CN105504566A - Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier - Google Patents
Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier Download PDFInfo
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- CN105504566A CN105504566A CN201610051635.3A CN201610051635A CN105504566A CN 105504566 A CN105504566 A CN 105504566A CN 201610051635 A CN201610051635 A CN 201610051635A CN 105504566 A CN105504566 A CN 105504566A
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract
The invention discloses a preparation method of a columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier. The method is characterized by including the steps of mixing styrene, divinyl benzene, benzoyl peroxide, methylbenzene, n-heptane and dichloroethane into a mixture, adding water, polyvinyl alcohol, calcium carbonate and sodium dodecyl benzene sulfonate into a reaction container, heating the materials to 25-40 DEG C over stirring, adding the mixture, heating the mixture to 70-90 DEG C, conducting stirring reaction for 7-9 hours, conducting filtering, washing and drying solid to prepare columnar styrene and divinyl benzene copolymer, mixing the copolymer with adhesives and polytetrafluoroethylene, filling a die with the mixture, pressing the mixture into a column, and drying the column to prepare the columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier. The prepared product and hydrophilic filler are filled and are high in matching degree, the pressure drop of a bed layer is small, and the method can be used for heavy water tritium extraction and waste water tritium removal and is good in effect.
Description
Technical field
The invention belongs to the preparation of the organic high molecular compound for heavy water detritiation, tritium-containing liquid waste detritiation, relate to a kind of preparation method of column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.The column styrene diethylene benzene copoly mer (being called for short SDB) that the present invention obtains, for heavy water detritiation, tritium-containing liquid waste detritiation, contributes to the through engineering approaches application of the heavy water detritiation of Pt/SDB hydrophobic catalyst, tritium-containing liquid waste detritiation especially.
Background technology
Along with the major issues such as the energy of facing mankind and environment are day by day remarkable, nuclear technique is as a clean energy technology, and it is subject to the attention of countries in the world; The exploitation of the novel energies such as fission energy, fusion energy and fusion-fission mixing energy, is considered to one of effective way solving energy dilemma; Utilize in heavy water reactor, magnetic confinement nuclear fusion, inertial confinement fusion, weapon tritium, hydrogen energy source, and other field relevant with hydrogen isotope, all relate to extracting and developing and the issues of purification of hydrogen isotope (deuterium, tritium).Greatly develop nuclear energy and list China's 2005 ~ the year two thousand twenty nuclear power Long-and Medium-term Development planning in, wherein the construction of inland Nuclear power plants is put on agenda, Inland Water dilution capacity is more weak relative to coastal Nuclear power plants, and what develop inland Nuclear power plants overriding concern is that a large amount of low dense discharge containing HTO is on the impact of environment or the pollution problem directly to tap water.The fast development of nuclear industry simultaneously; tritium is also progressively increasing as the operational ton of important nuclear matter; radiation safety and the radio-protective of tritium just more and more come into one's own; in the production of tritium, separation, purifying, transport; and store and in tritium and the interactional process of material, usually can produce tritium-containing liquid waste and the tritium polluting waste of different tritium activity.Therefore, existing nuclear power generating sets, and following fusion reactor, fusion-fission mixing energy heap etc. all face the process problem containing HTO.Tritium exists with HTO form in waste water, and removal means such as absorption, filtration, the ion-exchange etc. of existing radionuclide hardly may by HTO from H
2separate in O, the exploitation of thus novel tritium-containing liquid waste detritiation technology is very important, to realize " zero release " of tritium.Due to perviousness, diffustivity and active chemical reactivity that tritium is extremely strong, and the consistency high with other material, tritium-containing liquid waste process remains at larger technical barrier, and the treatment technology of tritium is badly in need of development and perfect.Hydrophobic catalyst is the chief component realizing liquid phase hydrogen water isotope catalytic exchange, and prepares high-performance and to meet the carrier of the hydrophobic catalyst of industrial requirements particularly crucial.From the fifties in last century, foreign study person is devoted to the research of the hydrophobic catalyst that can be used for hydrogen-water exchange always, requires that it not only has catalytic activity, also has mass-transfer performance and the hydrodynamic performance index of system.In order to improve the mass-transfer performance of system, hydrophobic catalyst always with hydrophilic filler with the use of.The research of China to Pt/SDB hydrophobic catalyst is started late, and mainly concentrates on the research of spherical Pt/SDB hydrophobic catalyst of small particle size, about the correlative study report of the synthesis of column Pt/SDB catalyzer is few.
Consider from economy and secure context, existing to containing tritium heavy water, tritium-containing liquid waste detritiation method generally all have employed hydrogen isotope liquid-phase catalysis permutoid reaction, in the reaction, Pt/SDB hydrophobic catalyst is critical material, is to play the Pt carrier of katalysis on the SDB carrier of porous.Prior art exist SDB microsphere diameter less than normal, lack column SDB product etc., due to the porosity between hydrophilic filler when thus causing Pt-SDB engineer applied, larger, a large amount of liquid buildup of the bed mass transfer resistance of hydrogen water liquid material exchange, easily liquid flooding etc. occurs, exchange efficiency is lower.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, provides a kind of preparation method of column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.The column SDB that the present invention obtains has good hydrophobicity (Static water contact angles>=110 °), higher ultimate compression strength, specific surface area (300 ~ 600m
2g
-1) and pore structure (mean pore size 5 ~ 8nm) and compacting before change not quite, and can improve and hydrophilic filler matching degree, have reduce bed resistance to mass transfer, prevent liquid flooding etc. special, contribute to the through engineering approaches application of the heavy water detritiation of such hydrophobic catalyst, tritium-containing liquid waste detritiation.
Content of the present invention is: a kind of preparation method of column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, it is characterized in that step is:
A, preparation (powder shaped, or claim Powdered, powdery) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 2 ~ 10 mass parts, Vinylstyrene 2 ~ 13 mass parts, benzoyl peroxide 0.02 ~ 0.6 mass parts, toluene 8 ~ 16 mass parts, normal heptane 6 ~ 13 mass parts, and ethylene dichloride 5 ~ 12 mass parts, mixing, obtains mixture, for subsequent use;
By water 100 ~ 200 mass parts, polyvinyl alcohol 0.1 ~ 0.5 mass parts, calcium carbonate 0.1 ~ 0.5 mass parts and Sodium dodecylbenzene sulfonate 0.01 ~ 0.06 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 25 ~ 40 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 70 ~ 90 DEG C, (carry out suspension polymerization) under stirring and react, being preferably and controlling stirring velocity is 70 ~ 200r/min, reaction times 7 ~ 9h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier).
B, preparation column (or claiming bar shape) styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 8 ~ 10 mass parts of step a, mix with binding agent 0.05 ~ 0.15 mass parts and tetrafluoroethylene 0.05 ~ 0.15 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1 ~ 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 1 ~ 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 90 ~ 100 DEG C, then dry 2 ~ 3h at the temperature of (reducing the temperature to) 70 ~ 80 DEG C, i.e. obtained column (or claiming bar shape) styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
In content of the present invention: polyvinyl alcohol described in step a is preferably polyvinyl alcohol-1899 (products production enterprise has: seven Chemical Co., Ltd., the Shanghai good Chemical Industry Science Co., Ltd of fond dream etc. are helped in Shanghai Nai Heng Industrial Co., Ltd., Chongqing, are existing commercially available prod).
In content of the present invention: binding agent described in step b can be any one in starch, polyvinylpyrrolidone (abbreviation PVP), carboxymethyl cellulose (abbreviation CMC) and polyvinyl alcohol (abbreviation PVA).
In content of the present invention: described water is preferably deionized water or distilled water.
Compared with prior art, the present invention has features and beneficial effect:
(1) the present invention is adopted, take vinylbenzene as monomer, Vinylstyrene is comonomer, linking agent, when particularly both mol ratios are 1:1, there is higher degree of crosslinking, make the structure of SDB become fine and close, contain a large amount of nonpolar C=C suspended double bond in SDB simultaneously, thus there is better mechanical strength, thermostability and hydrophobicity;
(2) the present invention is adopted, by adding binding agent (starch, Povidone, carboxymethyl cellulose or polyvinyl alcohol), utilize the functional group of binding agent self and powdery SDB to interact, reactive force between the two can be improved, improve the mechanical strength of bar shape SDB;
(3) adopt the present invention, by adding tetrafluoroethylene, on the one hand because its cohesive energy density(CED) is lower, and carbon-fluorine bond stability is stronger; On the other hand, the intermolecular magnetism of tetrafluoroethylene and surface energy lower, there is extremely low skin friction coefficient, the thermostability of column SDB, hydrophobicity can be improved, thus the easy demoulding in pressing process;
(4) the present invention is adopted, obtained bar shape styrene diethylene benzene copoly mer hydrophobic catalyst carrier and hydrophilic filler matching degree, there is the resistance to mass transfer reducing bed, the feature preventing liquid flooding in the mass transfer process of hydrogen-water liquid material exchange, contribute to the through engineering approaches application of such Pt/SDB hydrophobic catalyst in heavy water detritiation, tritium-containing liquid waste detritiation;
(5) product preparation process of the present invention is simple, and operation is easy, easily operates, practical.
The comparatively large and size adjustable of product size of the present invention, improve with hydrophilic filler matching degree, and have in the mass transfer process of hydrogen-water liquid material exchange reduce bed resistance to mass transfer, prevent the features such as liquid flooding, contribute to such hydrophobic catalyst through engineering approaches application.
Accompanying drawing explanation
Fig. 1 is the FT-IR spectrogram of column (or claiming bar shape) SDB adopting different binding agent to prepare in the embodiment of the present invention; As seen from the figure, compared with Powdered SDB, be that column SDB infared spectrum prepared by tackiness agent goes out 1071.91 and 1029.10cm with starch
-1place, the C-O stretching vibration of corresponding starch and the flexural vibration of O-H; Take PVP as the infrared curve of column SDB prepared by tackiness agent, 1655.79 and 1291.96cm
-1place, the stretching vibration of C-O and C-N of corresponding PVP; Be column SDB prepared by binding agent with CMC, at 1601.56cm
-1the asymmetric stretching vibration absorption peak of the COO-at place and 1418.53cm
-1the symmetrical stretching vibration absorption peak at place obviously strengthens, and this caused due to carbonyl characteristic peak in CMC; Take PVA as column SDB prepared by binding agent, compared to Powdered (or claiming powdery, powder shaped) SDB, due to the increase of alcoholic extract hydroxyl group amount, make 3426.62cm
-1there is stronger-OH absorption peak in place; And all at 1154cm
-1near, occur PTFE-CF charateristic avsorption band;
Fig. 2 is the TG curve of the column SDB adopting different tackiness agent in the embodiment of the present invention; As seen from the figure, column SDB prepared by different binding agent, carry out in two stages decomposing in the first stage, all samples all starts to have occurred obvious weightlessness at 300 DEG C, and namely its molecular backbone chain starts to decompose fracture.After 450 DEG C, occur the decomposition of subordinate phase, be the decompose themselves of tetrafluoroethylene; Compared with powdery SDB, due to adding of tackiness agent and tetrafluoroethylene, the thermostability of column SDB significantly improves;
To be column SDB carrier of the present invention respectively with stainless steel θ filler carry out mixing with volume filling ratio 1:4 Fig. 3 and Fig. 4 and layering is loaded, temperature of reaction 298K, and pressure drop of column is with the relation of gas-liquid change in flow; Along with the increase of gas flow rate and flow rate of liquid, pressure drop of column all increases.When flow rate of liquid one timing, gas flow rate rises, and bed pressure drop also obviously rises, and flow rate of liquid is larger, and Pressure Drop is larger; Along with the increase of gas flow rate, gas, under the traction effect of filler or carrier outer surface, destroys " the liquid capsule " between filler and carrier, liquid is sprawled along reaction bed cross section, resistance when gas passes through increases, thus the pressure drop gradient of bed is obviously increased; When gas flow rate is certain, flow rate of liquid increases, and cause the wetting areas of filler and carrier to increase, liquid film is thickening, reduces the porosity of bed, increase gas by time resistance, thus bed pressure drop gradient is increased.Because thickness of liquid film is thinner, the amplitude that pressure drop of column increases is less; Relative to gas flow rate, liquid speed is more weak on the impact of pressure drop gradient;
To be column SDB carrier of the present invention respectively with stainless steel θ filler carry out mixing with volume filling ratio 1:4 Fig. 5 and Fig. 6 and layering is loaded, temperature of reaction 298K, and dynamic liquid holdup is with the relation of gas-liquid change in flow; The bed dynamic liquid holdup variation tendency of column SDB and the identical of spheroid carrier, it changes greatly with the change of flow rate of liquid, and the impact of the change of gas flow rate on bed dynamic liquid holdup is less; This is the increase due to gas speed, and the traction that gas is produced at SDB carrier surface increases, and traction makes liquid leave solid surface, with air-flow rapidly by bed, causes dynamic liquid holdup in bed to reduce; Along with the increase of liquid speed, in bed, the hold-up of liquid increases, and namely dynamic liquid holdup increases.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 2 mass parts, Vinylstyrene 2 mass parts, benzoyl peroxide 0.02 mass parts, toluene 8 mass parts, normal heptane 6 mass parts, and ethylene dichloride 5 mass parts, mixing, obtains mixture, for subsequent use;
By water 100 mass parts, polyvinyl alcohol 0.1 mass parts, calcium carbonate 0.1 mass parts and Sodium dodecylbenzene sulfonate 0.01 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 25 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 70 DEG C, (carry out suspension polymerization) under stirring and react, control stirring velocity is 70r/min, reaction times 7h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 8 mass parts of step a, mix with binding agent 0.05 mass parts and tetrafluoroethylene 0.05 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 1h under column styrene diethylene benzene copoly mer being placed in the temperature of 90 DEG C, then dry 2h at the temperature of (reducing the temperature to) 70 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 115 °; By electronic universal tester, the ultimate compression strength 815MPa of working sample.
Embodiment 2:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 10 mass parts, Vinylstyrene 13 mass parts, benzoyl peroxide 0.6 mass parts, toluene 16 mass parts, normal heptane 13 mass parts, and ethylene dichloride 12 mass parts, mixing, obtains mixture, for subsequent use;
By water 200 mass parts, polyvinyl alcohol 0.5 mass parts, calcium carbonate 0.5 mass parts and Sodium dodecylbenzene sulfonate 0.06 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 40 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 90 DEG C, (carry out suspension polymerization) under stirring and react, control stirring velocity is 200r/min, reaction times 9h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 10 mass parts of step a, mix with binding agent 0.15 mass parts and tetrafluoroethylene 0.15 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 100 DEG C, then dry 3h at the temperature of (reducing the temperature to) 80 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 113 °; By electronic universal tester, the ultimate compression strength 850MPa of working sample.
Embodiment 3:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 6 mass parts, Vinylstyrene 7.5 mass parts, benzoyl peroxide 0.31 mass parts, toluene 12 mass parts, normal heptane 9 mass parts, and ethylene dichloride 8 mass parts, mixing, obtains mixture, for subsequent use;
By water 150 mass parts, polyvinyl alcohol 0.3 mass parts, calcium carbonate 0.3 mass parts and Sodium dodecylbenzene sulfonate 0.03 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 32 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 80 DEG C, (carry out suspension polymerization) under stirring and react, control stirring velocity is 130r/min, reaction times 8h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 9 mass parts of step a, mix with binding agent 0.1 mass parts and tetrafluoroethylene 0.1 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1.5MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 1.5h under column styrene diethylene benzene copoly mer being placed in the temperature of 95 DEG C, then dry 2.5h at the temperature of (reducing the temperature to) 75 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 120 °; By electronic universal tester, the ultimate compression strength 889MPa of working sample.
Embodiment 4:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 5 mass parts, Vinylstyrene 7 mass parts, benzoyl peroxide 0.3 mass parts, toluene 11 mass parts, normal heptane 9 mass parts, and ethylene dichloride 8 mass parts, mixing, obtains mixture, for subsequent use;
By water 160 mass parts, polyvinyl alcohol 0.3 mass parts, calcium carbonate 0.3 mass parts and Sodium dodecylbenzene sulfonate 0.03 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 30 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 78 DEG C, (carry out suspension polymerization) under stirring and react, being preferably and controlling stirring velocity is 150r/min, reaction times 9h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 9 mass parts of step a, mix with binding agent 0.8 mass parts and tetrafluoroethylene 0.8 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 90 DEG C, then dry 3h at the temperature of (reducing the temperature to) 70 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 125 °; By electronic universal tester, the ultimate compression strength 1012MPa of working sample.
Embodiment 5:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 8.3 mass parts, Vinylstyrene 10.4 mass parts, benzoyl peroxide 0.18 mass parts, toluene 9.2 mass parts, normal heptane 10 mass parts, and ethylene dichloride 11 mass parts, mixing, obtains mixture, for subsequent use;
By water 200 mass parts, polyvinyl alcohol 0.1 mass parts, calcium carbonate 0.2 mass parts and Sodium dodecylbenzene sulfonate 0.02 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 30 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 78 DEG C, (carry out suspension polymerization) under stirring and react, being preferably and controlling stirring velocity is 150r/min, reaction times 9h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 10 mass parts of step a, mix with binding agent 0.05 mass parts and tetrafluoroethylene 0.05 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1 ~ 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 90 DEG C, then dry 3h at the temperature of (reducing the temperature to) 70 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 132 °; By electronic universal tester, the ultimate compression strength 1760MPa of working sample.
Embodiment 6:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 8.3 mass parts, Vinylstyrene 10.4 mass parts, benzoyl peroxide 0.18 mass parts, toluene 9.2 mass parts, normal heptane 10 mass parts, and ethylene dichloride 11 mass parts, mixing, obtains mixture, for subsequent use;
By water 200 mass parts, polyvinyl alcohol 0.1 mass parts, in calcium carbonate 0.2 mass parts and Sodium dodecylbenzene sulfonate 0.02 mass parts (such as: there-necked flask etc.), being heated to temperature under stirring is 30 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 75 DEG C, (carry out suspension polymerization) under stirring and react, being preferably and controlling stirring velocity is 180r/min, reaction times 8h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier).
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 10 mass parts of step a, mix with binding agent 0.1 mass parts and tetrafluoroethylene 0.1 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1 ~ 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 100 DEG C, then dry 3h at the temperature of (reducing the temperature to) 80 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 130 °; By electronic universal tester, the ultimate compression strength 1975MPa of working sample.
Embodiment 7:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 8.3 mass parts, Vinylstyrene 10.4 mass parts, benzoyl peroxide 0.18 mass parts, toluene 9.2 mass parts, normal heptane 10 mass parts, and ethylene dichloride 11 mass parts, mixing, obtains mixture, for subsequent use;
By water 200 mass parts, polyvinyl alcohol 0.1 mass parts, calcium carbonate 0.2 mass parts and Sodium dodecylbenzene sulfonate 0.02 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 35 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 80 DEG C, (carry out suspension polymerization) under stirring and react, being preferably and controlling stirring velocity is 200r/min, reaction times 9h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 10 mass parts of step a, mix with binding agent 0.15 mass parts and tetrafluoroethylene 0.15 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1 ~ 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 90 DEG C, then dry 3h at the temperature of (reducing the temperature to) 80 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 128 °; By electronic universal tester, the ultimate compression strength 2120MPa of working sample.
Embodiment 8:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 9.4 mass parts, Vinylstyrene 11.7 mass parts, benzoyl peroxide 0.25 mass parts, toluene 9.2 mass parts, normal heptane 10.02 mass parts, and ethylene dichloride 11 mass parts, mixing, obtains mixture, for subsequent use;
By water 200 mass parts, polyvinyl alcohol 0.1 mass parts, calcium carbonate 0.1 mass parts and Sodium dodecylbenzene sulfonate 0.02 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 30 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 85 DEG C, (carry out suspension polymerization) under stirring and react, being preferably and controlling stirring velocity is 200r/min, reaction times 8h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 8 mass parts of step a, mix with binding agent 0.1 mass parts and tetrafluoroethylene 0.15 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1 ~ 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
C, aftertreatment: dry 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 100 DEG C, then dry 3h at the temperature of (reducing the temperature to) 70 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.Carry out performance test: by optical contact angle measuring instrument, the Static water contact angles of working sample 135 °; By electronic universal tester, the ultimate compression strength 2530MPa of working sample.
Embodiment 9 ~ 15:
A preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step is:
A, preparation (powder shaped) styrene diethylene benzene copoly mer (hydrophobic catalyst carrier):
Get vinylbenzene 2 ~ 10 mass parts, Vinylstyrene 2 ~ 13 mass parts, benzoyl peroxide 0.02 ~ 0.6 mass parts, toluene 8 ~ 16 mass parts, normal heptane 6 ~ 13 mass parts, and ethylene dichloride 5 ~ 12 mass parts, mixing, obtains mixture, for subsequent use;
In each embodiment, the concrete mass parts consumption of each component raw material sees the following form:
By water 100 ~ 200 mass parts, polyvinyl alcohol 0.1 ~ 0.5 mass parts, calcium carbonate 0.1 ~ 0.5 mass parts and Sodium dodecylbenzene sulfonate 0.01 ~ 0.06 mass parts join in reaction vessel (such as: there-necked flask etc.), being heated to temperature under stirring is 25 ~ 40 DEG C, be preferably after solids (all) dissolves, described mixture is joined in reaction vessel, being heated to temperature is 70 ~ 90 DEG C, (carry out suspension polymerization) under stirring and react, being preferably and controlling stirring velocity is 70 ~ 200r/min, reaction times 7 ~ 9h is (to sclerosis, aging), filter, water is used in turn by filtering the solids obtained, dehydrated alcohol, after washing with acetone, (the porous small ball shape solids after washing being purified again) is dry, i.e. obtained (powder shaped) styrene diethylene benzene copoly mer (being called for short SDB) (hydrophobic catalyst carrier),
In each embodiment, the concrete mass parts consumption of each component raw material sees the following form:
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 8 ~ 10 mass parts of step a, mix with binding agent 0.05 ~ 0.15 mass parts and tetrafluoroethylene 0.05 ~ 0.15 mass parts, to reinstall in mould and suppress and (tabletting machine or the compacting of other existing installation can be adopted, be preferably under pressure 1 ~ 2MPa) become column (can be cylindric, or cross section being square, rectangle or other polygonal bar shape) styrene diethylene benzene copoly mer;
In each embodiment, the concrete mass parts consumption of each component raw material sees the following form:
C, aftertreatment: dry 1 ~ 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 90 ~ 100 DEG C, then dry 2 ~ 3h at the temperature of (reducing the temperature to) 70 ~ 80 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
In above-described embodiment: polyvinyl alcohol described in step a is polyvinyl alcohol-1899 (products production enterprise has: seven Chemical Co., Ltd., the Shanghai good Chemical Industry Science Co., Ltd of fond dream etc. are helped in Shanghai Nai Heng Industrial Co., Ltd., Chongqing, are existing commercially available prod).
In above-described embodiment: binding agent described in step b can be any one in starch, polyvinylpyrrolidone (abbreviation PVP), carboxymethyl cellulose (abbreviation CMC) and polyvinyl alcohol (abbreviation PVA).
Following table 1 is the pore structure of the column SDB adopting different tackiness agent to prepare in the embodiment of the present invention; Compared with raw material SDB, mean pore size slightly increases, specific surface area and pore volume all slightly decline; SDB is vesicular structure, when binding agent mixes with carrier S DB, causes the aperture of SDB to reduce, but change is little in general; Usually in preparation Pt-SDB, the Pt metal of load is of a size of 1 ~ 3nm, is thus pressed into without larger difference after column, on its subsequent applications without impact.
Table 1
In above-described embodiment: described water is deionized water or distilled water.
In above-described embodiment: each raw material adopted is commercially available prod.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; Described quality (weight) part can be all gram.
In above-described embodiment: the processing parameter (temperature, time, speed etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (5)
1. a preparation method for column styrene diethylene benzene copoly mer hydrophobic catalyst carrier, is characterized in that step is:
A, prepare styrene diethylene benzene copoly mer:
Get vinylbenzene 2 ~ 10 mass parts, Vinylstyrene 2 ~ 13 mass parts, benzoyl peroxide 0.02 ~ 0.6 mass parts, toluene 8 ~ 16 mass parts, normal heptane 6 ~ 13 mass parts, and ethylene dichloride 5 ~ 12 mass parts, mixing, obtains mixture, for subsequent use;
Water 100 ~ 200 mass parts, polyvinyl alcohol 0.1 ~ 0.5 mass parts, calcium carbonate 0.1 ~ 0.5 mass parts and Sodium dodecylbenzene sulfonate 0.01 ~ 0.06 mass parts are joined in reaction vessel, being heated to temperature under stirring is 25 ~ 40 DEG C, described mixture is joined in reaction vessel, being heated to temperature is 70 ~ 90 DEG C, stir lower reaction, reaction times 7 ~ 9h, filter, after the solids that filtration obtains is used water, dehydrated alcohol, washing with acetone in turn, drying, i.e. obtained styrene diethylene benzene copoly mer;
B, preparation column styrene diethylene benzene copoly mer: get obtained styrene diethylene benzene copoly mer 8 ~ 10 mass parts of step a, mix with binding agent 0.05 ~ 0.15 mass parts and tetrafluoroethylene 0.05 ~ 0.15 mass parts, to reinstall in mould and to be pressed into column styrene diethylene benzene copoly mer;
C, aftertreatment: dry 1 ~ 2h under column styrene diethylene benzene copoly mer being placed in the temperature of 90 ~ 100 DEG C, then dry 2 ~ 3h at the temperature of 70 ~ 80 DEG C, i.e. obtained column styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
2., by the preparation method of column styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1, it is characterized in that: polyvinyl alcohol described in step a is polyvinyl alcohol-1899.
3., by the preparation method of column styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1 or 2, it is characterized in that: binding agent described in step b is any one in starch, polyvinylpyrrolidone, carboxymethyl cellulose and polyvinyl alcohol.
4., by the preparation method of column styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 1 or 2, it is characterized in that: water described in step a is deionized water or distilled water.
5., by the preparation method of column styrene diethylene benzene copoly mer hydrophobic catalyst carrier described in claim 3, it is characterized in that: water described in step a is deionized water or distilled water.
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