CN104119618A - Oil absorption material and preparation method and use thereof - Google Patents
Oil absorption material and preparation method and use thereof Download PDFInfo
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- CN104119618A CN104119618A CN201410346090.XA CN201410346090A CN104119618A CN 104119618 A CN104119618 A CN 104119618A CN 201410346090 A CN201410346090 A CN 201410346090A CN 104119618 A CN104119618 A CN 104119618A
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- Prior art keywords
- oil absorption
- absorption material
- oil
- powder
- expanded plastic
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 43
- 229920003023 plastic Polymers 0.000 claims abstract description 34
- 239000004033 plastic Substances 0.000 claims abstract description 34
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 6
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 6
- -1 polyethylene Polymers 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011368 organic material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 52
- 235000019198 oils Nutrition 0.000 description 52
- 239000006260 foam Substances 0.000 description 29
- 239000006261 foam material Substances 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 206010000269 abscess Diseases 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an oil absorption material and belongs to the field of preparation of organic materials. The invention further relates to a preparation method and use of the oil absorption material. The oil absorption material is powder made from foamed plastic. The powder made from foamed material provided by the invention has high oil absorption and low water absorption. The foamed material is cut and smashed to obtain powder with the grain size being about 2-1000 microns. The oil absorption of the obtained polyurethane foam block to gasoline is reduced by no greater than 10% but the water absorption is greatly reduced to below 20% of the original water absorption.
Description
Technical field
The present invention relates to oil absorption material, belong to organic materials preparation field.The invention still further relates to preparation method and the purposes of oil absorption material.
Background technology
Foam interior is the vesicular structure of latticed or film like, thereby it not only has great specific surface area, innerly also contains abundant capillary channel.Therefore when it contacts with oil-water mixture, not only Hui material section surface produces adsorption but also is accompanied by packing space absorption oil and water, is mainly by mesopore capillary condensation and macropore multilayer adsorption and filling.Therefore water and oil are all easier in this class A foam A microchannel, assemble, form certain thickness, in oil-water mixture, in oil suction, also absorb water, water-intake rate is generally 2-4 times of own wt, causes the rear oil-water mixture of absorption to need secondary separation aftertreatment difficulty.
According to foam adsorption mechanism, the oil absorption of foam mainly comes from the capillary condensation phenomenon in pore, only has small part to come from the absorption on foam materials surface.Absorption total amount equals surface excess and capillary condensation adsorptive capacity.Capillary condensation adsorptive capacity accounts for absorption the more than 70% of total amount.The oil absorption of foam materials derives from oil-retaining, and oil-retaining derives from capillary absorption.So because the existence of capillary condensation improves the oil-retaining of foam materials, thereby can adsorb more oil.A lot of papers of this area have been approved this oil suction mechanism, and have done on this basis a large amount of confirmatory experiments and prove this theory.So, in order to obtain better oil suction effect, to prepare less abscess, be a R&D direction of this area.
Conventionally, oil absorption material is all block, and every diameter or the length of side are generally 4-5cm, are made with like this 2 objects, the one, and for easy to use, the 2nd, in order to keep the stable of abscess.Because each cutting all can destroy a part of abscess, abscess has been lost and protect oily ability.Excessive, adsorb too slowly, too small, oil-retaining is too poor.
In prior art, mostly adopt flexible foams, adopt the polymerization single polymerization monomer of high oleophylic, to improve the water-absorbent of foam materials, the material with capillarity has good hydrophilic effect, so water-absorbent is still very high.
Summary of the invention
Yet present inventor, in a large amount of experimentations, finds, common foam materials, even if abscess is destroyed, also has the oil-retaining before being not less than abscess and not going to pot, and can also reduce the water-retaining capacity of foam materials simultaneously.
The application has overcome technology prejudice in the past, and particularly, the application provides a kind of oil absorption material, and described oil absorption material is the powder that expanded plastic is made.
The oily purposes that the application also provides oil absorption material to contain solid impurity in absorption.
In addition, the application also provides the preparation method of oil absorption material, and expanded plastic is made to powder, obtains oil absorption material.
The powder that foam materials provided by the invention is made has high oil absorbency and lower water-intake rate.
The present invention will after foam materials cutting and grinding, obtain particle diameter greatly about the powder of 2-1000 micron, the oil absorbency to gasoline of the polyurethane foamed blocks of acquisition reduces and is no more than 10%, water-intake rate is reduced to original below 20% greatly.
Embodiment
Oil absorption material, described oil absorption material is the powder that expanded plastic is made.
By being prepared into powder, destroyed original capillary absorption structure, the water-absorbent of oil absorption material is reduced greatly.Meanwhile, oil absorption can not reduce too much, and wherein possible mechanism is: powder particle surface exists surface adsorption, and adjacent powder particle is in conjunction with again forming capillary absorption structure.It should be noted that, the oil described in the application, not only refers to lipid acid, refers to the organic liquid that all can adsorb.
Described expanded plastic is selected from one or several in polystyrene, urethane, polyvinyl chloride, polyethylene, urea formaldehyde, phenolic aldehyde, polycarbonate, polyphenylene oxide, polysulfones.
The preferred semi-rigid expanded plastic of expanded plastic.
For urethane, expanded plastic is adjustable.
Porous plastics is as given a definition: form the matrix polymer of porous plastics more than crystalline melting point, if amorphous polymer, more than second-order transition temperature.In like manner, can be under rigid foam as give a definition: form the matrix polymer of porous plastics, with crystalline state, exist, or exist with metamict, but below second-order transition temperature.According to this differentiation, most of expanded polyolefin, unplasticizied polyvinyl chloride foam, phenol formaldehyde foam, polycarbonate foam, polyphenylene oxide foam, polysulfones foam, some polyurethane foam all belongs to rigid foam, and elastic polyurethane foam, some expanded polyolefin, the polyvinyl chloride foam of plasticising is all soft foam.
According to the regulation of ASTM standard, to soft and differentiation rigid foam, be at 18-29 ℃ of temperature, in times 5 s, around the pole of diameter 2.5cm one week, if do not ruptured, belong to flex foam,
Otherwise, belong to rigid foam.
Press the regulation of iso standard.Compression set reaches 50% rear release of pressure.Its thickness is compared with original thickness to reduce and is no more than 2% for flex foam, is greater than lO% person for rigid foam, and meson 2-10% person is semi-rigid foamed plastics.
Also have and using Young's modulus as distinguishing standard.All under 23 ℃ and this standard environment of relative humidity of 50%, Young's modulus is greater than 686MPa person for rigid foam.Being less than 68.6Mpa person for flex foam, is semi-rigid foamed plastics between 68.6-686MPa person.
Expanded plastic of the present invention judges whether to belong to hard or semi-rigid expanded plastic with above-mentioned any one standard.
Flex foam has open-celled structure mostly, and rigid foam has unicellular structure mostly.Porous plastics for oil suction in prior art is all nonrigid plastics, and the present invention adopts hard or semi-rigid expanded plastic, also has good oil suction effect after being ground into powder.
In order to obtain better oil suction effect, the median size of powder is 2-1000 micron, preferably 100-500 micron.
The preparation method of expanded plastic polystyrene, urethane, polyvinyl chloride, polyethylene, urea formaldehyde, phenolic aldehyde is all common practise of this area, generally comprises polymerization single polymerization monomer.Method by chemistry or physics foams and maintains the stable to obtain good foaming effect of foam, can control by a series of auxiliary agent the size of the bubble diameter of foam.The preferred 1-1000 micron of bubble diameter of the expanded plastic described in the application, more preferably 50-500 micron.
For different bubble diameters, can obtain better oil suction, soaking effect not by controlling the particle diameter of powder.Preferably powder diameter is 0.2-10 with the ratio of expanded plastic bubble diameter.More select 0.5-2.
Oil absorption material also comprises inert inorganic powder.
Inert inorganic powder can add when preparing expanded plastic, can when preparing expanded plastic powder, add.Preferably when preparing expanded plastic, add inert inorganic powder.
'inertia' in the application's inert inorganic powder refers to neither oleophylic, not hydrophilic again, and in the chemical stability with height.This is different from the inorganic combustion inhibitor in porous plastics.
Oil absorption material due to oil suction after, need to extrude and reuse, after using, the oil number of oil absorption material can decline at every turn.Inert inorganic powder can suppress the reunion occurring because of oil suction of Powdered foam material.This has improved the access times of foam materials and has reduced oil suction decay.
Selectable inert inorganic powder comprises metal-powder, water-insoluble silicate powder, water insoluble carbonate powder.In order to reduce hydrophilic and oleophilic, the inert inorganic powder of the smooth atresia of preferred surface.
In order to have improved the access times of foam materials, described inert inorganic powder diameter is 0.2-10 with the ratio in foam material aperture, preferably 0.5-2.
The oily purposes that oil absorption material contains solid impurity in absorption.With respect to block foam, the Powdered obstruction that is not more vulnerable to solid impurity.The access times of block foam reduce because stop up.Powderedly there is not this problem.
The preparation method of oil absorption material, makes powder by expanded plastic, obtains oil absorption material.
The method that block foam is made powder is a lot, and the application is not restricted.As the methods such as cutting grinding all can realize object of the present invention.
Below, will to the present invention, be described in more detail by embodiment.
Embodiment 1
Take Chinese patent CN200910060231.0 as example, and this patent relates to high oil absorption polyurethane foam material, its recipe ingredient following (being weight part, lower same):
30 parts of MDI
50 parts of polyvalent alcohols
1.5 parts of catalyzer
1.8 parts of suds-stabilizing agents (L600)
5 parts of whipping agents (deionized water)
3 parts of pore-creating agents (C-18)
15 parts of fire retardants (expanded graphite)
5 parts of Spherical Powder of Silicone Rubbers
1 part of coupling agent
The polyurethane foamed blocks obtaining to the oil absorbency of gasoline, be 25g/g, water-intake rate is 1.2g/g.
The polyurethane foam that present inventor adopts said components to be prepared from, will obtain particle diameter greatly about the powder of 2-500 micron after its cutting and grinding, the polyurethane foamed blocks of acquisition to the oil absorbency of gasoline, be 23g/g, water-intake rate is 0.28g/g.
Embodiment 2
Propylene glycol is 70 parts of the polyoxyethylene propylene oxide ethoxylated polyhydric alcohols of initiator
Glycerine is 30 parts of the polyoxyethylene propylene oxide ethoxylated polyhydric alcohols of initiator
1 part of diethanolamine
2.4 parts, water
0.3 part of 4-methyl hexamethylene diamine
0.1 part of triethylene diamine
49.6 parts of poly-MDI
40 degrees Celsius of die temperatures.Curing time 4 minutes, gel time 96 seconds, 163 seconds rise times.
The foaming density that obtains semi-rigid expanded plastic is 159kg/m3, final Shore C hardness 37, average 400 microns of bubble diameter.
Wherein, poly-MDI is the MR-200 of Japanese NPU company, the polyoxyethylene propylene oxide ethoxylated polyhydric alcohol hydroxyl value 28 that propylene glycol is initiator, molecular weight 4000, ethylene oxide content 20%.Glycerine is the polyoxyethylene propylene oxide ethoxylated polyhydric alcohol hydroxyl value 34 of initiator, molecular weight 5000, ethylene oxide content 18%.All the other are commercially available prod.
After cutting and grinding (approximately 30 microns of powder diameters), the oil absorbency 7g/g to gasoline, water-intake rate 0.2g/g.
Be crushed to after average 100 microns the oil absorbency 16g/g to gasoline, water-intake rate 0.2g/g.
Be crushed to after average 400 microns the oil absorbency 18g/g to gasoline, water-intake rate 0.2g/g.
Be crushed to after average 1000 microns the oil absorbency 15g/g to gasoline, water-intake rate 0.4g/g.
Be crushed to after average 2 millimeters the oil absorbency 12g/g to gasoline, water-intake rate 0.7g/g.
Be crushed to after average 4 millimeters the oil absorbency 10g/g to gasoline, water-intake rate 1.3g/g.
Be crushed to after average 10 millimeters the oil absorbency 13g/g to gasoline, water-intake rate 2.5g/g.
The cubes that is cut into the length of side and is 4 centimetres is block, to the oil absorbency of gasoline, is 15g/g, water-intake rate 4g/g.
Embodiment 3
The scheme that adopts embodiment 2, adds 3 parts, pure aluminium silicate subcircular powder, and 100,400,1000 microns of powder diameter average out to do not add pure aluminium silicate powder and compare simultaneously with embodiment 2.The foam powder obtaining is crushed to after average 400 microns.Oil number to useless gear oil (lubricating oil that contains anti-wear agent also has the broken wadding of metal, carbon particles etc.) is simultaneously roughly the same, is between 16-18g/g.The number of times that oil number decays to 50% oil number is respectively 10 times, 20 times, 7 times.The number of times that does not add pure aluminium silicate powder is 5 times.
Claims (10)
1. oil absorption material, is characterized in that, described oil absorption material is the powder that expanded plastic is made.
2. oil absorption material according to claim 1, is characterized in that, described expanded plastic is selected from one or several in polystyrene, urethane, polyvinyl chloride, polyethylene, urea formaldehyde, phenolic aldehyde, polycarbonate, polyphenylene oxide, polysulfones.
3. oil absorption material according to claim 1, is characterized in that, described expanded plastic is semi-rigid expanded plastic.
4. oil absorption material according to claim 1, is characterized in that, the median size of described powder is 2-1000 micron.
5. oil absorption material according to claim 1, is characterized in that, the bubble diameter of described expanded plastic is 1-1000 micron.
6. oil absorption material according to claim 1, is characterized in that, the ratio 0.2-10 of described powder diameter and the bubble diameter of expanded plastic.
7. oil absorption material according to claim 1, is characterized in that, described oil absorption material also comprises inert inorganic powder.
8. oil absorption material according to claim 7, is characterized in that, described inert inorganic powder diameter is 0.2-10 with the ratio in polyurethane foam material aperture.
9. according to the oil absorption material described in any one claim in claim 1-8, it is characterized in that, the preparation method of oil absorption material, is characterized in that, expanded plastic is made to powder, obtains oil absorption material.
10. the oily purposes that contains solid impurity according to the oil absorption material described in any one claim in claim 1-8 in absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410346090.XA CN104119618B (en) | 2014-07-21 | 2014-07-21 | Oil absorption material and its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410346090.XA CN104119618B (en) | 2014-07-21 | 2014-07-21 | Oil absorption material and its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104119618A true CN104119618A (en) | 2014-10-29 |
| CN104119618B CN104119618B (en) | 2016-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410346090.XA Active CN104119618B (en) | 2014-07-21 | 2014-07-21 | Oil absorption material and its production and use |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497987A (en) * | 2014-12-29 | 2015-04-08 | 江苏健神生物农化有限公司 | Cleaning agent for cleaning petroleum film in sea and preparation method thereof |
| CN108203218A (en) * | 2018-01-05 | 2018-06-26 | 金碳环境科技（天津）有限公司 | A kind of harmless treatment process of oily sludge |
| CN108249621A (en) * | 2018-01-31 | 2018-07-06 | 金碳环境科技（天津）有限公司 | A kind of oil-containing sewage treatment technique |
| CN109966156A (en) * | 2019-03-14 | 2019-07-05 | 龚海棠 | A kind of oil absorbent piece and its preparation process |
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| JPS5738875A (en) * | 1980-08-21 | 1982-03-03 | Taihoo Kogyo Kk | Oil adsorbent |
| DE3840670A1 (en) * | 1988-12-02 | 1990-06-07 | Ruediger Hesch | Pressed mouldings of rigid polyurethane foam, process for their production and their use for absorbing oil |
| CN1978511A (en) * | 2006-11-29 | 2007-06-13 | 上海宜可环保科技有限公司 | Recyclable oil-sorbent material |
| CN101787107A (en) * | 2010-02-21 | 2010-07-28 | 中国人民解放军63975部队 | Oil-absorbing polyurethane foam material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497987A (en) * | 2014-12-29 | 2015-04-08 | 江苏健神生物农化有限公司 | Cleaning agent for cleaning petroleum film in sea and preparation method thereof |
| CN104497987B (en) * | 2014-12-29 | 2017-05-24 | 濮阳市绿洲实业有限公司 | Cleaning agent for cleaning petroleum film in sea and preparation method thereof |
| CN107055684A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | Environment-friendly type is used to remove detersive of slick and preparation method thereof |
| CN107057645A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | Detersive for removing slick and preparation method thereof |
| CN107057646A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | A kind of environment-friendly type is used to remove detersive of slick and preparation method thereof |
| CN107055682A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | It is a kind of to be used to remove detersive of slick and preparation method thereof |
| CN107055683A (en) * | 2014-12-29 | 2017-08-18 | 胡妍 | A kind of detersive for being used to remove slick |
| CN108203218A (en) * | 2018-01-05 | 2018-06-26 | 金碳环境科技（天津）有限公司 | A kind of harmless treatment process of oily sludge |
| CN108249621A (en) * | 2018-01-31 | 2018-07-06 | 金碳环境科技（天津）有限公司 | A kind of oil-containing sewage treatment technique |
| CN109966156A (en) * | 2019-03-14 | 2019-07-05 | 龚海棠 | A kind of oil absorbent piece and its preparation process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104119618B (en) | 2016-07-06 |
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Effective date of registration: 20170615 Address after: 300204 Tianjin, Yongan Road, Rome garden, block A, building 2, 1101, Hexi District Patentee after: Golden carbon Environment Technology (Tianjin) Co., Ltd. Address before: 300204 Rome garden, Yongan Road, Tianjin, Hexi District A-I-1403 Patentee before: Li Linying |