CN101602779B - Method for preparing N-phosphonomethyliminodiacetic acid by using sulfuric acid as catalyst and preparing iminodiacetic acid by recovering and indiscriminately applying mother liquid thereof - Google Patents
Method for preparing N-phosphonomethyliminodiacetic acid by using sulfuric acid as catalyst and preparing iminodiacetic acid by recovering and indiscriminately applying mother liquid thereof Download PDFInfo
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- CN101602779B CN101602779B CN2009100079402A CN200910007940A CN101602779B CN 101602779 B CN101602779 B CN 101602779B CN 2009100079402 A CN2009100079402 A CN 2009100079402A CN 200910007940 A CN200910007940 A CN 200910007940A CN 101602779 B CN101602779 B CN 101602779B
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- sulfuric acid
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Abstract
The invention relates to a method for N-phosphonomethyliminodiacetic acid by using sulfuric acid as catalyst and preparing iminodiacetic acid by recovering and indiscriminately applying mother liquid thereof. In the method, sulfuric acid instead of hydrochloric acid is adopted as a catalyst, the reaction conversion rate of iminodiacetic acid and the selectivity of preparing N-(phosphonium acyl methyl)iminodiacetic acid are enhanced, the conversion rate of the iminodiacetic acid which is utilized by sulfuric acid mother liquid and is mechanically applied to a reaction of preparing the iminodiacetic acid by neutralizing iminodiacetic acid disodium salt can simultaneously reach 98% after the N-(phosphonium acyl methyl)iminodiacetic acid is filtered and separated out, and the sulfuric acid used as the catalyst can not generate acid waste gas in the reaction. No three-waste discharge exists in the entire reaction technology.
Description
Technical field
The present invention relates to a kind ofly make Preparation of Catalyst pmida98 and mother liquor recovery set thereof with the method that prepare iminodiethanoic acid, belong to the technical field that iminodiethanoic acid prepares with sulfuric acid.
Background technology
Glyphosate 62 IPA Salt, chemical name are N-(phosphonomethyl) glycocoll (English name is Glyphosate (PMG)), as a kind of low toxicity, broad spectrum weeding agent, many plants, weeds are all had validity, are one of maximum weedicides of global sales.
The Glyphosate 62 IPA Salt operational path mainly contains two kinds: glycine method and iminodiethanoic acid (IDA) method.
The sub product methyl chloride of glycine method has bigger pollution to environment, does not meet international environmental protection standard.
The IDA method is the technology that international business generally adopts.Iminodiethanoic acid (IDA) method is the advanced technologies of producing Glyphosate 62 IPA Salt at present: the employing iminodiethanoic acid is a raw material; Through contracting with formaldehyde, phosphorous acid and generating the midbody pmida98; Chemical name is N-(phosphonomethyl) iminodiethanoic acid (English name is N-(Phosphonomethyl) iminodiacetic acid (PMIDA)), is oxidized to the method for N-(phosphonomethyl) glycocoll at last.
The preparation method of the intermediate N phosphonomethyl iminodiethanoic acid of Glyphosate 62 IPA Salt adopts at present has following several kinds of technologies:
(1) the phosphorus trichloride legal system is equipped with N-(phosphonomethyl) iminodiethanoic acid: the Iminodiacetic acid sodium salt salt that makes through hydrolysis through dehydrogenation or NSC 263496 with diethylolamine; Add after phosphorus trichloride generates the Iminodiacetate hydrochlorate, again with phosphorous acid, formaldehyde through condensation prepared N-(phosphonomethyl) iminodiethanoic acid.Condensation reaction selectivity low (88%-90%), reaction can produce a large amount of saliferous and the strongly acid wastewater of impurity, and is very big to equipment corrosion, and emission standard can't handled and reach to this part sour water at present because of containing a large amount of salt, by-product and strongly-acid at all.
(2) the hydrochloric acid catalysis legal system is equipped with N-(phosphonomethyl) iminodiethanoic acid: adopt the imino-acetonitrile; Through processing Iminodiacetate with the hydrolysis of alkali; Select for use hydrochloric acid to make catalyzer in the neutralization procedure and generate acetimidic acid; Again with phosphorous acid, formaldehyde through condensation prepared N-(phosphonomethyl) iminodiethanoic acid, i.e. pmida98; In the preparation process of pmida98, employing hydrochloric acid is catalyzer, the selectivity of condensation reaction low (90%), and the yield of pmida98 is not high.Use owing to select for use hydrochloric acid to make catalyst excess, in reaction, can produce hydrogen chloride gas and to have a large amount of impure strongly acid wastewaters bigger to equipment corrosion, the structure deteriorate rate is high.
(3) utilize the dimethylphosphite raffinate to prepare N-(phosphonomethyl) iminodiethanoic acid: in the dimethylphosphite raffinate, to add iminodiethanoic acid, hydrochloric acid and water, slowly add quantitative methylal when producing and prepare N-(phosphonomethyl) iminodiethanoic acid when refluxing.The selectivity of this reaction low (＜90%), reaction produces tail gas, except methyl chloride, also has impurity such as acetal, alcohol, water, hydrogenchloride, formaldehyde, is difficult for handling.
Summary of the invention
One of the object of the invention is exactly to provide in order to overcome the defective that above-mentioned prior art exists a kind of and makes the method for Preparation of Catalyst pmida98 with sulfuric acid, and this method has higher conversion and higher selectivity, reduces the discharging of the three wastes simultaneously.
Two of the object of the invention provides a kind ofly utilizes mother liquor recovery set in the aforesaid method with preparing the method for iminodiethanoic acid.
Making the method for Preparation of Catalyst pmida98 as a kind of of first aspect present invention with sulfuric acid, is raw material with the iminodiethanoic acid, makes catalyzer and phosphorous acid, formaldehyde with sulfuric acid and carries out condensation reaction and prepare N-(phosphonomethyl) iminodiethanoic acid; This method adopts sulfuric acid to make catalyzer; The reaction preference of the reaction conversion ratio of iminodiethanoic acid and N-(phosphonomethyl) iminodiethanoic acid is all greater than 98%; Crystallization, filter in the sulfuric acid that the back recovery set is used as catalyzer and Iminodiacetic acid sodium salt salt prepares iminodiethanoic acid, no three wastes generation in the reaction process.
Said method comprising the steps of:
(1) in reactor drum, add iminodiethanoic acid and sulfuric acid, phosphorous acid, mixed dissolution obtains first solution under 40-100 ℃ of condition;
(2) temperature with first solution is elevated to 110-120 ℃;
(3) in first solution, drip formaldehyde subsequently, be cooled to 5-20 ℃ after formaldehyde dropwises and obtain second solution;
(4) second solution crystallisation by cooling 2-15 hour;
(5) second solution behind the crystallisation by cooling is filtered, isolate N-(phosphonomethyl) iminodiethanoic acid solid and sulfate liquor;
(6) prepare iminodiethanoic acid with Iminodiacetic acid sodium salt salt in the sulfate liquor that reclaims.
Said step (1) vitriolic mass percent concentration is 20%-70%;
Said step (1) is that 20-70% sulfuric acid dissolves salify at 40-100 ℃ with iminodiethanoic acid solid and mass percent concentration, and iminodiethanoic acid: the vitriolic mol ratio is 1: 0.2-1.0;
The said phosphorous acid mass percent concentration of said step (1) should be 70-99%, iminodiethanoic acid: the mol ratio of phosphorous acid is 1: 1-1.5;
The mass percent concentration of the said formalin of said step (3) is 20-37%, iminodiethanoic acid: the mol ratio of formaldehyde is 1: 1-1.5; The dropping time of formaldehyde was controlled at 0.5-3 hour, and when formaldehyde dripped, the temperature of first solution was controlled at 110-120 ℃;
Said step (3) Tc is 5-20 ℃;
Said step (4) crystallization time is 2-15 hour;
Mother liquor recovery set as second aspect present invention is used the method for preparing iminodiethanoic acid; It is characterized in that, will use recovery set behind preparation N-(phosphonomethyl) iminodiethanoic acid to be used as in the sulfate liquor of catalyzer and the Iminodiacetic acid sodium salt salt brine solution, in the control with endpoint pH at 2.1-2.3; In and after-filtration; Isolate the iminodiethanoic acid solid, wherein, neutral temperature 20-100 ℃.
Said recovery set uses the sulfate liquor mass percent concentration to be 20-70%.
The mass percent concentration of said Iminodiacetic acid sodium salt salt brine solution is 35-50%.
The present invention adopts sulfuric acid to replace hydrochloric acid to prepare pmida98 as catalyzer; Can improve iminodiethanoic acid reaction conversion ratio and preparation N-(phosphonomethyl) iminodiethanoic acid selectivity; To filter, isolate the sulfate liquor behind N-(phosphonomethyl) iminodiethanoic acid simultaneously; Prepare iminodiethanoic acid with the Iminodiacetic acid sodium salt salt brine solution in being used for; Have no three wastes generation and transformation efficiency and the high characteristics of selection in whole preparation N-(phosphonomethyl) the iminodiethanoic acid technology, reaction process is more reasonable.
Reaction equation of the present invention is following:
(1) sulfuric acid is made the reaction formula of Preparation of Catalyst N-(phosphonomethyl) iminodiethanoic acid:
HN(CH
2COOH)
2+H
3PO
3+H
2CO+H
2SO
4→
(HO)
2P(O)CH
2N(CH
2COOH)
2+H
2SO
4+H
2O
(2) prepare the reaction formula of iminodiethanoic acid with the Iminodiacetic acid sodium salt salt brine solution in the reclaim(ed) sulfuric acid mother liquor:
HN(CH
2COONa)
2+H
2SO
4→HN(CH
2COOH)
2+Na
2SO
4+H
2O
Beneficial effect of the present invention:
1. carry out condensation reaction with sulfuric acid as catalyzer, in the reaction iminodiacetic acid conversion with generate N-(phosphonomethyl) iminodiethanoic acid selectivity and all can reach 98%, making the catalyzer method with hydrochloric acid, to compare selectivity all high by 10% with transformation efficiency.
2. make catalyzer with sulfuric acid and instead in reaction, can not produce acid waste gas, corrosion on Equipment property is made the technology of catalyzer far below hydrochloric acid.
3. product N-(phosphonomethyl) iminodiethanoic acid that decrystallizes of condensation reaction after-filtration; The sulfate liquor that reclaims is capable of circulation to be applied mechanically to the neutralization reaction of Iminodiacetic acid sodium salt salt and prepares iminodiethanoic acid; Through reclaim(ed) sulfuric acid sodium as by product, three-waste free discharge in the entire reaction technology.
Description of drawings
Further specify the present invention below in conjunction with accompanying drawing and embodiment.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
In order to make technique means of the present invention, creation characteristic, to reach purpose and effect and be easy to understand and understand,, further set forth the present invention below in conjunction with concrete diagram.
Embodiment 1
As shown in Figure 1, with iminodiethanoic acid (95%, 0.5mol) and sulfuric acid (mass percent concentration 20-70%; 0.2-1.0mol), after phosphorous acid (0.5-0.75mol) drops into and to stir, to mix, be heated to 100 ℃ of insulations 0.5 hour, dissolving, salify in the three mouthfuls of reaction flasks of 1000ml have whisking appliance and TM, the elevated temperature holding temperature is at 110-120 ℃, dropping formaldehyde (0.5-0.75mol) 3 hours; N-in the reaction process (phosphonomethyl) iminodiethanoic acid solid is separated out gradually, after formaldehyde drips and finishes, and insulation reaction 2 hours; Be cooled to 20 ℃, cooling and stirring, crystallization 10-15 hour filter out N-(phosphonomethyl) iminodiethanoic acid solid and obtain sulfate liquor; Oven dry post analysis content 98.50%; The solid yield is 94.86%, contains in the sulfate liquor: iminodiethanoic acid 0.61%, N-(phosphonomethyl) iminodiethanoic acid 2.12%, sulfuric acid 22.62%; Iminodiacetic acid conversion is 98.13%, and selectivity is 98.22%.
Above-mentioned sulfate liquor is recycled; And add sulfuric acid, be fed in the aqueous solution of imido-oxalic acid disodium salt (the quality percentage composition is 35-50%) neutralize, acidifying, terminal point control pH2.1-2.3; Filter, isolate the iminodiethanoic acid solid after the neutralization; The solid yield is 95.31%, and it is capable of circulation that the sulfate liquor after the separation is isolated sodium sulfate through concentrated after-filtration, applies mechanically to following batch of preparation iminodiethanoic acid.
Embodiment 2
With iminodiethanoic acid (95%, 0.5mol) and sulfuric acid (20-70%, 0.2-1.0mol), after phosphorous acid (0.5-0.75mol) drops into and to stir, to mix, be heated to 100 ℃ of 0.5 hours, dissolving, salify in the three mouthfuls of reaction flasks of 1000ml have whisking appliance and TM; The elevated temperature holding temperature dripped formaldehyde (0.5-0.75mol) 3 hours at 110-120 ℃, and N-in the reaction process (phosphonomethyl) iminodiethanoic acid solid is separated out gradually; After formaldehyde dripped and finishes, insulation reaction 2 hours was cooled to 20 ℃; Cooling and stirring, crystallization 10-15 hour; Filter out N-(phosphonomethyl) iminodiethanoic acid solid and obtain sulfate liquor, oven dry post analysis content 98.10%, the solid yield is 94.10%; Contain in the sulfate liquor: iminodiethanoic acid 0.65%; N-(phosphonomethyl) iminodiethanoic acid 2.15%, sulfuric acid 22.62%, iminodiacetic acid conversion is 98.12%, selectivity is 98.52%.
Sulfate liquor and N-(phosphonomethyl) iminodiacetic acid (salt) acid mother liquor in this instance and the sulfuric acid of adding with above-mentioned instance 1 recovery; Be fed in the aqueous solution of imido-oxalic acid disodium salt (the quality percentage composition is 35-50%) neutralize, acidifying; To pH2.1-2.3; Filter, isolate the iminodiethanoic acid solid and obtain sulfate liquor; The solid yield is 95.44%, and it is capable of circulation that sulfate liquor is isolated sodium sulfate through the after-filtration that concentrates, dewaters, and applies mechanically to following batch of preparation iminodiethanoic acid.
Embodiment 3
With iminodiethanoic acid (95%, 0.5mol) and sulfuric acid (20-70%, 0.2-1.0mol), after phosphorous acid (0.5-0.75mol) drops into and to stir, to mix, be heated to 100 ℃ of 0.5 hours, dissolving, salify in the three mouthfuls of reaction flasks of 1000ml have whisking appliance and TM; The elevated temperature holding temperature dripped formaldehyde (0.5-0.75mol) 3 hours at 110-120 ℃, and N-in the reaction process (phosphonomethyl) iminodiethanoic acid solid is separated out; After formaldehyde dripped and finishes, insulation reaction 2 hours was cooled to 20 ℃; Cooling and stirring, crystallization 10-15 hour; Filter out N-(phosphonomethyl) iminodiethanoic acid solid and obtain sulfate liquor, oven dry post analysis content 98.68%, the solid yield is 93.99%; Contain in the sulfate liquor: iminodiethanoic acid 0.74%; N-(phosphonomethyl) iminodiethanoic acid 2.25%, sulfuric acid 22.69%, iminodiacetic acid conversion is 98.19%, selectivity is 98.16%.
With the sulfate liquor behind the sodium sulfate of above-mentioned instance 2 recovery and N-(phosphonomethyl) iminodiacetic acid (salt) acid mother liquor in this instance and the sulfuric acid of adding; Be fed in the solution of imido-oxalic acid disodium salt (the quality percentage composition is 35-50%) and be neutralized to pH2.1-2.3; Filter, isolate the iminodiethanoic acid solid and obtain sulfate liquor; The solid yield is 95.12%; And obtain sulfate liquor through concentrate, that the dehydration after-filtration is isolated sodium sulfate is capable of circulation, apply mechanically to following batch to prepare iminodiethanoic acid.
In the sodium sulfate mother liquor that above-mentioned instance 2 is reclaimed and this instance and obtain neutralizing in the solution that sulfate liquor is fed into imido-oxalic acid disodium salt (mass percentage concentration is 35-50%), acidifying; To pH2.1-2.3; Filter, isolate the iminodiethanoic acid solid; The solid yield is 95.12%, and sulfate liquor is capable of circulation after concentrating after-filtration to isolate sodium sulfate, applies mechanically to following batch of preparation iminodiethanoic acid.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; The present invention also has various changes and modifications under the prerequisite that does not break away from spirit and scope of the invention, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (1)
1. making the method for Preparation of Catalyst pmida98 with sulfuric acid for one kind, is raw material with the iminodiethanoic acid, makes catalyzer and phosphorous acid, formaldehyde with sulfuric acid and carries out condensation reaction and prepare N-(phosphonomethyl) iminodiethanoic acid, it is characterized in that, may further comprise the steps:
With the sulfuric acid 0.2-1.0mol of 95% iminodiethanoic acid 0.5mol and mass percent concentration 20-70%, phosphorous acid 0.5-0.75mol drop into stirs, mix, be heated to 100 ℃ of insulations 0.5 hour, dissolving, salify in the three mouthfuls of reaction flasks of 1000ml that have whisking appliance and TM after, the elevated temperature holding temperature is at 110-120 ℃, dropping 0.5-0.75mol formaldehyde 3 hours; N-in the reaction process (phosphonomethyl) iminodiethanoic acid solid is separated out gradually; After formaldehyde dripped and finishes, insulation reaction 2 hours was cooled to 20 ℃; Cooling and stirring, crystallization 10-15 hour; Filter out N-(phosphonomethyl) iminodiethanoic acid solid and obtain sulfate liquor, oven dry post analysis content 98.50%, the solid yield is 94.86%; Contain in the sulfate liquor: iminodiethanoic acid 0.61%; N-(phosphonomethyl) iminodiethanoic acid 2.12%, sulfuric acid 22.62%, iminodiacetic acid conversion is 98.13%, selectivity is 98.22%;
Above-mentioned sulfate liquor is recycled; And add sulfuric acid, be fed into contain in the aqueous solution that the quality percentage composition is a 35-50% Iminodiacetic acid sodium salt salt neutralize, acidifying, terminal point control pH2.1-2.3; Filter, isolate the iminodiethanoic acid solid after the neutralization; The solid yield is 95.31%, and it is capable of circulation that the sulfate liquor after the separation is isolated sodium sulfate through concentrated after-filtration, applies mechanically to following batch of preparation iminodiethanoic acid.
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| CN2009100079402A CN101602779B (en) | 2008-12-10 | 2009-02-28 | Method for preparing N-phosphonomethyliminodiacetic acid by using sulfuric acid as catalyst and preparing iminodiacetic acid by recovering and indiscriminately applying mother liquid thereof |
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| CN103554181B (en) * | 2013-11-22 | 2015-06-10 | 重庆紫光化工股份有限公司 | Method for catalyzed synthesis of N-(phosphonomethyl) iminodiacetic acid by p-toluenesulfonic acid |
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