CN105597540A - Forward permeating absorbing fluid, application thereof, organic phosphine compound applied to forward permeating absorbing fluid and preparation method thereof - Google Patents
Forward permeating absorbing fluid, application thereof, organic phosphine compound applied to forward permeating absorbing fluid and preparation method thereof Download PDFInfo
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- CN105597540A CN105597540A CN201610072716.1A CN201610072716A CN105597540A CN 105597540 A CN105597540 A CN 105597540A CN 201610072716 A CN201610072716 A CN 201610072716A CN 105597540 A CN105597540 A CN 105597540A
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- phosphine compound
- organic phosphine
- liquid
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- -1 phosphine compound Chemical class 0.000 title claims abstract description 73
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012530 fluid Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims description 73
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000011574 phosphorus Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 230000008595 infiltration Effects 0.000 claims description 13
- 238000001764 infiltration Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 6
- 229910020667 PBr3 Inorganic materials 0.000 claims description 3
- 239000012466 permeate Substances 0.000 claims description 3
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 claims description 3
- 230000004907 flux Effects 0.000 abstract description 21
- 150000003839 salts Chemical class 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 230000003204 osmotic effect Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 150000007513 acids Chemical class 0.000 description 15
- 238000009938 salting Methods 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 238000009292 forward osmosis Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 125000005499 phosphonyl group Chemical group 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
- B01D61/005—Osmotic agents; Draw solutions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a forward permeating absorbing fluid and an application thereof. The forward permeating absorbing fluid comprises 5%-50% by weight of an organic phosphine compound. The organic phosphine compound has the chemical structural formula shown in formula I, wherein m is 1-6, n is 0-6, x is 0-2m+4n+8, and Y is Na, K or Li. The invention also discloses the organic phosphine compound applied to the forward permeating absorbing fluid and a preparation method thereof. The organic phosphine compound provided by the invention is applied to a forward permeating process, is high in osmotic pressure, large in water flux and low in reverse salt flux and has excellent scale inhibition property.
Description
Technical field
The invention belongs to positive infiltration technology field, more specifically, relate to one and just permeating and draw liquid and application thereof, Yi JiyiPlant for just permeating organic phosphine compound drawing liquid and preparation method thereof.
Background technology
Along with the continuous growth of population, the shortage of fresh water problem that the continuous deterioration of environment causes is just affecting the mankindNormal life, and the application of membrane separation technique is expected to alleviate this difficult problem of water supply. Just permeating is that a kind of nature extensively existsSpontaneous physical phenomenon, the poor driving hydrone of effective infiltration drawing between liquid and feed liquid passes through from high water chemistry gesture feed liquid sidePermselectivity membrane flows to low water chemistry gesture and draws liquid one side. Positive process of osmosis only needs a small amount of ambient pressure can realize waterSeparation process, and forward osmosis membrane itself can effectively reduce film pollute, the rate of recovery of water is high, draws liquid recoverable, denseWater discharge is few, pollute little, energy-conserving and environment-protective. Therefore this technology is widely used in wastewater treatment, desalinization, food concentration of juices,Medicine control and release, aerospace desalt and recycling, the fields such as generating.
Just permeating and drawing the key element that liquid is the normal work of positive permeability apparatus, it has determined the performance of positive process of osmosisAnd efficiency. The active component that draws liquid in currently available technology mainly contains the magnetic nanoparticle of surface modification, ammonium carbonate salts, phaseChange switch compound, organometallic complex, polyamine amino acid (IndEngChemRes2014,53,16170-16175.),Organic carboxylic acid sodium salt (BioresourceTechnol2012,122,207-216.), phosphorous organic carboxylic acid sodium salt(Desalination2013,312,130-136) etc.; Wherein, not only ecological environment compatibility of phosphorous organic carboxylic acid sodium salt's solutionGood, thereby and in water, easily dissociate ion and produce and there is very high osmotic pressure, high water flux finally obtained.
But organic carboxylic acid sodium salt has following shortcoming: one, physicochemical properties are unstable, easily by the micro-life in waterThing degraded; Two, it does not possess antibacterial and anti-dirt ability, and after long-time use, not only feeding liquid one side form surface easily produces carbonic acidThe inorganic foulants such as calcium, and draw the organic contamination that liquid one side form surface can produce film due to bacterial growth, seriously cause fenestraStop up, affected the separating property of forward osmosis membrane, and increased film decontamination dirt and the cost that renews film; Three, known major partOrganic carboxylic acid sodium salt also has certain environment toxic action, should not use on a large scale; Four, organic carboxylic acid sodium salt's moleculeAmount is generally less than 500Da, and the permeable membrane kind rareness matching with it, expensive, need to disappear while reclaiming equal unit water gagingConsume more electric energy, caused the wasting of resources.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides one just permeating draw liquid and shouldWith and a kind of for just permeating organic phosphine compound drawing liquid and preparation method thereof, its object is by a kind of moleculeVolume is larger, and hydrophilicity is good, and eco-friendly just infiltration drawn liquid, solves thus existing just infiltration and draws liquid discharge and haveLimit, reverse flux salt is large, easily fouling, the technical problem being easily degraded by microorganisms.
For achieving the above object, according to one aspect of the present invention, provide one just permeating and drawn liquid, comprised that quality dividesNumber is 5%～50% organic phosphine compound, and described organic phosphine compound has suc as formula the chemical structural formula shown in I, wherein, and mBe that 1～6, n is that 0～6, x is 0～2m+4n+8, Y is Na, K or Li.
Preferably, described just infiltration drawn liquid and comprised that mass fraction is 15%～35% organic phosphine compound.
It is preferably, described that just to permeate the pH value of drawing liquid be 6～10.
According to another aspect of the present invention, a kind of positive permeability apparatus is provided, use above-mentioned just infiltration to draw liquid.
According to another aspect of the present invention, also provide a kind of for the above-mentioned organic phosphine compound that draws liquid that just permeating,Have suc as formula the chemical structural formula shown in I, wherein, m is that 1～6, n is that 1～6, x is 0～2m+4n+8, and Y is Na, K or Li.
Preferably, m=3, n=6; Or m=1, n=2.
According to another aspect of the present invention, also provide a kind of preparation method of above-mentioned organic phosphine compound, chemical reactionFormula is as follows:
Preferably, described preparation method is: at 40 DEG C～60 DEG C, add formaldehyde in precursor water solution, then 30DEG C add below phosphorus Halides, make the fully reaction in the aqueous solution of described presoma, formaldehyde and phosphorus Halides, finally 80 DEG C～At 120 DEG C, heat described precursor water solution the hydrogen halides of reaction generation is fully volatilized, obtain organic phosphine compound solution;Wherein, the mol ratio of described presoma, formaldehyde and phosphorus Halides is 1:5:5～1:19:19, and described presoma has suc as formula II instituteThe chemical structural formula showing, and m is that 1～6, n is 1～6, described phosphorus Halides is PCl3Or PBr3
Preferably, described preparation method also comprises, adds highly basic, regulates the pH value to 6 of described organic phosphine compound solution～10, described highly basic is LiOH, NaOH or KOH.
Preferably, described preparation method also comprises, remove described organic phosphine compound molecules in solution amount 500Da～Little molecule below 800Da, then removes the moisture in described organic phosphine compound solution, obtains organic phosphine compound solid.
In general, the above technical scheme of conceiving by the present invention compared with prior art, can obtain down and showBeneficial effect fruit:
1, to adopt molecular weight be that the organic phosphine compound of 800Da～10000Da draws matter as just permeating in the present invention, due toThe hole that the increase of its molecular weight makes its volume be greater than film is difficult for seeing through forward osmosis membrane, thereby it is large effectively to solve reverse flux saltProblem, and can also reduce the follow-up energy resource consumption in liquid removal process of drawing;
2, provided by the invention just infiltration drawn liquid, and under equal quality mark, osmotic pressure average specific polyamine amino acid salt is highGo out approximately 1.5 times, draw liquid exceed 33% than organic carboxylic acid sodium salt, than 1 times of phosphorous organic carboxylic acid sodium salt, water flux is greater than polyamine amine0.5 times of hydrochlorate, draws liquid than organic carboxylic acid sodium salt and exceeds 1/4th, and reverse flux salt is 1/4th of polyamine amino acid salt;
3, the present invention use organic phosphine compound to nontoxic to ecology, meanwhile because there is phosphonyl group, this compoundThere is anti-dirt and antibacterial ability, pollute and membrane degradation thereby effectively reduce film;
4, the present invention is just permeating and is drawing interception capacity while using molecular interception rate for 800Da nanofiltration membrane treatment in liquid removal processReach more than 97%, be easy to reclaim, thereby reduced energy consumption;
5, the present invention has obtained the organic phospho acid with higher phosphonyl group content by the method for organic synthesis, thereby increasesThe strong performance of positive penetrating fluid;
6, the synthetic organic phosphonate of the present invention also can be used for as antisludging agent simultaneously, and organic phospho acid concentration of salt solution existsWhen 0.7ppm is above, have outstanding anti-calcium carbonate dirt ability, along with the increase (being the increase of phosphonyl group) of molecular weight, it is anti-Calcium carbonate dirt ability further strengthens; This extracellular concentration can also the organic dirt of very effective removal at 1000ppm; Have extensivelyApplication prospect.
Brief description of the drawings
Fig. 1 is positive permeability apparatus structural representation;
Fig. 2 is the osmotic pressure test result figure that organic phosphine draws liquid;
Fig. 3 is positive infiltration water flux test result figure;
Fig. 4 is just permeating reverse flux salt test result figure;
In institute's drawings attached, identical Reference numeral is used for representing identical element or structure, wherein: 1-flowmeter, 2-Pump, 3-pure water, 4-forward osmosis membrane pond, 5-is just permeating and is drawing liquid.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, rightThe present invention is further elaborated. Should be appreciated that specific embodiment described herein is only in order to explain the present invention, andBe not used in restriction the present invention. In addition,, in each embodiment of described the present invention, involved technical characterictic needs onlyNot forming each other conflict just can combine mutually.
The invention provides one and just permeating and draw liquid, described just to permeate the pH value of drawing liquid be 6～10, comprises that quality dividesNumber is the organic phosphine compound of 5%～50% (being preferably 15%～35%), and described organic phosphine compound has suc as formula shown in IChemical structural formula, wherein, m is that 1～6, n is that 0～6, x is 0～2m+4n+8, Y is Na, K or Li, this is just permeating and is drawing liquid and can answerFor positive permeability apparatus.
That the present invention also provides is a kind of for the above-mentioned organic phosphine compound that draws liquid that just permeating, and has suc as formula shown in IChemical structural formula, wherein, m is that 1～6, n is that 1～6, x is 0～2m+4n+8, Y is Na, K or Li; Because Li ion volume is lessAnd easily by permeable membrane, K ion price is comparatively expensive, therefore, Y is preferably Na, and for example organic phosphine compound can be preferably
The preparation method of above-mentioned organic phosphine compound carries out according to following chemical equation:
Because phosphorus Halides can first react and can not get target compound with precursor water solution, and precursor water solution is stickyDegree affects mobility greatly, so this preparation method is specially: first, at 40 DEG C～60 DEG C, add first in precursor water solutionAldehyde, after precursor water solution and formaldehyde are fully mixed, cools to 30 DEG C and slowly adds below phosphorus Halides again, to avoid phosphorus HalidesReact very exothermic with water system heated up rapidly, then make phosphorus Halides and water temperature and react and generate phosphoric acid and hydrogen halides, orderDescribed presoma, formaldehyde, phosphoric acid fully react with hydrogen halides, obtain organic phosphine compound solution; Finally at 80 DEG C～120 DEG CHeating 0.5h～4h, except the hydrogen halides of the excessive generation of dereaction; Wherein, described presoma has suc as formula the chemical constitution shown in IIFormula, and m is that 1～6, n is 1～6, described phosphorus Halides is PCl3Or PBr3 The mol ratio of presoma, phosphorus Halides and formaldehyde is 1:5:5～1:19:19, determines according to the chemical structural formula of presoma, and m or n are moreGreatly, need formaldehyde and the phosphorus Halides of participation reaction more;
(2) add highly basic solid or strong base solution, regulate pH value to 6～10 of described organic phosphine compound solution, described inHighly basic is LiOH, NaOH or KOH;
(3) remove little below 500Da～800Da of described organic phosphine compound molecules in solution amount by methods such as dialysisMolecule, then removes the moisture in described organic phosphine compound solution by methods such as vacuum drying, obtains organic phosphine compound solidBody.
Following content is embodiment:
Embodiment 1
(1) will buy the diethylene triamine pentamethylene phosphonic of returning, with NaOH adjusting pH to 7, obtain divinyl threeThe water solution mixture of amine five methylenephosphonic acids and NaOH.
(2), by the diethylene triamine pentamethylene phosphonic obtaining in step (1) and the water solution mixture of NaOH, useThe molecular weight that dams is 500 bag filter purifying three times, obtains clean mixed liquor;
(3) by the clean mixed liquor obtaining in step (2), decompression removes and anhydrates, and dry in vacuum drying chamber at 80 DEG CDry 5 hours, obtain described DTPMP-xNa solid, its chemical structural formula is as follows
Embodiment 2
(1) under room temperature environment, the TEPA of 1 equivalent is evenly mixed with 250mL water, be warmed up to after 40 DEG C, slowThe slow formaldehyde that drips 7.25 equivalents, drips complete 60 DEG C of reactions one hour that is warmed up to, and cools to afterwards below 40 DEG C, is added dropwise to 7.25 and works asThe phosphorus trichloride of amount and holding temperature below 40 DEG C, drip to finish and be warmed up to 120 DEG C of insulations 1 hour to remove the hydrogen chloride of generation, obtainsObtain the thick liquid of soluble sodium salting liquid of described TEPA seven methylenephosphonic acids.
(2) by the thick liquid of soluble sodium salting liquid of TEPA seven methylenephosphonic acids that obtain in step (1), use hydroxideSodium regulates pH to 7;
(3) by the thick liquid of soluble sodium salting liquid of TEPA seven methylenephosphonic acids of the pH=7 obtaining in step (2),Purify three times with the bag filter of molecular interception rate 500, the soluble sodium salt that obtains clean TEPA seven methylenephosphonic acids is moltenLiquid;
(4) by the soluble sodium salting liquid of clean TEPA seven methylenephosphonic acids that obtain in step (3), decompression is removedWater, and in vacuum drying chamber, be dried 5 hours at 80 DEG C, obtaining TPHMP-xNa solid, its chemical structural formula is as follows
Embodiment 3
(1) under room temperature environment, the polymine of 1 equivalent 600 is evenly mixed with 250mL water, be warmed up to after 40 DEG C,Slowly drip the formaldehyde of 9.25 equivalents, drip complete 60 DEG C of reactions one hour that is warmed up to, cool to afterwards below 40 DEG C, be added dropwise to 9.25The phosphorus trichloride of equivalent and holding temperature be below 40 DEG C, drip to finish to be warmed up to 120 DEG C of insulations 1 hour to remove the hydrogen chloride of generation,Obtain the thick liquid of soluble sodium salting liquid of described TEPA seven methylenephosphonic acids.
(2) by the thick liquid of soluble sodium salting liquid of polymine 600 methylenephosphonic acids that obtain in step (1), use hydrogen-oxygenChange sodium and regulate pH to 7;
(3) by the thick liquid of soluble sodium salting liquid of polymine 600 methylenephosphonic acids of the pH=7 obtaining in step (2),Purify three times with the bag filter that molecular interception rate is 500Da, obtain the soluble sodium of clean polymine 600 methylenephosphonic acidsSalting liquid;
(4) will in step (3), obtain the soluble sodium salting liquid of clean polymine 600 methylenephosphonic acids, decompression removesAnhydrate, and in vacuum drying chamber, be dried 5 hours at 80 DEG C, obtain PEI-600-PO3H2-xNa solid, its chemical structural formula is
Embodiment 4
(1) under room temperature environment, the polymine of 1 equivalent 1800 is evenly mixed with 250mL water, be warmed up to 40 DEG CAfter, slowly drip the formaldehyde of 19.25 equivalents, drip to finish and be warmed up to 60 DEG C of reactions one hour, cool to afterwards below 40 DEG C, be added dropwise toThe phosphorus trichloride of 19.25 equivalents and holding temperature be below 40 DEG C, drips to finish to be warmed up to 120 DEG C of insulations 1 hour to remove the chlorine of generationChange hydrogen, obtain the thick liquid of soluble sodium salting liquid of described polymine 1800 methylenephosphonic acids.
(2) by the thick liquid of soluble sodium salting liquid of polymine 1800 methylenephosphonic acids that obtain in step (1), use hydrogen-oxygenChange sodium and regulate pH to 7;
(3) by thick the soluble sodium salting liquid of polymine 1800 methylenephosphonic acids of the pH=7 obtaining in step (2)Liquid, purifies three times with the bag filter of molecular interception rate 500, obtains the soluble sodium of clean polymine 1800 methylenephosphonic acidsSalting liquid;
(4) by the soluble sodium salting liquid of clean polymine 1800 methylenephosphonic acids that obtain in step (3), decompression removesAnhydrate, and in vacuum drying chamber, be dried 5 hours at 80 DEG C, obtain PEI-1800-PO3H2-xNa solid, its chemical structural formula is
Interpretation
By described, solid in embodiment 1-4 is dissolved in to deionized water, obtains respectively 0.1gmL-1、0.2gmL-1、0.3gmL-1、0.4gmL-1And 0.5gmL-1The aqueous solution, make just permeating and draw liquid. Test its osmotic pressure, and use businessHTI-TFC flat sheet membrane is carried out positive penetration testing according to the flow process shown in Fig. 1 and is drawn with examination water flux and the reverse salt that liquid producesFlux, wherein, 1-flowmeter, 2-pump, 3-pure water, 4-forward osmosis membrane pond, 5-is just permeating and is drawing liquid, and the direction of arrow represents that current are logicalDirection; Test condition is 25 ± 0.5 DEG C of water temperatures, effective film area 18.9cm2, water velocity 0.3Lmin-1, every two hours testA concentration draw liquid, each concentration is at least tested three times, averages.
Wherein, osmotic pressure result as shown in Figure 2: embodiment 1-4 is at 0.5gmL-1Under concentration, can produce respectively 106bar,The osmotic pressure of 129bar, 124bar and 166bar. Meanwhile, just permeating result as Fig. 3, shown in 4: result shows embodiment 1-4 toolThere are higher water flux and lower salt flowage; At 0.5gmL-1Under concentration, the selection layer of film is towards drawing under liquid pattern, embodiment1 water flux can reach 27.85LM-2H-1, average reverse flux salt is lower than 1.15gM-2H-1, the water flux of embodiment 2 can reach31.85LM-2H-1, average reverse flux salt is lower than 0.85gM-2H-1, the water flux of embodiment 3 can reach 29.25LM-2H-1, flatAll reverse flux salt is lower than 0.46gM-2H-1, embodiment 4 water fluxes can reach 20.8LM-2H-1, average reverse flux salt lower than0.43gM-2H-1。
Preparation contains a certain amount of calcium chloride (CaCl2), sodium sulphate (Na2SO4), sodium acid carbonate (NaHCO3) synthetic water in,Make in synthesis of aqueous solution containing Ca2+Concentration is 200ppm, HCO3 -Concentration is 500ppm, and pH value of solution is 8.8, and stirs and evenly mixs constant temperature25 DEG C for subsequent use. The soluble sodium salt of the prepared methylenephosphonic acid of embodiment 1-4 is made into series concentration in 1～16ppm scopeSolution. Then the soluble sodium salting liquid of the methylenephosphonic acid of above-mentioned 1～16ppm is added to respectively in above-mentioned synthesis of aqueous solution, in75 DEG C of reactions, after 10 hours, are carried out titration with the EDTA of 0.02M, are calculated as follows scale inhibition performance:
Wherein, A is scale inhibition performance, VT1Consume the volume (mL) of EDTA when having antisludging agent, VT0Consume when without antisludging agentThe volume (mL) of EDTA, VT2Consume the volume (mL) of EDTA when measuring total calcium.
Adopt static-state scale inhibition rate assay method to measure the scale-inhibiting properties of embodiment 1-embodiment 4. Experimental result shows: methenePhosphonic acids soluble sodium salt has good scale-inhibiting properties, and is increase tendency with the scale-inhibiting properties that increases of methylenephosphonic acid number; This, increase inhibitor concentration outward, scale inhibition performance also increases thereupon. Scale inhibitor dosage has good resistance calcium carbonate scale in the time that 7ppm is abovePerformance.
In sum, osmotic pressure experiment shows: organic phosphine provided by the invention is just permeating and drawing liquid, has high osmotic pressureValue; Positive permeability test shows: in used business HT-TFC film test, there is higher water flux, and low-down reverseFlux salt. Study and show under the pattern of drawing liquid at film: organic phosphine provided by the invention is just permeating and drawing liquid, its water fluxFar away high, also keep low reverse flux salt simultaneously. Therefore, described serial organic phosphine compound draws liquid for the preparation of just permeating,Performance ideal.
Those skilled in the art will readily understand, the foregoing is only preferred embodiment of the present invention, not in order toRestriction the present invention, all any amendments of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should compriseWithin protection scope of the present invention.
Claims (10)
1. just permeating and drawing a liquid, it is characterized in that, comprising that mass fraction is 5%～50% organic phosphine compound, described inOrganic phosphine compound has suc as formula the chemical structural formula shown in I, and wherein, m is that 1～6, n is that 0～6, x is 0～2m+4n+8, and Y isNa, K or Li
2. as claimed in claim 1 just infiltration drawn liquid, it is characterized in that, described just infiltration drawn liquid and comprised that mass fraction is15%～35% organic phosphine compound.
3. as claimed in claim 1 just infiltration drawn liquid, it is characterized in that, described just to permeate the pH value of drawing liquid be 6～10.
4. a positive permeability apparatus, is characterized in that, uses the just infiltration as described in any one in claim 1-3 to drawLiquid.
5. for just permeating an organic phosphine compound that draws liquid as described in claim 1-3 any one, its feature existsIn, have suc as formula the chemical structural formula shown in I, wherein, m is that 1～6, n is that 1～6, x is 0～2m+4n+8, Y is Na, K or Li
6. organic phosphine compound as claimed in claim 5, is characterized in that, m=3, n=6; Or m=1, n=2.
7. a preparation method for the organic phosphine compound as described in claim 5 or 6, is characterized in that, chemical equation asUnder:
。
8. preparation method as claimed in claim 7, is characterized in that, at 40 DEG C～60 DEG C, in precursor water solution, addsFormaldehyde, then adds phosphorus Halides below at 30 DEG C, makes described presoma, formaldehyde and phosphorus Halides fully react, finally at 80 DEG CAt～120 DEG C, heat described precursor water solution the hydrogen halides of reaction generation is fully volatilized, obtain organic phosphine compound moltenLiquid; Wherein, the mol ratio of described presoma, formaldehyde and phosphorus Halides is 1:5:5～1:19:19, described presoma have suc as formulaChemical structural formula shown in II, and m is that 1～6, n is 1～6, described phosphorus Halides is PCl3Or PBr3
9. preparation method as claimed in claim 8, is characterized in that, also comprises, adds highly basic, regulates described organic phosphine chemical combinationPH value to 6～10 of thing solution, described highly basic is LiOH, NaOH or KOH.
10. preparation method as claimed in claim 8 or 9, is characterized in that, also comprises, removes described organic phosphine compound moltenIn liquid, the little molecule of molecular weight below 500Da～800Da, then removes the moisture in described organic phosphine compound solution, obtainsObtain organic phosphine compound solid.
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