CN105368432A - Pour point depressant for crude oil, preparation method for pour point depressant and application of pour point depressant - Google Patents
Pour point depressant for crude oil, preparation method for pour point depressant and application of pour point depressant Download PDFInfo
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Abstract
The invention discloses a pour point depressant for crude oil, a preparation method for the pour point depressant and application of the pour point depressant. The pour point depressant is prepared from the following ingredients in parts by weight: 2-15 parts of sodium 1,4-bis(1,3-dimethylbutyl) sulphonatosuccinate, 4-16 parts of polyvinyl pyrrolidone, 4-13 parts of hexadecyl dimethyl tertiary amine, 5-19 parts of sodium valproate, 5-18 parts of ammonium oxalate, 1-11 parts of nano-scale palladium borate, 400-600 parts of 10ppm-250ppm polyvinyl acid, 3-15 parts of 4-(1-methylethyl)cyclohexadiene-1-ethanol formate, 2-15 parts of polyacrylamide, 7-21 parts of cross-linker, 2-18 parts of vinylethylene carbonate, 2-12 parts of 4,4'-dimethoxytrityl chloride, 1-4 parts of 3,5-dibromomethyl toluene and 5-7 parts of sodium ethylenediamine tetramethylene phosphate. The pour point depressant for the crude oil, disclosed by the invention, is efficient and is stable in chemical property, and under the condition of low temperature, wax crystals cannot be precipitated when high-wax crude oil is transported by a pipeline; and the viscosity of the high-wax crude oil cannot be improved along with the drop of temperature, and the rheological property of the high-wax crude oil is not changed along with temperature drop.
Description
Technical field
The invention belongs to petrochemical industry, particularly relate to a kind of pour point depressant for crude oil and its preparation method and application.
Background technology
The crude oil mainly high-wax oil of China's major part field produces, when temperature reduces, crude oil can separate out wax crystalline substance, and along with the continuous decline of temperature, wax crystalline substance increases gradually, finally forms tridimensional network, greatly reduces the mobility of crude oil.Waxy crude oil mobility, to this defect of very temperature sensitive, has a strong impact on Oil extraction, accumulating and safety in production.Therefore, waxy crude oil viscosity and the research of rheological improvement opportunity, become the heat subject of the current alleviation oil production of China and transportation technology problem.
Pour point depressant is a kind of oil dope, it just can change the crystal habit of paraffin in oil product largely when adding tiny dose, the interfacial state of change system and rheological property, reduce condensation point and the viscosity of crude oil and oil product, improve crude oil recovering the oil, collect defeated, quality in the operation such as storage and efficiency, improve the use properties of oil product, widen the cutting width of cut during crude refining, increase economic efficiency and the utilization ratio of resource.Pour point depressant can rely on self molecule feature, changes the wax crystal particle of separating out in high-wax oil process of cooling, suppresses wax crystalline substance to form tridimensional network in crude oil, thus improves the low-temperature fluidity of crude oil.Davis found in nineteen twenty-nine, and the condenses of clorafin and naphthalene is the pour point depressant of effective processed oil, and after this, the research work about pour point depressant just starts to develop rapidly; Pour point depressant for crude oil grows up on the basis of cut pour point depressant.
Chinese patent 200610170673.7 discloses a kind of highly effective pour depressant for thermodynamic oil extraction process, effectively can reduce condensation point of crude oil.But there is following defect in the prior art: the oils that this invention adopts is: diesel oil, solvent oil, heavy aromatics oil fuel or plastics, rubber cracking oil; The close flash point of described plastics, rubber cracking oil is greater than the commodity such as 40 DEG C as active principle, and is specified from GB13690-92, and the organic liquid that all close flash points are less than or equal to 65 DEG C is inflammable and explosive hazardous chemical; Thus causing " highly effective pour depressant " danger described in this invention comparatively large, security is poor, in accumulating, use, there are major safety risks.
Summary of the invention
The technical problem solved: in order to overcome the defect of prior art, obtain a kind of viscosity can stablizing high-wax oil, makes it can not decline and rise by Yin Wendu; Rheological property is stablized, and not with temperature change, uses simple; Reduce the condensation point of high-wax oil, be applicable to crude oil production, transport, each stage of accumulating; And having that toxic side effect is little, security is high, production technique is simple, is easy to the pour point depressant promoted the use of, the invention provides a kind of pour point depressant for crude oil and its preparation method and application.
Technical scheme: a kind of pour point depressant for crude oil, by following component by weight proportioning form: sulfosuccinate two (1, 3 diformazan butanols) ester sodium salt 2 ~ 15 parts, Polyvinylpyrolidone (PVP) 4 ~ 16 parts, hexadecyldimethyl benzyl ammonium tertiary amine 4 ~ 13 parts, Sodium Valproate 5 ~ 19 parts, ammonium oxalate 5 ~ 18 parts, nano level boric acid palladium 1 ~ 11 part, concentration is the acid polyethylene 400 ~ 600 parts of 10ppm ~ 250ppm, 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate 3 ~ 15 parts, polyacrylamide 2 ~ 15 parts, linking agent 7 ~ 21 parts, vinylethylene carbonate 2 ~ 18 parts, 4,4-Dimethoxytrityl chloride 2 ~ 12 parts, 3, 5-bis-Monobromoxylene 1 ~ 4 part, ethylenediamine tetramethylene sodium phosphate 5 ~ 7 parts.
Preferably, described pour point depressant by following component by weight proportioning form: sulfosuccinate two (1, 3 diformazan butanols) ester sodium salt 3 ~ 13 parts, Polyvinylpyrolidone (PVP) 8 ~ 12 parts, hexadecyldimethyl benzyl ammonium tertiary amine 5 ~ 10 parts, Sodium Valproate 6 ~ 17 parts, ammonium oxalate 7 ~ 15 parts, nano level boric acid palladium 5 ~ 10 parts, concentration is the acid polyethylene 450 ~ 560 parts of 20ppm ~ 200ppm, 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate 6 ~ 11 parts, polyacrylamide 3 ~ 13 parts, linking agent 8 ~ 11 parts, vinylethylene carbonate 4 ~ 14 parts, 4,4-Dimethoxytrityl chloride 5 ~ 10 parts, 3, 5-bis-Monobromoxylene 2 ~ 3 parts, ethylenediamine tetramethylene sodium phosphate 6 ~ 7 parts.
Preferably, described linking agent is any one in 1-ethyl-(3-dimethylaminopropyl)-carbodiimide hydrochloride, N-hydroxy-succinamide, 2-(N-morpholine) ethyl sulfonic acid-hydrate, BDDE.
Preferably, the particle diameter of described nano level boric acid palladium is 10nm ~ 20nm.
A preparation method for pour point depressant for crude oil, comprises following steps:
1st step, add the ultrapure water 300 ~ 900 parts that specific conductivity is 0.0005 μ S/cm ~ 0.01 μ S/cm in a kettle., start agitator in reactor, rotating speed is 120rpm ~ 150rpm, starts heat pump, makes reactor temperature rise to 30 DEG C ~ 60 DEG C; Add sulfosuccinate two (1 successively, 3 diformazan butanols) ester sodium salt, Polyvinylpyrolidone (PVP), hexadecyldimethyl benzyl ammonium tertiary amine, be stirred to and dissolve completely, adjust ph is 4.0 ~ 8.5, agitator speed is adjusted to 20rpm ~ 50rpm, temperature is 50 ~ 60 DEG C, esterification 1 ~ 3 hour;
2nd step, get Sodium Valproate, ammonium oxalate pulverize, powder diameter is 400 ~ 500 orders; Add nano level boric acid palladium to mix, be laid in pallet, tiling thickness is 2 ~ 5 centimetres, and employing dosage is 1kGy ~ 4kGy, alpha-ray irradiation that energy is 1MeV ~ 10MeV 5 ~ 30 minutes;
3rd step, be dissolved in acid polyethylene through the mixed powder of the 2nd step process, add reactor, agitator speed is 50rpm ~ 80rpm, and temperature is 60 DEG C ~ 70 DEG C, starts vacuum pump and makes the vacuum tightness of reactor reach-0.001MPa ~-0.05MPa; Passing into nitrogen makes reacting kettle inner pressure be 0.005 ~ 0.01MPa, and insulation leaves standstill 30 ~ 60 minutes; Agitator speed is promoted to 80rpm ~ 150rpm, and the pressure release of simultaneous reactions still is to 0MPa; Add 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate successively, after polyacrylamide dissolves completely, add linking agent and be uniformly mixed, make the hydrophile-lipophile balance value of reactor solution be 5.3 ~ 9.5, insulation leaves standstill 60 ~ 120 minutes;
4th step, when agitator speed is 80rpm ~ 150rpm, add vinylethylene carbonate, 4,4-Dimethoxytrityl chloride, 3 successively, 5-bis-Monobromoxylene and ethylenediamine tetramethylene sodium phosphate, pressure is 0.05MPa ~ 0.1MPa, temperature is 110 DEG C ~ 120 DEG C, polyreaction 2 ~ 20 hours; After having reacted, reacting kettle inner pressure is down to 0MPa, be cooled to 35 DEG C ~ 50 DEG C, discharging can obtain pour point depressant for crude oil.
The application of described pour point depressant for crude oil in the pour point depression process of high-wax oil.
Preferably, described high-wax oil is the crude oil containing 20 carbocyclic aliphatic acid esters, 1,2,4-trichlorine tetracosa carbon fatty acid ester, dimethylbenzene 22 carbocyclic aliphatic acid esters.
Preferably, the mass ratio of pour point depressant and high-wax oil is 1:450 ~ 880.
Beneficial effect: (1) pour point depressant for crude oil of the present invention has efficiently, stable chemical nature, under cryogenic, high-wax oil adopts during pipeline transportation can not separate out wax crystalline substance; The viscosity of high-wax oil, do not decline along with temperature and rise, its rheological property does not change with temperature drop; (2) this pour point depressant for crude oil in use non-stimulated smell, can not produce precipitation, and pollution-free to surrounding enviroment; (3) pour point depressant for crude oil of the present invention is applied widely, can both play efficient depression effeCt under any pH value condition.
Accompanying drawing explanation
Fig. 1 is the viscous flow shear rate change curve in time of embodiment 1 ~ 3 and reference examples;
Fig. 2 is that crude oil zero pour is with pour point depressant for crude oil addition change curve;
Fig. 3 is the viscosity of crude curve over time of embodiment 1 ~ 3 and reference examples.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the amendment do the inventive method, step or condition and replacement, all belong to scope of the present invention.If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
Embodiment 1
Following methods is adopted to prepare pour point depressant for crude oil:
1st step, add the ultrapure water 300 parts that specific conductivity is 0.01 μ S/cm in a kettle., start agitator in reactor, rotating speed is 120rpm, starts heat pump, makes reactor temperature rise to 30 DEG C; Add sulfosuccinate two (1,3 diformazan butanols) ester sodium salt 2 parts, Polyvinylpyrolidone (PVP) 4 parts, hexadecyldimethyl benzyl ammonium tertiary amine 4 parts successively, be stirred to and dissolve completely, adjust ph is 4.0, agitator speed is adjusted to 20rpm, and temperature is 50 DEG C, esterification 1 hour;
2nd step, get Sodium Valproate 5 parts, ammonium oxalate 5 parts pulverizing, powder diameter is 400 orders; Add nano level boric acid palladium 1 part to mix, be laid in pallet, tiling thickness is 2 centimetres, and employing dosage is 1kGy, alpha-ray irradiation that energy is 1MeV 5 minutes;
3rd step, be dissolved in 100ppm acid polyethylene 400 parts through the mixed powder of the 2nd step process, add reactor, agitator speed is 50rpm, and temperature is 60 DEG C, starts vacuum pump and makes the vacuum tightness of reactor reach-0.001MPa; Passing into nitrogen makes reacting kettle inner pressure be 0.005MPa, and insulation leaves standstill 30 minutes; Agitator speed is promoted to 80rpm, and the pressure release of simultaneous reactions still is to 0MPa; Add 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate 3 parts successively, after polyacrylamide 2 parts dissolves completely, add linking agent 7 parts and be uniformly mixed, make the hydrophile-lipophile balance value of reactor solution be 5.3, insulation leaves standstill 60 minutes;
4th step, when agitator speed is 80rpm, add vinylethylene carbonate 2 parts, 4,4-Dimethoxytrityl chloride 2 parts, 3,5-bis-Monobromoxylene 1 part and ethylenediamine tetramethylene sodium phosphate 5 parts successively, pressure is 0.05MPa, temperature is 110 DEG C, polyreaction 2 hours; After having reacted, reacting kettle inner pressure is down to 0MPa, is cooled to 35 DEG C, discharging can obtain pour point depressant for crude oil.
Embodiment 2
Following methods is adopted to prepare pour point depressant for crude oil:
1st step, add the ultrapure water 900 parts that specific conductivity is 0.0005 μ S/cm in a kettle., start agitator in reactor, rotating speed is 150rpm, starts heat pump, makes reactor temperature rise to 60 DEG C; Add sulfosuccinate two (1,3 diformazan butanols) ester sodium salt 15 parts, Polyvinylpyrolidone (PVP) 16 parts, hexadecyldimethyl benzyl ammonium tertiary amine 13 parts successively, be stirred to and dissolve completely, adjust ph is 8.5, agitator speed is adjusted to 50rpm, and temperature is 60 DEG C, esterification 3 hours;
2nd step, get Sodium Valproate 19 parts, ammonium oxalate 18 parts pulverizing, powder diameter is 500 orders; Add nano level boric acid palladium 11 parts to mix, be laid in pallet, tiling thickness is 5 centimetres, and employing dosage is 4kGy, alpha-ray irradiation that energy is 10MeV 30 minutes;
3rd step, be dissolved in 250ppm acid polyethylene 600 parts through the mixed powder of the 2nd step process, add reactor, agitator speed is 80rpm, and temperature is 70 DEG C, starts vacuum pump and makes the vacuum tightness of reactor reach-0.05MPa; Passing into nitrogen makes reacting kettle inner pressure be 0.01MPa, and insulation leaves standstill 60 minutes; Agitator speed is promoted to 150rpm, and the pressure release of simultaneous reactions still is to 0MPa; Add 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate 15 parts successively, after polyacrylamide 15 parts dissolves completely, add linking agent 21 parts and be uniformly mixed, make the hydrophile-lipophile balance value of reactor solution be 9.5, insulation leaves standstill 120 minutes;
4th step, when agitator speed is 150rpm, add vinylethylene carbonate 18 parts, 4,4-Dimethoxytrityl chloride 12 parts, 3,5-bis-Monobromoxylene 4 parts and ethylenediamine tetramethylene sodium phosphate 7 parts successively, pressure is 0.1MPa, temperature is 120 DEG C, polyreaction 20 hours; After having reacted, reacting kettle inner pressure is down to 0MPa, is cooled to 50 DEG C, discharging can obtain pour point depressant for crude oil.
Embodiment 3
Following methods is adopted to prepare pour point depressant for crude oil:
1st step, add the ultrapure water 500 parts that specific conductivity is 0.005 μ S/cm in a kettle., start agitator in reactor, rotating speed is 130rpm, starts heat pump, makes reactor temperature rise to 50 DEG C; Add sulfosuccinate two (1,3 diformazan butanols) ester sodium salt 8 parts, Polyvinylpyrolidone (PVP) 10 parts, hexadecyldimethyl benzyl ammonium tertiary amine 10 parts successively, be stirred to and dissolve completely, adjust ph is 7.0, agitator speed is adjusted to 40rpm, and temperature is 55 DEG C, esterification 2 hours;
2nd step, get Sodium Valproate 8 parts, ammonium oxalate 10 parts pulverizing, powder diameter is 450 orders; Add nano level boric acid palladium 8 parts to mix, be laid in pallet, tiling thickness is 3 centimetres, and employing dosage is 2kGy, alpha-ray irradiation that energy is 5MeV 20 minutes;
3rd step, be dissolved in 180ppm acid polyethylene 500 parts through the mixed powder of the 2nd step process, add reactor, agitator speed is 70rpm, and temperature is 65 DEG C, starts vacuum pump and makes the vacuum tightness of reactor reach-0.002MPa; Passing into nitrogen makes reacting kettle inner pressure be 0.009MPa, and insulation leaves standstill 40 minutes; Agitator speed is promoted to 100rpm, and the pressure release of simultaneous reactions still is to 0MPa; Add 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate 8 parts successively, after polyacrylamide 9 parts dissolves completely, add linking agent 15 parts and be uniformly mixed, make the hydrophile-lipophile balance value of reactor solution be 6.3, insulation leaves standstill 80 minutes;
4th step, when agitator speed is 110rpm, add vinylethylene carbonate 8 parts, 4,4-Dimethoxytrityl chloride 8 parts, 3,5-bis-Monobromoxylene 2 parts and ethylenediamine tetramethylene sodium phosphate 6 parts successively, pressure is 0.09MPa, temperature is 112 DEG C, polyreaction 10 hours; After having reacted, reacting kettle inner pressure is down to 0MPa, is cooled to 45 DEG C, discharging can obtain pour point depressant for crude oil.
Reference examples
Certain brand pour point depressant for crude oil commercially available is adopted to be applied to the pour point depression process of high-wax oil.
Embodiment 4
Adopt the pour point depressant for crude oil process high-wax oil that embodiment 1 ~ 3 and reference examples obtain, the mass ratio of pour point depressant and high-wax oil is 1:450 ~ 880.Embodiment 1 ~ 3 is as shown in table 1 with the result data of the pour point depressant for crude oil process high-wax oil described in reference examples, as seen from the table: the more commercially available result of pour point depressant for crude oil to high-wax oil of the obtained pour point depressant for crude oil of embodiment 1 ~ 3 is better, namely, when addition is obviously less, pour point depressant of the present invention still effectively can reduce the zero pour of high-wax oil, and pour point depression rate is higher.In addition, the viscous flow shear rate of the high-wax oil after embodiment 1 ~ 3 and reference examples process, crude oil zero pour and viscosity of crude are detected respectively, result is as shown in Fig. 1 ~ 2, as seen from the figure: the pour point depressant for crude oil that embodiment 1 ~ 3 prepares has raising crude oil viscous flow shear rate compared with pour point depressant commercially available in prior art, reduces the advantage of viscosity of crude and zero pour.
The result data of table 1 embodiment 1 ~ 3 and reference examples process high-wax oil
Claims (8)
1. a pour point depressant for crude oil, it is characterized in that, by following component by weight proportioning form: sulfosuccinate two (1, 3 diformazan butanols) ester sodium salt 2 ~ 15 parts, Polyvinylpyrolidone (PVP) 4 ~ 16 parts, hexadecyldimethyl benzyl ammonium tertiary amine 4 ~ 13 parts, Sodium Valproate 5 ~ 19 parts, ammonium oxalate 5 ~ 18 parts, nano level boric acid palladium 1 ~ 11 part, concentration is the acid polyethylene 400 ~ 600 parts of 10ppm ~ 250ppm, 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate 3 ~ 15 parts, polyacrylamide 2 ~ 15 parts, linking agent 7 ~ 21 parts, vinylethylene carbonate 2 ~ 18 parts, 4,4-Dimethoxytrityl chloride 2 ~ 12 parts, 3, 5-bis-Monobromoxylene 1 ~ 4 part, ethylenediamine tetramethylene sodium phosphate 5 ~ 7 parts.
2. a kind of pour point depressant for crude oil according to claim 1, it is characterized in that, by following component by weight proportioning form: sulfosuccinate two (1, 3 diformazan butanols) ester sodium salt 3 ~ 13 parts, Polyvinylpyrolidone (PVP) 8 ~ 12 parts, hexadecyldimethyl benzyl ammonium tertiary amine 5 ~ 10 parts, Sodium Valproate 6 ~ 17 parts, ammonium oxalate 7 ~ 15 parts, nano level boric acid palladium 5 ~ 10 parts, concentration is the acid polyethylene 450 ~ 560 parts of 20ppm ~ 200ppm, 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate 6 ~ 11 parts, polyacrylamide 3 ~ 13 parts, linking agent 8 ~ 11 parts, vinylethylene carbonate 4 ~ 14 parts, 4,4-Dimethoxytrityl chloride 5 ~ 10 parts, 3, 5-bis-Monobromoxylene 2 ~ 3 parts, ethylenediamine tetramethylene sodium phosphate 6 ~ 7 parts.
3. a kind of pour point depressant for crude oil according to claim 1 and 2, it is characterized in that, described linking agent is any one in 1-ethyl-(3-dimethylaminopropyl)-carbodiimide hydrochloride, N-hydroxy-succinamide, 2-(N-morpholine) ethyl sulfonic acid-hydrate, BDDE.
4. a kind of pour point depressant for crude oil according to claim 1 and 2, is characterized in that, the particle diameter of described nano level boric acid palladium is 10nm ~ 20nm.
5. the preparation method of a kind of pour point depressant for crude oil described in claim 1 or 2, is characterized in that, comprise following steps:
1st step, add the ultrapure water 300 ~ 900 parts that specific conductivity is 0.0005 μ S/cm ~ 0.01 μ S/cm in a kettle., start agitator in reactor, rotating speed is 120rpm ~ 150rpm, starts heat pump, makes reactor temperature rise to 30 DEG C ~ 60 DEG C; Add sulfosuccinate two (1 successively, 3 diformazan butanols) ester sodium salt, Polyvinylpyrolidone (PVP), hexadecyldimethyl benzyl ammonium tertiary amine, be stirred to and dissolve completely, adjust ph is 4.0 ~ 8.5, agitator speed is adjusted to 20rpm ~ 50rpm, temperature is 50 ~ 60 DEG C, esterification 1 ~ 3 hour;
2nd step, get Sodium Valproate, ammonium oxalate pulverize, powder diameter is 400 ~ 500 orders; Add nano level boric acid palladium to mix, be laid in pallet, tiling thickness is 2 ~ 5 centimetres, and employing dosage is 1kGy ~ 4kGy, alpha-ray irradiation that energy is 1MeV ~ 10MeV 5 ~ 30 minutes;
3rd step, be dissolved in acid polyethylene through the mixed powder of the 2nd step process, add reactor, agitator speed is 50rpm ~ 80rpm, and temperature is 60 DEG C ~ 70 DEG C, starts vacuum pump and makes the vacuum tightness of reactor reach-0.001MPa ~-0.05MPa; Passing into nitrogen makes reacting kettle inner pressure be 0.005 ~ 0.01MPa, and insulation leaves standstill 30 ~ 60 minutes; Agitator speed is promoted to 80rpm ~ 150rpm, and the pressure release of simultaneous reactions still is to 0MPa; Add 4-(1-methylethyl) cyclohexadiene-1-ethanol manthanoate successively, after polyacrylamide dissolves completely, add linking agent and be uniformly mixed, make the hydrophile-lipophile balance value of reactor solution be 5.3 ~ 9.5, insulation leaves standstill 60 ~ 120 minutes;
4th step, when agitator speed is 80rpm ~ 150rpm, add vinylethylene carbonate, 4,4-Dimethoxytrityl chloride, 3 successively, 5-bis-Monobromoxylene and ethylenediamine tetramethylene sodium phosphate, pressure is 0.05MPa ~ 0.1MPa, temperature is 110 DEG C ~ 120 DEG C, polyreaction 2 ~ 20 hours; After having reacted, reacting kettle inner pressure is down to 0MPa, be cooled to 35 DEG C ~ 50 DEG C, discharging can obtain pour point depressant for crude oil.
6. the application of the pour point depressant for crude oil described in claim 1 or 2 in the pour point depression process of high-wax oil.
7. application according to claim 6, is characterized in that, described high-wax oil is the crude oil containing 20 carbocyclic aliphatic acid esters, 1,2,4-trichlorine tetracosa carbon fatty acid ester, dimethylbenzene 22 carbocyclic aliphatic acid esters.
8. application according to claim 6, is characterized in that, the mass ratio of pour point depressant and high-wax oil is 1:450 ~ 880.
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| CN106082949A (en) * | 2016-06-06 | 2016-11-09 | 徐州工程学院 | A kind of manganese slag light-weight ceramic tile base substrate reinforcing agent and production method thereof |
| CN106083071A (en) * | 2016-06-06 | 2016-11-09 | 徐州工程学院 | A kind of Redispersable latex type manganese slag light-weight ceramic tile flexible adhesion agent and preparation method thereof |
| CN110577828A (en) * | 2019-09-06 | 2019-12-17 | 西安长庆化工集团有限公司 | Nano-particle wax-proof pour point depressant for oil well as preparation method and application thereof |
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