CN105597540B - It is a kind of it is positive infiltration draw liquid and its application and it is a kind of for just permeate draw organic phosphine compound of liquid and preparation method thereof - Google Patents
It is a kind of it is positive infiltration draw liquid and its application and it is a kind of for just permeate draw organic phosphine compound of liquid and preparation method thereof Download PDFInfo
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- CN105597540B CN105597540B CN201610072716.1A CN201610072716A CN105597540B CN 105597540 B CN105597540 B CN 105597540B CN 201610072716 A CN201610072716 A CN 201610072716A CN 105597540 B CN105597540 B CN 105597540B
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- organic phosphine
- phosphine compound
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- 239000007788 liquid Substances 0.000 title claims abstract description 76
- -1 phosphine compound Chemical class 0.000 title claims abstract description 59
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 35
- 238000001764 infiltration Methods 0.000 title claims abstract description 33
- 230000008595 infiltration Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000012466 permeate Substances 0.000 title description 4
- 239000000126 substance Substances 0.000 claims abstract description 13
- 230000035699 permeability Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 45
- 230000004907 flux Effects 0.000 abstract description 24
- 150000003839 salts Chemical class 0.000 abstract description 13
- 230000002441 reversible effect Effects 0.000 abstract description 12
- 230000003204 osmotic effect Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 150000003003 phosphines Chemical class 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 239000002253 acid Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 239000011734 sodium Substances 0.000 description 17
- 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 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- 239000012528 membrane Substances 0.000 description 15
- 238000009938 salting Methods 0.000 description 14
- 229920002873 Polyethylenimine Polymers 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000009292 forward osmosis Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 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 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000012423 maintenance 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
- 238000004321 preservation 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
- 229910020667 PBr3 Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000006837 decompression Effects 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 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
- 238000010248 power generation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment Methods 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 kind of positive infiltrations to draw liquid and its application, which draws liquid and include the organic phosphine compound that mass fraction is 5%~50%, and the organic phosphine compound has chemical structural formula shown in formula I, wherein, it is 0~6 that m, which is 1~6, n, x is 0~2m+4n+8, Y Na, K or LiThe invention also discloses organic phosphine compounds that liquid is drawn for the positive infiltration and preparation method thereof.Liquid is drawn in organic phosphine provided by the invention just infiltration, and applied to positive process of osmosis, not only osmotic pressure is high, and water flux is big, and reverse flux salt is low, also with outstanding scale-inhibiting properties.
Description
Technical field
The invention belongs to positive infiltration technology fields, and liquid and its application, Yi Jiyi are drawn more particularly, to a kind of positive infiltration
Kind draws organic phosphine compound of liquid and preparation method thereof for just permeating.
Background technology
With the continuous growth of population, the shortage of fresh water problem caused by the continuous deterioration of environment is influencing the mankind just
Often life, and the application of membrane separation technique is expected to alleviate water supply this problem.Positive infiltration is that a kind of nature is widely present
Spontaneous physical phenomenon, the effective infiltration difference driving hydrone drawn between liquid and feed liquid passes through from high water chemistry gesture feed liquid side
Permselectivity membrane flows to low water chemistry gesture and draws liquid side.Positive process of osmosis only needs a small amount of ambient pressure that water can be realized
Separation process, and forward osmosis membrane can effectively reduce fouling membrane in itself, and the rate of recovery of water is high, draws liquid recoverable, dense
Water discharge is few, pollutes small, energy conservation and environmental protection.Therefore the technology is widely used in wastewater treatment, sea water desalination, food concentration of juices,
Drug is controlled with release, the purifying of aerospace water with recycling, the fields such as power generation.
The key element that liquid is the normal work of positive permeability apparatus is drawn in positive infiltration, and which determine the performances of positive process of osmosis
And efficiency.The magnetic nanoparticle that the active constituent of liquid mainly has surface to be modified, ammonium carbonate salts, phase are drawn in currently available technology
Transformation switch compound, organometallic complex, polyamine amino acid (IndEngChem Res 2014,53,16170-16175.),
Organic carboxylic acid sodium salt (BioresourceTechnol 2012,122,207-216.), phosphorous organic carboxylic acid sodium salt
(Desalination2013,312,130-136) etc.；Wherein, phosphorous organic carboxylic acid sodium salt's solution not only ecological environment compatibility
It is good, and ion is easily dissociateed in water so as to generate with very high osmotic pressure, finally obtain high water flux.
However, organic carboxylic acid sodium salt has the disadvantages that：First, physicochemical properties are unstable, easily by micro- life in water
Object is degraded；2nd, it does not have antibacterial and anti-dirt ability, and not only one film surface of feeding liquid is also easy to produce carbonic acid after long-time use
The inorganic foulants such as calcium, and one film surface of liquid is drawn since bacterial growth can generate the organic contamination of film, seriously lead to fenestra
It blocks, affects the separating property of forward osmosis membrane, and increase film and remove dirt and renew the cost of film；3rd, known major part
Organic carboxylic acid sodium salt also has certain environment toxic action, should not carry out large-scale use；4th, the molecule of organic carboxylic acid sodium salt
Amount is generally less than 500Da, and matched permeable membrane kind is rare, expensive, needs to disappear when recycling equal unit amount water
More electric energy are consumed, cause the wasting of resources.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, draw liquid the present invention provides a kind of positive infiltration and its answer
With and it is a kind of for just permeating the organic phosphine compound and preparation method thereof for drawing liquid, its object is to pass through a kind of molecule
Volume is larger, and hydrophilicity is good, and liquid is drawn in environmental-friendly positive infiltration, thus solves existing positive infiltration and draw liquid water flow to have
Limit, reverse flux salt are big, easy fouling, the technical issues of being easily degraded by microorganisms.
To achieve the above object, one side according to the invention provides a kind of positive infiltration and draws liquid, including quality point
Number is 5%~50% organic phosphine compound, and the organic phosphine compound has chemical structural formula shown in formula I, wherein, m
For 1~6, n be 0~6, x it is 0~2m+4n+8, Y Na, K or Li.
Preferably, it is described it is positive infiltration draw liquid include mass fraction be 15%~35% organic phosphine compound.
Preferably, the pH value that liquid is drawn in the positive infiltration is 6~10.
It is another aspect of this invention to provide that providing a kind of positive permeability apparatus, liquid is drawn using above-mentioned positive infiltration.
It is another aspect of this invention to provide that a kind of organic phosphine compound that liquid is drawn for above-mentioned positive infiltration is additionally provided,
With chemical structural formula shown in formula I, wherein, it be 1~6, x is 0~2m+4n+8, Y Na, K or Li that m, which is 1~6, n,.
Preferably, m=3, n=6；Or m=1, n=2.
It is another aspect of this invention to provide that additionally providing a kind of preparation method of above-mentioned organic phosphine compound, chemically react
Formula is as follows：
Preferably, the preparation method is：At 40 DEG C~60 DEG C, formaldehyde is added in precursor water solution, then 30
Below DEG C add in phosphorus Halides, the presoma, formaldehyde and phosphorus Halides is enabled fully to react in aqueous solution, finally 80 DEG C~
The precursor water solution is heated at 120 DEG C so that reaction generation hydrogen halides fully volatilize, obtain organic phosphine compound solution；
Wherein, the molar ratio of the presoma, formaldehyde and phosphorus Halides is 1:5:5~1:19:19, the presoma has such as II institute of formula
The chemical structural formula shown, and it is 1~6 that m, which is 1~6, n, the phosphorus Halides is PCl3Or PBr3
Preferably, the preparation method further includes, and adds in highly basic, adjusts the pH value of the organic phosphine compound solution to 6
~10, the highly basic is LiOH, NaOH or KOH.
Preferably, the preparation method further includes, remove the organic phosphine compound molecules in solution amount 500Da~
Then the small molecule of below 800Da removes the moisture in the organic phosphine compound solution, obtain organic phosphine compound solid.
In general, by the above technical scheme conceived by the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1st, the present invention uses molecular weight to draw matter as positive infiltration for the organic phosphine compound of 800Da~10000Da, due to
The increase of its molecular weight is so that the hole that its volume is more than film is not easy through forward osmosis membrane, so that it is big effectively to solve reverse flux salt
The problem of, and can also reduce and subsequently draw energy consumption in liquid removal process；
2nd, liquid is drawn in positive infiltration provided by the invention, and under equal quality score, osmotic pressure average specific polyamine amino acid salt is high
Go out about 1.5 times, drawing liquid than organic carboxylic acid sodium salt is higher by 33%, and than phosphorous 1 times of organic carboxylic acid sodium salt, water flux is more than polyamine amine
0.5 times of hydrochlorate draws liquid than organic carboxylic acid sodium salt and is higher by a quarter, and reverse flux salt is a quarter of polyamine amino acid salt；
3rd, the organic phosphine compound that uses of the present invention is to nontoxic to ecology, meanwhile, because with phosphonyl group, the compound
With anti-dirt and antibacterial ability, so as to effectively reduce fouling membrane and membrane degradation；
4th, interception capacity when using molecular interception rate as 800Da nanofiltration membrane treatments in liquid removal process is drawn in the positive infiltration of the present invention
Up to more than 97%, it is easily recycled, so as to reduce energy expenditure；
5th, the present invention obtains the organic phospho acid with higher phosphonyl group content by the method for organic synthesis, so as to increase
The strong performance of positive penetrating fluid；
6th, the organic phosphonate that the present invention synthesizes is also useful as antisludging agent simultaneously, and organic phospho acid concentration of salt solution exists
With outstanding anti-calcium carbonate scale ability during more than 0.7ppm, with the increase (i.e. the increase of phosphonyl group) of molecular weight, it is anti-
Calcium carbonate scale ability further enhances；This extracellular concentration can also the very effective organic dirt of removal in 1000ppm；With extensive
Application prospect.
Description of the drawings
Fig. 1 is positive permeability apparatus structure diagram；
Fig. 2 is the osmotic pressure test result figure that organic phosphine draws liquid；
Fig. 3 is positive osmotic water flux test result figure；
Fig. 4 is just to permeate reverse flux salt test result figure；
In all the appended drawings, identical reference numeral is used for representing identical element or structure, wherein：1- flowmeters, 2-
Liquid is drawn in pump, 3- pure water, 4- forward osmosis membranes pond, 5- just infiltrations.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The present invention provides a kind of positive infiltrations to draw liquid, and the pH value that liquid is drawn in the positive infiltration is 6~10, including quality point
Organic phosphine compound of the number for 5%~50% (preferably 15%~35%), the organic phosphine compound have shown in formula I
Chemical structural formula, wherein, it be 0~6, x is 0~2m+4n+8, Y Na, K or Li that m, which is 1~6, n, which, which draws liquid, to answer
For positive permeability apparatus.
The present invention also provides a kind of organic phosphine compounds that liquid is drawn for above-mentioned positive infiltration, have shown in formula I
Chemical structural formula, wherein, it be 1~6, x is 0~2m+4n+8, Y Na, K or Li that m, which is 1~6, n,；Since Li ion volumes are smaller
And easily by permeable membrane, costly, therefore, Y is preferably Na to K ions price, such as organic phosphine compound is preferably
The preparation method of above-mentioned organic phosphine compound is carried out according to following chemical equation：
It cannot get target compound, and precursor water solution is glued since phosphorus Halides can first be reacted with precursor water solution
Degree is big and influences mobility, so the preparation method is specially：First at 40 DEG C~60 DEG C, added in into precursor water solution
Formaldehyde makes precursor water solution with after the abundant mixing of formaldehyde, cooling to less than 30 DEG C and being slow added into phosphorus Halides, to avoid halogenation
Phosphorus reacts very exothermic with water is brought rapidly up system, then make phosphorus Halides and water temperature and react generation phosphoric acid and hydrogen halides,
The presoma, formaldehyde, phosphoric acid is enabled fully to be reacted with hydrogen halides, obtains organic phosphine compound solution；Finally at 80 DEG C~120 DEG C
Lower heating 0.5h~4h, the hydrogen halides excessively generated except dereaction；Wherein, the presoma has the chemistry knot as shown in formula II
Structure formula, and it is 1~6 that m, which is 1~6, n, the phosphorus Halides is PCl3Or PBr3 Forerunner
The molar ratio of body, phosphorus Halides and formaldehyde is 1:5:5~1:19:19, depending on the chemical structural formula of presoma, m or n are bigger,
Then need the formaldehyde for participating in reacting and phosphorus Halides then more；
(2) strong basic solid or strong base solution are added in, adjusts the pH value of the organic phosphine compound solution to 6~10, it is described
Highly basic is LiOH, NaOH or KOH；
(3) the organic phosphine compound molecules in solution amount is removed in the small of 500Da~below 800Da with the methods of dialysis
Then molecule removes the moisture in the organic phosphine compound solution with the methods of vacuum drying, obtains organic phosphine compound and consolidate
Body.
The following contents is embodiment：
Embodiment 1
(1) diethylene triamine pentamethylene phosphonic come will be bought back, adjusts pH to 7 with sodium hydroxide, obtain divinyl three
The water solution mixture of five methylenephosphonic acid of amine and sodium hydroxide.
(2) diethylene triamine pentamethylene phosphonic and the water solution mixture of sodium hydroxide that will be obtained in step (1), uses
The bag filter purifying that the molecular weight that shuts off is 500 three times, obtains clean mixed liquor；
(3) the clean mixed liquor that will be obtained in step (2) is removed under reduced pressure water, and is done in vacuum drying chamber at 80 DEG C
Dry 5 hours, the DTPMP-xNa solids are obtained, chemical structural formula is as follows
Embodiment 2
(1) under room temperature environment, the tetraethylenepentamine of 1 equivalent with 250mL water is uniformly mixed, after being warming up to 40 DEG C, is delayed
The slow formaldehyde that 7.25 equivalents are added dropwise, drop, which finishes, to be warming up to 60 DEG C and reacts one hour, is cooled to 40 DEG C later and is worked as hereinafter, being added dropwise to 7.25
Phosphorus trichloride and 40 DEG C of the temperature of maintenance of amount are warming up to 120 DEG C of heat preservations, the 1 hour hydrogen chloride generated with removing hereinafter, drop finishes, and obtain
Obtain the thick liquid of soluble sodium salting liquid of seven methylenephosphonic acid of tetraethylenepentamine.
(2) the thick liquid of soluble sodium salting liquid of seven methylenephosphonic acid of tetraethylenepentamine that will be obtained in step (1), uses hydroxide
Sodium adjusts pH to 7；
(3) the thick liquid of soluble sodium salting liquid of seven methylenephosphonic acid of tetraethylenepentamine of pH=7 that will be obtained in step (2),
Purified three times with the bag filter of molecular interception rate 500, the soluble sodium salt for obtaining clean seven methylenephosphonic acid of tetraethylenepentamine is molten
Liquid；
(4) the soluble sodium salting liquid of net seven methylenephosphonic acid of tetraethylenepentamine that will be obtained in step (3), is removed under reduced pressure
Water, and it is 5 hours dry in vacuum drying chamber at 80 DEG C, TPHMP-xNa solids are obtained, chemical structural formula is as follows
Embodiment 3
(1) under room temperature environment, the polyethyleneimine 600 of 1 equivalent is uniformly mixed with 250mL water, after being warming up to 40 DEG C,
It is slowly added dropwise the formaldehyde of 9.25 equivalents, drop, which finishes, to be warming up to 60 DEG C and react one hour, cools to 40 DEG C later hereinafter, being added dropwise to 9.25
Phosphorus trichloride and 40 DEG C of the temperature of maintenance of equivalent are warming up to 120 DEG C of heat preservations, the 1 hour hydrogen chloride generated with removing hereinafter, drop finishes,
Obtain the thick liquid of soluble sodium salting liquid of seven methylenephosphonic acid of tetraethylenepentamine.
(2) the thick liquid of soluble sodium salting liquid of 600 methylenephosphonic acid of polyethyleneimine that will be obtained in step (1), uses hydrogen-oxygen
Change sodium and adjust pH to 7；
(3) the thick liquid of soluble sodium salting liquid of 600 methylenephosphonic acid of polyethyleneimine of pH=7 that will be obtained in step (2),
The bag filter for being 500Da with molecular interception rate is purified three times, obtains the soluble sodium of clean 600 methylenephosphonic acid of polyethyleneimine
Salting liquid；
(4) the soluble sodium salting liquid for clean 600 methylenephosphonic acid of polyethyleneimine being obtained in step (3), decompression remove
Water is removed, and 5 hours dry in vacuum drying chamber at 80 DEG C, obtain PEI-600-PO3H2- xNa solids, chemical structural formula are
Embodiment 4
(1) under room temperature environment, the polyethyleneimine 1800 of 1 equivalent with 250mL water is uniformly mixed, is warming up to 40 DEG C
Afterwards, it is slowly added dropwise the formaldehyde of 19.25 equivalents, drop, which finishes, to be warming up to 60 DEG C and react one hour, cools to 40 DEG C later hereinafter, being added dropwise to
Phosphorus trichloride and 40 DEG C of the temperature of maintenance of 19.25 equivalents are warming up to 120 DEG C of heat preservations, the 1 hour chlorine generated with removing hereinafter, drop finishes
Change hydrogen, obtain the thick liquid of soluble sodium salting liquid of 1800 methylenephosphonic acid of polyethyleneimine.
(2) the thick liquid of soluble sodium salting liquid of 1800 methylenephosphonic acid of polyethyleneimine that will be obtained in step (1), uses hydrogen-oxygen
Change sodium and adjust pH to 7；
(3) it is the soluble sodium salting liquid of 1800 methylenephosphonic acid of polyethyleneimine of the pH=7 obtained in step (2) is thick
Liquid is purified three times with the bag filter of molecular interception rate 500, obtains the soluble sodium of clean 1800 methylenephosphonic acid of polyethyleneimine
Salting liquid；
(4) the soluble sodium salting liquid of net 1800 methylenephosphonic acid of polyethyleneimine that will be obtained in step (3), decompression remove
Water is removed, and 5 hours dry in vacuum drying chamber at 80 DEG C, obtain PEI-1800-PO3H2- xNa solids, chemical structural formula are
Analysis of experimental results
Solid in the 1-4 by embodiment is dissolved in deionized water, obtains 0.1g mL respectively-1、0.2gmL-1、0.3g
mL-1、0.4g mL-1And 0.5g mL-1Aqueous solution, obtain positive infiltration and draw liquid.Its osmotic pressure is tested, and with commercially
HTI-TFC plate membranes carry out positive penetration testing to examine or check the water flux for drawing liquid generation and reverse salt according to flow shown in FIG. 1
Flux, wherein, 1- flowmeters, 2- pumps, 3- pure water, 4- forward osmosis membranes pond, 5-, which just permeates, draws liquid, and arrow direction represents that flow is led to
Direction；Test condition be 25 ± 0.5 DEG C of water temperature, effective membrane area 18.9cm2, water velocity 0.3L min-1, every two hours test
One concentration draws liquid, and each concentration is at least tested three times, is averaged.
Wherein, the results are shown in Figure 2 for osmotic pressure：Embodiment 1-4 is in 0.5gmL-1Under concentration, can generate respectively 106bar,
The osmotic pressure of 129bar, 124bar and 166bar.Meanwhile positive Permeation Results such as Fig. 3, shown in 4：The result shows that embodiment 1-4 has
There are higher water flux and relatively low salt stream；In 0.5g mL-1Under concentration, the selection layer direction of film is drawn under liquid pattern, embodiment
1 water flux is up to 27.85L M-2H-1, average reverse flux salt is less than 1.15g M-2H-1, the water flux of embodiment 2 is reachable
31.85L M-2H-1, average reverse flux salt is less than 0.85g M-2H-1, the water flux of embodiment 3 is up to 29.25L M-2H-1, put down
Reverse flux salt is less than 0.46g M-2H-1, 4 water flux of embodiment is up to 20.8L M-2H-1, average reverse flux salt is less than
0.43gM-2H-1。
Wherein, A is scale inhibition performance, VT1The volume (mL) of EDTA, V are consumed during to there is antisludging agentT0To be consumed during no antisludging agent
The volume (mL) of EDTA, VT2The volume (mL) of EDTA is consumed during to measure total calcium.
The scale-inhibiting properties of embodiment 1- embodiments 4 are measured using static-state scale inhibition rate assay method.The experimental results showed that：Methene
Phosphonic acids soluble sodium salt has preferable scale-inhibiting properties, and increases scale-inhibiting properties in increase tendency with methylenephosphonic acid number；This
Outside, increase inhibitor concentration, scale inhibition performance also increases therewith.Scale inhibitor dosage is in more than 7ppm with excellent resistance calcium carbonate scale
Performance.
In conclusion osmolarity test is shown：Liquid is drawn in organic phosphine provided by the invention just infiltration, has high osmotic pressure
Value；Positive permeability test is shown：There is higher water flux and low-down reverse in the test of used business HT-TFC films
Flux salt.In film towards drawing under the pattern of liquid research shows that：Liquid, water flux are drawn in organic phosphine provided by the invention just infiltration
It is remote high, while also keep low reverse flux salt.Therefore, the serial organic phosphine compound is used to prepare positive infiltration and draws liquid,
Performance is preferable.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made all within the spirits and principles of the present invention etc., should all include
Within protection scope of the present invention.
Claims (2)
1. organic phosphine compound draws the application of liquid as positive infiltration, which is characterized in that the positive infiltration draws liquid and includes quality point
Number is 15%~35% organic phosphine compound, and the organic phosphine compound has chemical structural formula shown in formula I, wherein, m
For 1~6, n be 0~6, x it is 0~2m+4n+8, Y Na, K or LiIt is described
The pH value that liquid is drawn in positive infiltration is 6~10.
2. a kind of positive permeability apparatus, which is characterized in that draw liquid using positive infiltration as described in claim 1.
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| CN108976258B (en) * | 2017-06-01 | 2021-04-20 | 财团法人工业技术研究院 | Multi-branched cationic phosphonium salt, forward osmosis extract containing same, and forward osmosis seawater desalination process |
| CN109316965B (en) * | 2018-10-22 | 2020-11-24 | 华中科技大学 | Application of organic phosphonate as forward osmosis drawing solute and forward osmosis device |
| CN114011241B (en) * | 2021-11-29 | 2024-03-26 | 中新国际联合研究院 | Responsive mixed drawing liquid containing organic molecules or polymers and inorganic salts and application thereof |
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