CN109437137A - A kind of method that the purification of crude product sodium pyrophosphate produces tertiary sodium phosphate and sodium chloride - Google Patents
A kind of method that the purification of crude product sodium pyrophosphate produces tertiary sodium phosphate and sodium chloride Download PDFInfo
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- CN109437137A CN109437137A CN201811619725.3A CN201811619725A CN109437137A CN 109437137 A CN109437137 A CN 109437137A CN 201811619725 A CN201811619725 A CN 201811619725A CN 109437137 A CN109437137 A CN 109437137A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/305—Preparation from phosphorus-containing compounds by alkaline treatment
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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
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/80—Compositional purity
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Abstract
The invention discloses the methods of a kind of phosphorous brine waste by-product crude product sodium pyrophosphate purification production tertiary sodium phosphate such as glyphosate mother solution and sodium chloride product.The Special use method that crude product sodium pyrophosphate mixed solution dispersibility and process water are improved using oxidisability auxiliary agent is improved phosphoric acid, improves crystallization effect.Tricresyl phosphate sodium salt and sodium chloride are extracted using the dissolubility difference of sodium pyrophosphate in crude product sodium pyrophosphate and its hydrolysate, sodium chloride under different temperatures, pH value condition and promoter effect.Production process solution rate is fast, and product quality is excellent, and wastewater flow rate is small, and environmental protection treatment cost declines to a great extent, and has reaction advantage, environment-friendly advantage, quality-advantage, cost advantage.
Description
Technical field
The invention belongs to three-protection design production technical field, the high sodium chloride phosphorus-containing wastewater such as specially a kind of glyphosate mother solution
In the refining methd for the crude product sodium pyrophosphate that burning or high-temperature oxydation obtain, it is particularly suitable for glycine method or IDA method glyphosate
Mother liquor burns or the purification of high-temperature oxydation gained crude product sodium pyrophosphate.
Background technique
Glyphosate mother solution processing is professional problem, either glycine method or IDA method production glyphosate, and mother liquor is all
Has the characteristics that high COD, high TP, with high salt, complicated component, difficult to degrade, processing difficulty is very big, at high cost.At present at mainstream mother liquor
Science and engineering skill is that mainly have incineration method, high-temperature oxidation, medium temperature oxidizing process, low using oxidizing process degradation mother liquor and recycling P elements
Warm oxidizing process etc. also passes through membrane separation technique or evaporation and concentration recycling sodium chloride and phosphate during mother liquid disposal.Example
Such as: UF membrane recycles sodium chloride and glyphosate and other substances, is concentrated by evaporation recycling glyphosate and sodium chloride, concentrated mother liquor are fixed
Sodium pyrophosphate is recycled to conversion, mother liquor catalytic oxidation recycles phosphate, etc..Every kind of method has superiority and inferiority, several glyphosate masters
Want big producer that different treatment process is respectively adopted, and above-mentioned several techniques are combined processing glyphosate by most enterprises
Mother liquor.Currently, there are concentrated mother liquor orientation conversion production sodium pyrophosphate in Xingfa Group, new Anhua work, Shandong Run Fengdeng company
Device, the obtained main content 40-85% of burnt sodium crude product, sodium chloride content is according to the difference of each business processes technique in 3-35% model
It encloses, also the impurity such as containing sodium carbonate, sodium bicarbonate, sodium sulfite, sodium hydrogensulfite, organic phosphorus.For the route, either at film
Reason desalination is still concentrated by evaporation desalination process, contains higher sodium chloride in final gained sodium pyrophosphate crude product, product impurity is more,
Colour-difference has peculiar smell, main content low, of poor quality, and the market price is low, and application is also restrained, needs further to purify,
Improve main content and quality.
Crude product sodium pyrophosphate is refining to obtain sodium pyrophosphate by part company, but in production process, there are crude product pyrophosphoric acids
The problem of sodium dissolution is slow, dissolution fluid viscosity is big, processing capacity is small and wastewater flow rate is big, at high cost and poor product quality, phosphoric acid
Sodium chloride, organophosphorus residue amount are big in product salt, of poor quality.Such as a kind of pair of glyphosate mother solution advanced treating of CN206915770U
The system that phosphor resource afterwards is purified.CN106809811A it is a kind of using crude product sodium pyrophosphate prepare the method for sodium pyrophosphate with
And a kind of crude product sodium pyrophosphate purification of CN106882781A produces the method decolourized when sodium pyrophosphate product and directly refines extraction coke
Sodium phosphate, equally there is also the dissolutions of crude product sodium pyrophosphate during handling crude product sodium pyrophosphate slowly, dissolution fluid viscosity is big, device
Processing capacity is small and sodium pyrophosphate product in the high problem of sodium chloride content.Therefore it needs that material feature is combined to develop new technique
Method.
Summary of the invention
The method of crude product sodium pyrophosphate purification production tertiary sodium phosphate sodium salt and sodium chloride provided by the present invention, in crude product coke
In sodium phosphate subtractive process, using each component in crude product sodium pyrophosphate and hydrolysate in different temperatures, pH value condition and auxiliary agent
The characteristics of effect lower dissolution sex differernce separation phosphoric acid trisodium salt, sodium chloride.According to market sale needs, the tricresyl phosphate sodium salt
Can specifically be produced as sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate or sodium dihydrogen phosphate and disodium hydrogen phosphate mixture,
Or the mixture of disodium hydrogen phosphate and tertiary sodium phosphate, the hydrated product of the specially described sodium ascorbyl phosphate can be by adjusting temperature, pH
Value etc. is realized.Handled using phosphoric acid and with oxidizing substance as auxiliary agent, promote by-product crude product sodium pyrophosphate dissolution, hydrolysis and
Crystallization realizes raising crystallization effect by changing phosphoric acid while removing impurity, improves tricresyl phosphate sodium salt and chlorination
Sodium quality.First sodium chloride is extracted in filtering from the mixed slurry after the dissolution of crude product sodium pyrophosphate, hydrolysis, then extracts from filtrate
Tricresyl phosphate sodium salt.Then the sodium chloride crude product and tricresyl phosphate sodium salt crude product that extract are refined respectively.Filter B is separating
The liquor B obtained during tricresyl phosphate sodium salt returns to hydrolysis kettle and carries out recycled.
In traditional glyphosate mother solution treatment process, the mother liquor generated in crude product sodium pyrophosphate subtractive process is usually to cover toward grass
The devices such as sweet phosphine mother liquor mvr evaporation, multiple-effect evaporation are evaporated concentration desalination, and the mother liquor after desalination burns again, are formed one big
Circulation, the technique have the characteristics that long flow path, processing cost are high, wastewater flow rate is big.In this method production process, since phosphorus will be purified
Recycling Mother Solution set after hydrochlorate is for dissolving crude product sodium pyrophosphate, into the water in system finally with tertiary sodium phosphate salt hydrate
Form is taken out of, and the enriched crystallization of the sodium chloride in crude product is also constantly precipitated, rather than reuses evaporating and concentrating process desalination, removes
Water reduces steam consumption, cost and environmental protection treatment pressure so significantly reducing the consumption and waste water yield of fresh water.
The crude product sodium pyrophosphate is that the phosphorous sodium chloride-containing waste water such as glyphosate mother solution is burned or high-temperature oxydation obtains
Sodium pyrophosphate crude product.
A kind of method that the purification of crude product sodium pyrophosphate produces tertiary sodium phosphate and sodium chloride, including following technique:
1. ingredient and analysis salt: initial when driving, by crude product sodium pyrophosphate and water according to 1:(0.5-2.0) mass ratio in water
Solution kettle (hydrolytic tank) is mixed, and phosphoric acid control mixed material pH value is added dropwise in 1.0-8.8 range.
During continuous operation, by crude product sodium pyrophosphate and the process water (filtrate after heat exchanger preheats and heats is applied
Other process waters described in B2, cleaning solution A and implementation steps) according to 1:(0.5-2.0) mass ratio hydrolysis kettle (hydrolysis
Pond) it is mixed, phosphoric acid control mixed material pH value is added dropwise in 1.0-8.8 range.
After crude product sodium pyrophosphate is partly dissolved, oxidisability auxiliary agent sodium perchlorate, chloric acid are added into hydrolysis kettle (hydrolytic tank)
One or more of sodium, sodium chlorite, sodium hypochlorite, carry out oxidation and colloidal sol reaction, and the additional amount of auxiliary agent is sodium pyrophosphate
0.005% (50ppm) -2.5% of crude product quality；After the auxiliary agent is added, solution viscosity is reduced, and solution rate is further promoted；
Control 70-120 DEG C at a temperature of stirring 5-60min so that crude product sodium pyrophosphate is sufficiently dissolved and is hydrolyzed；
Preferably, the temperature is 80-95 DEG C.
Preferably, the pH value is in 6.8-8.8 range.
The oxidisability auxiliary agent, it is therefore preferable to which one of sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate are several
The mixture of kind.Preferably, the oxidisability auxiliary agent is sodium chlorate；It is further preferred that the oxidisability auxiliary agent is sodium chlorate
With the sodium hypochlorite mixture of 1:0.2-1.2 in mass ratio.
As crude product dissolves, phosphate and sodium chloride content are incrementally increased in mixed solution, and sodium chloride is opposite because of solubility
It is smaller, first reach saturation, when crude product continues investment, sodium chloride constantly crystallizes precipitation, phosphatic content constantly mentions in system
It rises.
2. sodium chloride Product recycling:
Slurry in hydrolysis kettle described in step 1 is discharged filtering while hot, obtains sodium chloride product (filter residue A) and filtrate
(filtrate A), the filtrate main component are water, tertiary sodium phosphate and sodium chloride, and the filtrate tertiary sodium phosphate, sodium chloride have been satisfied and reached
It arrives and state.
Filter residue A (i.e. sodium chloride) is carried out using the liquor B 2 of the heat formed after heat exchanger preheating and heater heating
Material is washed, gained cleaning solution A is back to use hydrolysis kettle recycled.Gained sodium chloride product reaches " glyphosate by-product Nacl: chlorination
Sodium " standard.
Aforementioned sodium chloride product produces as product or further goes to sodium chloride deep refining device and further purifies.It is excellent
Selection of land, cleaning solution or filtrate of the sodium chloride deep refining device in purification sodium chloride product process return to hydrolysis kettle and are covered
With.
Obtained sodium chloride is produced it is further preferred that making leaching extraction agent using the alcoholic solution of hydrochloric acid or alcoholic solution or hydrogen chloride
Product carry out leaching extraction purification, and for the sodium chloride product through refining using a small amount of liquid alkaline adjustment pH value to neutrality, sodium chloride product quality is excellent
In " glyphosate by-product Nacl: sodium chloride " standard, residue of glyphosate is reduced within 0.02% (mass ratio), total phosphorus drop
Down within 0.08%.
Preferably, the hydrochloric acid after leaching extraction is back to glyphosate mother solution postprocessing working procedures, for adjusting mother liquor pH value, returns simultaneously
The phosphorus for soaking and extracting out is received, leaching extracts remaining impurity out with mother liquor oxidation processes.
Preferably, the alcoholic solution evaporation recycling alcohol after leaching extraction, obtained phosphorous concentrate deoxidation recycling, the alcohol of recycling follow
Ring set is used.
Hydrochloric acid is back to glyphosate mother solution postprocessing working procedures, for adjusting mother liquor pH value, while recycling the phosphorus for soaking and extracting out,
Remaining impurity is with mother liquor oxidation processes.
The alcohol is the mixture of one or more of methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol.
3. tertiary sodium phosphate product salt recycles:
After the cold liquor B 1 that the filtrate A of heat comes out through heat exchanger and filter B exchanges heat, mixed in mixer with alkali
Conjunction obtains solution A 2, controls the pH value of mixed solution A 2 in 10-13 range, gradually generates tertiary sodium phosphate.Solution A 2 is through filter C
Crystallization kettle is gone to after filtering out a small amount of impurity.
Suitable quantity of water is added into crystallization kettle, controls 0-30 DEG C of crystallisation by cooling 2-8h of temperature.In temperature-fall period, tricresyl phosphate sodium salt
Solubility rapid decrease, reaches hypersaturated state, and tricresyl phosphate sodium salt is constantly precipitated.Solubility of the sodium chloride in mixed solution with
Temperature decline is smaller, therefore sodium chloride is stayed in slurry mother liquor and is not precipitated.
Another technical solution is that will mix in mixer after the cooling of filtrate described in step (3) with alkali, and control mixing is molten
Liquid pH value generates tertiary sodium phosphate crude product, goes to crystallization kettle after filter filters out impurity in 10-13 range, (excellent to 90-105 DEG C
Select temperature be 100 DEG C) heat filtrate in add water and tertiary sodium phosphate crystal, then again temperature be 0-30 DEG C of crystallisation by cooling 2-
12 hypophosphite monohydrate trisodiums are precipitated in 8h, and the slurry filtration after sufficient crystallising is separated, 12 hypophosphite monohydrate trisodium products are obtained.
Slurry after sufficient crystallising is gone to filter B and is separated by filtration, and obtained filter residue B is tertiary sodium phosphate product (12
Hypophosphite monohydrate trisodium).Obtained 12 hypophosphite monohydrate trisodium can also go to deep refining device and further purify.
The alkali is the combination of one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate.
The mass ratio of the water and crude product coke sodium is (0-5): 1, it is therefore preferable to (1-3): 1.The weight of tertiary sodium phosphate crystal
For the 0.05-0.2% of the tertiary sodium phosphate of production.
Preferably, the pH value is in 11.1-12.1.
5. Recycling Mother Solution is applied:
Water, 30% or so sodium chloride and 10% or so the phosphate that mother liquor (i.e. liquor B) ingredient is about 60%.Cold
Liquor B goes to technique water storage tank after heat exchanger and the filtrate A of heat heat exchange, then heated device further heat after return to dissolution kettle
Recycled is carried out, continues to dissolve crude product sodium pyrophosphate.
Preferably, using the liquor B 2 of the heat formed after heat exchanger preheating and heater heating to filter residue A (i.e. chlorine
Change sodium) it carries out washing material, gained cleaning solution A is back to use hydrolysis kettle recycled.
Preferably, diffuser B and tricresyl phosphate sodium salt deep refining device washing during purifying tertiary sodium phosphate product salt
It washs liquid or filtrate returns to hydrolysis kettle and applied.
Preferably, cleaning solution or filtrate of the sodium chloride deep refining device in purification sodium chloride product process return to hydrolysis
Kettle is applied.
The present invention also provides the dresses that a kind of crude product sodium pyrophosphate purifies production tertiary sodium phosphate and sodium chloride in the above content
It sets, hydrolysis kettle bottom is connect with filter A；Filter device A is connect with heat exchanger, and heat exchanger is connect with mixer, mixer with
Filter C connection, filter C are connect with crystallization kettle, and crystallization kettle is connect with filter B, and filter B is connect with material device B is washed, and are washed
Material device B is connected to phosphate deep refining device.
The filter B is washed material device B and is connect respectively through pipeline with heat exchanger, heat exchanger connected water storage tank again with
Heater connection, heater are connected to hydrolysis kettle.
The bottom filter A is connect through pipeline with material device A is washed, and is washed material mono- tunnel device A and is connected to sodium chloride deep refining dress
(13) are set, are connected to heat exchanger all the way.
Wash the connecting pipe that material device A is connected between heater and hydrolysis kettle through pipeline line.
Technical solution of the present invention has the following beneficial effects:
1. the advantage of reaction, power savings advantages are obvious.This method dissolution, the speed of hydrolysis sodium pyrophosphate crude product is fast, reaction is thorough,
Unit time treating capacity is big, and monomer unit production capacity greatly improves.Only 5-20min can be completely dissolved, the more traditional work of dissolution time
Skill substantially shortens.
2. economy, environmental benefit are good.Crude product sodium pyrophosphate purifies the later mother liquor (i.e. liquor B) of tricresyl phosphate sodium salt can be with
Recycled, the dissolution of crude product sodium pyrophosphate are combined (hydrolysis with the water and sodium pyrophosphate in hydrolytic process, applied in process water
Reaction and hydration reaction), the final extraction system in the form of tricresyl phosphate sodium salt combination water of water in addition system, it is only necessary to regular pole
Arrange on a small quantity dense, the water resource in reuse technology water is recycled.The sodium chloride in crude product sodium pyrophosphate is due to saturation simultaneously
It is precipitated and realizes separation.Therefore for wastewater flow rate is with respect to other techniques such as catalytic wet oxidation extraction phosphate in purification purification process
Reduce 92% or more.The purity and reduction waste water yield, environmental benefit of the raising tricresyl phosphate sodium salt of maximizing are very prominent
Out, good economy performance.
3. this method can recycle sodium chloride product, chlorine resource is recycled, reduces the discharge amount liquid and waste slag produced containing chlorine.This method
The cost for recycling sodium chloride is far below the cost that sodium chloride is recycled using evaporating concentrating method, and quality might as well.
4. tricresyl phosphate sodium salt obtained by this method and sodium chloride product impurity are few, purity is high.(1) this method is accelerated using phosphoric acid
The dissolution of sodium pyrophosphate crude product does not introduce new anionic impurity, while the waste water incinerations such as glyphosate mother solution being generated in the process
The removal of the anionic impurities such as carbonate, bicarbonate radical, inferior sulfate radical, sulfate radical, the removal of sulfide reduce product peculiar smell.
(2) this method is using oxidisability auxiliary agent on the one hand by TOC, COD and NH remaining in mother liquor burning process3- N oxidation removal, and
It brightens and eliminates the unusual smell effect, while promoting colloid dispergation in mixed system, material particle is fully dispersed, reduces viscosity of sludge
To 30mPas hereinafter, so crystallization effect is good, synergistic effect, gained tertiary sodium phosphate are further produced under these types effect
Salt crystal and sodium chloride crystal purity is high.(3) because crude product sodium pyrophosphate purifies tricresyl phosphate sodium salt, later mother liquor system is returned again
The recycled into system, so can improve as far as possible washing water in waste water acceptable range limits, improve phosphorus
The purity of sour trisodium salt, the features impurity indexs such as sodium chloride, non-positive phosphorus substance significantly improve.(4) mother liquor after sodium chloride purification
System comes back to recycled in system, so washing water can be improved as far as possible in waste water acceptable range limits
Amount, improves the purity of sodium chloride.(5) sodium chloride content can be down to 0.08% hereinafter, chlorine in the tricresyl phosphate sodium salt of this method recycling
Change the level that sodium content level refines gained sodium pyrophosphate or tricresyl phosphate sodium salt 3-15% sodium chloride far below traditional handicraft.
5. phosphoric acid salt residual quantity is very low in sodium chloride product, sodium ascorbyl phosphate recycling is thorough.Because crude product sodium pyrophosphate purifies
The later mother liquor system of sodium ascorbyl phosphate comes back to recycled in system, thus can in waste water acceptable range limits,
Improving washing water as far as possible reduces the loss of sodium ascorbyl phosphate while improving sodium chloride quality.
Detailed description of the invention
Fig. 1 is the process flow chart of crude product sodium pyrophosphate purification production tertiary sodium phosphate and sodium chloride, wherein 1. hydrolysis kettles,
2. filter A, 3. wash material device A, 4. heat exchangers, 5. water storage tanks, 6. mixers, 7. filter C, 8. crystallization kettles, 9. filters
B, 10. wash material device B, 11. phosphate deep refining devices, 12. heaters.
Specific embodiment
Embodiment 1
A kind of method that the purification of crude product sodium pyrophosphate produces tertiary sodium phosphate and sodium chloride, includes the following steps:
1. ingredient: when initial driving, by crude product sodium pyrophosphate and water according to the mass ratio of 1:2.0 at hydrolysis kettle (hydrolytic tank)
It is mixed, phosphoric acid control mixed material pH value is added dropwise in 1.0-8.8 range.
After crude product sodium pyrophosphate is partly dissolved, the oxidisability auxiliary agent (oxidisability is added into hydrolysis kettle (hydrolytic tank)
Auxiliary agent is sodium chlorate and the sodium hypochlorite mixture of 1:1 in mass ratio), temperature is 80-95 DEG C, pH value is in 6.8-8.8 range
Under carry out oxidation and colloidal sol reaction, the additional amount of auxiliary agent is the 0.025% of sodium pyrophosphate crude product quality；It is molten after the auxiliary agent is added
Fluid viscosity reduces, and solution rate is further promoted；Control 80-95 DEG C at a temperature of stirring 5-60min make crude product sodium pyrophosphate
Sufficiently dissolution and hydrolysis；
2. analysing salt: as crude product dissolves, phosphate and sodium chloride content are incrementally increased in mixed solution, and sodium chloride is because of dissolution
It spends relatively small, first reaches saturation, when crude product continues investment, sodium chloride constantly crystallizes precipitation, phosphatic content in system
Constantly promoted.
3. sodium chloride Product recycling: discharging filtering while hot obtains filtrate A and filter residue A.Filter residue A is thick sodium chloride product,
It is washed material and obtains sodium chloride product, sodium chloride deep refining device can also be gone to and further purified.Pyrophosphoric acid in filtrate A
Sodium, sodium chloride, which have been satisfied, to be reached and state.
4. tertiary sodium phosphate product salt recycles:
After the cold liquor B 1 that the filtrate A of heat comes out through heat exchanger and filter B exchanges heat, with sodium bicarbonate in mixer
It carries out being mixed to get solution A 2, controls the pH value of mixed solution A 2 in 11.1-12.1 range, gradually generate tertiary sodium phosphate.Solution
A2 goes to crystallization kettle after filter C filters out a small amount of impurity.
It will be mixed in mixer after the cooling of filtrate described in above-mentioned rapid 4 will be walked with alkali, control mixed solution pH value exists
11.1-12.1 range generates tertiary sodium phosphate crude product, goes to crystallization kettle after filter filters out impurity, the filtrate hot to 100 DEG C
Water and tertiary sodium phosphate crystal are inside added, in temperature is again then 0-30 DEG C of crystallisation by cooling 2-8h, in temperature-fall period, tertiary sodium phosphate sodium
Salt solubility rapid decrease, reaches hypersaturated state, and tertiary sodium phosphate sodium salt is constantly precipitated.Dissolution of the sodium chloride in mixed solution
Degree is smaller with temperature decline, therefore sodium chloride is stayed in slurry mother liquor and is not precipitated.By the slurry filtration separation after sufficient crystallising, obtain
To 12 hypophosphite monohydrate trisodium products.
The mass ratio of the water and crude product sodium pyrophosphate is 3:1；The weight of tertiary sodium phosphate crystal is the tertiary sodium phosphate of production
0.1%.
Slurry after sufficient crystallising is gone to filter B and is separated by filtration, and obtained filter residue B is tertiary sodium phosphate product (12
Hypophosphite monohydrate trisodium).Obtained tertiary sodium phosphate can also go to deep refining device and further purify.
5. Recycling Mother Solution is applied:
Water, 30% or so sodium chloride and 10% or so the phosphate that mother liquor (i.e. liquor B) ingredient is about 60%.Cold
Liquor B 1 goes to technique water storage tank after heat exchanger and the filtrate A of heat heat exchange, then heated device further heat after return to dissolution
Kettle carries out recycled, continues to dissolve crude product sodium pyrophosphate.
Filter residue A (i.e. sodium chloride) is washed using the liquor B 2 of the heat after heat exchanger preheating and heater are heated
Material, gained cleaning solution A are back to use hydrolysis kettle recycled.
Described washes material device B and tricresyl phosphate sodium salt deep refining device washing during purifying tertiary sodium phosphate product salt
It washs liquid or filtrate returns to hydrolysis kettle and applied.
Cleaning solution or filtrate of the sodium chloride deep refining device in purification sodium chloride product process return to hydrolysis
Kettle is applied.
Table 1: crude product sodium pyrophosphate hydrolysate and sodium chloride dissolubility data
Embodiment 2
A kind of crude product sodium pyrophosphate purification produces the device of sodium pyrophosphate and sodium chloride, 1 bottom of hydrolysis kettle and filter A2
Connection；Filter device A 2 is connect with heat exchanger 4, and heat exchanger 4 is connect with mixer 6, and mixer 6 is connect with filter C 7, mistake
Filter C 7 is connect with crystallization kettle 8, and crystallization kettle 8 is connect with filter B 9, and filter B 9 is connect with material device B 10 is washed, and washes material
Device B 10 is connected to sodium pyrophosphate deep refining device 11.
Filter B 9 washes and expects that device B 10 is connect through pipeline with heat exchanger 4 respectively, and heat exchanger 4 is through connecting water storage tank 5 again
It is connect with heater 12, heater 12 is connected to hydrolysis kettle 1.
2 bottom filter A is connect through pipeline with material device A 3 is washed, and is washed material 3 one tunnel device A and is connected to sodium chloride depth
Refining plant 13 is connected to heat exchanger 4 all the way.
Heater 12 is connected to through pipeline washes material device A 3.
It is provided with pyrophosphoric acid crude product on the hydrolysis kettle 1 and enters pipeline, phosphoric acid pipeline, auxiliary agent pipeline, water pipeline, steam
Pipeline.
Material device A 3 is washed, washes and expects that being provided with water on device B 10 enters pipeline.
Crystallization water pipeline is provided on crystallization kettle 8.
Claims (9)
1. a kind of method of crude product sodium pyrophosphate purification production tertiary sodium phosphate and sodium chloride product, it is characterised in that: including as follows
Step:
(1) ingredient and analysis salt: crude product sodium pyrophosphate and water are mixed, and phosphoric acid control mixed material pH value is added dropwise in 1.0-8.8 model
It encloses, the at a temperature of stirring 5-60min after oxidized form auxiliary agent at 70-120 DEG C, which is added, to be dissolved crude product sodium pyrophosphate and hydrolyze；
(2) sodium chloride Product recycling: slurry in hydrolysis kettle as described in step (1) is discharged filtering while hot, obtains sodium chloride production
Product and filtrate；
(3) tertiary sodium phosphate product salt recycles: will mix in mixer after the cooling of filtrate described in step (2) with alkali, control is mixed
Solution ph is closed in 10-13 range, tertiary sodium phosphate crude product is generated, crystallization kettle is gone to after filter filters out impurity, to 90-105
Water and tertiary sodium phosphate crystal are added in DEG C hot filtrate, controls 0-30 DEG C of crystallisation by cooling 2-8h of temperature, and 12 hypophosphite monohydrates are precipitated
Slurry filtration after sufficient crystallising is separated, obtains 12 hypophosphite monohydrate trisodium products by trisodium.
2. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: the crude product sodium pyrophosphate is glyphosate mother solution, the phosphorous sodium chloride-containing waste water of pmida mother liquor is burned or high temperature
The sodium pyrophosphate crude product that obtained main component is sodium pyrophosphate and sodium chloride is aoxidized, is grey, canescence or greyish black toner
Shape, bulk, granular mixture, main component are sodium pyrophosphate and sodium chloride, the main content 40-85% of sodium pyrophosphate, chlorination
Sodium content 3-35%, total organic carbon is in 0.1-0.3%, also containing sodium carbonate, sodium bicarbonate, sodium sulfite, sodium hydrogensulfite, organic phosphorus
Impurity, pH value of water solution 9.5-10.55.
3. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: the mass ratio of crude product sodium pyrophosphate and water as described in step (1) is 1:(0.5-2.0).
4. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: the additional amount of oxidized form auxiliary agent described in step (2) is the 0.005%-2.5% of sodium pyrophosphate crude product quality.
5. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: oxidized form auxiliary agent described in step (2) is sodium perchlorate, sodium chlorate, sodium chlorite, any one in sodium hypochlorite
Kind or several combinations.
6. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: oxidisability auxiliary agent described in step (2) is sodium chlorate, the sodium hypochlorite mixture of 1:0.2-1.2 in mass ratio.
7. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: alkali described in step (3) is the combination of one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate.
8. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: the mass ratio of crude product sodium pyrophosphate is (0-5) in the quality and raw material of the water of addition described in step (3): 1；Phosphoric acid
The weight of three sodium crystals is the 0.05-0.2% of the sodium dihydrogen phosphate of production.
9. the method for crude product sodium pyrophosphate purification production tertiary sodium phosphate according to claim 1 and sodium chloride product, special
Sign is: when slurry solution is down to 90-105 DEG C, water and tertiary sodium phosphate crystal is added.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811619725.3A CN109437137B (en) | 2018-12-28 | 2018-12-28 | Method for producing trisodium phosphate and sodium chloride by purifying crude sodium pyrophosphate |
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| CN201811619725.3A CN109437137B (en) | 2018-12-28 | 2018-12-28 | Method for producing trisodium phosphate and sodium chloride by purifying crude sodium pyrophosphate |
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| CN109437137A true CN109437137A (en) | 2019-03-08 |
| CN109437137B CN109437137B (en) | 2022-10-21 |
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| CN110812877A (en) * | 2019-10-12 | 2020-02-21 | 西安交通大学 | Glyphosate mother liquor treatment method and device |
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| CN112062141A (en) * | 2020-08-25 | 2020-12-11 | 合众思(北京)环境工程有限公司 | Process for producing sodium chloride and phosphate from sodium hypochlorite wastewater |
| CN114148996A (en) * | 2021-10-29 | 2022-03-08 | 雷波凯瑞磷化工有限责任公司 | Method for producing sodium pyrophosphate and sodium chloride by purifying crude sodium pyrophosphate |
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|---|---|---|---|---|
| CN110467231A (en) * | 2019-07-26 | 2019-11-19 | 新疆中泰化学阜康能源有限公司 | The peace and quiet waste water carnallite refining treatment apparatus of acetylene gas sodium hypochlorite and method |
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| CN112062141A (en) * | 2020-08-25 | 2020-12-11 | 合众思(北京)环境工程有限公司 | Process for producing sodium chloride and phosphate from sodium hypochlorite wastewater |
| CN114148996A (en) * | 2021-10-29 | 2022-03-08 | 雷波凯瑞磷化工有限责任公司 | Method for producing sodium pyrophosphate and sodium chloride by purifying crude sodium pyrophosphate |
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