aber process is mainly used to synthesize ammonia using nitrogen and hydrogen as base stock, wherein the source of hydrogen has
Two kinds.One is use coal, natural gas or oven gas to be synthesized for raw material by processes such as conversion, transformation, decarburization, synthesis
Ammonia, this method need to consume unrenewable fossil energy, need to carry out under high-temperature and high-pressure conditions, while generating a large amount of
CO2Discharge causes global warning；But this method energy efficiency and ammonia synthesis efficiency are higher, lead in current industry synthetic ammonia
It still occupies an leading position in domain.Existing patent document CN 101850988 " ammonia synthesis process " discloses a kind of is using coke-oven plant's raw coke oven gas
The ammonia synthesis process of raw material, the effective component of raw material raw coke oven gas are CO and H2, CO is converted by CO after purification and transformation2, so
After slough CO2Hydrogen is made, then hydrogen and nitrogen are synthesized into synthesis ammonia with aber process.The raw coke oven gas that this method uses is still
The product of fossil energy can not get rid of the dependence to non-renewable energy resources；Simultaneously by transformed CO2For producing bicarbonate
Ammonium does not generate CO really not2Technology.
Another kind is the hydrogen production process without using fossil energy, is such as urged using electric energy hydrogen production by water decomposition, using solar energy
Change hydrogen manufacturing, using solar energy or chemistry of nuclear energy hydrogen manufacturing etc., especially electric energy decomposing hydrogen-production, uses solar energy, wind energy, water energy etc.
After Green power generation technology solves the problems, such as that electric energy is expensive, there is very big promotional value；But the nitrogen and hydrogen of this method
Reaction process be still high-pressure synthesis process, energy consumption is higher than the process route of fossil energy hydrogen manufacturing on the whole.Existing hair
Bright 102348642 A of patent publication us CN " ammonia synthesis " discloses a kind of electrolysis water and obtains hydrogen and oxygen, using seperation film
Separate oxygen, then the method for utilizing aber process to synthesize ammonia with nitrogen obtained hydrogen.This method there is no solve reaction need to be
The problem of being carried out under condition of high voltage.
To solve the problems, such as that Haber ammonia process needs to carry out under high-temperature and high-pressure conditions, people are had investigated without using hydrogen
The method for synthesizing ammonia, existing 103108997 B of patent document CN " synthetic method of ammonia " disclose under a kind of normal temperature and pressure with
Water and nitrogen are the electrolysis ammonia method of raw material, and this method provides the energy with the visible light of sunlight or illumination light irradiation,
Water decomposition is proton (H by anode region+), electronics and oxygen, be passed through nitrogen in cathodic region and form N3-, then by the proton of anode region
It is transferred to cathodic region reaction, obtains ammonia.This method is more demanding to anode, cathode material, needs using visible-light response type
Catalyst, and provided using light source and react required energy, have the shortcomings that unstability and effective power are low.
Utility model content
There is provided that a kind of structure is simple, process flow is set the purpose of the utility model is to overcome defect in the prior art
Meter does not consume fossil energy directly rationally, or not without CO2The reactant discharge, used can be recycled effectively, can be reacted under normal pressure
With reduction energy consumption without CO2The ammonia preparation facilities of discharge.
Purpose of the utility model is realized as follows: the preparation facilities includes electrolytic cell, anode slot is equipped in electrolytic cell
And cathode can, anode slot is interior to be equipped with anode stub and reactant gas delivery path road, is equipped with cathode bar, anode stub and cathode in cathode can
Power supply is equipped between stick, the bottom of cathode can is connected by pipeline with reacting furnace, and the bottom of reacting furnace is equipped with nitrogen delivery pipe
The top in road, reacting furnace is connected with hydrolytic tank, and hydrolytic tank is connected with centrifuge, centrifuge outlet at bottom and drying system phase
Even, the bottom of drying system is equipped with metal hydroxides pipeline.
Preferably, the inside of the electrolytic cell is equipped with the electric heating wire being connected with power supply, electric heating wire and PLC control system
Output end be connected, the input terminal of PLC control system is connected with the temperature sensor being located inside electrolytic cell.
Preferably, reaction gas recovery channel is equipped in the anode slot.
Preferably, the mixture conduit of the centrifuge and drying system is connected with rectifier unit respectively, rectifier unit
Top is equipped with ammonia pipeline, and the bottom liquid phases pipeline of rectifier unit is connected with the moisturizing pipeline of hydrolytic tank.
Preferably, the material of the electrolytic cell is alumina ceramic material, and the material of anode slot and cathode can is aluminium oxide
Porous ceramic film material, the material of anode stub are graphite, and the material of cathode bar is Fe, W, Ti or Pt.
With structure, simple, technical flow design rationally, directly consumes fossil energy, without CO to the utility model2Discharge,
The advantages of reactant used can be recycled effectively, can react under normal pressure and reduce energy consumption.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the utility model.
Fig. 2 is the structural schematic diagram of the example one of the utility model.
Fig. 3 is the structural schematic diagram of the example two of the utility model.
Specific embodiment
For a clearer understanding of the technical features, objectives and effects of the utility model, now compareing Detailed description of the invention
Specific embodiment of the present utility model, identical label indicates identical component in the various figures.To make simplified form, in each figure
Part relevant to utility model is only schematically shown, they do not represent its practical structures as product.
As shown in Figure 1, the utility model is a kind of no CO2The ammonia preparation facilities of discharge, including electrolytic cell 1, electrolytic cell 1
It is interior to be equipped with anode slot 2 and cathode can 3, it is equipped with anode stub 4 and reactant gas delivery path road 5 in anode slot 2, is equipped in cathode can 3
Cathode bar 6 is equipped with power supply 7 between anode stub 4 and cathode bar 6, the bottom of cathode can 3 is connected by pipeline with reacting furnace 8, instead
The bottom of furnace 8 is answered to be equipped with nitrogen gas delivery-line 9, the top of reacting furnace 8 is connected with hydrolytic tank 10, hydrolytic tank 10 and centrifuge 11
It is connected, 11 outlet at bottom of centrifuge is connected with drying system 12, and the bottom of drying system 12 is equipped with metal hydroxides pipeline 13.
The inside of the electrolytic cell 1 is equipped with the electric heating wire 16 being connected with power supply, the output end of electric heating wire 16 and PLC control system 17
It is connected, the input terminal of PLC control system 17 is connected with the temperature sensor 18 being located inside electrolytic cell 1.It is set in the anode slot 2
There is reaction gas recovery channel 14.The mixture conduit 15 of the centrifuge 11 and drying system 12 respectively with 19 phase of rectifier unit
Even, the top of rectifier unit 19 is equipped with ammonia pipeline 20, the bottom liquid phases pipeline of rectifier unit 19 and the water supply pipe of hydrolytic tank 10
Road 21 is connected.The material of the electrolytic cell 1 is alumina ceramic material, and the material of anode slot 2 and cathode can 3 is aluminum oxide porous
Ceramic material, the material of anode stub 4 are graphite, and the material of cathode bar 6 is Fe, W, Ti or Pt.
A kind of no CO2The preparation method of the ammonia preparation facilities of discharge, the preparation method use reactant for metal hydrogen-oxygen
The preparation method or reactant of compound are the preparation method of metal chloride；
A, reactant is the preparation method of metal hydroxides, is included the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the hydroxide of Li, Na or Mg are conveyed into anode slot 2 by reactant gas delivery path road 5, and connects electricity
Source 7 makes reactant in anode slot 2 that cell reaction occur, and after cell reaction, the product in anode slot 2 is oxygen and vapor,
Product in cathode can 3 is to obtain the metal simple-substance of molten state on cathode bar 6；The voltage of the power supply 7 is 3-5V；The oxygen
It can be directly vented with vapor or condensing recovery；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to hydroxide and recycling, ammonia and water after separation in reactant gas delivery path road 5 are entered by metal hydroxides pipeline 13
Mixture can be separated directly as Fertilizer application or to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 20 of hydrolytic tank 10, to be recycled；
B, reactant is the preparation method of metal chloride, is included the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the chloride of Li, Na or Mg are conveyed into anode slot 2 by reactant gas delivery path road 5, and is powered on
7, make reactant in anode slot 2 that cell reaction occur, after cell reaction, the product in anode slot 2 is chlorine, in cathode can 3
Product be cathode bar 6 on obtain the metal simple-substance of molten state；The voltage of the power supply 7 is 3-5V；The chlorine passes through reaction
Gas recovery conduit 14 is recycled；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to after hydroxide is collected by metal oxide pipeline 13 and recycling, the mixture of ammonia and water after separation can be directly as fertilizer
Material is used or is separated to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 21 of hydrolytic tank 10, to be recycled.
Preferably, reactant gas delivery path road 5 in the step of reactant is the preparation method of metal hydroxides two
When material is LiOH, the temperature of molten salt of molten condition is 460-500 DEG C in step 1；Reactant gas delivery path in the step 2
When the material in road 5 is NaOH, the temperature of molten salt of molten condition is 300-350 DEG C in step 1；Reactant in the step 2
The material of conveyance conduit 5 is Mg (OH)2When, the temperature of molten salt of molten condition is 340-400 DEG C in step 1.
Preferably, the reactant gas delivery path road 5 in the step of reactant is the preparation method of metal chloride two
When material is LiCl, the temperature of molten salt of molten condition is 600-650 DEG C in step 1；The reactant is the system of metal chloride
The material in the reactant gas delivery path road 5 in the step of Preparation Method two is MgCl2When, the temperature of molten salt of molten condition is in step 1
710-750℃；The material in the reactant gas delivery path road 5 in the step of reactant is the preparation method of metal chloride two is
When NaCl, the temperature of molten salt of molten condition is 800-840 DEG C in step 1.
Preferably, the reactant is LiOH, NaOH, Mg (OH)2、LiCl、MgCl2Or when NaCl, not according to material
Together, the temperature of molten salt data of molten condition in electrolytic cell 1 are transmitted in PLC control system 17 by temperature sensor 18, work as temperature
When more than corresponding temperature range, PLC control system 17 controls electric heating wire 16 and stops heating, when temperature is lower than corresponding
When temperature range, PLC control system 17 controls electric heating wire 16 and begins to warm up.
Fused salt described in the utility model is a kind of mixture being made of several inorganic oxides, is used as heat-conducting medium
(similar steam or conduction oil, but temperature is higher).The fused salt can be the KNO that mass fraction is 50%3With 50%
NaNO3, can be the KNO that mass fraction is 50%3With 50% NaNO2, can be mass fraction be 30% KCl, 20%
The BaCl of NaCl and 50%2, can be KOH, NaOH or KNO3.In addition, the cell reaction of the utility model in electrolytic cell 1 into
Row, 1 material selection high temperature resistant of electrolytic cell, resistant material, preferably alumina ceramic material；It is placed with fused salt in electrolytic cell 1, is melted
Salt is kept molten by under the action of electric heating wire 16 and under the control of PLC control system 17.The anode slot 2 and cathode
The material of slot 3 is alumina porous ceramic material, and the material of anode stub 4 is graphite, and the material of cathode bar 6 is Fe, W, Ti or Pt.
Above-mentioned alumina porous ceramic material is isolated by the electrode in electrolytic cell 1 with fused salt.Active metal compound preferred Li, Na, Mg
Hydroxide, chloride etc., particularly preferred LiOH；Wave metallic compound living adds in the anode slot 2 of electrolytic cell 1, in fused salt
Heat effect under melt, applied voltage effect under be electrolysed, anode generate oxygen/chlorine；Metal ion is turned by fused salt
The surface for moving on to cathode bar 6 obtains electronically forming metal simple-substance, and melts under the heat effect of fused salt, accumulates on cathode sky
Between.Its key reaction in electrolytic cell 1 is (but being not limited to following reaction):
Anode: 4OH-→2H2O+O2↑+4e-Or 2Cl-→Cl2↑+2e-
Cathode: Me++e-→ Me or Me2++2e→Me
Overall reaction: 4MeOH → 4Me+2H2O+O2↑ or 2MeCl → 2Me+Cl2↑
Or 2Me (OH)2→2Me+2H2O+O2↑ or MeCl2→Me+Cl2↑
The N after product (i.e. metal simple-substance) in above-mentioned cathode can 3 enters in reacting furnace 8 and in reacting furnace 82Reaction life
Metal nitride is produced, metal simple-substance and nitrogen, which react, generates metal nitride, and typical reaction is (being not limited to following reaction):
Me+N2→Me3N or Me+N2→Me3N2
Above-mentioned reaction can react at normal temperature, and outer secondary heat can also be used to accelerate reaction rate, furthermore it is possible to utilize
The waste heat of metal simple-substance accelerates hair and answers rate；Preferable reaction temperature is between 60~100 DEG C.
After under entrainment of the metal nitride in excessive nitrogen by entering hydrolytic tank 10, metal nitride reacts life with water
Ammonification and metal hydroxides, typical reaction are as follows:
Me3N+H2O→NH3+ MeOH or Me3N2+6H2O→2NH3+3Me(OH)2
It, can be by cycling and reutilization after being centrifuged, drying, when active gold when active metal compound is metal hydroxides
Belonging to when compound is metal chloride may be recovered；Separating liquid is the mixture of ammonia and water, can directly as Fertilizer application or
As commodity selling, or enter rectifier unit 19, isolate ammonia and water by rectifying, ammonia compressed, condense after become liquid
Body is sold outside as a raw material for production or directly.It should be noted that drying system 12 described in the utility model is drying oven or does
Dry tower etc. is dried in the form of hot wind or infrared ray etc.；The rectifier unit 19 is rectifying column；It prepares through the above way
Ammonia has a characteristic that 1, with N2And H2O is raw material, does not consume fossil energy directly, former caused by can avoid because of energy shortage
Material price rise problem；It 2, being capable of continuous production ammonia；3, there is no CO in reaction process2Discharge meets the relevant section of country
It can emission reduction policy；4, using metal nitride and H2O, which directly reacts, generates ammonia, has bypassed aber process and has utilized H2And N2High pressing
At reaction, whole process can carry out under normal pressure；Electrolysis energy consumption and quite (the electric energy hydrogen manufacturing, the sun of other hydrogen production process energy consumptions
Can photocatalysis hydrogen production etc.), but can consume without reaction under high pressure relatively low；5, the active metal that the utility model uses
Closing object can recycle during the reaction, it is only necessary to which a small amount of supplement can maintain the lasting progress of reaction；6, the utility model
Described in power supply be merely capable of maintain cell reaction, so electrolysis the energy can be used green energy resource, such as solar energy, wind
The electric energy of the generations such as energy, water energy reaches close and even lower than synthesizes ammonia using fossil energy so that energy consumption be greatly lowered
Tradition ammonia method energy consumption level.
For more detailed explanation the utility model, the utility model is further elaborated now in conjunction with embodiment.Tool
Body embodiment is as follows:
Example one
As shown in Fig. 2, a kind of no CO2The ammonia preparation facilities of discharge, including electrolytic cell 1, electrolytic cell 1 is interior to be equipped with anode slot
2 and cathode can 3, anode stub 4 and reactant gas delivery path road 5 are equipped in anode slot 2, are equipped with cathode bar 6, anode in cathode can 3
Power supply 7 is equipped between stick 4 and cathode bar 6, the bottom of cathode can 3 is connected by pipeline with reacting furnace 8, the bottom of reacting furnace 8
Equipped with nitrogen gas delivery-line 9, the top of reacting furnace 8 is connected with hydrolytic tank 10, and hydrolytic tank 10 is connected with centrifuge 11, centrifuge
11 outlet at bottom are connected with drying system 12, and the bottom of drying system 12 is equipped with metal hydroxides pipeline 13.The metallic hydrogen
Oxidation conduit 13 is connected with reactant gas delivery path road 5.The inside of the electrolytic cell 1 is equipped with the electric heating wire being connected with power supply
16, electric heating wire 16 is connected with the output end of PLC control system 17, the input terminal of PLC control system 17 and is located in electrolytic cell 1
The temperature sensor 18 in portion is connected.The mixture conduit 15 of the centrifuge 11 and drying system 12 respectively with 19 phase of rectifier unit
Even, the top of rectifier unit 19 is equipped with ammonia pipeline 20, the bottom liquid phases pipeline of rectifier unit 19 and the water supply pipe of hydrolytic tank 10
Road 21 is connected.The material of the electrolytic cell 1 is alumina ceramic material, and the material of anode slot 2 and cathode can 3 is aluminum oxide porous
Ceramic material, the material of anode stub 4 are graphite, and the material of cathode bar 6 is Fe.
A kind of no CO2The preparation method of the ammonia preparation facilities of discharge, the preparation method use reactant for metal hydrogen-oxygen
The preparation method of compound, includes the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the hydroxide of Li is conveyed into anode slot 2 by reactant gas delivery path road 5, and powers on 7, is made
Cell reaction occurs for the reactant in anode slot 2, and after cell reaction, the product in anode slot 2 is oxygen and vapor, cathode can
Product in 3 is to obtain the metal simple-substance of molten state on cathode bar 6；The voltage of the power supply 7 is 3-5V；The oxygen and water steam
Gas can be directly vented or condensing recovery；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to hydroxide and recycling, ammonia and water after separation in reactant gas delivery path road 5 are entered by metal hydroxides pipeline 13
Mixture can be separated directly as Fertilizer application or to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 20 of hydrolytic tank 10, to be recycled；
The material in reactant gas delivery path road 5 is in the step of reactant is the preparation method of metal hydroxides two
When LiOH, the temperature of molten salt of molten condition is 460-500 DEG C in step 1；Temperature sensor 18 is by molten condition in electrolytic cell 1
Temperature of molten salt data be transmitted in PLC control system 17, when temperature is more than 500 DEG C, PLC control system 17 control electric heating
Silk 16 stops heating, and when temperature is lower than 460 DEG C, PLC control system 17 controls electric heating wire 16 and begins to warm up.
Example two
As shown in figure 3, a kind of no CO2The ammonia preparation facilities of discharge, including electrolytic cell 1, electrolytic cell 1 is interior to be equipped with anode slot
2 and cathode can 3, anode stub 4 and reactant gas delivery path road 5 are equipped in anode slot 2, are equipped with cathode bar 6, anode in cathode can 3
Power supply 7 is equipped between stick 4 and cathode bar 6, the bottom of cathode can 3 is connected by pipeline with reacting furnace 8, the bottom of reacting furnace 8
Equipped with nitrogen gas delivery-line 9, the top of reacting furnace 8 is connected with hydrolytic tank 10, and hydrolytic tank 10 is connected with centrifuge 11, centrifuge
11 outlet at bottom are connected with drying system 12, and the bottom of drying system 12 is equipped with metal hydroxides pipeline 13.The metallic hydrogen
Oxidation conduit 13 is connected with reactant gas delivery path road 5.The inside of the electrolytic cell 1 is equipped with the electric heating wire being connected with power supply
16, electric heating wire 16 is connected with the output end of PLC control system 17, the input terminal of PLC control system 17 and is located in electrolytic cell 1
The temperature sensor 18 in portion is connected.Reaction gas recovery channel 14 is equipped in the anode slot 2.The centrifuge 11 and dry system
The mixture conduit 15 of system 12 is connected with rectifier unit 19 respectively, and the top of rectifier unit 19 is equipped with ammonia pipeline 20, rectifying dress
19 bottom liquid phases pipeline is set to be connected with the moisturizing pipeline 21 of hydrolytic tank 10.The material of the electrolytic cell 1 is aluminium oxide ceramics material
The material of material, anode slot 2 and cathode can 3 is alumina porous ceramic material, and the material of anode stub 4 is graphite, the material of cathode bar 6
Matter is W.
A kind of no CO2The preparation method of the ammonia preparation facilities of discharge, the preparation method use reactant for metal hydrogen-oxygen
The preparation method of compound, includes the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the hydroxide of Na is conveyed into anode slot 2 by reactant gas delivery path road 5, and powers on 7, is made
Cell reaction occurs for the reactant in anode slot 2, and after cell reaction, the product in anode slot 2 is oxygen and vapor, cathode can
Product in 3 is to obtain the metal simple-substance of molten state on cathode bar 6；The voltage of the power supply 7 is 3-5V；The oxygen and water steam
Gas can be directly vented or condensing recovery；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to hydroxide and recycling, ammonia and water after separation in reactant gas delivery path road 5 are entered by metal hydroxides pipeline 13
Mixture can be separated directly as Fertilizer application or to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 20 of hydrolytic tank 10, to be recycled；
When the material in the reactant gas delivery path road 5 in the step 2 is NaOH, the fused salt temperature of molten condition in step 1
Degree is 300-350 DEG C；The temperature of molten salt data of molten condition in electrolytic cell 1 are transmitted to PLC control system by temperature sensor 18
In 17, when temperature is more than 350 DEG C, PLC control system 17 controls electric heating wire 16 and stops heating, when temperature is lower than 300 DEG C,
PLC control system 17 controls electric heating wire 16 and begins to warm up.
Example three
A kind of no CO2The ammonia preparation facilities of discharge, including electrolytic cell 1, electrolytic cell 1 is interior to be equipped with anode slot 2 and cathode can
3, anode slot 2 is interior to be equipped with anode stub 4 and reactant gas delivery path road 5, is equipped with cathode bar 6, anode stub 4 and cathode in cathode can 3
Power supply 7 is equipped between stick 6, the bottom of cathode can 3 is connected by pipeline with reacting furnace 8, and it is defeated that the bottom of reacting furnace 8 is equipped with nitrogen
Pipeline 9 is sent, the top of reacting furnace 8 is connected with hydrolytic tank 10, and hydrolytic tank 10 is connected with centrifuge 11,11 outlet at bottom of centrifuge
It is connected with drying system 12, the bottom of drying system 12 is equipped with metal hydroxides pipeline 13.The metal hydroxides pipeline
13 are connected with reactant gas delivery path road 5.The inside of the electrolytic cell 1 is equipped with the electric heating wire 16 being connected with power supply, electric heating wire
16 are connected with the output end of PLC control system 17, and the input terminal of PLC control system 17 is passed with the temperature being located inside electrolytic cell 1
Sensor 18 is connected.Reaction gas recovery channel 14 is equipped in the anode slot 2.The mixing of the centrifuge 11 and drying system 12
Conduit 15 is connected with rectifier unit 19 respectively, and the top of rectifier unit 19 is equipped with ammonia pipeline 20, the bottom of rectifier unit 19
Liquid pipe is connected with the moisturizing pipeline 21 of hydrolytic tank 10.The material of the electrolytic cell 1 is alumina ceramic material, anode slot 2
Material with cathode can 3 is alumina porous ceramic material, and the material of anode stub 4 is graphite, and the material of cathode bar 6 is Ti.
A kind of no CO2The preparation method of the ammonia preparation facilities of discharge, the preparation method use reactant for metal hydrogen-oxygen
The preparation method of compound, includes the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the hydroxide of Mg is conveyed into anode slot 2 by reactant gas delivery path road 5, and powers on 7, is made
Cell reaction occurs for the reactant in anode slot 2, and after cell reaction, the product in anode slot 2 is oxygen and vapor, cathode can
Product in 3 is to obtain the metal simple-substance of molten state on cathode bar 6；The voltage of the power supply 7 is 3-5V；The oxygen and water steam
Gas can be directly vented or condensing recovery；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to hydroxide and recycling, ammonia and water after separation in reactant gas delivery path road 5 are entered by metal hydroxides pipeline 13
Mixture can be separated directly as Fertilizer application or to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 20 of hydrolytic tank 10, to be recycled；
The material in the reactant gas delivery path road 5 in the step 2 is Mg (OH)2When, the fused salt of molten condition in step 1
Temperature is 340-400 DEG C.The temperature of molten salt data of molten condition in electrolytic cell 1 are transmitted to PLC control system by temperature sensor 18
In system 17, when temperature is more than 400 DEG C, PLC control system 17 controls electric heating wire 16 and stops heating, when temperature is lower than 340 DEG C
When, PLC control system 17 controls electric heating wire 16 and begins to warm up.
Example four
A kind of no CO2The ammonia preparation facilities of discharge, including electrolytic cell 1, electrolytic cell 1 is interior to be equipped with anode slot 2 and cathode can
3, anode slot 2 is interior to be equipped with anode stub 4 and reactant gas delivery path road 5, is equipped with cathode bar 6, anode stub 4 and cathode in cathode can 3
Power supply 7 is equipped between stick 6, the bottom of cathode can 3 is connected by pipeline with reacting furnace 8, and it is defeated that the bottom of reacting furnace 8 is equipped with nitrogen
Pipeline 9 is sent, the top of reacting furnace 8 is connected with hydrolytic tank 10, and hydrolytic tank 10 is connected with centrifuge 11,11 outlet at bottom of centrifuge
It is connected with drying system 12, the bottom of drying system 12 is equipped with metal hydroxides pipeline 13.The inside of the electrolytic cell 1 is equipped with
The electric heating wire 16 being connected with power supply, electric heating wire 16 are connected with the output end of PLC control system 17, PLC control system 17
Input terminal is connected with the temperature sensor 18 being located inside electrolytic cell 1.Reaction gas recovery channel is equipped in the anode slot 2
14.The mixture conduit 15 of the centrifuge 11 and drying system 12 is connected with rectifier unit 19 respectively, the top of rectifier unit 19
Portion is equipped with ammonia pipeline 20, and the bottom liquid phases pipeline of rectifier unit 19 is connected with the moisturizing pipeline 21 of hydrolytic tank 10.The electrolysis
The material in pond 1 is alumina ceramic material, and the material of anode slot 2 and cathode can 3 is alumina porous ceramic material, anode stub 4
Material be graphite, the material of cathode bar 6 is Pt.
A kind of no CO2The preparation method of the ammonia preparation facilities of discharge, the preparation method use reactant for metal chlorination
The preparation method of object, includes the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the chloride of Li is conveyed into anode slot 2 by reactant gas delivery path road 5, and powers on 7, makes sun
Cell reaction occurs for the reactant in pole slot 2, and after cell reaction, the product in anode slot 2 is chlorine, the product in cathode can 3
To obtain the metal simple-substance of molten state on cathode bar 6；The voltage of the power supply 7 is 3-5V；The chlorine is returned by reaction gas
It is recycled in closed tube road 14；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to after hydroxide is collected by metal oxide pipeline 13 and recycling, the mixture of ammonia and water after separation can be directly as fertilizer
Material is used or is separated to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 21 of hydrolytic tank 10, to be recycled.
The material in the reactant gas delivery path road 5 in the step of reactant is the preparation method of metal chloride two is
When LiCl, the temperature of molten salt of molten condition is 600-650 DEG C in step 1；Temperature sensor 18 is by molten condition in electrolytic cell 1
Temperature of molten salt data be transmitted in PLC control system 17, when temperature is more than 650 DEG C, PLC control system 17 control electric heating
Silk 16 stops heating, and when temperature is lower than 600 DEG C, PLC control system 17 controls electric heating wire 16 and begins to warm up.
Example five
A kind of no CO2The ammonia preparation facilities of discharge, including electrolytic cell 1, electrolytic cell 1 is interior to be equipped with anode slot 2 and cathode can
3, anode slot 2 is interior to be equipped with anode stub 4 and reactant gas delivery path road 5, is equipped with cathode bar 6, anode stub 4 and cathode in cathode can 3
Power supply 7 is equipped between stick 6, the bottom of cathode can 3 is connected by pipeline with reacting furnace 8, and it is defeated that the bottom of reacting furnace 8 is equipped with nitrogen
Pipeline 9 is sent, the top of reacting furnace 8 is connected with hydrolytic tank 10, and hydrolytic tank 10 is connected with centrifuge 11,11 outlet at bottom of centrifuge
It is connected with drying system 12, the bottom of drying system 12 is equipped with metal hydroxides pipeline 13.The inside of the electrolytic cell 1 is equipped with
The electric heating wire 16 being connected with power supply, electric heating wire 16 are connected with the output end of PLC control system 17, PLC control system 17
Input terminal is connected with the temperature sensor 18 being located inside electrolytic cell 1.Reaction gas recovery channel is equipped in the anode slot 2
14.The mixture conduit 15 of the centrifuge 11 and drying system 12 is connected with rectifier unit 19 respectively, the top of rectifier unit 19
Portion is equipped with ammonia pipeline 20, and the bottom liquid phases pipeline of rectifier unit 19 is connected with the moisturizing pipeline 21 of hydrolytic tank 10.The electrolysis
The material in pond 1 is alumina ceramic material, and the material of anode slot 2 and cathode can 3 is alumina porous ceramic material, anode stub 4
Material be graphite, the material of cathode bar 6 is W.
A kind of no CO2The preparation method of the ammonia preparation facilities of discharge, the preparation method use the reactant to be for reactant
The preparation method of metal chloride, includes the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the chloride of Mg is conveyed into anode slot 2 by reactant gas delivery path road 5, and powers on 7, makes sun
Cell reaction occurs for the reactant in pole slot 2, and after cell reaction, the product in anode slot 2 is chlorine, the product in cathode can 3
To obtain the metal simple-substance of molten state on cathode bar 6；The voltage of the power supply 7 is 3-5V；The chlorine is returned by reaction gas
It is recycled in closed tube road 14；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to after hydroxide is collected by metal oxide pipeline 13 and recycling, the mixture of ammonia and water after separation can be directly as fertilizer
Material is used or is separated to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 21 of hydrolytic tank 10, to be recycled.
The material in the reactant gas delivery path road 5 in the step of reactant is the preparation method of metal chloride two is
MgCl2When, the temperature of molten salt of molten condition is 710-750 DEG C in step 1；Temperature sensor 18 is by molten condition in electrolytic cell 1
Temperature of molten salt data be transmitted in PLC control system 17, when temperature is more than 750 DEG C, PLC control system 17 control electric heating
Silk 16 stops heating, and when temperature is lower than 710 DEG C, PLC control system 17 controls electric heating wire 16 and begins to warm up.
Example six
A kind of no CO2The ammonia preparation facilities of discharge, including electrolytic cell 1, electrolytic cell 1 is interior to be equipped with anode slot 2 and cathode can
3, anode slot 2 is interior to be equipped with anode stub 4 and reactant gas delivery path road 5, is equipped with cathode bar 6, anode stub 4 and cathode in cathode can 3
Power supply 7 is equipped between stick 6, the bottom of cathode can 3 is connected by pipeline with reacting furnace 8, and it is defeated that the bottom of reacting furnace 8 is equipped with nitrogen
Pipeline 9 is sent, the top of reacting furnace 8 is connected with hydrolytic tank 10, and hydrolytic tank 10 is connected with centrifuge 11,11 outlet at bottom of centrifuge
It is connected with drying system 12, the bottom of drying system 12 is equipped with metal hydroxides pipeline 13.The inside of the electrolytic cell 1 is equipped with
The electric heating wire 16 being connected with power supply, electric heating wire 16 are connected with the output end of PLC control system 17, PLC control system 17
Input terminal is connected with the temperature sensor 18 being located inside electrolytic cell 1.Reaction gas recovery channel is equipped in the anode slot 2
14.The mixture conduit 15 of the centrifuge 11 and drying system 12 is connected with rectifier unit 19 respectively, the top of rectifier unit 19
Portion is equipped with ammonia pipeline 20, and the bottom liquid phases pipeline of rectifier unit 19 is connected with the moisturizing pipeline 21 of hydrolytic tank 10.The electrolysis
The material in pond 1 is alumina ceramic material, and the material of anode slot 2 and cathode can 3 is alumina porous ceramic material, anode stub 4
Material be graphite, the material of cathode bar 6 is Ti.
A kind of no CO2The preparation method of the ammonia preparation facilities of discharge, the preparation method use reactant for metal chlorination
The preparation method of object, includes the following steps:
Step 1: electrolytic cell 1 is provided with fused salt, so that fused salt is kept molten by using external heat and temperature control system
State；
Step 2: the chloride of Na is conveyed into anode slot 2 by reactant gas delivery path road 5, and powers on 7, makes sun
Cell reaction occurs for the reactant in pole slot 2, and after cell reaction, the product in anode slot 2 is chlorine, the product in cathode can 3
To obtain the metal simple-substance of molten state on cathode bar 6；The voltage of the power supply 7 is 3-5V；The chlorine is returned by reaction gas
It is recycled in closed tube road 14；
Step 3: the product in cathode can 3 described in step 2 enters reacting furnace 8 by the pipeline of 3 bottom of cathode can
Interior, nitrogen gas delivery-line 9 conveys excessive nitrogen into reacting furnace 8, and nitrogen is reacted with the metal simple-substance of molten state generates metal
Nitride；The purity of the nitrogen is 99.9%；
Step 4: metal nitride described in step 3 under the entrainment of excessive nitrogen by enter hydrolytic tank 10 in,
Excessive water is contained in hydrolytic tank 10, hydrolysis occurs in hydrolytic tank 10 for metal nitride, generates metal hydroxides
And ammonia；
Step 5: metal hydroxides and ammonia in step 4, which enter in centrifuge 11, to be separated, the metal after separation
Hydroxide obtains dry metal hydroxides, dry gold by entering progress physical dryness in drying system 12 after precipitating
Belong to after hydroxide is collected by metal oxide pipeline 13 and recycling, the mixture of ammonia and water after separation can be directly as fertilizer
Material is used or is separated to ammonia；
Step 6: when needing the ammonia in the mixture to ammonia and water in step 5 to separate, make 11 He of centrifuge
The mixture of ammonia and water in drying system 12, which enters, carries out rectifying in rectifier unit 19, the water after rectifying passes through rectifier unit 19
The liquid pipe of bottom, which enters in the moisturizing pipeline 21 of hydrolytic tank 10, to be recycled.
The material in the reactant gas delivery path road 5 in the step of reactant is the preparation method of metal chloride two is
When NaCl, the temperature of molten salt of molten condition is 800-840 DEG C in step 1.Temperature sensor 18 is by molten condition in electrolytic cell 1
Temperature of molten salt data be transmitted in PLC control system 17, when temperature is more than 840 DEG C, PLC control system 17 control electric heating
Silk 16 stops heating, and when temperature is lower than 840 DEG C, PLC control system 17 controls electric heating wire 16 and begins to warm up.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term is " even
Connect ", " connected " etc. shall be understood in a broad sense, for example, it may be being fixedly connected, be integrally connected, may be a detachable connection；
The connection being also possible to inside two elements；It can be directly connected, it can also indirectly connected through an intermediary, for ability
For the those of ordinary skill in domain, the concrete meaning of above-mentioned term in the present invention can be understood as the case may be.On
The detailed description of text is illustrated only for the feasible embodiment of the utility model, they are not to limit this
The protection scope of utility model, it is all equal without departing from equivalent implementations made by the utility model skill spirit, change and transformation
It should be included within the scope of protection of this utility model.
Claims (5)
1. a kind of no CO2The ammonia preparation facilities of discharge, it is characterised in that: the preparation facilities includes electrolytic cell (1), electrolytic cell (1)
It is interior to be equipped with anode slot (2) and cathode can (3), anode stub (4) and reactant gas delivery path road (5) are equipped in anode slot (2), cathode
Cathode bar (6) are equipped in slot (3), are equipped with power supply (7) between anode stub (4) and cathode bar (6), the bottom of cathode can (3) passes through
Pipeline is connected with reacting furnace (8), and the bottom of reacting furnace (8) is equipped with nitrogen gas delivery-line (9), the top of reacting furnace (8) and water
Solution slot (10) is connected, and hydrolytic tank (10) is connected with centrifuge (11), centrifuge (11) outlet at bottom and drying system (12) phase
Even, the bottom of drying system (12) is equipped with metal hydroxides pipeline (13).
2. a kind of no CO according to claim 12The ammonia preparation facilities of discharge, it is characterised in that: the electrolytic cell (1)
Inside be equipped with the electric heating wire (16) that is connected with power supply, electric heating wire (16) is connected with the output end of PLC control system (17),
The input terminal of PLC control system (17) temperature sensor (18) internal with electrolytic cell (1) is located at is connected.
3. a kind of no CO according to claim 12The ammonia preparation facilities of discharge, it is characterised in that: the anode slot (2)
It is interior to be equipped with reaction gas recovery channel (14).
4. a kind of no CO according to claim 12The ammonia preparation facilities of discharge, it is characterised in that: the centrifuge (11)
It is connected respectively with rectifier unit (19) with the mixture conduit (15) of drying system (12), the top of rectifier unit (19) is equipped with ammonia
Feed channel (20), the bottom liquid phases pipeline of rectifier unit (19) are connected with the moisturizing pipeline (21) of hydrolytic tank (10).
5. a kind of no CO according to claim 12The ammonia preparation facilities of discharge, it is characterised in that: the electrolytic cell (1)
Material be alumina ceramic material, the material of anode slot (2) and cathode can (3) is alumina porous ceramic material, anode stub
(4) material is graphite, and the material of cathode bar (6) is Fe, W, Ti or Pt.
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Address after: 453731 Xinxiang Economic Development Zone, Henan Province (Xiaoji Town) Patentee after: Henan Xinlianxin Chemical Industry Group Co., Ltd. Address before: 453731 Henan Xinxiang Economic Development Zone Xiaoji Town Henan Xinlianxin Chemical Fertilizer Co., Ltd. Patentee before: Henan XInlianxin Fertiliser Limited Company |