CN102302922A - Formed shellfish-based regular photocatalytic adsorbent and preparation method thereof - Google Patents
Formed shellfish-based regular photocatalytic adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a formed shellfish-based regular photocatalytic adsorbent and a preparation method thereof. The photocatalytic adsorbent is characterized by comprising the following components by weight percent: 50-80wt% of shellfish-based material, 15-40wt% of binder, 0.1-1.0wt% of photocatalyst, 0.3-10wt% of pore-forming agent and 0.1-0.9wt% of lubricant. The photocatalytic adsorbent has the advantages of wide shellfish-based material source, low price and no secondary pollution, belongs to waste recovery, can be repeatedly regenerated and recycled, can be widely used for oil contamination purification and environmental protection in seacoast, river bank, lakeshore and the like, and has wide application prospect.
Description
Technical field
The present invention relates to a kind of adsorbent of handling with the Yu Haiyang oil leaking pollution and preparation method thereof, particularly a kind of moulding shellfish base optic catalytic adsorbent that utilizes discarded natural shellfish preparation and preparation method thereof.
Background technology
21 century is the epoch of ocean, and the ocean is global life-support system, also is the regulating system of receiving of Global climate change, and the mankind's sustainable development is played important supporting role.There is very long coastline in China, and have an appointment 50% people of the whole nation lives near the coastline, and the GDP in the whole nation nearly 70% is from seashore one line city and area; Coastal fishery, aquaculture, the shipping industry of not only carrying; And, also be the flourishing zone of China's tourist industry, the economic activity Showed Very Brisk.Be accompanied by the discovery of oil and be widely used, the oil of leakage has become the main arch-criminal of marine pollution, in recent years; The frequent ocean oil leaking pollution that takes place, for example, nearest U.S.'s Gulf of Mexico leakage of oil incident; Ecological environment is caused the broken ring that can not repair reverse, caused the concern in the whole world day by day.According to statistics, annual 500 leakage of oil incidents, the about 0.5% impouring ocean of global oil total output of approximately taking place, the whole world; There are every year ten thousand tons of oil of 300-1000 to flow into the ocean approximately; Get in the pollution oil of oceans at these, have 8% to be the nature overflow approximately, 92% petroleum pollution in ocean that causes for mankind's activity.Oil content in the coastal seawater of China surpasses 3-8 times of national water quality regulation.The United Nations and China all classify petroleum pollution in ocean as " great agenda of 21 century ".Simultaneously, along with the back arriving of petroleum times, land oil is accused fragrant day by day, and offshore oil exploitation and sea transport will be more actively with active, and the possibility that the ocean receives oil leaking pollution more unprecedentedly strengthens.Just not long ago, the leakage of oil incident has also taken place in the drilling platforms in the 19-3 oil field, Peng Lai, Bohai Sea Gulf of China National Offshore Oil Corporation and the cooperative development of U.S. Concophillips Company.Therefore, the processing new technology of research and development sea pollution by oil has important practical significance and strategic importance to China.
Being broadly divided into of petroleum pollution in ocean incident: oil spilling, leakage and daily operation discharging, wherein 92% seawater greasy dirt is caused by the mankind's economic activity.Sea pollution by oil is handled with recovery technique and is started from the 70-80 age in last century, and in the coastal sea pollution by oil of countries such as Europe, America, Asia is handled, applies very soon.At present processing method is broadly divided into: 1. surfactant-dispersed method; Promptly; Through to sprayed chemical agent by the sea of oil pollution; Like polymer and crosslinking agent, greasy dirt molecule aggregation, molecular weight increasing, viscosity are improved, and then the black thing after these polymerizations is salvaged collection put into cabin; The characteristics of this method are to spray soon; Processing region is big, can pass through aircraft, steamer etc. and implement to spray, but spray agent can cause secondary pollution; 2. porous light solid oil absorbent; Rice hull active carbon oil absorbent like Japan's exploitation; But though this method is safe from harm to marine environment, still there is the problem that processing cost is high, difficulty is big in the big 6-10 of absorptance own wt greasy dirt doubly to the large tracts of land greasy dirt that disperses; 3. artificial synthetic organic polymer has absorption and solidifies double action greasy dirt like the polystyrene polymer resin, and greasy dirt runs into this resin will become spongy greasy dirt, thereby conveniently greasy dirt is reclaimed; 4. hydrophobicity silicic acid material, it can adsorb greasy dirt as sponge, and greasy dirt is become greasy filth, and then collects; 5. oil-absorbing ship absorbs greasy dirt, utilizes physicochemical properties such as proportion different of greasy dirt and seawater, absorbs water structural design partly through oil well pump and ship, the greasy dirt that runs in the foot can be collected in the ship; 6. biological treatment is promptly bitten oily bacterium through ectogenic, through its digestive system greasy dirt is converted into resin acid emulsion, and the excreta of bacterium polluted-water not.
More than these processing methods each has something to recommend him, length is arranged mutually, all brought into play important function in revealing handling offshore oil; But also there are various shortcomings; Drive less than the bank like the greasy dirt ship, chemical reagent severe contamination water body, bacterium has unpredictability or the like to visitor's health.
Summary of the invention
To the problems referred to above, the purpose of this invention is to provide a kind of regular photocatalysis adsorbent that utilizes discarded shellfish preparation, realize photocatalytic degradation greasy dirt under the sunshine, reach the purpose that turns waste into wealth and curb environmental pollution.
Another object of the present invention provides the regular photocatalysis preparation of adsorbent method of above-mentioned shellfish base.
Technical scheme of the present invention is following: the regular photocatalysis adsorbent of a kind of moulding shellfish base is characterized in that said catalyst-sorbent consists of: shellfish sill content is that the content of 50-80wt%, binding agent is that 15-40wt%, photochemical catalyst content are that the content of 0.1-1.0 wt %, pore creating material is that the content of 0.3-10wt%, lubricant is 0.1-0.9wt%.
Described shellfish sill is one or more the mixture in naiad and the seawater shellfish shellfish.
Described photochemical catalyst is TiO
2, BiVO
4, Cu
2The mixture of one or more among the O.
Described binding agent is one or more mixture and/or pitch, natural gum, polyvinyl alcohol, desulfurated plaster, cement, one or more the mixture in the clay in waterglass, aluminium colloidal sol, Ludox, dextrin, starch, natural gum, the bentonite.
Described pore creating material is one or more the mixture in active carbon, activated coke, carboxymethyl cellulose, polyacrylamide, molasses, the POLYPROPYLENE GLYCOL.
Described lubricant is one or more the mixture in talcum powder, graphite, dolomol or other stearate.
The regular photocatalysis preparation of adsorbent method of above-mentioned moulding shellfish base is characterized in that it may further comprise the steps: 1. with shellfish sill crushing grinding to the 20-300 order; 2. the shellfish sill that 1. step is obtained adds water with photochemical catalyst, binding agent, pore creating material and lubricant and mixes, moulding then; 3. the shaped article that 2. step is obtained is in 60-150 ℃ of following steam maintenance 7-28 days, the adsorbent that obtains having certain intensity; 4. the product that 3. step is obtained with dipping calcination method or binder method even load method with photochemical catalyst load to get final product on the adsorbent the regular photocatalysis adsorbent of moulding shellfish base.
The preparation condition of the 4. described dipping calcination method of step is: the sol-gel of preparation corresponding light catalyst, and dip time is 1-24 hour, and the dipping number of times is 1-8 time, and calcining heat is 250-600 ℃.
The present invention utilizes the regular photocatalysis adsorbent of marine natural shellfish preparation to have following function: 1) pH slow releasing function can guarantee that photochemical catalytic oxidation carries out under suitable basic surface condition; 2) photocatalytic oxidation, utilizing the oxygen in light and the atmosphere will be nontoxic little molecule H by the mobile naturally oxidizing hydrocarbon that brings and be trapped in the surperficial oil of adsorbent of ocean current
2O and CO
2, utilize the energy of sunshine to break the catalytic oxidation thermodynamic limitation, accelerate the oil stain decomposition oxidation rate; 3) big flux, big rejection, corrosion-resistant, high wellability and long-life because the photocatalysis adsorbent external form of processing is pressed the design of ocean current ripple shifting principle, characteristic picture pottery, thus greatly flux pass through seawater, but can hold back greasy dirt, and anti-seawater corrosion; 4) but the folding regular photochemical catalytic oxidation adsorbent of corrugated plating building block system modular design becomes many " views ", can not cause " harm " along the line to seashore.
Advantage of the present invention is shell sill wide material sources, and is cheap, belongs to twice laid, and prepared photocatalysis adsorbent iterative regenerable recycles non-secondary pollution.Can be widely used in greasy dirts such as seashore, riverbank and loke shore and purify in the environmental protection, have broad application prospects.
Description of drawings
Fig. 1 contains TiO
2The degradation rate of the photocatalysis adsorbent degrading crude oil of catalyst is schemed over time.
Fig. 2 contains Cu
2O and BiVO
4The degradation rate of the photocatalysis adsorbent degrading crude oil of catalyst is schemed over time.
The specific embodiment
Describe the present invention in detail through specific embodiment below.
Embodiment 1:
After 40-100 order oyster shell whiting, 24.5 wt % cement (binding agent), 4.9 wt % molasses (pore creating material), the 0.5 wt % talcum powder (lubricant) of 70 wt % added water and mix, put into mould in 28Mpa pressurization 30min moulding down; Under 120 ℃ water vapor conditions, carry out maintenance 25 days, make regular photocatalysis adsorbent with certain intensity; Preparation TiO
2Colloidal sol flooded regular photocatalysis adsorbent 10 hours therein, and the dipping number of times is 8 times (making catalyst content is 0.1wt%), after calcining under 550 ℃, makes the adsorbent with photocatalytic activity.Photocatalytic degradation crude oil is tested as follows: add 1ml crude oil in the 400ml seawater, and 300W iodine-tungsten lamp (simulated solar irradiation) irradiation, the degradation rate of crude oil changes as shown in Figure 1 in time.By finding out that the oil degradation rate is along with the growth of time increases gradually among the figure, when reaction reached 16h, the degradation rate of crude oil can reach 86%, and during accumulative total reaction time 30h, the clearance of crude oil can reach more than 95%, had reached the purpose that greasy dirt is handled.
Embodiment 2:
After 100-200 order oyster shell whiting, 22.5 wt % cement (binding agent), 0.5wt % graphite (lubricant) and the 6 wt % molasses (pore creating material) of 70wt % are added water and mix, put into mould in 25Mpa pressurization 30min moulding down; Under 150 ℃ water vapor conditions, carry out maintenance 28 days, make regular photocatalysis adsorbent with certain intensity; With silica sol binder (content 1wt%) with a certain amount of Cu
2O and BiVO
4Photochemical catalyst mixes back (making catalyst content is 1.0wt%), evenly is bonded to and makes the catalyst with photocatalytic activity on the adsorbent surface.Photocatalytic degradation crude oil is tested as follows: add 1ml crude oil in the 400ml seawater, and 300W iodine-tungsten lamp (simulated solar irradiation) irradiation, the oil degradation rate is over time as shown in Figure 2.By finding out that the oil degradation rate is along with the growth of time increases gradually among the figure, when reaction reached 16h, the clearance of crude oil can reach 82%, and during accumulative total reaction time 30h, the clearance of crude oil can reach more than 92%, equally also can reach the purpose that greasy dirt is handled.
Claims (8)
1. the regular photocatalysis adsorbent of moulding shellfish base, it is characterized in that said catalyst-sorbent consists of: shellfish sill content is that 50-80wt%, binder content are that 15-40wt%, photochemical catalyst content are that 0.1-1.0wt%, pore creating material content are that 0.3-10wt%, lubricant content are 0.1-0.9wt%.
2. the regular photocatalysis adsorbent of moulding shellfish according to claim 1 base is characterized in that described shellfish sill is one or more the mixture in naiad and the seawater shellfish shellfish.
3. the regular photocatalysis adsorbent of moulding shellfish base according to claim 1 is characterized in that described photochemical catalyst is TiO
2, BiVO
4, Cu
2The mixture of one or more among the O.
4. according to the regular photocatalysis adsorbent of the moulding shellfish described in the claim 1 base, it is characterized in that described binding agent is one or more mixture and/or pitch, natural gum, polyvinyl alcohol, desulfurated plaster, cement, one or more the mixture in the clay in waterglass, aluminium colloidal sol, Ludox, dextrin, starch, natural gum, the bentonite.
5. the regular photocatalysis adsorbent of moulding shellfish according to claim 1 base is characterized in that described pore creating material is one or more the mixture in active carbon, activated coke, carboxymethyl cellulose, polyacrylamide, molasses, the POLYPROPYLENE GLYCOL.
6. the regular photocatalysis adsorbent of moulding shellfish according to claim 1 base is characterized in that described lubricant is one or more the mixture in talcum powder, graphite, dolomol or other stearate.
7. one kind like the regular photocatalysis preparation of adsorbent method of any described moulding shellfish base among the claim 1-6, it is characterized in that it may further comprise the steps: 1. with shellfish sill crushing grinding to the 20-300 order; 2. the shellfish sill that 1. step is obtained adds water with photochemical catalyst, binding agent, pore creating material and lubricant and mixes, moulding then; 3. the shaped article that 2. step is obtained is in 60-150 ℃ of following steam maintenance 7-28 days, the adsorbent that obtains having certain intensity; 4. the product that 3. step is obtained with dipping calcination method or binder method even load method with photochemical catalyst load to get final product on the adsorbent the regular photocatalysis adsorbent of moulding shellfish base.
8. according to the regular photocatalysis preparation of adsorbent method of the base of the moulding shellfish described in the claim 7; The preparation condition that it is characterized in that the 4. described dipping calcination method of step is: the sol-gel of preparation corresponding light catalyst; Dip time is 1-24 hour; The dipping number of times is 1-8 time, and calcining heat is 250-600 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102626660A (en) * | 2012-03-28 | 2012-08-08 | 中国海洋大学 | Becky regular catalytic filter for sea water flue gas desulfurization and preparation method thereof |
| CN103566893A (en) * | 2013-09-26 | 2014-02-12 | 蚌埠华纺滤材有限公司 | Oyster shell modified activated carbon desulfurizing agent, and preparation method thereof |
| CN104907043A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent capable of recovering carbon monoxide |
| CN104907039A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Composite volcanic rock absorbent |
| CN104923178A (en) * | 2015-05-21 | 2015-09-23 | 安徽凤凰滤清器股份有限公司 | Modified volcanic-rock acid-resistant adsorbent |
| CN109317111A (en) * | 2018-11-05 | 2019-02-12 | 浙江海洋大学 | A kind of preparation method for the floatability type foamed absorbent carrying nano-photocatalyst |
| CN113198430A (en) * | 2021-05-15 | 2021-08-03 | 兰州城市学院 | Preparation method of composite nano material |
| CN114904571A (en) * | 2022-03-15 | 2022-08-16 | 宁波中金石化有限公司 | Aromatic hydrocarbon disproportionation and transalkylation catalyst, and preparation method and application thereof |
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| CN103880122B (en) * | 2014-03-17 | 2015-08-26 | 山东大学 | A kind of method preparing the anti-granular unburned iron-carbon micro-electrolysis filler that hardens |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626660A (en) * | 2012-03-28 | 2012-08-08 | 中国海洋大学 | Becky regular catalytic filter for sea water flue gas desulfurization and preparation method thereof |
| CN103566893A (en) * | 2013-09-26 | 2014-02-12 | 蚌埠华纺滤材有限公司 | Oyster shell modified activated carbon desulfurizing agent, and preparation method thereof |
| CN104907043A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent capable of recovering carbon monoxide |
| CN104907039A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Composite volcanic rock absorbent |
| CN104923178A (en) * | 2015-05-21 | 2015-09-23 | 安徽凤凰滤清器股份有限公司 | Modified volcanic-rock acid-resistant adsorbent |
| CN109317111A (en) * | 2018-11-05 | 2019-02-12 | 浙江海洋大学 | A kind of preparation method for the floatability type foamed absorbent carrying nano-photocatalyst |
| CN109317111B (en) * | 2018-11-05 | 2021-12-17 | 浙江海洋大学 | Preparation method of floatable foaming adsorbent loaded with nano photocatalyst |
| CN113198430A (en) * | 2021-05-15 | 2021-08-03 | 兰州城市学院 | Preparation method of composite nano material |
| CN114904571A (en) * | 2022-03-15 | 2022-08-16 | 宁波中金石化有限公司 | Aromatic hydrocarbon disproportionation and transalkylation catalyst, and preparation method and application thereof |
| CN114904571B (en) * | 2022-03-15 | 2023-10-10 | 宁波中金石化有限公司 | Aromatic hydrocarbon disproportionation and alkyl transfer catalyst and preparation method and application thereof |
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