CN101781224B - Cleaning production process of iminodiacetic acid - Google Patents
Cleaning production process of iminodiacetic acid Download PDFInfo
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- CN101781224B CN101781224B CN201010131635.7A CN201010131635A CN101781224B CN 101781224 B CN101781224 B CN 101781224B CN 201010131635 A CN201010131635 A CN 201010131635A CN 101781224 B CN101781224 B CN 101781224B
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- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 238000004140 cleaning Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000012528 membrane Substances 0.000 claims abstract description 32
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical class [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 15
- 238000000909 electrodialysis Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011345 viscous material Substances 0.000 claims description 3
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 2
- 238000001728 nano-filtration Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001223 reverse osmosis Methods 0.000 claims description 2
- 229910052722 tritium Inorganic materials 0.000 claims description 2
- FUXALCGRSSRCQE-UHFFFAOYSA-N 2-(2,3-dihydro-1-benzofuran-7-yl)ethanamine Chemical compound NCCC1=CC=CC2=C1OCC2 FUXALCGRSSRCQE-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 230000010354 integration Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000029219 regulation of pH Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 244000025254 Cannabis sativa Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 241000377209 Unicorn Species 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a cleaning production process of preparing iminodiacetic acid with iminodiacetic acid sodium salts as raw materials. The invention is characterized in that iminodiacetic acid sodium salts are used as the raw materials and a membrane integration technique is used to prepare iminodiacetic acid. The particular process comprises the following steps: 1) iminodiacetic acid sodium salts are used as the raw materials, softened water or crystallized mother liquors of diacetate is added, and the weight percentage of the iminodiacetic acid sodium salts is diluted to 5%-30%; 2) the solution in the step 1 passes through a multi-medium filter containing activated carbons at a flow rate of 2-20 m/h for removing mechanical impurities and sticky substances and is filtered through one or more combination of a precision filter, a micropore filter and a ultrafiltration membrane for removing micron, sub-micron and macromolecular impurities; 3) the solution is introduced to an electrodialyzer for electrodialysis to control PH=1-5 at a salt chamber for obtaining the iminodiacetic acid solution and obtain a sodium hydroxide solution at a base chamber; 4) the temperature of the iminodiacetic acid solution obtained in the step 3) is reduced to the temperature of -5 to 20 DEG C or the temperature of 5 DEG C below zero to 20 DEG C following the regulation of pH=1.2 -3 to precipitate the IDA solid, and then the residual mother liquor is concentrated with a membrane to remove water and the concentrated liquid returns to crystallization.
Description
Technical field
The present invention relates to a kind ofly take iminodiacetic acid sodium salt and prepare a kind of process for cleanly preparing of iminodiethanoic acid as raw material, belong to the preparation method field of chemical products intermediate iminodiethanoic acid.
Background technology
Iminodiethanoic acid (IDA), is important source material and the intermediates such as tensio-active agent, complexing agent, synthetic metal finishing material and ion exchange resin, and the purposes of its maximum is that production weedicide grass is sweet bony.At present, the technology of suitability for industrialized production iminodiethanoic acid mainly contains chloroactic acid method, nitrilotriacetic acid method, prussic acid method and diethanolamine method, these techniques are all first to produce iminodiacetic acid sodium salt, then through desalination, obtain iminodiethanoic acid, use or the desalination method through reporting have hcl acidifying method, sulfuric acid acidation method, heat filtering method, calcium salt complex-precipitation method etc.The a large amount of sodium-chlor of hcl acidifying method by-product is more difficult, affects throughput, and also can dissolve a certain amount of iminodiethanoic acid in acidified mother liquor, and yield is lower.Sulfuric acid acidation method by-product sodium sulfate is difficult.Heat filtering method need to be through thickening filtration repeatedly, and complex process is miscellaneous, and energy consumption is large, and cost is high, and this method only implements according to the difference of Solubility of Substances, and iminodiethanoic acid is lost in a large number.The method that US patent 3852344 proposition hcl acidifyings and heat filtering combine, first by hcl acidifying to iso-electric point, separate out iminodiethanoic acid, after separated, mother liquor is 80～120 ℃ of concentrated precipitated sodium chloride precipitations, and after filtering separation, filtrate is cooled to 10～30 ℃ again and separates out IDA, constantly repeats above-mentioned steps.This method technique is loaded down with trivial details, and the production cycle is long, and carries IDA secretly in sodium chloride salt, contains again sodium-chlor in iminodiacetic acid (salt) acid product, makes product yield and purity all on the low side.Chinese patent CN1663945A has proposed calcium salt complex-precipitation method, this method is in acidified mother solution of iminodiacetic acid, to add calcium hydroxide, make iminodiethanoic acid form huge legendary turtle compound precipitation, will after complex compound sediment separation, use hcl acidifying again, crystallisation by cooling obtains iminodiethanoic acid.This method, because iminodiethanoic acid has very strong complexing action, is easy to form calcium precipitation, and yield is very high, in the time of still with hcl acidifying, has generated again a large amount of waste solution of calcium chloride, more difficult, has caused water pollution.Chinese patent CN101186581A proposes a kind of without producing iminodiethanoic acid processing step, directly with iminodiacetic acid sodium salt, produce the sweet bony method of grass, a large amount of sodium-chlor that so just made to produce in the technique of two sweet unicorns by-product, cause whole system thickness, whipping device seriously corroded, not only affect throughput, and wastewater flow rate is very large.Chinese patent CN 101445465A proposes to take iminodiacetic acid sodium salt as starting raw material, adds water and stirs decolouring dissolving, drips the vitriol oil and controls pH=1.8～2.1, and centrifugation obtains iminodiethanoic acid.In acidified mother liquor, add alkaline matter pH=4～7, at 5～10 ℃ of crystallization NaZ50410H2O, vacuum filtration, filtrate cycle continuous production iminodiethanoic acid, this method not only will consume sulfuric acid, but also consumes alkali, produces unmanageable sodium sulfate simultaneously.The people such as Yang Hongquan are at < < Study on Preparation of Iminodiacetic Acid > > (Chemical Manufacture and technology .2007,14 (2) .28～31) in a literary composition, adopt electroosmose process to prepare IDA, products obtained therefrom quality is good, yield is high and non-wastewater discharge, but this method has only been used cationic exchange membrane, cause that plant efficiency is low, complicated operation, and produce a large amount of hydrogen and oxygen, have potential safety hazard.The people such as Xu Liuxing are at sweet unicorn intermediate iminodiethanoic acid new synthetic process > > (the agricultural chemicals .2006 of < < grass, 45 (11) .751～753) in, propose to carry out with the vitriol oil method that work DA is prepared in acidifying, product purity reaches 99.3%, but yield only 85%, can not meet industrialization demand.Zeng little Jun is the application > > (fine chemistry industry in iminodiethanoic acid preparation at < < bipolar electrodialysis film, 2002 the 4th phases) method with bipolar electrodialysis film preparation iminodiethanoic acid is proposed in a literary composition, the good product quality, the yield that make are high, but the solution after electrodialysis need evaporate recrystallize, mother liquor after crystallization need evaporate again, and this has just caused the problem that steam consumption is high, energy dissipation is large.
Above method is not complex process, cost is high, energy consumption is large, is exactly that raw material consumption is large, the three wastes are many, and these are difficult to accept in industrial production.
Summary of the invention
Purpose of design: avoid the weak point in background technology, a kind of process for cleanly preparing that imino-diacetic sodium salt is starting raw material of take is provided.
Design: in order to realize above-mentioned purpose of design.The application be take iminodiacetic acid sodium salt as raw material, adopts membrane integrating technique to prepare iminodiethanoic acid, and concrete technology step is as follows:
1) take iminodiacetic acid sodium salt as raw material, add the oxalic acid mother liquor after softening water or crystallization, the mass percent of iminodiacetic acid sodium salt is diluted to 5%～30%; The object of doing is like this: prevent iminodiacetic acid sodium salt crystallization.
2) solution step 1) with the flow velocity of 2～20m/h by containing the more medium filter of gac, remove mechanical impurity and viscous substance, through the one or more combination of accurate filter, millipore filter, ultra-filtration membrane, filter again, remove micron, submicron and macromole impurity; The object of doing is like this: the requirement that solution is met enter electrodialyzer, prevent that film and dialyzer from being polluted, and increase the service life.
3) above-mentioned solution enters electrodialyzer and carries out electrodialysis process, and salt chamber is controlled PH=1～5 and obtained iminodiethanoic acid (IDA) solution, and alkali chamber obtains sodium hydroxide (NaOH) solution;
4) iminodiethanoic acid step 3) obtaining (IDA) solution cools to-5～20 ℃, and the solubleness of iminodiethanoic acid is reduced, and improves the primary recovery of oxalic acid; Or regulate PH=1.2～3, and the iso-electric point that reaches oxalic acid cools to-5～20 ℃ again and separates out IDA solid, and remaining mother liquor concentrates to remove moisture with film again, and concentrated solution is got back to crystallization.
The present invention compares with background technology, and the one, take iminodiacetic acid sodium salt as starting raw material, adopt membrane integrating technique to carry out the preparation of iminodiethanoic acid, there is no chemical reaction, without additional any raw material, the good product quality, the yield that therefore obtain are high; The 2nd, do not produce any by product, three-waste free pollution; The 3rd, the sodium hydroxide that electrodialysis process produces can recycle, and has saved the production cost of iminodiacetic acid sodium salt.
Accompanying drawing explanation
Fig. 1 is a kind of Production Flow Chart of process for cleanly preparing of iminodiethanoic acid.
Fig. 2 is the electrodialysis process flow process described in the application.
Embodiment
Embodiment 1: with reference to attached Fig. 1 and 2.A process for cleanly preparing for iminodiethanoic acid, take iminodiacetic acid sodium salt as raw material, adopts membrane integrating technique to prepare iminodiethanoic acid, and concrete technology step is as follows:
1) take iminodiacetic acid sodium salt as raw material, add the oxalic acid mother liquor after softening water or crystallization, the mass percent of iminodiacetic acid sodium salt is diluted to 5%～30% and comprise end value, as 5%, 6%, 7%, 8%, 9%, 10%, 11% ..., 26%, 27%, 28%, 29%, 30%, and comprise the decimal point value that forms 1;
2) solution step 1) with the flow velocity of 2～20m/h by containing the more medium filter of gac, to remove mechanical impurity and viscous substance, through the one or more combination of accurate filter, millipore filter, ultra-filtration membrane, filter again, to remove micron, submicron and macromole impurity;
3) above-mentioned solution enters electrodialyzer and carries out electrodialysis process, in electrodialytic salt chamber, pass into iminodiacetic acid sodium salt, in alkali chamber, to pass into massfraction be 0～10% sodium hydroxide solution and comprise that end value is as 0, 1%, 2%, 9%, 10%, and comprise the decimal point value that forms 1, salt chamber is controlled PH=1～5 and is obtained iminodiethanoic acid (IDA) solution, the massfraction that sodium hydroxide (NaOH) is controlled in alkali chamber is 3～30% and comprises that end value is as 3%, 4%, 5%, 6%, 7%, 8%, 9%, 26%, 27%, 28%, 29%, 30%, and comprise the decimal point value that forms 1,
4) iminodiethanoic acid step 3) obtaining (IDA) solution cools to-5～20 ℃ and comprise end value, as-5 ℃ ,-4 ℃ ,-3 ℃ ,-2 ℃ ,-1 ℃, 0 ℃, 1 ℃, 2 ℃, 3 ℃ ..., 18 ℃, 19 ℃, 20 ℃, and comprise the decimal point value that forms 1; Or regulate PH=1.2～3 and comprise end value as 1.2,1.3,1.4,1.5 ..., 1,2,3, cool to again-5～20 ℃ and comprise end value, as-5 ℃ ,-4 ℃ ,-3 ℃ ,-2 ℃ ,-1 ℃, 0 ℃, 1 ℃, 2 ℃, 3 ℃ ..., 18 ℃, 19 ℃, 20 ℃, separate out IDA solid, after filtration, centrifugation obtains the IDA mother liquor of IDA wet-milling, wet-milling drying obtain massfraction be 90～99.5% and comprise end value as 90%, 91% ..., 98%, 99%, 99.5% the former powder of IDA.
5) with film, concentrate to remove moisture, concentrated solution and step 3 again) IDA solution mixes, by step 4) process, like this circulation obtains the former powder of IDA.
6) IDA mother liquor step 4) can also mix with the solution of iminodiacetic acid sodium salt and carries out electrodialysis process.
Above-mentioned steps 4) the iminodiacetic acid (salt) acid solution obtaining can also not carry out crystallisation by cooling, is directly used in the production of rear operation, for example, add phosphorous acid and Formaldehyde Production pmida98.
The mixture of the sodium salt that above-described iminodiacetic acid sodium salt is iminodiethanoic acid or the disodium salt of iminodiethanoic acid or two kinds of sodium salts.
Above-described iminodiacetic acid sodium salt is that diethanolamine technique is prepared gained, can be also that iminodiacetonitrile method, prussic acid method, chloroactic acid method or nitrogen tritium nitrilotriacetic legal system are for gained.
Above-described 3～30% sodium hydroxide solution (and comprise end value as 3%, 4%, 5%, 6%, 7%, 8%, 9% ..., 26%, 27%, 28%, 29%, 30%, and comprise the decimal point value that forms 1) can be for diethanolamine method, iminodiacetonitrile method, prussic acid legal system the raw material for iminodiacetic acid sodium salt.Also can be used as commodity for sale, for the raw material of other Chemicals.
The film that above-described membrane concentration adopts is reverse osmosis membrane or nanofiltration membrane, and its form can be rolling, board-like, tubular fibre.When concentrated, temperature is controlled at 5～80 ℃ and comprise end value, as 1 ℃, 2 ℃, 3 ℃, 78 ℃, 79 ℃, 80 ℃, and comprise the decimal point value that forms 1, preferably 20～40 ℃ and comprise end value, as 20 ℃, 21 ℃, 22 ℃, 38 ℃, 39 ℃, 40 ℃, and comprise the decimal point value that forms 1, working pressure is controlled at 0.5～7.0MPa and comprises that end value is as 0.5, 0.6, , 0.7, 0.8, 0.9, 1.0, 5.0, 6.0, 7.0MPa, preferably 1.0～4.0MPa is as 1.0, 2.0, 3.0, 4.0MPa and comprise the decimal point value that forms 1.
The moisture that above-described membrane concentration is removed can for the preparation of 0～10% sodium hydroxide solution and comprise end value as 0,1%, 2% ..., 9%, 10%, as the feed liquor of electrodialysis alkali chamber.Can also use as process water.
It is to be understood that: although above-described embodiment is to the mentality of designing of the present invention detailed text description of contrasting; but these text descriptions; just the simple text of mentality of designing of the present invention is described; rather than the restriction to mentality of designing of the present invention; any combination, increase or modification that does not exceed mentality of designing of the present invention, all falls within the scope of protection of the present invention.
Claims (6)
1. a process for cleanly preparing for iminodiethanoic acid, is characterized in that: take iminodiacetic acid sodium salt as raw material, adopt membrane integrating technique to prepare iminodiethanoic acid, concrete technology step is as follows:
1) take iminodiacetic acid sodium salt as raw material, add the oxalic acid mother liquor after softening water or crystallization, the mass percent of iminodiacetic acid sodium salt is diluted to 5% ~ 30%;
2) solution of step 1) with the flow velocity of 2 ~ 20m/h by containing the more medium filter of gac, remove mechanical impurity and viscous substance, through the one or more combination of accurate filter, millipore filter, ultra-filtration membrane, filter again, remove micron, submicron and macromole impurity;
3) above-mentioned solution enters electrodialyzer and carries out electrodialysis process, and salt chamber is controlled PH=1 ~ 5 and obtained iminodiethanoic acid IDA solution, and alkali chamber obtains sodium hydroxide NaOH solution; The mass percent that described alkali chamber obtains sodium hydroxide (NaOH) solution is 3% ~ 30%;
4) the iminodiethanoic acid IDA solution that step 3) obtains cools to-5 ~ 20 ℃ or regulate PH=1.2～3 to cool to-5 ~ 20 ℃ to separate out IDA solid again, and remaining mother liquor concentrate with removal moisture with film again, and concentrated solution is got back to crystallization;
5) described remaining mother liquor concentrates that to take the film of removing described in moisture be a kind of of reverse osmosis membrane, nanofiltration membrane or combination again with film, describedly concentrated the mass percent of iminodiethanoic acid in mother liquor is brought up to 5～20%;
6) in described residue mother liquor, iminodiethanoic acid IDA solution can be without concentrated, and direct and iminodiacetic acid sodium salt mixed cycle is carried out electrodialysis process.
2. the process for cleanly preparing of a kind of iminodiethanoic acid according to claim 1, is characterized in that: described iminodiacetic acid sodium salt is the mixture of iminodiacetic acid disodium salt or iminodiethanoic acid one sodium salt or two kinds of sodium salts, its PH=6 ~ 14.
3. the process for cleanly preparing of a kind of iminodiethanoic acid according to claim 1, is characterized in that: this process application is in adopting diethanolamine method, prussic acid method, iminodiacetonitrile method, chloroactic acid method or the standby iminodiacetic acid sodium salt of nitrogen tritium nitrilotriacetic legal system.
4. the process for cleanly preparing of a kind of iminodiethanoic acid according to claim 1, it is characterized in that: described electrodialyzer one side and opposite side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with anolyte compartment's (II) of built-in anode, between cathode compartment and anolyte compartment, be provided with film pair, one film forms the Bipolar Membrane (BP) by space and a cationic exchange membrane (C), the anode that described film is Bipolar Membrane to the relative position of Bipolar Membrane and cationic exchange membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, between two Bipolar Membrane, be provided with a cationic exchange membrane, described film forms alkali chamber (III) to the cathode direction of Bipolar Membrane and anode membrane, anode membrane and Bipolar Membrane anode direction form salt chamber (IV).
5. the process for cleanly preparing of a kind of iminodiethanoic acid according to claim 1, it is characterized in that: described electrodialysis process is to pass into iminodiacetic acid sodium salt in described salt chamber, described alkali passes into water or dilute NaOH solution in chamber, and described negative electrode and anode pass into direct current.
6. the process for cleanly preparing of a kind of iminodiethanoic acid according to claim 4, is characterized in that: described cationic exchange membrane is homogeneous membrane or heterogeneous membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010131635.7A CN101781224B (en) | 2010-03-20 | 2010-03-20 | Cleaning production process of iminodiacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010131635.7A CN101781224B (en) | 2010-03-20 | 2010-03-20 | Cleaning production process of iminodiacetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101781224A CN101781224A (en) | 2010-07-21 |
| CN101781224B true CN101781224B (en) | 2014-01-29 |
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| CN103787919B (en) * | 2012-12-27 | 2016-06-29 | 三达膜科技（厦门）有限公司 | A kind of discoloration method of Iminodiacetonitrile 1,1'-Imidodiacetonitrile |
| CN104003830B (en) * | 2014-01-27 | 2016-08-17 | 重庆紫光化工股份有限公司 | Amino acid separation and the method for iminodicarboxylic acid from the aqueous solution of amino acid whose alkali metal salt |
| CN104098602B (en) * | 2014-07-08 | 2016-08-24 | 重庆紫光化工股份有限公司 | A kind of energy-saving clean production method of PMIDA |
| CN105063658B (en) * | 2015-08-12 | 2017-07-18 | 江苏安凯特科技股份有限公司 | The method for preparing iminodiacetic acid |
| CN105063656B (en) * | 2015-08-12 | 2017-07-18 | 江苏安凯特科技股份有限公司 | The method for processing iminodiacetic acid |
| CN111450673A (en) * | 2020-03-31 | 2020-07-28 | 成都思达能环保设备有限公司 | Desulfurization equipment and desulfurization method for recovering sulfur element into acid solution |
-
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Non-Patent Citations (4)
| Title |
|---|
| 亚氨基二乙酸母液的电渗析脱盐实验;沈江南等;《农药》;20081031;第47卷(第10期);全文 * |
| 双极性膜电渗析技术在亚氨基二乙酸制备中的应用;曾小君;《精细化工》;20020430;第19卷(第4期);1.实验部分，图1 * |
| 曾小君.双极性膜电渗析技术在亚氨基二乙酸制备中的应用.《精细化工》.2002,第19卷(第4期), |
| 沈江南等.亚氨基二乙酸母液的电渗析脱盐实验.《农药》.2008,第47卷(第10期), |
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