CN106315711B

CN106315711B - Delay the layer-by-layer sustained release water treatment agent and preparation method thereof of seawater fouling membrane

Info

Publication number: CN106315711B
Application number: CN201610854461.4A
Authority: CN
Inventors: 赵瑾; 王文华; 姜天翔; 王静; 张雨山
Original assignee: Tianjin Institute of Seawater Desalination and Multipurpose Utilization MNR
Current assignee: Tianjin Institute of Seawater Desalination and Multipurpose Utilization MNR
Priority date: 2016-09-26
Filing date: 2016-09-26
Publication date: 2019-08-30
Anticipated expiration: 2036-09-26
Also published as: CN106315711A

Abstract

A kind of layer-by-layer sustained release water treatment agent and preparation method thereof delaying seawater fouling membrane is related to being sustained water treatment agent technical field.Delay the layer-by-layer sustained release water treatment agent of seawater fouling membrane, it is made of adsorbent internal layer, flocculation aid wrapping layer and flocculant outer layer, inner layer adsorption agent is Powdered Activated Carbon, diatomite, wrapping layer flocculation aid is polyacrylamide, polydimethyl diallyl ammonium chloride, and outer layer flocculant is iron series, AlSnSi alloy.Delay the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane: Powdered Activated Carbon, diatomite being put into pelletizer and carry out circle rotation；Diluted flocculation aid solution is added on the Powdered Activated Carbon and diatomite of rotation and is wrapped up, particle is formed；Flocculant is added to the outermost layer for being wrapped in particle, is rotated, it is dry.Collecting flocculation of the present invention helps solidifying, absorption, Dynamic Membrane function in one, and layer-by-layer release structures are synergistic, reduce membrane pollution resistance, lessening membrane fouling；Preparation process is simple, easy to operate, and application prospect is good.

Description

Delay the layer-by-layer sustained release water treatment agent and preparation method thereof of seawater fouling membrane

Technical field

The present invention relates to sustained release water treatment agent technical fields, more particularly to a kind of layer-by-layer sustained release for delaying seawater fouling membrane Water treatment agent and preparation method thereof.

Background technique

Ultrafiltration is widely used membrane separating technology, and the aperture of ultrafiltration is 0.002-0.200 μm, and ultrafiltration is pre- as seawater Treatment process can remove suspended matter, colloid and microorganism in seawater, and producing water ratio is big, stable effluent quality.But hyperfiltration membrane assembly It can block, fouling membrane leads to flux depression, reduces film service life, increases cleaning frequency membrane, limits the wide of ultrafiltration General application.Dynamic Membrane refer to add precoating paint or stoste itself pass through filtration medium membrane surface formed have point Cake layer or film from performance.Dynamic Membrane material source is abundant, wherein flocculation is the conventional preprocess method of decelerating membrane pollution, it can Improve effluent quality, flocculation, which is formed by wadding body, to form one layer of loose cake layer in ultrafiltration membrane surface, can stop little particle Pollutant enters fenestra and causes irreversible membrane fouling, and then plays the purpose of decelerating membrane pollution.

Conventional flocculant has a single function, and for the preventing membrane pollution under briny environment and is not suitable for, and is in particular in following Several respects: the organic matters such as humic acid, fulvic acid, protein in seawater can be adsorbed on suspended particulates surface, form aquation protection Layer makes suspended particulates have stronger dispersion stabilization, and then increases flocculated difficulty；Seawater is in low turbid state throughout the year, hangs The negligible amounts of floating particle, the wadding body of formation is tiny, causes cake layer structure closely knit, increases filtration resistance；In addition, northern China There is the freezeup period up to 5 months in offshore sea waters every year, and the seawater viscosity under low-temperature condition is larger, affects the water of flocculant Speed is solved, the speed of growth of wadding body is slower, increases process treatment time.The effective way for solving this problem is using a variety of The water treatment agent or composite water disposal agent of different function replace single flocculant.

Currently, having the correlation report using the water treatment agent or composite water disposal agent of a variety of different function come lessening membrane fouling Road, as (China is specially for patent of invention " a kind of method that diatomite dynamic membrane processing raw water further decreases delivery turbidity in the process " Benefit number: disclosing a kind of method for extending the Dynamic Membrane duty cycle in 102557197 B of CN), this method passes through in filtration system In divide different batches to add diatomite and aluminium polychloride, macropore stainless (steel) wire surface formed one layer of compound Dynamic Membrane, with drop Low delivery turbidity.This method adds aluminium polychloride additives again after the circulation precoating of diatomite initial stage, although can improve silicon Diatomaceous earth Dynamic Membrane structure of filtering layer, but the wadding body cake layer that aluminium polychloride is formed is not loose enough, cannot reduce filtration resistance well Power, and the time for adding medicament in batches is difficult to accurately control, administration apparatus process control is more complicated, increase operation at This.One kind is disclosed in patent of invention " a kind of antifilm contaminative composite drug " (China Patent No.: 1321917 C of CN) to be used for The preventing membrane pollution composite drug of sewage treatment, including Powdered Activated Carbon, aluminium polychloride, ferric trichloride, calcium hydroxide and poly- third Amide can improve the filtering feature of mixed liquor in membrane bioreactor, maintain higher membrane flux, reduce fouling membrane, but this The each group of composite drug is divided into simple uniformly mixing, is unable to control the dissolution process of each component, each component is difficult to give full play to Respective effect is unable to reach best use effect, and the technical problems such as waste and secondary pollution for causing medicament.

Summary of the invention

The problem to be solved by the present invention is that overcoming drawbacks described above existing for the technology of taking over, and one kind is provided and delays sea The layer-by-layer sustained release water treatment agent and preparation method thereof of moisture film pollution.

Delay the layer-by-layer sustained release water treatment agent of seawater fouling membrane, internal layer is one of Powdered Activated Carbon, diatomite or two Kind mixing, and mixed by one or both of polyacrylamide (PAM), polydimethyl diallyl ammonium chloride (PDMDAAC) It is coated, outer layer is the mixing of one or more of iron series, AlSnSi alloy.The shape of water treatment agent of the present invention is ball Shape is close to spherical shape, particle diameter 1-3mm.

Delay the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane are as follows: by the powder of shared weight ratio 40-60% The mixing of one or both of last active carbon, diatomite, which is put into pelletizer, carries out circle rotation, by shared weight ratio 10-15% Polyacrylamide (PAM), the mixing of one or both of polydimethyl diallyl ammonium chloride (PDMDAAC) use same ratio Distilled water dilute dissolution, and by peristaltic pump by polyacrylamide (PAM), polydimethyl diallyl ammonium chloride One or both of (PDMDAAC) mixed solution injection is wrapped up on the Powdered Activated Carbon and diatomite of rotation, is formed Continue to rotate after circular granular；One or more of the aluminium system of shared weight ratio 30-45%, iron-based flocculating agent are mixed, used After the distilled water dilution of same ratio mixes, flocculant solution is injected on bead by peristaltic pump, flocculant is wrapped in The outermost layer of small spherical particles, rotates 10-20min to stabilization again after molding, then dry 1h at 60-70 DEG C, obtains successively sustained release Water treatment agent.

Water treatment agent of the present invention plays a role according to different time serieses.The iron series of outer layer, AlSnSi alloy are first It first dissolves, charge neutrality effect is carried out by compression double electric layer, capture suspended particulates, colloid, larger molecular organics etc. in seawater, Form thin and small wadding body；The polyacrylamide (PAM) of subsequent wrapping layer, polydimethyl diallyl ammonium chloride (PDMDAAC) Start to dissolve, play Coagulation aiding, can not only enhance charge neutrality effect, moreover it is possible to improve adsorption bridging ability, wadding body is promoted to grow up； Finally, inner layer adsorption agent Powdered Activated Carbon, diatomite start to play a role, the organic matter of the adsorbable remnants of cellular structure, And the Dynamic Membrane of different pore size is formed in ultrafiltration membrane surface together with wadding body, membrane pollution resistance is reduced, the blocking of ultrafiltration membrane is slowed down.

This case first purpose, which is to provide one kind, to be had the function of Collecting flocculation, helps solidifying, absorption, Dynamic Membrane in one, is successively sustained Structure, multiple efficacies are synergistic, reduce membrane pollution resistance, lessening membrane fouling, application prospect is good, especially can effectively delay low The layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane of the features such as warm seawater Pollution of Ultrafiltration Membrane.

The present invention delays the layer-by-layer sustained release water treatment agent of seawater fouling membrane to take following technical scheme to realize:

A kind of layer-by-layer sustained release water treatment agent delaying seawater fouling membrane, which is characterized in that delay the layer-by-layer of seawater fouling membrane Sustained release water treatment agent be made of adsorbent internal layer, flocculation aid wrapping layer and flocculant outer layer, inner layer adsorption agent be Powdered Activated Carbon, The mixing of one or both of diatomite, wrapping layer flocculation aid are polyacrylamide, in polydimethyl diallyl ammonium chloride One or two mixing, outer layer flocculant are the mixing of one or more of iron series, AlSnSi alloy.

This case delays the layer-by-layer sustained release water treatment agent of seawater fouling membrane can also be using following technical measures come further real It is existing:

The layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein inner layer adsorption agent, wrapping layer flocculation aid and The mass ratio of outer layer flocculant is 40-60: 10-15: 30-45.

The layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein delay the layer-by-layer sustained release of seawater fouling membrane Water treatment agent shape is spherical or spherical particle, particle diameter 1-3mm.

The layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein inner layer adsorption agent Powdered Activated Carbon, diatom The partial size of soil is 90-106 μm.

The layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein iron-based flocculating agent is iron chloride, sulfuric acid Iron, poly-ferric chloride or bodied ferric sulfate, AlSnSi alloy are aluminium chloride, aluminum sulfate, aluminium polychloride or polyaluminium sulfate.

This case second purpose, which is to provide one kind, has simple process, easy to operate, and product Collecting flocculation helps solidifying, absorption, dynamic Film function is in one, and layer-by-layer release structures, multiple efficacies are synergistic, reduces membrane pollution resistance, lessening membrane fouling, application prospect The preparation method of the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane of the features such as good.

It is that following technical scheme is taken that the present invention, which delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, It realizes:

Delay the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, which is characterized in that delay seawater fouling membrane The preparation process of layer-by-layer sustained release water treatment agent be that one or both of Powdered Activated Carbon, diatomite are mixed and are put into Circle rotation is carried out in pelletizer；Diluted flocculation aid solution is added on the Powdered Activated Carbon and diatomite of rotation and is wrapped It wraps up in, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, so that flocculant is wrapped in the outermost layer of particle, revolve Turn, it is dry, obtain the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane.

This case delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane that can also use following technical measures To further realize:

The preparation method of the layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein diluted flocculation aid is molten Liquid is injected on the Powdered Activated Carbon and/or diatomite of rotation using peristaltic pump and is wrapped up, and continues to revolve after forming circular granular Turn；It will be injected on circular granular after flocculation dilution agent by peristaltic pump, flocculant made to be wrapped in the outermost layer of circular granular.

The preparation method of the layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein diluted flocculation aid is molten Liquid is diluted using distilled water, and the mass percentage composition of flocculation aid is 40-60%.

The preparation method of the layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein flocculation dilution agent uses Distilled water is diluted, and the mass percentage composition of flocculant is 40-60%.

A preparation method of the layer-by-layer sustained release water treatment agent above-mentioned for delaying seawater fouling membrane, wherein flocculant is wrapped in After the outermost layer of grain, then 10-20min is rotated to stabilization, then dry 0.5-2h under the conditions of 60-70 DEG C, obtains shape as ball Shape is spherical, the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane of particle diameter 1-3mm.

In addition, the present invention delays the layer-by-layer sustained release water treatment agent of seawater fouling membrane to take following technical scheme to realize:

A kind of layer-by-layer sustained release water treatment agent delaying seawater fouling membrane, wherein delay the layer-by-layer sustained release water of seawater fouling membrane Inorganic agent is made of adsorbent internal layer, flocculation aid wrapping layer and flocculant outer layer, and inner layer adsorption agent is Powdered Activated Carbon, diatomite One or both of mixing, wrapping layer flocculation aid be one of polyacrylamide, polydimethyl diallyl ammonium chloride or Two kinds of mixing, outer layer flocculant are the mixing of one or more of iron series, AlSnSi alloy；Inner layer adsorption agent, wrapping layer help solidifying The mass ratio of agent and outer layer flocculant is 40-60: 10-15: 30-45；

Inner layer adsorption agent Powdered Activated Carbon, diatomite partial size be 90-106 μm.

Wherein, delay the layer-by-layer sustained release water treatment agent shape of seawater fouling membrane for spherical or spherical particle, particle diameter For 1-3mm.

Wherein, iron-based flocculating agent is iron chloride, ferric sulfate, poly-ferric chloride or bodied ferric sulfate, and AlSnSi alloy is chlorine Change aluminium, aluminum sulfate, aluminium polychloride or polyaluminium sulfate.

Further more, it is to take following technical side that the present invention, which delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, Case is realized:

A kind of preparation method for the layer-by-layer sustained release water treatment agent delaying seawater fouling membrane such as aforementioned any one, wherein delay The preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is, by one of Powdered Activated Carbon, diatomite or two Kind mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon and diatomite of rotation On wrapped up, formed particle after continue to rotate；It will be added on particle after flocculation dilution agent, flocculant made to be wrapped in particle most Outer layer rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent wherein, inhale by internal layer Attached dose, the mass ratio of wrapping layer flocculation aid and outer layer flocculant be 40-60: 10-15: 30-45.

Wherein, diluted flocculation aid solution using peristaltic pump be injected in rotation Powdered Activated Carbon and/or diatomite it is enterprising Row package, continues to rotate after forming circular granular；It will be injected on circular granular after flocculation dilution agent by peristaltic pump, make to flocculate Agent is wrapped in the outermost layer of circular granular；The water treatment agent wherein, the partial size of inner layer adsorption agent Powdered Activated Carbon, diatomite It is 90-106 μm.

Wherein, diluted flocculation aid solution is diluted using distilled water, and the mass percentage composition of flocculation aid is 40- 60%.

Wherein, flocculation dilution agent is diluted using distilled water, and the mass percentage composition of flocculant is 40-60%.

A kind of preparation method for the layer-by-layer sustained release water treatment agent delaying seawater fouling membrane such as aforementioned any one, wherein delay The preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is, by one of Powdered Activated Carbon, diatomite or two Kind mixing, which is put into pelletizer, carries out circle rotation, and diluted flocculation aid solution is added in the Powdered Activated Carbon and diatomite of rotation On wrapped up, formed particle after continue to rotate；It will be added on particle after flocculation dilution agent, flocculant made to be wrapped in particle most Outer layer rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent wherein, inhale by internal layer Attached dose, the mass ratio of wrapping layer flocculation aid and outer layer flocculant be 40-60: 10-15: 30-45.

Wherein, after flocculant is wrapped in the outermost layer of particle, then 10-20min is rotated to stabilization, then in 60-70 DEG C of item Dry 0.5-2h under part, obtains shape as spherical or spherical, the layer-by-layer sustained release for delaying seawater fouling membrane of particle diameter 1-3mm Water treatment agent.

The present invention has significant advantages and beneficial effects compared with prior art.From the above technical scheme, this hair The bright layer-by-layer sustained release water treatment agent and preparation method thereof for delaying seawater fouling membrane, at least following advantage:

1, it generallys use at present and adds flocculant or adsorbent carrys out lessening membrane fouling, function is more single, lessening membrane fouling Effect it is limited.The present invention is Collecting flocculation, helps solidifying, absorption, Dynamic Membrane function in the water treatment agent of one, and inorganic flocculating agent plays Compression double electric layer effect capture suspended particulates, colloid etc. form wadding body；PAM, PDMDAAC organic flocculant have played adsorption bridging Effect, promote growing up for wadding body；Powdered Activated Carbon, diatomite etc. play the organic matter in suction-operated removal seawater.It is more Kind effect plays jointly, reduces membrane pollution resistance, lessening membrane fouling.

2, in view of the low-temperature and low turbidity characteristic of seawater, conventional flocculant handles seawater, and the effect is unsatisfactory, and the wadding body of generation is small And it is thin, cause the wadding body dynamic membrane structure generated closely knit, increases filtration resistance.

The wadding body that the present invention is formed is big and loose, and water penetration is stronger, the dynamic collectively constituted with Powdered Activated Carbon, diatomite Film, the multiplet with different pore size, improves dynamic membrane structure, the significantly more efficient blocking for slowing down ultrafiltration membrane.The present invention Water treatment agent be suitable for briny environment, especially can effectively delay low temperature seawater Pollution of Ultrafiltration Membrane.

3, the use of current various medicaments, in order to reach respective effect, it usually needs thrown in batches according to dissolution time Add, process is relatively complicated.Water treatment agent of the invention is layer-by-layer release structures, passes through the dissolution of the structural adjustment each component of medicament Timing, each component play respective effect by certain time sequence, it is ensured that the independence and dissolution time that each component plays a role Continuity, it is synergistic, while improving the dosing method of medicament, simplify dispensing process.

The present invention compares the prior art significant contribution and a progress, strictly with novelty, creativeness, practicability Good technology.

Detailed description of the invention

Fig. 1 is the attenuation curve of low temperature seawater ultra-filtration process membrane flux under 5 different agents of embodiment；

Fig. 2 is the attenuation curve of normal temperature seawater ultra-filtration process membrane flux under 6 different agents of embodiment.

Specific embodiment

A specific embodiment of the invention is shown in detail by following embodiment.

In conjunction with the preferred embodiment, to specific embodiment, step, feature and its effect provided according to the present invention, Detailed description are as follows.

Embodiment 1

A kind of layer-by-layer sustained release water treatment agent delaying seawater fouling membrane, by adsorbent internal layer, flocculation aid wrapping layer and flocculation Agent outer layer is constituted, and inner layer adsorption agent is Powdered Activated Carbon, and wrapping layer flocculation aid is polyacrylamide, and outer layer flocculant is polymerization chlorine Change iron.Inner layer adsorption agent Powdered Activated Carbon partial size is 90 μm.Inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant quality Than being 40: 15: 45.Delay the layer-by-layer sustained release water treatment agent shape of seawater fouling membrane for spherical shape, particle diameter 1mm.

Gained is successively sustained to water treatment agent as a result, to be added in seawater, each component successively discharges molten according to time series Solution had not only played the effect of flocculant compression double electric layer, but also had played flocculation aid charge neutrality and adsorption bridging effect, while there are also inhale Attached effect overcomes the single medicament low disadvantage of efficiency in the seawater.

Embodiment 2

A kind of layer-by-layer sustained release water treatment agent delaying seawater fouling membrane, by adsorbent internal layer, flocculation aid wrapping layer and flocculation Agent outer layer is constituted, and inner layer adsorption agent is diatomite, and wrapping layer flocculation aid is polydimethyl diallyl ammonium chloride, outer layer flocculant For aluminium polychloride.Inner layer adsorption agent Powdered Activated Carbon, diatomite partial size be 90-106 μm.Inner layer adsorption agent, wrapping layer help The mass ratio of solidifying agent and outer layer flocculant is 60: 10: 30.The layer-by-layer sustained release water treatment agent shape for delaying seawater fouling membrane is class ball Shape particle, particle diameter 3mm.

Gained is successively sustained to water treatment agent as a result, to be added in seawater, aluminium polychloride plays flocculation first, catches It obtains suspended particulates, colloid in seawater etc. and forms tiny wadding body；Secondly polydimethyl diallyl ammonium chloride plays Coagulation aiding, Keep wadding body big and loose；Last diatomite plays suction-operated.

After being flocculated, helping solidifying, suction-operated, the pollutant load in seawater is significantly reduced at this time, can effectively be slowed down to super The pollution level of filter membrane.

Embodiment 3

A kind of layer-by-layer sustained release water treatment agent delaying seawater fouling membrane, by adsorbent internal layer, flocculation aid wrapping layer and flocculation Agent outer layer is constituted, and inner layer adsorption agent is Powdered Activated Carbon and diatomite, and Powdered Activated Carbon and diatomite are mixed by 1: 1 mass ratio, Wrapping layer flocculation aid is the polyacrylamide of mass ratio 1: 1 and polydimethyl diallyl ammonium chloride mixing, outer layer flocculant are The iron chloride and aluminium chloride of mass ratio 1: 1 mix.Inner layer adsorption agent Powdered Activated Carbon, diatomite partial size be 100 μm.Internal layer is inhaled Attached dose, the mass ratio of wrapping layer flocculation aid and outer layer flocculant be 50: 13: 37.Delay at the layer-by-layer sustained release water of seawater fouling membrane Reason dosage form shape is spheric granules, particle diameter 2mm.

Gained is successively sustained to water treatment agent as a result, to be added in seawater, each component successively plays wadding according to time series It coagulates, help solidifying, suction-operated, form the Dynamic Membrane with multiplet collectively constituted by wadding body and Powdered Activated Carbon, diatomite, Water penetration is stronger, and interception function is significant.

Embodiment 4

A kind of preparation method for the layer-by-layer sustained release water treatment agent delaying seawater fouling membrane, preparation process is, by powder The mixing of one or both of last active carbon, diatomite, which is put into pelletizer, carries out circle rotation；Flocculation aid using distilled water into Row dilution dissolution, the mass concentration of flocculation aid solution are 50%, and flocculation aid solution is injected in the powder of rotation by peristaltic pump It is wrapped up on active carbon and/or diatomite, continues to rotate after forming circular granular；Aluminium system and/or iron-based flocculating agent are using steaming Distilled water is diluted dissolution, and the mass concentration of flocculant solution is 50%, and flocculant solution is injected in circle by peristaltic pump On particle, flocculant is made to be wrapped in the outermost layer of circular granular, then rotates 10-20min to stabilization, then in 60-70 DEG C of condition Lower dry 1h obtains shape as spherical or spherical, the layer-by-layer sustained release water process for delaying seawater fouling membrane of particle diameter 2mm Agent.

Gained is successively sustained to water treatment agent as a result, to be added in seawater, each component is according to flocculant, flocculation aid, absorption The sequencing of agent, which successively discharges, to be dissolved and plays a role, synergistic, both be ensure that the independence for playing effect, is in turn ensured The continuity of time.

Embodiment 5

A kind of preparation method for the layer-by-layer sustained release water treatment agent delaying seawater fouling membrane is successively sustained water treatment agent for locating Low temperature seawater is managed, preparation process:

The Powdered Activated Carbon and diatomite that partial size is 90-106 μm are obtained using vibration sieve instrument, by the powder of shared weight ratio 50% Last active carbon and diatomite are put into pelletizer by 1: 1 mixing and carry out circle rotation, by the polyacrylamide of shared weight 10% (PAM) dissolution is diluted with the distilled water of same ratio, and polyacrylamide (PAM) solution is injected in by rotation by peristaltic pump It is wrapped up on diatomite, continues to rotate after forming circular granular；By the poly-ferric chloride and polymerised sulphur of shared weight ratio 40% Flocculant solution is injected in bead by peristaltic pump after being mixed with the distilled water dilution of same ratio by 1: 1 mixing by sour aluminium On, flocculant is wrapped in the outermost layer of small spherical particles, rotates 10-20min after molding again to stabilization, is then done at 60-70 DEG C Dry 1h obtains successively sustained release water treatment agent.

Add what 50mg/L was mixed by 1: 1 mixed Powdered Activated Carbon and diatomite, by 1: 1 respectively into 4-8 DEG C of seawater Poly-ferric chloride and flocculant of polymeric aluminium chloride are successively sustained water treatment agent, pass through at 200r/min through quickly mixing 2min Ultrafiltration cup, is driven using nitrogen pressure, filter pressure 80KPa, is automatically continuously measured with electronic balance, and different agents pair are investigated The influence of fouling membrane, and compared with the seawater ultra-filtration process of non-adding medicine.Test result shows: with no adding of agent phase Than under the membrane flux for adding poly-ferric chloride, polyaluminium sulfate mixed flocculation agent and Powdered Activated Carbon, diatomite mixed adsorbent Drop is alleviated, and membrane flux loss late is respectively 35%, 28%；In contrast, adding the membrane flux of successively sustained release water treatment agent Decline minimum, membrane flux loss late is only 13%, lessening membrane fouling significant effect.

Embodiment 6

A kind of preparation method for the layer-by-layer sustained release water treatment agent delaying seawater fouling membrane is successively sustained water treatment agent for locating Normal temperature seawater is managed, preparation process:

The diatomite that partial size is 90-106 μm is obtained using vibration sieve instrument, the diatomite of shared weight ratio 40% is put into granulation Circle rotation is carried out in machine, by the polydimethyl diallyl ammonium chloride (PDMDAAC) of shared weight 15% same ratio Distilled water dilution dissolution, and polydimethyl diallyl ammonium chloride (PDMDAAC) solution is injected in by rotation by peristaltic pump It is wrapped up on diatomite, continues to rotate after forming circular granular；By the poly-ferric chloride of shared weight ratio 45%, on year-on-year basis with phase After the distilled water dilution of example mixes, flocculant solution is injected on bead by peristaltic pump, flocculant is wrapped in small variole The outermost layer of grain, rotates 10-20min to stabilization again after molding, then dry 1h at 60-70 DEG C, obtains successively sustained release water process Agent.

The present embodiment adds the diatom of 60mg/L into 14-21 DEG C of seawater under the experimental condition that embodiment 5 describes respectively Soil, poly-ferric chloride are successively sustained water treatment agent, and compare with the seawater ultra-filtration process of non-adding medicine.Test result table It is bright: in the case where no adding of agent, the flux depression most serious of seawater ultra-filtration process, membrane flux loss late up to 40% with On；The fouling membrane for adding poly ferric chloride flocculant agent and diatomite adsorbant is alleviated, membrane flux loss late is respectively 26%, 29%；In contrast, the flux depression for adding successively sustained release water treatment agent is minimum, membrane flux loss late is 12%, delays film Pollution effects are significant.

The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, it is all It is any simple modification, equivalent change and modification to the above embodiments according to the technical essence of the invention, still falls within In the range of technical solution of the present invention.

Claims

1. a kind of layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane, which is characterized in that delay the layer-by-layer slow of seawater fouling membrane It releases water treatment agent to be made of adsorbent internal layer, flocculation aid wrapping layer and flocculant outer layer, inner layer adsorption agent is Powdered Activated Carbon, silicon The mixing of one or both of diatomaceous earth, wrapping layer flocculation aid are polyacrylamide, one in polydimethyl diallyl ammonium chloride Kind or two kinds of mixing, outer layer flocculant are the mixing of one or more of iron series, AlSnSi alloy；Inner layer adsorption agent, wrapping layer The mass ratio of flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；The grain of inner layer adsorption agent Powdered Activated Carbon, diatomite Diameter is 90-106 μm.

2. a kind of layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane, which is characterized in that delay the layer-by-layer slow of seawater fouling membrane It releases water treatment agent to be made of adsorbent internal layer, flocculation aid wrapping layer and flocculant outer layer, inner layer adsorption agent is Powdered Activated Carbon, silicon The mixing of one or both of diatomaceous earth, wrapping layer flocculation aid are polyacrylamide, one in polydimethyl diallyl ammonium chloride Kind or two kinds of mixing, outer layer flocculant are the mixing of one or more of iron series, AlSnSi alloy；Inner layer adsorption agent, wrapping layer The mass ratio of flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；The grain of inner layer adsorption agent Powdered Activated Carbon, diatomite Diameter is 90-106 μm；

Wherein, delay the layer-by-layer sustained release water treatment agent shape of seawater fouling membrane for spherical or spherical particle, particle diameter 1- 3mm。

3. a kind of layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane, which is characterized in that delay the layer-by-layer slow of seawater fouling membrane It releases water treatment agent to be made of adsorbent internal layer, flocculation aid wrapping layer and flocculant outer layer, inner layer adsorption agent is Powdered Activated Carbon, silicon The mixing of one or both of diatomaceous earth, wrapping layer flocculation aid are polyacrylamide, one in polydimethyl diallyl ammonium chloride Kind or two kinds of mixing, outer layer flocculant are the mixing of one or more of iron series, AlSnSi alloy；Inner layer adsorption agent, wrapping layer The mass ratio of flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；The grain of inner layer adsorption agent Powdered Activated Carbon, diatomite Diameter is 90-106 μm；

Wherein, iron-based flocculating agent be iron chloride, ferric sulfate, poly-ferric chloride or bodied ferric sulfate, AlSnSi alloy be aluminium chloride, Aluminum sulfate, aluminium polychloride or polyaluminium sulfate.

4. a kind of layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane, which is characterized in that delay the layer-by-layer slow of seawater fouling membrane It releases water treatment agent to be made of adsorbent internal layer, flocculation aid wrapping layer and flocculant outer layer, inner layer adsorption agent is Powdered Activated Carbon, silicon The mixing of one or both of diatomaceous earth, wrapping layer flocculation aid are polyacrylamide, one in polydimethyl diallyl ammonium chloride Kind or two kinds of mixing, outer layer flocculant are the mixing of one or more of iron series, AlSnSi alloy；Inner layer adsorption agent, wrapping layer The mass ratio of flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；The grain of inner layer adsorption agent Powdered Activated Carbon, diatomite Diameter is 90-106 μm；

Wherein, delay the layer-by-layer sustained release water treatment agent shape of seawater fouling membrane for spherical or spherical particle, particle diameter 1- 3mm；

5. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45.

6. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

Wherein, diluted flocculation aid solution is injected on the Powdered Activated Carbon and/or diatomite of rotation using peristaltic pump and is wrapped It wraps up in, continues to rotate after forming circular granular；It will be injected on circular granular after flocculation dilution agent by peristaltic pump, make flocculant packet It is rolled in the outermost layer of circular granular；The water treatment agent wherein, inner layer adsorption agent Powdered Activated Carbon, diatomite partial size be 90-106μm。

7. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；Wherein, diluted Flocculation aid solution is diluted using distilled water, and the mass percentage composition of flocculation aid is 40-60%.

8. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

Wherein, diluted flocculation aid solution is injected on the Powdered Activated Carbon and/or diatomite of rotation using peristaltic pump and is wrapped It wraps up in, continues to rotate after forming circular granular；It will be injected on circular granular after flocculation dilution agent by peristaltic pump, make flocculant packet It is rolled in the outermost layer of circular granular；The water treatment agent wherein, inner layer adsorption agent Powdered Activated Carbon, diatomite partial size be 90-106μm；

Wherein, diluted flocculation aid solution is diluted using distilled water, and the mass percentage composition of flocculation aid is 40-60%.

9. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

10. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

11. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

Wherein, diluted flocculation aid solution is diluted using distilled water, and the mass percentage composition of flocculation aid is 40-60%；

12. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

13. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

Wherein, after flocculant is wrapped in the outermost layer of particle, then 10-20min is rotated to stabilization, then under the conditions of 60-70 DEG C Dry 0.5-2h obtains shape to be spherical or spherical, and particle diameter 1-3mm's delays at the layer-by-layer sustained release water of seawater fouling membrane Manage agent.

14. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

15. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

16. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

17. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

Wherein, flocculation dilution agent is diluted using distilled water, and the mass percentage composition of flocculant is 40-60%；

18. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

19. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；

20. a kind of any one of claim 1-4 delays the preparation method of the layer-by-layer sustained release water treatment agent of seawater fouling membrane, feature It is, the preparation process of the layer-by-layer sustained release water treatment agent of seawater fouling membrane is delayed to be, it will be in Powdered Activated Carbon, diatomite One or two mixing, which is put into pelletizer, carries out circle rotation；Diluted flocculation aid solution is added in the Powdered Activated Carbon of rotation It is wrapped up on diatomite, continues to rotate after forming particle；It will be added on particle after flocculation dilution agent, be wrapped in flocculant The outermost layer of particle rotates, dry, obtains the layer-by-layer sustained release water treatment agent for delaying seawater fouling membrane；The water treatment agent its In, the mass ratio of inner layer adsorption agent, wrapping layer flocculation aid and outer layer flocculant is 40-60: 10-15: 30-45；