A kind for the treatment of process of pmida98 mother liquorTechnical field
The present invention relates to a kind for the treatment of process of pmida98 mother liquor, particularly a kind of iminodiacetic acid (salt) acid system is produced the treatment process of the pmida98 mother liquor that glyphosate obtains.
Technical background
Glyphosate is as the steriland herbicide of a kind of efficient, wide spectrum, low toxicity, range of application is more and more extensive, become the present in the world weedicide of consumption maximum, the method that Present Domestic prepares glyphosate is a lot, dialkyl phosphite method and the iminodiacetic acid (salt) acid systems of adopting more, can produce the acid mother liquid of the Multiple components such as chloride ion-containing, sodium ion, pmida98 when adopting the iminodiethanoic acid route to prepare glyphosate, in present production process, process comparatively difficulty of this kind mother liquor, usually fall as wastewater treatment, not only waste resource, but also contaminate environment.
Only the sodium-chlor in the waste water is recycled in the patent application of Chinese patent CN1422275A and CN1837105A, pmida98 is utilized; Recycled the pmida98 in the waste water in the patent application of Chinese patent CN101041527A, but complex process wastes time and energy; Chinese patent CN101348266A adopts the nanofiltration membrane concentrated mother liquor, reclaim the pmida98 in the concentrated solution, light liquid is through evaporative crystallization, and roasting, dephosphorization are processed and obtained refining sodium-chlor, although reclaimed pmida98 and byproduct sodium chloride, but the rate of recovery is also not bery high, from the data of embodiment 1, it only is 91.2% that pmida98 reclaims, and the sodium-chlor rate of recovery does not reach 90%.And treatment step is comparatively loaded down with trivial details, and processing cost is not low yet.
Now, seek a kind of can be high yield reclaim Recyclable in the mother liquor, can reduce again waste water and discharge, alleviate environmental protection pressure, the treatment process that can produce higher secondary benefit and the simple pmida98 mother liquor of technique simultaneously is the problem that the industry needs to be resolved hurrily.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides the treatment process that a kind of iminodiacetic acid (salt) acid system is produced the PMIDA synthesis mother liquor that glyphosate obtains.The present invention can effectively reclaim the material in the pmida98 mother liquor, and technique is simple, and is easy to operate.
Concrete technical scheme of the present invention is as follows:
A kind for the treatment of process of pmida98 mother liquor may further comprise the steps:
(1) in the pmida98 mother liquor, add alkaline matter, make the mother liquor pH regulator to 9-12, concentrated through multiple-effect evaporation, filter, get filter cake and filtrate;
(2) get filter cake, remove organic substance through washing, namely get inorganic salt;
(3) get filtrate, through burning, namely get pyrophosphate salt.Further, also comprise waste heat and the solid that reclaims in the incineration flue gas.
Described pmida98 mother liquor is when adopting the standby glyphosate of iminodiethanoic acid legal system, the acid mother liquid of synthetic pmida98 gained.
In the above-mentioned steps (1), alkaline matter is sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide.Inventing used alkaline matter is pH adjusting agent, and its state, concentration are not particularly limited, for considering of wastewater flow rate and processing cost, and preferred solid sodium hydroxide.
In the above-mentioned steps (3), multiple-effect evaporation is concentrated into 60 ~ 90% of former weight.
In the above-mentioned steps (3), incineration temperature is 600 ~ 900 ℃.
Adopting the present invention to process PMIDA synthesis mother liquor has the following advantages:
(1) technique is simple, efficient, the chlorion transformation efficiency is more than 98%, step (2) gained waste water is after biochemical system is processed, the waste water COD of discharging is less than 20mg/L, TP is less than 0.5mg/L, and ammonia nitrogen has been realized the zero release of waste water substantially less than 10mg/L, efficiently solve the processing problem of pmida98 mother liquor, environmental benefit of the present invention is outstanding;
(2) gained pyrophosphate salt content is more than 95%, and the phosphorus containg substances transformation efficiency reaches more than 98%;
(3) the gained Industrial Salt can be used for the industries such as chemical industry, papermaking, building, and the trisodium phosphate of gained can be used for chemical industry, plating, wool spinning, paper industry, so economic benefit of the present invention is outstanding.
Embodiment
Below by specific embodiment the present invention is further set forth, should be understood that, following explanation only is in order to explain the present invention, its particular content not to be limited.
Embodiment 1
Get pmida98 mother liquor 1000g, chlorion 13.8% is arranged after testing, total phosphorus 0.9%, add the 30wt% sodium hydroxide solution, make mother liquor pH regulator to 9 after, multiple-effect evaporation is concentrated into 60% of former weight, filter, filter cake is removed organism through washing, namely gets sodium-chlor 223.12g, the chlorion transformation efficiency is 98.1%, and waste water is COD 18mg/L after biochemical treatment, TP 0.4mg/L, ammonia nitrogen 8mg/L, filtrate namely gets trisodium phosphate 38.5g through 600 ℃ of burnings, content 98.3%, phosphorus containg substances transformation efficiency 98.0%.Reclaim simultaneously waste heat and solid in the incineration flue gas.
Embodiment 2
To containing chlorion 13.8%, add the 40wt% sodium hydroxide solution among the pmida98 mother liquor 1000g of total phosphorus 0.9%, make mother liquor pH regulator to 10 after, multiple-effect evaporation is concentrated into 70% of former weight, filters, and filter cake is removed organism through washing, namely get sodium-chlor 223.92g, the chlorion transformation efficiency is 98.5%, and waste water is COD 17mg/L after biochemical treatment, TP 0.3mg/L, ammonia nitrogen 7mg/L, filtrate namely gets trisodium phosphate 38.4g through 700 ℃ of burnings, content 98.6%, phosphorus containg substances transformation efficiency 98.1%.Reclaim simultaneously waste heat and solid in the incineration flue gas.
Embodiment 3
To containing chlorion 13.8%, add the 50wt% sodium hydroxide solution among the pmida98 mother liquor 1000g of total phosphorus 0.9%, make mother liquor pH regulator to 11 after, multiple-effect evaporation is concentrated into 80% of former weight, filters, and filter cake is removed organism through washing, namely get sodium-chlor 224.4g, the chlorion transformation efficiency is 98.7%, and waste water is COD 12mg/L after biochemical treatment, TP 0.3mg/L, ammonia nitrogen 6mg/L, filtrate namely gets trisodium phosphate 38.5g through 800 ℃ of burnings, content 98.7%, phosphorus containg substances transformation efficiency 98.4%.Reclaim simultaneously waste heat and solid in the incineration flue gas.
Embodiment 4
To containing chlorion 13.8%, add sodium hydroxide among the pmida98 mother liquor 1000g of total phosphorus 0.9%, make mother liquor pH regulator to 12 after, multiple-effect evaporation is concentrated into 90% of former weight, filters, and filter cake is removed organism through washing, namely get sodium-chlor 227.04g, the chlorion transformation efficiency is 99.8%, and waste water is COD 10mg/L after biochemical treatment, TP 0.1mg/L, ammonia nitrogen 5mg/L, filtrate namely gets trisodium phosphate 38.6g through 900 ℃ of burnings, content 99.6%., phosphorus containg substances transformation efficiency 99.6%.Waste heat and solid in the while recovered flue gas.
Embodiment 5
To containing chlorion 13.8%, add solid potassium hydroxide among the pmida98 mother liquor 1000g of total phosphorus 0.9%, make mother liquor pH regulator to 10.5 after, multiple-effect evaporation is concentrated into 75% of former weight, filters, and filter cake is removed a small amount of organism through washing, namely get Repone K 284.4g, the chlorion transformation efficiency is 98.1%, and waste water is COD 12mg/L after biochemical treatment, TP 0.4mg/L, ammonia nitrogen 8mg/L, filtrate namely gets potassium pyrophosphate 47.8g through 750 ℃ of burnings, content 98.3%, phosphorus containg substances transformation efficiency 98.1%.Waste heat and solid in the while recovered flue gas.
Embodiment 6
To containing chlorion 13.8%, add the solid hydrogen calcium oxide among the pmida98 mother liquor 1000g of total phosphorus 0.9%, make mother liquor pH regulator to 10.5 after, multiple-effect evaporation is concentrated into 75% of former weight, filters, and filter cake is removed a small amount of organism through washing, namely get calcium chloride 211.8g, the chlorion transformation efficiency is 98.2%, and waste water is COD 15mg/L after biochemical treatment, TP 0.3mg/L, ammonia nitrogen 7mg/L, filtrate namely gets Calcium Pyrophosphate 36.8g through 650 ℃ of burnings, content 98.4%, phosphorus containg substances transformation efficiency 98.1%.Waste heat and solid in the while recovered flue gas.
Embodiment 7
To containing chlorion 13.8%, add solid oxidation calcium among the pmida98 mother liquor 1000g of total phosphorus 0.9%, make mother liquor pH regulator to 10.5 after, multiple-effect evaporation is concentrated into 75% of former weight, filters, and filter cake is removed a small amount of organism through washing, namely get calcium chloride 212.4g, the chlorion transformation efficiency is 98.4%, and waste water is COD 17mg/L after biochemical treatment, TP 0.4mg/L, ammonia nitrogen 8mg/L, filtrate namely gets Calcium Pyrophosphate 36.9g through 850 ℃ of burnings, content 98.3%, phosphorus containg substances transformation efficiency 98.3%.Waste heat and solid in the while recovered flue gas.