CN103936901A - Drag reducer and preparation method thereof - Google Patents
Drag reducer and preparation method thereof Download PDFInfo
- Publication number
- CN103936901A CN103936901A CN201310017083.0A CN201310017083A CN103936901A CN 103936901 A CN103936901 A CN 103936901A CN 201310017083 A CN201310017083 A CN 201310017083A CN 103936901 A CN103936901 A CN 103936901A
- Authority
- CN
- China
- Prior art keywords
- separant
- silicone oil
- alpha
- poly
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/34—Hydrogen distribution
Abstract
The invention provides a drag reducer and a preparation method thereof. The drag reducer comprises poly(alpha-alkene) suspension particles adhered with an isolating agent and silicone oil; wherein the average density of the poly(alpha-alkene) suspension particles is in a range of 0.92 to 1.02 g/cm<3>. The preparation method comprises the following steps: (1) subjecting alpha-alkene to coordination polymerization in silicone oil; (2) mixing the system obtained in the step (1) with an isolating agent after the coordination polymerization so as to form poly(alpha-alkene) suspension particles adhered with an isolating agent; wherein the average density of the poly(alpha-alkene) suspension particles is in a range of 0.92 to 1.02 g/cm<3>. The drag reducer has the advantages of good stability, low viscosity, good fluidity, and user-friendliness. The preparation method is simple and can be easily applied to industry.
Description
Technical field
The invention provides a kind of flow improver and preparation method thereof.
Background technology
Flow improver is a kind of chemical agent that reduces fluid flow resistance, and the energy-saving and cost-reducing and raising pipeline throughput rate of the defeated process of fluid pipe is significant.
For the course of conveying of crude oil and processed oil, what drag-reduction effect was best is homopolymer or the multipolymer of alpha-olefin, generally in oil, adds the poly-alpha olefins of several ppm to tens ppm, just can reach very high drag-reduction effect.For the poly-alpha olefins of flow improver, general monomer is containing carbon number between 2～30, and better carbon number range is between 8～14.Molecular weight is the basic parameter that affects poly-alpha olefins resistance reducing performance, and drag reduction efficiency starts to increase with the increase of molecular weight, reaches subsequently balance.
Early stage polymerization methods adopts solution polymerization process more, and directly the product of solution polymerization is applied to oil pipeline, but because the viscosity of polymerisate own is large, the content of polymkeric substance is lower, therefore gives transport and uses and brought very large difficulty.
The mid-90 in 20th century, develop bulk polymerization.This method has improved the transformation efficiency of monomer and the molecular weight of polymkeric substance greatly, and the performance of flow improver is greatly enhanced.A problem of mass polymerization is, because the reaction heat that mass polymerization produces is high, system viscosity is very big, so polymerization reactant must be divided in relatively little reaction vessel in the time implementing polymerization, then be placed under low temperature environment and react, operating process is very loaded down with trivial details.Another problem of mass polymerization is, what mass polymerization obtained is rubber-like drag reducer polymerization thing solid, must by pulverize at low temperature and be distributed to water or alcohol-water in, making slurries could use, this process is called the aftertreatment of flow improver.Last handling process generally need to add separant, as CN1891736A.
There is the hydroxyl of some amount on the surface of silicon-dioxide, and these silicon hydroxyls are higher than the acidity of alcoholic extract hydroxyl group and phenolic hydroxyl group, makes silicon-dioxide have higher polarity and wetting ability.Existing numerous bibliographical informations that silica sphere carried out to hydrophobic treatment, the method relating to is a lot, and the method that wherein has industrial value is mainly pyroprocessing and with alcohol, acid, organochlorosilane processing.
Summary of the invention
The invention provides a kind of flow improver and preparation method thereof.This flow improver stability in storage is good, viscosity is low, good fluidity, easy to use.This preparation method is simple, is easy to industrial application.
A preparation method for flow improver, comprising:
(1) in silicone oil, alpha-olefin is carried out to polycoordination;
(2) system after step (1) polymerization is mixed with separant, form the poly-alpha olefins suspended particle that is bonded with separant; Described separant meets makes the mean density of described suspended particle at 0.92～1.02g/cm
3between.
Preferably, described separant is satisfied makes the mean density of described suspended particle at 0.95～0.99g/cm
3between.
Silicone oil is liquid polysiloxane, is generally linear structure, can be the polysiloxane of homopolymerization type, can be also the polysiloxane of copoly type.Should be understood that in method of the present invention, silicone oil mainly uses as reaction solvent and dispersion agent, and those skilled in the art can select suitable silicone oil according to basic general knowledge.Silicone oil is preferably, molecule has a silica chain, the group being connected with Siliciumatom in chain is one or more in hydrogen and C1～C8 alkyl, as being selected from one or more in dimethyl silicone oil, diethyl silicone oil, phenylbenzene silicone oil, hydrogen methyl-silicone oil, hydrogen ethyl silicon oil, hydrogen phenyl silicone oil, methyl phenyl silicone oil and ethylphenyl silicone oil.Silicone oil can, between 5 centipoise～5000 centipoises, be more preferably under between 10 centipoise～2000 centipoises the viscosity of 25 DEG C.
Described 'alpha '-olefin monomers comprises all 'alpha '-olefin monomers that can be used for flow improver.In preferred situation, described 'alpha '-olefin monomers is selected from C
2-C
30linear alpha-olefin in one or more; In preferred situation, described 'alpha '-olefin monomers is selected from C
4-C
20linear alpha-olefin in one or more; In further preferred situation, described 'alpha '-olefin monomers is selected from C
8-C
14linear alpha-olefin in one or more.
Although the present invention has adopted a kind of new polycoordination system (taking silicone oil as solvent), inventor's discovery, polymerization still can adopt existing coordination catalyst system, and completes under known polymerizing condition.Polycoordination system generally adopts Ziegler-Natta catalyst system, also can adopt newer single-site catalyzed system, as metallocene catalysis system and non-luxuriant catalyst system.Above-mentioned three kinds of catalyst system, particularly Ziegler-Natta catalyst system, have numerous descriptions in prior art, the present invention repeats no more this.
For polycoordination field, in slurry polymerization, controlling polymer particle size is basic general knowledge, and the present invention also repeats no more this.The present invention has no particular limits the granularity of poly-alpha olefins, as long as finally can form more stable suspension.Generally the granularity of poly-alpha olefins is controlled at below 1000 microns, is controlled at 500 microns of following effects better.
In the present invention, the ratio of silicone oil and alpha-olefin can change in wider scope.In order to obtain better drag-reduction effect, the mass ratio of the two is preferably 1～20:1, more preferably 1.5～10:1.
There is the poor problem of stability in storage in the flow improver slurries that slurry polymerization directly obtains, on the one hand, because the granularity of poly-alpha olefins is less, specific surface free enthalpy is higher, has the tendency that is agglomerated into piece; Because poly-alpha olefins and silicone oil exist density difference, extend in time on the other hand, poly-alpha olefins can separate with silicone oil, swims in silicone oil upper strata.Separant can stick to poly-alpha olefins particle surface, thereby slow down poly-alpha olefins particle and mutually collide bonding, if but still there is sizable density difference between the suspended particle that use separant forms and silicone oil, long storage time, suspended particle still can separate with silicone oil, or float on silicone oil upper strata, or be sunken to silicone oil lower floor.In order to solve this technical problem, the present invention needs to select suitable separant to regulate the mean density of suspended particle in step (2), both can use a kind of separant, also can adopt multiple separant, and make the mean density of described suspended particle at 0.92～1.02g/cm as long as can meet
3between.A kind of embodiment provided by the invention is to adopt multiple separant, according to the density of separant, can select different separants and adjust its ratio, making the density of the poly-alpha olefins that is stained with separant more approach the density of silicone oil, thereby further stablize flow improver suspension system.According to content disclosed by the invention, those skilled in the art, can easily select the kind of separant and determine its ratio by simple experiment.
The invention provides a kind of concrete embodiment is, in step (2), the system after step (1) polymerization is mixed with the first separant and the second separant; Described the first separant is the silicon-dioxide through hydrophobically modified, and described the second separant is stearic acid, stearate, stearic amide or stearate.The mass ratio of the first separant and the second separant is 2:1～1:1.
The described silicon-dioxide through hydrophobic treatment, both can, by commercially available, also can prepare by literature method.
Described silicon-dioxide is preferably the silicon-dioxide of processing with straight chain alcohol or straight-chain carboxylic acid.The optimization carbon number range of described straight chain alcohol is between 2～18; Described straight-chain carboxylic acid's optimization carbon number range is between 2～18.A kind of simple dewatering process method is: by silicon-dioxide and properties-correcting agent (alcohol, carboxylic acid) and organic solvent, at certain pressure, temperature, heated and boiled together, then separates, is dried.
In step (2), the dosage of described separant be in step (1) alpha-olefin quality 20%～100%, preferably 20%～50%.
The present invention is in step (2), and there is no particular limitation to add the mixing time of separant, as long as can meet, separant fully sticked to poly-alpha olefins particle surface.Mixing time is preferably greater than 5min, more preferably greater than 30min.
The suspension that step (2) obtains can directly be used as flow improver.
Separately it should be noted that, each concrete technical characterictic described in the invention, in reconcilable situation, can combine by any mode, and for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
A kind of flow improver, comprises the poly-alpha olefins suspended particle and the silicone oil that are stained with separant; The mean density of the described poly-alpha olefins suspended particle that is stained with separant is at 0.92～1.02g/cm
3between.
Preferably, described in, be stained with the mean density of poly-alpha olefins suspended particle of separant at 0.95～0.99g/cm
3between.
The present invention has adopted a kind of brand-new flow improver synthetic method, taking silicone oil as solvent, by slurry process synthesizing poly alpha-olefin.The method can be directly granular poly-alpha olefins, the poly-alpha olefins of its molecular weight and mass polymerization is suitable.The poly-alpha olefins slurry that the method obtains can directly apply to crude oil and Transportation of product oil through pipeline drag reduction, thereby has saved the aftertreatment links such as pulverize at low temperature, has simplified production technique.There is the poor problem of stability in storage in the flow improver slurries that slurry polymerization directly obtains, on the one hand, because the granularity of poly-alpha olefins is less, specific surface free enthalpy is higher, has the tendency that is agglomerated into piece; Because poly-alpha olefins and silicone oil exist density difference, extend in time on the other hand, poly-alpha olefins can separate with silicone oil, swims in silicone oil upper strata.Separant can stick to poly-alpha olefins particle surface, thereby slow down poly-alpha olefins particle and mutually collide bonding, if but still there is sizable density difference between the suspended particle that use separant forms and silicone oil, long storage time, suspended particle still can separate with silicone oil, or float on silicone oil upper strata, or be sunken to silicone oil lower floor.In order to solve this technical problem, the present invention needs to select suitable separant in step (2), according to the density of separant, can select one or more separants, and adjust as required the ratio of multiple separant, make the density of the poly-alpha olefins that is stained with separant more approach the density of silicone oil, thereby stablize better flow improver suspension system.
Embodiment
In embodiment, leave standstill after certain hour with flow improver slurries, volume and the cumulative volume of separating out silicone oil are in a ratio of eduction rate, are used for characterizing the stability of suspension system.Eduction rate is less, represents that the stability of suspension system is higher.
Embodiment 1
The present embodiment is for illustrating the preparation method of poly-alpha olefins/dimethyl silicone oil slurries.
Polymerizing catalyst used is prepared by the following method: after 2.0 grams of magnesium ethylate particulate carriers (mean particle dia is 40-50 micron), toluene 30ml are added and be uniformly dispersed in reaction flask, cool the temperature to-10 DEG C, add 10ml (6.0mol) TiCl
4, stop 0.5 hour, be warming up to 80 DEG C and add 0.6ml (0.39mol) diisobutyl phthalate, be warming up to 110 DEG C of reactions 2 hours, sedimentation, filters, the hot washed twice of toluene (each 20ml), secondary carries titanium, adds 5ml (3.0mmol) TiCl
4with 30ml toluene reaction 1 hour, sedimentation, filter, hexane washing 4 times, 72 DEG C obtain catalyst solid constituent after dry.In catalyzer, the quality percentage composition of titanium is 2.87%.
Will through the 1-octene 35g of molecular sieve refinement treatment (purchased from ACROS reagent company) with through the dimethyl silicone oil 65g(of molecular sieve refinement treatment purchased from Beijing Ding Ye Trade Co., Ltd., the viscosity of 25 DEG C is 300 centipoises) mix, anhydrous, under oxygen free condition, add the triisobutylaluminum toluene solution of 2.5mL1.1M and the Cyclohexyl Methyl Dimethoxysilane solution of 0.3mL1.0M, at-7 DEG C, pressure is under 0.1MPa, stir after 10 minutes, add 70mg catalyzer, at-7 DEG C, pressure is under 0.1MPa, stirring reaction 6 hours, obtain poly-alpha olefins/dimethyl silicone oil slurries.At 25 DEG C, by poly-alpha olefins/dimethyl silicone oil slurries and Virahol mix and blend, filtration, repeat after 4-5 time, 70 DEG C of oven dry, obtain poly-alpha olefins 33g.
Embodiment 2
Prepare poly-alpha olefins/dimethyl silicone oil slurries by the identical method of embodiment 1, after polyreaction, to the silicon-dioxide 6g and the calcium stearate 3g that add n-Heptyl alcohol modification in slurries, stir after 30min, obtain flow improver slurries A, stability in storage is in table 1.
Embodiment 3
Prepare poly-alpha olefins/dimethyl silicone oil slurries by the identical method of embodiment 1, after polyreaction, to the silicon-dioxide 5g and the calcium stearate 4g that add n-Heptyl alcohol modification in slurries, stir after 30min, obtain flow improver slurries B, stability in storage is in table 1.
Embodiment 4
Prepare poly-alpha olefins/dimethyl silicone oil slurries by the identical method of embodiment 1, after polyreaction, to the silicon-dioxide 4.5g and the calcium stearate 4.5g that add dimethyldichlorosilane(DMCS) modification in slurries, stir after 30min, obtain flow improver slurries C, stability in storage is in table 1.
Comparative example 1
Prepare poly-alpha olefins/dimethyl silicone oil slurries by the identical method of embodiment 1, after polyreaction, to the silicon-dioxide 9g that adds n-Heptyl alcohol modification in slurries, stir 30min, obtain flow improver slurries D, stability in storage is in table 1.
Comparative example 2
Prepare poly-alpha olefins/dimethyl silicone oil slurries by the identical method of embodiment 1, after polyreaction, in slurries, add calcium stearate 9g, stir after 30min, obtain flow improver slurries E, stability in storage is in table 1.
The stability in storage comparison of table 1 flow improver slurries
Embodiment 4
The present embodiment is for illustrating the effect of flow improver of the present invention.
Flow improver slurries are carried out to twice shearing, investigate and shear forward and backward drag reducing efficiency variation, test-results is in table 2.
In embodiment, measure the drag reducing efficiency that drag reduction hits, standard No.: SY/T6578-2003 according to the industry standard of China National Petroleum pipeline science and technology research centre establishment.Test condition: 20 DEG C of temperature, flow velocity 57L/min.Before test, flow improver is made into the diesel oil solution that mass concentration is 3mg/g, be placed in thinning tank, being diluted to mass concentration is 16 μ g/g again, when pipeline flows while stablizing, read blank pressure drop and add the pressure drop flow improver from differential manometer respectively, drag reducing efficiency calculation formula is as follows:
Δ P is the Pressure Drop that does not add flow improver, and Δ Pd is the Pressure Drop adding after flow improver.
As shown in Table 2, add after separant, drag reducing efficiency is without considerable change.
The drag-reduction effect of table 2 flow improver
Embodiment 5
Table 3 is the density of the dispersate that obtains of the different proportionings of compound separant, and wherein the density of nano silicon is about 2.65g/cm
3, the density of calcium stearate is 1.08g/cm
3, the density of polymkeric substance is about 0.87g/cm
3, separant accounts for 30% of polymer quality.Table 3 can find out, in the time that the mass ratio of two kinds of separant improved silicas and calcium stearate is 2:1～1:1, the density of the dispersate that obtains is suitable with the density 0.97 of dispersion agent dimethyl silicone oil, the mixed serum energy stable existence that therefore both form.
The different proportionings of the compound separant of table 3 and the density of dispersate
| Improved silica: calcium stearate | Mix separant density | Dispersate density |
| 100：50 | 1.75 | 0.984 |
| 100：60 | 1.69 | 0.979 |
| 100：70 | 1.64 | 0.975 |
| 100：80 | 1.59 | 0.971 |
| 100：90 | 1.55 | 0.968 |
| 100：100 | 1.52 | 0.965 |
Claims (15)
1. a preparation method for flow improver, comprising:
(1) in silicone oil, alpha-olefin is carried out to polycoordination;
(2) system after step (1) polymerization is mixed with separant, form the poly-alpha olefins suspended particle that is bonded with separant; Described separant meets makes the mean density of described suspended particle at 0.92～1.02g/cm
3between.
2. in accordance with the method for claim 1, it is characterized in that, described silicone molecule has a silica chain, and the group being connected with Siliciumatom in chain is one or more in hydrogen and C1～C8 alkyl.
3. in accordance with the method for claim 1, it is characterized in that, described silicone oil is selected from one or more in dimethyl silicone oil, diethyl silicone oil, phenylbenzene silicone oil, hydrogen methyl-silicone oil, hydrogen ethyl silicon oil, hydrogen phenyl silicone oil, methyl phenyl silicone oil and ethylphenyl silicone oil.
4. according to the arbitrary described method of claim 1～3, it is characterized in that, described silicone oil the viscosity of 25 DEG C between 5 centipoise～5000 centipoises.
5. in accordance with the method for claim 1, it is characterized in that, described 'alpha '-olefin monomers is selected from C
2-C
30linear alpha-olefin in one or more.
6. in accordance with the method for claim 1, it is characterized in that, described 'alpha '-olefin monomers is selected from C
8-C
14linear alpha-olefin in one or more.
7. according to the method described in claim 1 or 5, it is characterized in that, the mass ratio of silicone oil and alpha-olefin is 1～20:1.
8. in accordance with the method for claim 1, it is characterized in that, in step (2), the system after step (1) polymerization is mixed with the first separant and the second separant; Described the first separant is the silicon-dioxide through hydrophobically modified, and described the second separant is stearic acid, stearate, stearic amide or stearate.
9. in accordance with the method for claim 8, it is characterized in that, described silicon-dioxide is the silicon-dioxide of processing with straight chain alcohol or straight-chain carboxylic acid.
10. in accordance with the method for claim 9, it is characterized in that, the carbon number range of described straight chain alcohol is between 2～18; Described straight-chain carboxylic acid's carbon number range is between 2～18.
11. in accordance with the method for claim 8, it is characterized in that, total dosage of separant is that the 20%～100%, first separant of step (1) 'alpha '-olefin monomers quality and the mass ratio of the second separant are 2:1～1:1.
Method described in 12. claims 11, is characterized in that, total dosage of separant is 20%～50% of step (1) 'alpha '-olefin monomers quality.
13. in accordance with the method for claim 1, it is characterized in that, described separant meets makes the mean density of described suspended particle at 0.95～0.99g/cm
3between.
14. 1 kinds of flow improvers, comprise the poly-alpha olefins suspended particle and the silicone oil that are stained with separant; The mean density of the described poly-alpha olefins suspended particle that is stained with separant is at 0.92～1.02g/cm
3between.
15. according to the flow improver described in claim 14, it is characterized in that, described in be stained with separant the mean density of poly-alpha olefins suspended particle at 0.95～0.99g/cm
3between.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310017083.0A CN103936901B (en) | 2013-01-17 | 2013-01-17 | A kind of flow improver and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310017083.0A CN103936901B (en) | 2013-01-17 | 2013-01-17 | A kind of flow improver and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103936901A true CN103936901A (en) | 2014-07-23 |
| CN103936901B CN103936901B (en) | 2016-03-02 |
Family
ID=51184801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310017083.0A Active CN103936901B (en) | 2013-01-17 | 2013-01-17 | A kind of flow improver and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103936901B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151349A (en) * | 2017-06-06 | 2017-09-12 | 青岛福凯橡塑新材料有限公司 | A kind of blob of viscose interleaving agent crushed for natural rubber and preparation method thereof |
| CN108264616A (en) * | 2017-12-28 | 2018-07-10 | 凤阳力拓新型材料有限公司 | A kind of functionalization silicone oil of Graft Modification of Polyolefine |
| CN109796551A (en) * | 2017-11-17 | 2019-05-24 | 中国石油化工股份有限公司 | Preparation method, drag reducing polymerization composition granule and the application of frictional reducing polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891736A (en) * | 2005-07-01 | 2007-01-10 | 中国石油天然气股份有限公司 | Drag-reducing polymer oil-base dispersing method |
| CN101037507A (en) * | 2007-04-09 | 2007-09-19 | 中国石油化工集团公司 | Preparation method of multifunctional resistance-reducing polymer suspension |
| CN102653607A (en) * | 2011-03-04 | 2012-09-05 | 涿州市亚立特精细化工厂 | Drag reduction object and manufacturing method thereof |
-
2013
- 2013-01-17 CN CN201310017083.0A patent/CN103936901B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891736A (en) * | 2005-07-01 | 2007-01-10 | 中国石油天然气股份有限公司 | Drag-reducing polymer oil-base dispersing method |
| CN101037507A (en) * | 2007-04-09 | 2007-09-19 | 中国石油化工集团公司 | Preparation method of multifunctional resistance-reducing polymer suspension |
| CN102653607A (en) * | 2011-03-04 | 2012-09-05 | 涿州市亚立特精细化工厂 | Drag reduction object and manufacturing method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151349A (en) * | 2017-06-06 | 2017-09-12 | 青岛福凯橡塑新材料有限公司 | A kind of blob of viscose interleaving agent crushed for natural rubber and preparation method thereof |
| CN109796551A (en) * | 2017-11-17 | 2019-05-24 | 中国石油化工股份有限公司 | Preparation method, drag reducing polymerization composition granule and the application of frictional reducing polymer |
| CN108264616A (en) * | 2017-12-28 | 2018-07-10 | 凤阳力拓新型材料有限公司 | A kind of functionalization silicone oil of Graft Modification of Polyolefine |
| CN108264616B (en) * | 2017-12-28 | 2020-12-01 | 凤阳力拓新型材料有限公司 | Polyolefin graft-modified functional silicone oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103936901B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103936898B (en) | A kind of flow improver and preparation method thereof | |
| CN101824118B (en) | Porous polymer nanoparticles and preparation method thereof | |
| CN103304177B (en) | Preparation method of modified silicon powder | |
| CN103936899B (en) | A kind of flow improver and preparation method thereof | |
| CN103936897B (en) | A kind of flow improver and preparation method thereof | |
| CN103936901B (en) | A kind of flow improver and preparation method thereof | |
| CN108947570A (en) | A kind of porous ceramics microballoon and preparation method thereof | |
| JP2008535963A5 (en) | ||
| CN103936900B (en) | A kind of flow improver and preparation method thereof | |
| CN103030853B (en) | Drag reduction composition and preparation method thereof | |
| CN115011323A (en) | Viscosity reducer for hydrothermal cracking of heavy oil and preparation method and application thereof | |
| CN103694382B (en) | The preparation method of bimodulus pore-size distribution silica-gel carrier | |
| CN103030855B (en) | Anti-drag composition and preparation method of anti-drag composition | |
| CN105440394A (en) | Drag-reduction agent slurry and preparation method thereof | |
| CN107090134B (en) | A kind of preparation method of drag reducer slurries | |
| CN103030854B (en) | Drag reduction composition and preparation method thereof | |
| CN105562114A (en) | Preparation method for silicon-based monolithic carrier with high specific surface area | |
| Fernández et al. | Hybrid composites octyl-silica-methacrylate agglomerates as enzyme supports | |
| CN111054284B (en) | Method for preparing spherical solid defoaming agent through micro-channel | |
| CN103030726A (en) | Preparation method of powdered drag reducing agent for crude oil transportation | |
| CN105330872A (en) | Drag reducer slurry and preparation method thereof | |
| CN103130924B (en) | Catalyst carrier used for olefin polymerization and preparation method thereof | |
| CN103214603A (en) | Magnesium ethoxide/montmorillonite/titanium tetrachloride polyethylene catalyst, and preparation method and application thereof | |
| CN102898554B (en) | Preparation method, product and application of particulate poly-alpha-olefin | |
| CN109160966A (en) | A kind of tripolite loading metallocene catalyst and the preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |