CN101607969B - Cycling application of condensation evaporated water of N-phosphonomethyliminodiacetic acid - Google Patents
Cycling application of condensation evaporated water of N-phosphonomethyliminodiacetic acid Download PDFInfo
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- CN101607969B CN101607969B CN2008101267029A CN200810126702A CN101607969B CN 101607969 B CN101607969 B CN 101607969B CN 2008101267029 A CN2008101267029 A CN 2008101267029A CN 200810126702 A CN200810126702 A CN 200810126702A CN 101607969 B CN101607969 B CN 101607969B
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Abstract
The invention relates to a method for recycling waste water containing acid and aldehyde, which comprises the following steps: evaporated water of a condensation working section in the process of producing N-phosphonomethyliminodiacetic acid is recycled, and partial waste water is hydrolyzed with phosphorus trichloride to prepare a mixed aqueous solution of phosphorous acid and hydrochloric acid according to a proportion required by the condensation working section; partial water is used for absorbing hydrogen chloride which is the hydrolysis tail gas of the phosphorus trichloride so as to generate the hydrochloric acid, and then the hydrochloric acid is used for acidifying iminodiacetic acid disodium salt; and iminodiacetic acid sodium salt which is an acidification product, a methanal aqueous solution and the obtained mixed aqueous solution of the phosphorous acid and the hydrochloric acid are together used for synthesizing the N-phosphonomethyliminodiacetic acid. The method greatly reduces a large amount of water consumed in the process of preparing the phosphorous acid by hydrolyzing the phosphorus trichloride and generated waste hydrochloric acid tail gas so as to ensure that the waste water which is evaporated in the condensation reaction and contains acid and aldehyde is recycled, thereby avoiding extra processing.
Description
Technical field
The present invention relates to steam in two sweet condensation workshop sections of seeing the recycling of sour water.
Background technology
The pmida98 chemical name is N-phosphorus carboxylic methylene radical-iminodiethanoic acid, or N, N-phosphoryl methyl iminodiethanoic acid.The preparation of pmida98 is to be raw material with diethanolamine or iminodiacetonitrile, and reaction obtains Iminodiacetic acid sodium salt salt in liquid caustic soda, adds hydrochloric acid again and carries out acidifying and obtain iminodiethanoic acid one sodium salt solution.Then in the presence of hydrochloric acid, add phosphorous acid, the synthetic pmida98 of formaldehyde temperature reaction again, neutralize at last, separate and obtain two sweet solids of seeing.In known technology, containing acid in the existing production contains aldehyde and steams formaldehyde and the hydrogenchloride that contains a great deal of in the water, very difficult in the processing, 1 ton of pmida98 of every production simultaneously will produce the hydrochloric formaldehyde that contains and steam about 1.5 tons in water, if both caused environmental pollution, cause raw-material serious waste again as wastewater treatment.
Therefore, this is hydrochloricly contained that formaldehyde steams the processing of water and utilization is the problem that present industrial needs solve.
Summary of the invention
Purpose of the present invention provides a kind of hydrochloric formaldehyde that contains to steam the processing of water and utilize method, and condensation is hydrochloric in particularly two sweet preparations of seeing contains the recycling technology that formaldehyde steams water.
Purpose of the present invention is achieved through the following technical solutions:
Collect in condensation workshop section contain 1%～15% hydrochloric acid and 1%～5% formaldehyde steams water, a part steams water and is used for the phosphorus trichloride hydrolysis, produce phosphorous acid hydrochloric acid mixed aqueous solution, this aqueous solution Central Asia phosphorus acid content 20%～40%, content of hydrochloric acid is about 20%～40%, hydrochloric acid: phosphorous acid (mol than)=1.5～3.0: 1.The hydrochloric formaldehyde-containing wastewater of another part is used for the absorption of hydrolytic process hydrogen chloride tail gas, form 20%～36% hydrochloric acid soln, deliver to Iminodiacetic acid sodium salt hydrochloric acid chemical industry section and be used for acidification reaction, iminodiacetic acid sodium salt that obtains and formaldehyde mixed aqueous solution and the phosphorous acid hydrochloric acid mixed aqueous solution one that steams aquatic output with first part are used from the building-up reactions of pmida98.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
The inventive method has been saved the phosphorus trichloride hydrolysis greatly and has been prepared the big water gaging that consumes in the phosphorous acid process and the tail gas abraum salt acid of generation, makes the acid that contains that steams in the condensation reaction contain aldehyde and all recycled.
Embodiment
Embodiment 1: begin the water that steams that contains formaldehyde 2%, hydrochloric acid 5% that drips phosphorus trichloride and reclaim from pmida98 production, mother liquor shop fixtures in the one-stage hydrolysis still simultaneously.Phosphorus trichloride rate of addition 3t/h steams water droplet acceleration 4.49t/h.Control one-stage hydrolysis still temperature is at 45 ℃ ± 2 ℃ in the dropping process, and transfer of heat is cooled off realization outward by still.Material flows into the secondary hydrolysis kettle from overflow port, overflow port adopts liquid to flow into down, the hydrogen chloride gas that the one-stage hydrolysis still produces feeds the secondary hydrolysis kettle by extension tubing, secondary hydrolysis kettle controlled temperature is at 45 ℃ ± 2 ℃, the hydrogen chloride gas that the secondary hydrolysis kettle comes out enters two-stage water absorption system through condenser, absorb the hydromining water that steams that contains formaldehyde 2%, hydrochloric acid 5% that from pmida98 production, reclaims, obtain the acidifying that 26% hydrochloric acid soln is used for Iminodiacetic acid sodium salt salt and obtain iminodiethanoic acid one sodium salt solution, tail gas enters alkali and absorbs the tail gas absorption system.The aqueous solution of overflowing from secondary hydrolysis kettle hydrolysis kettle is product, for containing 29% phosphorous acid and 30% aqueous solution of hydrochloric acid miscellany (hydrochloric acid is 2.32 with the mol ratio of phosphorous acid) approximately, the building-up reactions that is used from pmida98 with above-mentioned 19.5% iminodiethanoic acid, one sodium salt that obtains and formaldehyde one.
Embodiment 2: begin the water that steams that contains formaldehyde 1.5%, hydrochloric acid 8% that drips phosphorus trichloride and reclaim from pmida98 production, mother liquor shop fixtures in the one-stage hydrolysis still simultaneously.Phosphorus trichloride rate of addition 2t/h steams water droplet acceleration 2.99t/h.Control one-stage hydrolysis still temperature is at 40 ℃ ± 2 ℃ in the dropping process, and transfer of heat is cooled off realization outward by still.Material flows into the secondary hydrolysis kettle from overflow port, overflow port adopts liquid to flow into down, the hydrogen chloride gas that the one-stage hydrolysis still produces feeds the secondary hydrolysis kettle by extension tubing, secondary hydrolysis kettle controlled temperature is at 40 ℃ ± 2 ℃, the hydrogen chloride gas that the secondary hydrolysis kettle comes out enters level Four falling liquid film water absorption system through condenser, absorb the hydromining water that steams that contains formaldehyde 1.5%, hydrochloric acid 8% that from pmida98 production, reclaims, obtain the acidifying that 31% hydrochloric acid soln is used for Iminodiacetic acid sodium salt salt and obtain iminodiethanoic acid one sodium salt solution, tail gas enters water and absorbs the tail gas absorption system.The aqueous solution of overflowing from secondary hydrolysis kettle hydrolysis kettle is product, for containing 27% phosphorous acid and 31% aqueous solution of hydrochloric acid miscellany (hydrochloric acid is 2.57 with the mol ratio of phosphorous acid) approximately, the building-up reactions that is used from pmida98 with above-mentioned 21% iminodiethanoic acid, one sodium salt that obtains and formaldehyde one.
Embodiment 3: begin the water that steams that contains formaldehyde 4%, hydrochloric acid 10% that drips phosphorus trichloride and reclaim from pmida98 production, mother liquor shop fixtures in the one-stage hydrolysis still simultaneously.Phosphorus trichloride rate of addition 3t/h steams water droplet acceleration 4.49t/h.Control one-stage hydrolysis still temperature is at 35 ℃ ± 2 ℃ in the dropping process, and transfer of heat is cooled off realization outward by still.Material flows into the secondary hydrolysis kettle from overflow port, overflow port adopts liquid to flow into down, the hydrogen chloride gas that the one-stage hydrolysis still produces feeds the secondary hydrolysis kettle by extension tubing, secondary hydrolysis kettle controlled temperature is at 35 ℃ ± 2 ℃, the hydrogen chloride gas that the secondary hydrolysis kettle comes out enters two-stage water absorption system through condenser, absorb the hydromining water that steams that contains formaldehyde 4%, hydrochloric acid 10% that from pmida98 production, reclaims, obtain the acidifying that 31% hydrochloric acid soln is used for Iminodiacetic acid sodium salt salt and obtain iminodiethanoic acid one sodium salt solution, tail gas enters alkali and absorbs the tail gas absorption system.The aqueous solution of overflowing from secondary hydrolysis kettle hydrolysis kettle is product, for containing 25% phosphorous acid and 31% aqueous solution of hydrochloric acid miscellany (hydrochloric acid is 2.79 with the mol ratio of phosphorous acid) approximately, the building-up reactions that is used from pmida98 with above-mentioned 21% iminodiethanoic acid, one sodium salt that obtains and formaldehyde one.
Embodiment 4: begin the water that steams that contains formaldehyde 3%, hydrochloric acid 12% that drips phosphorus trichloride and reclaim from pmida98 production, mother liquor shop fixtures in the one-stage hydrolysis still simultaneously.Phosphorus trichloride rate of addition 3t/h steams water droplet acceleration 4.49t/h.Control one-stage hydrolysis still temperature is at 60 ℃ ± 2 ℃ in the dropping process, and transfer of heat is cooled off realization outward by still.Material flows into the secondary hydrolysis kettle from overflow port, overflow port adopts liquid to flow into down, the hydrogen chloride gas that the one-stage hydrolysis still produces feeds the secondary hydrolysis kettle by extension tubing, secondary hydrolysis kettle controlled temperature is at 60 ℃ ± 2 ℃, the hydrogen chloride gas that the secondary hydrolysis kettle comes out enters level Four falling liquid film water absorption system through condenser, absorb the hydromining water that steams that contains formaldehyde 3%, hydrochloric acid 12% that from pmida98 production, reclaims, obtain the acidifying that 36% hydrochloric acid soln is used for Iminodiacetic acid sodium salt salt and obtain iminodiethanoic acid one sodium salt solution, tail gas enters alkali and absorbs the tail gas absorption system.The aqueous solution of overflowing from secondary hydrolysis kettle hydrolysis kettle is product, for containing 40% phosphorous acid and 27% aqueous solution of hydrochloric acid miscellany (hydrochloric acid is 1.51 with the mol ratio of phosphorous acid) approximately, the building-up reactions that is used from pmida98 with above-mentioned 23.5% iminodiethanoic acid, one sodium salt that obtains and formaldehyde one.
Embodiment 5: begin the water that steams that contains formaldehyde 3%, hydrochloric acid 6% that drips phosphorus trichloride and reclaim from pmida98 production, mother liquor shop fixtures in the one-stage hydrolysis still simultaneously.Phosphorus trichloride rate of addition 2t/h steams water droplet acceleration 2.99t/h.Control one-stage hydrolysis still temperature is at 55 ℃ ± 2 ℃ in the dropping process, and transfer of heat is cooled off realization outward by still.Material flows into the secondary hydrolysis kettle from overflow port, overflow port adopts liquid to flow into down, the hydrogen chloride gas that the one-stage hydrolysis still produces feeds the secondary hydrolysis kettle by extension tubing, secondary hydrolysis kettle controlled temperature is at 55 ℃ ± 2 ℃, the hydrogen chloride gas that the secondary hydrolysis kettle comes out enters level Four water absorption system through condenser, absorb the hydromining water that steams that contains formaldehyde 3%, hydrochloric acid 6% that from pmida98 production, reclaims, obtain the acidifying that 33% hydrochloric acid soln is used for Iminodiacetic acid sodium salt salt and obtain iminodiethanoic acid one sodium salt solution, tail gas enters alkali and absorbs the tail gas absorption system.The aqueous solution of overflowing from secondary hydrolysis kettle hydrolysis kettle is product, for containing 35% phosphorous acid and 28% aqueous solution of hydrochloric acid miscellany (hydrochloric acid is 1.80 with the mol ratio of phosphorous acid) approximately, the building-up reactions that is used from pmida98 with above-mentioned 22% iminodiethanoic acid, one sodium salt that obtains and formaldehyde one.
Embodiment 6: begin the water that steams that contains formaldehyde 1.5%, hydrochloric acid 3% that drips phosphorus trichloride and reclaim from pmida98 production, mother liquor shop fixtures in the one-stage hydrolysis still simultaneously.Phosphorus trichloride rate of addition 3t/h steams water droplet acceleration 4.49t/h.Control one-stage hydrolysis still temperature is at 50 ℃ ± 2 ℃ in the dropping process, and transfer of heat is cooled off realization outward by still.Material flows into the secondary hydrolysis kettle from overflow port, overflow port adopts liquid to flow into down, the hydrogen chloride gas that the one-stage hydrolysis still produces feeds the secondary hydrolysis kettle by extension tubing, secondary hydrolysis kettle controlled temperature is at 50 ℃ ± 2 ℃, the hydrogen chloride gas that the secondary hydrolysis kettle comes out enters level Four water absorption system through condenser, absorb the hydromining water that steams that contains formaldehyde 1.5%, hydrochloric acid 3% that from pmida98 production, reclaims, obtain the acidifying that 31% hydrochloric acid soln is used for Iminodiacetic acid sodium salt salt and obtain iminodiethanoic acid one sodium salt solution, tail gas enters water and absorbs the tail gas absorption system.The aqueous solution of overflowing from secondary hydrolysis kettle hydrolysis kettle is product, for containing 32% phosphorous acid and 29% aqueous solution of hydrochloric acid miscellany (hydrochloric acid is 2.04 with the mol ratio of phosphorous acid) approximately, the building-up reactions that is used from pmida98 with above-mentioned 21% iminodiethanoic acid, one sodium salt that obtains and formaldehyde one.
Claims (4)
1. the recoverying and utilizing method that steams water in the pmida98 condensation workshop section, it comprises the steps:
The hydrochloric formaldehyde that contains of collecting in condensation workshop section steams water, and a part steams water and is used for the phosphorus trichloride hydrolysis, produces phosphorous acid hydrochloric acid mixed aqueous solution; The hydrochloric formaldehyde-containing wastewater of another part is used for the absorption of hydrolytic process hydrogen chloride tail gas, form hydrochloric acid soln, deliver to Iminodiacetic acid sodium salt hydrochloric acid chemical industry section and be used for acidification reaction, iminodiacetic acid sodium salt that obtains and formaldehyde mixed aqueous solution are used for the building-up reactions of pmida98.
2. according to the process of claim 1 wherein,
Collect in condensation workshop section contain 1%～15% hydrochloric acid and 1%～5% formaldehyde steams water, a part steams water and is used for the phosphorus trichloride hydrolysis, produce phosphorous acid hydrochloric acid mixed aqueous solution, this aqueous solution Central Asia phosphorus acid content 20%～40%, content of hydrochloric acid 20%～40%, hydrochloric acid: phosphorous acid mol ratio=(1.5～3.0): 1; The hydrochloric formaldehyde-containing wastewater of another part is used for the absorption of hydrolytic process hydrogen chloride tail gas, form 20%～36% hydrochloric acid soln, deliver to Iminodiacetic acid sodium salt hydrochloric acid chemical industry section and be used for acidification reaction, iminodiacetic acid sodium salt that obtains and formaldehyde mixed aqueous solution, it is used from the building-up reactions of pmida98 with the phosphorous acid hydrochloric acid mixed aqueous solution one that steams aquatic output with first part.
3. recoverying and utilizing method according to claim 1 and 2, wherein, this Iminodiacetic acid sodium salt salt is obtained by the diethanolamine dehydrogenation or the iminodiacetonitrile alkaline hydrolysis obtains.
4. according to the said recoverying and utilizing method of claim 1, wherein, the absorption pattern of tail gas hydrogenchloride is secondary or multistage absorption.
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| CN2008101267029A CN101607969B (en) | 2008-06-20 | 2008-06-20 | Cycling application of condensation evaporated water of N-phosphonomethyliminodiacetic acid |
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| CN101607969B true CN101607969B (en) | 2011-07-20 |
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| CN106744757A (en) * | 2016-12-18 | 2017-05-31 | 南通江山农药化工股份有限公司 | The method that phosphorous acid is produced using industrial wastewater resource |
| CN107879322A (en) * | 2017-04-25 | 2018-04-06 | 湖南比德生化科技股份有限公司 | A kind of method for producing spent acid and preparing high content phosphorous acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762835A (en) * | 2005-08-23 | 2006-04-26 | 浙江龙游绿得农药化工有限公司 | Hydrochloric acid recovery and separation method from waste liquid of N-phosphonomethyl iminodiacetic acid production |
| CN101208348A (en) * | 2005-04-25 | 2008-06-25 | 孟山都技术公司 | Altering the crystal size distribution of N-(phosphonomethyl) iminodiacetic acid for improved filtration and product quality |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208348A (en) * | 2005-04-25 | 2008-06-25 | 孟山都技术公司 | Altering the crystal size distribution of N-(phosphonomethyl) iminodiacetic acid for improved filtration and product quality |
| CN1762835A (en) * | 2005-08-23 | 2006-04-26 | 浙江龙游绿得农药化工有限公司 | Hydrochloric acid recovery and separation method from waste liquid of N-phosphonomethyl iminodiacetic acid production |
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