CN104262521B - The preparation method of styrene divinylbenzene copolymer hydrophobic catalyst carrier - Google Patents
The preparation method of styrene divinylbenzene copolymer hydrophobic catalyst carrier Download PDFInfo
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- CN104262521B CN104262521B CN201410449037.2A CN201410449037A CN104262521B CN 104262521 B CN104262521 B CN 104262521B CN 201410449037 A CN201410449037 A CN 201410449037A CN 104262521 B CN104262521 B CN 104262521B
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Abstract
The invention discloses the preparation method of styrene divinylbenzene copolymer hydrophobic catalyst carrier, it is characterized in that：Deionized water, organic matter polyvinyl alcohol 1799, inorganic salts and neopelex are added in reaction vessel, 25~40 DEG C are heated under agitation, add the mixture of the styrene mixed, divinylbenzene, benzoyl peroxide, toluene, normal heptane and dichloroethanes, it is heated to 70~90 DEG C, after 7~9h of the lower progress suspension polymerization of stirring, filtering；The solids obtained after reaction is washed with deionized water, absolute ethyl alcohol, 12~48h is extracted in apparatus,Soxhlet's with acetone again, then after solids is washed with methanol, deionized water, dry, screening, that is, styrene divinylbenzene copolymer hydrophobic catalyst carrier is made.The Pt/SDB hydrophobic catalysts prepared using product of the present invention as carrier are good for heavy water detritiation, waste water detritiation, using effect.
Description
Technical field
The invention belongs to the preparation of organic high molecular compound, is related to styrene diethylene benzene copoly mer (abbreviation SDB)
The preparation method of hydrophobic catalyst carrier.It is copolymerized with big particle diameter (2~5mm of φ) styrene-divinylbenzene produced by the present invention
Thing is Pt/SDB hydrophobic catalysts prepared by carrier, has and reduces the resistance to mass tranfer of bed, prevents liquid flooding, and improves fluid and hand over
The advantages that changing efficiency, the engineering application especially suitable for heavy water detritiation, waste water detritiation etc..
Background technology
Continuous ripe and nuclear industry with nuclear technology develops rapidly, and tritium is as crucial nuclear material, and its dosage is increasingly
Increase, therefore, the radiation protection of tritium and safety are more and more important.Fusion reactor, hybrid fusion-fission reactor, Yi Ji great
The exploitation of area nuclear energy will be faced with the process problem of the heavy water containing tritium to become increasingly conspicuous, especially because the inland construction of nuclear power station is big
Power develops, and the solution containing HTO of a greater amount of (such as annual upper tons), has formed the operation for restricting inland nuclear power station and hair
" bottleneck " of exhibition.Consider from economy and secure context, hydrogen isotope catalysis is all employed to the processing containing tritium in HTO (heavy water)
Exchange reaction, traditional inorganic hydrophilic catalyst, such as platinum/alundum (Al2O3) (Pt/Al2O3), exchanged applied to hydrogen-water catalysis
During reaction, the problems such as aqueous water is easy to be poisoned, inactivated is run into, and hydrophobic catalyst can accelerate hydrogen isotope to urge ideally
Change the progress of reaction, thus hydrophobic catalyst is the critical material for completing hydrogen-water liquid-phase catalysis exchange.In the prior art, it is hydrophobic
The research of catalyst is all concentrated on the catalyst such as Pt/PTFE, Pt/C/PTFE and Pt/SDB.Using PTFE (polytetrafluoroethylene (PTFE))
For the hydrophobic catalyst of carrier, catalytic stability problem is still faced.Pt/SDB turns into current primary study and the species of application,
But the preparation method of prior art mainly there is problems：SDB hydrophobic catalyst carrier hydrophobic stabilities are poor, SDB is hydrophobic
The deficiencies of catalytic activity deficiency and catalytic stability of catalyst are poor, and catalyst particle size diameter is less than normal, it is impossible to reach work
Journeyization requirement, thus be extremely necessary to carry out the preparation research of big particle diameter (2~5mm of φ) SDB hydrophobic catalyst carriers.
The content of the invention
The purpose of the present invention is intended to overcome deficiency of the prior art, there is provided a kind of styrene diethylene benzene copoly mer
The preparation method of hydrophobic catalyst carrier, prepare that particle diameter is big, pore structure is controllable, compression strength so as to provide a kind of suspension polymerization
The method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier high, hydrophobicity is excellent.
Present disclosure is：The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, its feature
It is that step is：
A, dispensing：By the mass parts of deionized water 100~200, the mass parts of organic matter 0.1~0.5, the matter of inorganic salts 0.1~0.5
Measure part, the mass parts of neopelex 0.01~0.06, the mass parts of styrene 2~10, the mass of divinylbenzene 2~13
Part, the mass parts of benzoyl peroxide 0.02~0.6, the mass parts of toluene 8~16, the mass parts of normal heptane 6~13 and dichloroethanes
The mass ratio of 5~12 mass parts takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be any of calcium phosphate, magnesium carbonate, sodium chloride and calcium hydroxy phosphate；
B, the crude product of styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts and 12
Sodium alkyl benzene sulfonate (abbreviation SDBS) be added to reaction vessel (such as：Three-necked flask) in, 25~40 DEG C are heated under stirring, is treated
After solids (whole) dissolving, then by the styrene mixed, divinylbenzene, benzoyl peroxide, toluene, normal heptane and two
The mixture of chloroethanes is added in reaction vessel, is heated to temperature as 70~90 DEG C, stirs lower progress suspension polymerization, instead
Between seasonable after 7~9h (to hardening, aging), filtering, solids is the crude product of styrene diethylene benzene copoly mer；
C, styrene diethylene benzene copoly mer hydrophobic catalyst carrier is prepared：Solids (the i.e. benzene that will be obtained after reaction
The crude product of ethene-divinyl benzene copolymer) sequentially washed with deionized water, absolute ethyl alcohol, to remove responseless benzene
The impurity such as ethene and divinylbenzene monomers and organic matter solubility dispersant；The acetone of 3~8 times of quality of solids quality is used again
After solids is extracted into 12~48h in apparatus,Soxhlet's (can industrially use the existing equipment with identical function effect),
Filtering, to remove the organic impurities such as toluene and normal heptane mixing pore-foaming agent and dichloroethanes, pore structure is formed, then by solids
Sequentially washed with methanol, deionized water, be fixed pore structure；Again by (the porous small ball shape after purification) solids it is dry,
Screening, that is, (white big particle diameter) styrene diethylene benzene copoly mer (abbreviation SDB) hydrophobic catalyst carrier is made.
In present disclosure：It is preferable to 1 for the dosage quality of organic matter described in step a and inorganic salts mass parts:
1。
In present disclosure：Styrene described in step a and the dosage mass ratio of divinylbenzene mass parts are preferable
It is 1:1.3
In present disclosure：The mass parts dosage preferably 0.1 of (initiator) benzoyl peroxide described in step a
~0.6 mass parts.
In present disclosure：Stirred described in step b it is lower carry out suspension polymerization be agitator speed for 10~
Suspension polymerization is carried out under conditions of 300rpm/min；Under conditions of preferably agitator speed is 85~125rpm/min
Carry out suspension polymerization.
In present disclosure：Temperature is heated to described in step b as 70~90 DEG C；Temperature is preferably heated to as 80
~85 DEG C.
In present disclosure：It is that solids is suitable that solids described in step c is sequentially washed with deionized water, absolute ethyl alcohol
Secondary to be washed 2~4 times with deionized water, absolute ethyl alcohol respectively, each washing is solids with deionized water, the quality of absolute ethyl alcohol
3~8 times of quality.
In present disclosure：It is that solids sequentially divides that solids described in step c is sequentially washed with methanol, deionized water
Do not washed 2~4 times with methanol, deionized water, each washing is with deionized water, 3 that the quality of absolute ethyl alcohol is solids quality
~8 times.
In present disclosure：Described in step c dry, sieve be by solids temperature be 50~60 DEG C, pressure be
12~36h is dried under conditions of 0.1MPa, then sieves and (crosses 2~5mm sieves), that is, white, 2~5mm of particle diameter φ big particle diameter is made
Styrene diethylene benzene copoly mer hydrophobic catalyst carrier；The ratio of the big particle diameter is up to 35%~40%.
In present disclosure：The each component raw material used can first carry out refinement treatment：The commercially available benzene second of purchase
Alkene carries out distillation and refined before the use, and step is as follows：1. 500mL styrene (abbreviation St) monomer is added to 1000mL's
In separatory funnel, washed three times with the 150mL5% NaOH aqueous solution；2. repeatedly washed with deionized water until neutrality (pH 7
~8), it is put into a little anhydrous MgSO4It is drying to liquid clarification；3. the styrene rectification under vacuum after above-mentioned drying, collect
Cut after distillation, it is standby.The still-process of divinylbenzene (abbreviation DVB) monomer is as styrene monomer.Benzoyl peroxide
Formyl (abbreviation BPO) uses chloroform as solvent, CH3OH makees precipitating reagent, handled using recrystallizing and refining etc..
Using the present invention, the specific surface area of obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier and hole
The relation for holding (i.e. pore structure) and DVB (divinylbenzene) dosage see the table below：
From in table, the specific surface area and pore volume of catalyst and DVB dosage are proportionate, average pore size is used with DVB
Measure negatively correlated；The increase of DVB concentration, it is easier to obtain smaller protomere, their tight agglomerations are grown up, and are more densely tied
Conjunction cause caused by space it is smaller, small hole number gradually increases, thus reduces the SDB beads average pore size that finally gives, than
Surface area and pore volume increase.SDB average pore size is distributed between 5.5~8.9nm in table, and PtCl6 2-Ionic radius rPt4+
(6) it is 0.063nm；Thus be advantageous to the Pt that the ligancy is 64+Into in duct, and it is easy subsequently through the Pt of reduction deposition
Reach several nano-scales.
Compared with prior art, the present invention has following features and beneficial effect：
(1) using the present invention, using styrene as monomer, divinylbenzene is comonomer, crosslinking agent, benzoyl peroxide
For initiator, toluene+normal heptane is mixing pore-foaming agent, and dichloroethanes is binding agent, and the grade of organic matter polyvinyl alcohol -1799 is high score
Sub- dispersant, neopelex are surfactant, dispersion aids, and inorganic salts are inorganic dispersant；The present invention utilizes
Inorganic salts and water-soluble polymer are made the collaboration that composite dispersing agent and anion surfactant are made between dispersion aids and made
With preparing big particle diameter (2~5mm of φ) porous SDB hydrophobic catalyst carriers of different cross-linked structures, big particle size content is up to 35%
~40%, that is, the big particle diameter of controlledly synthesis (2~5mm of φ) SDB hydrophobic catalyst carriers are advantageous to using composite dispersing agent, and have
There is the ability of expanding production；
(2) using the present invention, big particle diameter (2~5mm of φ) benzene second is prepared using suspension polymerisation (i.e. suspension crosslinking is copolymerized) method
Alkene-divinyl benzene copolymer hydrophobic catalyst carrier；Suspension polymerisation be prepare styrene-divinylbenzene bead have efficacious prescriptions
Method.Monomer and pore-foaming agent are mixed into uniform oil phase, initiator is added in oil phase, makes its dissolving, finally oil phase is added
Into the aqueous phase for having dissolved composite dispersing agent.Stir and composite dispersing agent effect under, drop by constantly disperse and combine,
So as to obtain relatively more uniform bead.During the course of the reaction, constantly it is cross-linked with each other between strand, ultimately forms three-dimensional space
Between network structure copolymer, the cross-linked copolymer strand can not dissolve in oil phase, progressively separate out, be separated.This
When, polymer is solid phase, and unreacted monomer and mixing pore-foaming agent are liquid phase.After reaction terminates, sphere polymers are obtained.Due to
Mixing pore-foaming agent is remained among spheroid, when the method washed or extracted with solvent removes pore-foaming agent, will be formed and is mutually communicated
Hole, make polymer that there is larger specific surface area and pore volume.
(3) suspension polymerization that the present invention uses, there is the characteristics of simple and easy to do, in particular by composite dispersing agent and ten
Dialkyl benzene sulfonic acids sodium has more preferable dispersion effect than single dispersant, readily available big particle diameter SDB, realizes to carrier
Specific surface area, aperture, the controlledly synthesis such as compression strength；From in infrared spectrum, substantial amounts of suspended double bond is contained in carrier,
The suspended double bond has weight to the performances of SDB hydrophobic catalyst carriers, and the catalytic activity of Pt/SDB catalyst and stability
The influence wanted；
(4) existed using the present invention, the specific surface area of obtained styrene diethylene benzene copoly mer hydrophobic catalyst carrier
300~500m2/ g, 2~10nm of aperture, contact angle are more than 350 DEG C, bead more than 100 °, 10~30N/ of compression strength grains, heatproof
2~5mm of diameter；The Pt/SDB hydrophobic catalysts prepared using styrene diethylene benzene copoly mer produced by the present invention as carrier,
The advantages that with reducing the resistance to mass tranfer of bed, preventing liquid flooding, and improve fluid communication efficiency, for heavy water detritiation, waste water
The engineering application such as detritiation, high catalytic efficiency, hydrophobic stability are excellent, can normal temperature use, using effect is good；
(5) product preparation process of the present invention is simple, and process is easy, and easily operation, practical.
Brief description of the drawings
The FT-IR spectrums that Fig. 1 is SDB (styrene diethylene benzene copoly mer) under different DVB (divinylbenzene) dosage
Figure；As seen from the figure, 1640cm-1The absworption peak at place corresponds to the stretching vibration of C=C keys, 989cm-1The absworption peak at place correspond to=
The out-of-plane deformation vibration of C-H keys, and do not have the two characteristic peaks in pure PS and occur, and with the increasing of DVB and St mol ratios
Greatly, the intensity of absworption peak is remarkably reinforced.Illustrate that divinylbenzene does not have full entry polymerisation, cause part unreacted outstanding
Hang double bond left behind, suspended double bond reserved is proportionate with DVB dosages；
Fig. 2 is SDB (styrene diethylene benzene copoly mer) room temperatures under different DVB (divinylbenzene) dosage to 800 DEG C
Thermogravimetric (TG) curve；As seen from the figure, all samples equal massless loss before 300 DEG C；Pure PS occurs bright since 300 DEG C
Aobvious weightlessness, i.e. its molecular backbone start to decompose fracture；As DVB dosages increase, SDB thermostabilization gradually rises, DVB with
St mol ratios are 1:5~1:When 1, SDB is before 345~375 DEG C almost without weightlessness；Show that DVB dosages increase, put forward the degree of cross linking
Height, the initial decomposition temperature of sample improve, and SDB heat resistance has obtained different degrees of improvement；
Fig. 3 is influence of DVB (divinylbenzene) dosages to SDB (styrene diethylene benzene copoly mer) compression strength
Curve；Each sample chooses 50 SDB beads and carries out intensity test respectively, takes its average value as final pressure resistance
Degree, is as a result shown in Fig. 3；From the figure 3, it may be seen that with the increase of DVB dosages, compression strength also increases therewith, illustrates SDB molecular structures
It is middle to be crosslinked increase of counting out, the rigidity reinforced of bead；As n (DVB):N (St)=1:When 1, compression strength reaches 27N/ grains, shows it
Mechanical mechanics property is excellent；The impact of excellent, the resistance to deuterium-oxide of SDB mechanical mechanics properties of this experiment synthesis, have preferably stable
Property；
Fig. 4 (a) and Fig. 4 (b) are respectively the SDB carrier photos before and after supporting Pt, Fig. 4 (c) and Fig. 4 (d) under the conditions of 200 DEG C
SDB soaks the scattered photo after 30d in water respectively before and after supporting Pt；
As the SDB carriers shown in Fig. 4 (a) and Fig. 4 (b), photo is understood before and after supporting Pt under the conditions of 200 DEG C, after load
SDB color is changed into grey black from white, and it is relevant that this is due to that Pt is supported on carrier surface；After Pt Metal Supporteds, due to SDB's
Mechanical mechanics property is excellent, and in loading process, its shape does not change；Fig. 4 (c) and Fig. 4 (d) is SDB before and after load in water
Scattered photo after middle immersion 30d, it is found that all big particle diameter SDB and Pt/SDB with good hydrophobicity due to floating
Float on the surface, do not there is sinking, after illustrating load, SDB still has excellent hydrophobicity, the hydrophobic catalyst that can be reacted as LPCE
Agent.
Embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention
It is whole, still fall within protection scope of the present invention.
Embodiment 1：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
200g deionized waters, 0.5g polyvinyl alcohol -1799,0.5g calcium phosphate, the 12 of 0.06g are added in three-necked flask
Sodium alkyl benzene sulfonate, uniform aqueous phase is made into, stirs, be heated to 30 DEG C, after all dissolving, then the 10gSt that will have been mixed
(i.e. styrene), 13gDVB (i.e. divinylbenzene), 0.2gBPO (i.e. benzoyl peroxide), 15.8g toluene, 12.4g normal heptanes
And 11.6g dichloroethanes is added in there-necked flask, rotating speed needed for adjustment is 100rpm/min, is heated to 85 DEG C, stirs lower carry out
Suspension polymerization, after reaction time 8h, filtering, solids is the crude product of styrene diethylene benzene copoly mer；Will be solid
Body thing is sequentially washed with deionized water, absolute ethyl alcohol, then with the acetone of 5 times of quality of solids quality by solids in surname extraction
In device extract 30h after, filtering, then solids sequentially wash with methanol, deionized water, then by solids drying, sieve, i.e.,
Styrene diethylene benzene copoly mer hydrophobic catalyst carrier is made.
Utilize the chemical composition by determination of infrared spectroscopy SDB hydrophobic catalyst carriers, its infrared spectrum such as Fig. 1 institutes
Show.As seen from the figure, divinylbenzene does not have full entry polymerisation, causes the unreacted suspended double bond in part left behind,
Suspended double bond reserved is proportionate with DVB dosages.
Embodiment 2：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
200g deionized waters, 0.35g polyvinyl alcohol -2099,0.5g calcium phosphate, the ten of 0.06g are added in three-necked flask
Dialkyl benzene sulfonic acids sodium, uniform aqueous phase is made into, stirs, be heated to 30 DEG C, after all dissolving, then will mixed
10gSt, 13gDVB, 0.2gBPO, 15.8g toluene, 12.4g normal heptanes and 11.6g dichloroethanes are added in there-necked flask, adjustment
Required rotating speed is 100rpm/min, is heated to 85 DEG C, progress suspension polymerization under stirring, after reaction time 7h, filtering, and solid
Thing is the crude product of styrene diethylene benzene copoly mer；Solids is sequentially washed with deionized water, absolute ethyl alcohol, then
After solids to extract in apparatus,Soxhlet's to 48h with the acetone of 3 times of quality of solids quality, filtering, it is then that solids is suitable
It is secondary to be washed with methanol, deionized water, then by solids is dry, screening, that is, it is made that styrene diethylene benzene copoly mer is hydrophobic to urge
Agent carrier.
From Fig. 2 thermogravimetric curves, all samples equal massless loss before 300 DEG C.Pure PS occurs since 300 DEG C
Obvious weightless, i.e., its molecular backbone starts to decompose fracture.Show that DVB dosages increase, improve the degree of cross linking, the starting point of sample
Solve temperature to improve, SDB heat resistance has obtained different degrees of improvement.From the figure 3, it may be seen that with the increase of DVB dosages, resistance to compression
Intensity also increases therewith, illustrates to be crosslinked increase of counting out, the rigidity reinforced of bead in SDB molecular structures.As n (DVB):n(St)
=1:When 1, compression strength reaches 27N/ grains, shows that its mechanical mechanics property is excellent.As shown in Table 1, the specific surface area of catalyst and
Pore volume and DVB dosage are proportionate, and average pore size and DVB dosages are negatively correlated.The increase of DVB concentration, it is easier to obtain more
Small protomere, their tight agglomerations are grown up, and more densely the space with reference to caused by causing is smaller, and small hole number gradually increases
It is more, thus the SDB beads average pore size for making to finally give reduces, specific surface area and pore volume increase.Can by Fig. 4 (a) and Fig. 4 (b)
Know, SDB color is changed into grey black from white after load, and it is relevant that this is due to that Pt is supported on carrier surface.Fig. 4 (c) and Fig. 4
(d) understand, all big particle diameter SDB and Pt/SDB do not have sinking, explanation due to being swum in good hydrophobicity on the water surface
After load, SDB still has excellent hydrophobicity, the hydrophobic catalyst that can be reacted as LPCE.
Embodiment 3：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
The addition 200g deionized waters in three-necked flask, 0.2g polyvinyl alcohol -2499,0.5g calcium phosphate, the 12 of 0.06g
Sodium alkyl benzene sulfonate, be made into uniform aqueous phase, stir, be heated to 30 DEG C, after all dissolve after, then by the 10gSt mixed,
13gDVB, 0.2gBPO, 15.8g toluene, 12.4g normal heptanes and 11.6g dichloroethanes are added in there-necked flask, are turned needed for adjustment
Speed is 100rpm/min, is heated to 85 DEG C, progress suspension polymerization under stirring, and after reaction time 9h, is filtered, solids is
The crude product of styrene diethylene benzene copoly mer；Solids is sequentially washed with deionized water, absolute ethyl alcohol, then uses solid
The acetone of 8 times of quality of amount of substance solids extracts in apparatus,Soxhlet's to 12h after, filtering, solids is sequentially then used into first
Alcohol, deionized water washing, then solids drying, screening, i.e., obtained styrene diethylene benzene copoly mer hydrophobic catalyst are carried
Body.
Embodiment 4：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
The addition 200g deionized waters in three-necked flask, 0.1g polyvinyl alcohol -2699,0.5g calcium phosphate, the 12 of 0.06g
Sodium alkyl benzene sulfonate, be made into uniform aqueous phase, stir, be heated to 30 DEG C, after all dissolve after, then by the 10gSt mixed,
13gDVB, 0.2gBPO, 15.8g toluene, 12.4g normal heptanes and 11.6g dichloroethanes are added in there-necked flask, are turned needed for adjustment
Speed is 100rpm/min, is heated to 85 DEG C, progress suspension polymerization under stirring, and after reaction time 8h, is filtered, solids is
The crude product of styrene diethylene benzene copoly mer；Solids is sequentially washed with deionized water, absolute ethyl alcohol, then uses solid
The acetone of 6 times of quality of amount of substance solids extracts in apparatus,Soxhlet's to 40h after, filtering, solids is sequentially then used into first
Alcohol, deionized water washing, then solids drying, screening, i.e., obtained styrene diethylene benzene copoly mer hydrophobic catalyst are carried
Body.
Embodiment 5~7：
Organic matter is hydroxyethyl cellulose, gelatin, sodium carboxymethylcellulose respectively, each species respectively corresponding to dosage be
0.5g、0.2g、0.1g；Inorganic salts are magnesium carbonate, sodium chloride, calcium hydroxy phosphate respectively, and dosage is 0.5g；Other component raw materials
And dosage, reaction condition are same as Example 1, omit.
Embodiment 8~13：
Mixing speed be respectively 10rpm/min, 50rpm/min, 85rpm/min, 125rpm/min, 165rpm/min,
300rpm/min；It is other same as Example 1, omit.
Embodiment 14~17：
Initiator B PO (i.e. benzoyl peroxide) dosage is respectively 0.1g, 0.16g, 0.2g, 0.6g；Other component raw materials
And dosage, reaction condition are same as Example 1, omit.
Embodiment 18~20：
It is respectively 70~75 DEG C, 75~80 DEG C, 85~90 DEG C to be heated to suspension polymerization temperature；It is other and embodiment
1 is identical, omits.
Embodiment 21~24：
Divinylbenzene dosage is respectively 10.4g, 7.8g, 5.2g, 2.6g；Other component raw materials and dosage, reaction condition
It is same as Example 1, omit.
Embodiment 25：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
A, dispensing：By the mass parts of deionized water 150, the mass parts of organic matter 0.3, the mass parts of inorganic salts 0.3, detergent alkylate
The mass parts of sodium sulfonate 0.03, the mass parts of styrene 6, divinylbenzene 7.8, the mass parts of benzoyl peroxide 0.3, the mass of toluene 12
The mass ratio of part, the mass parts of normal heptane 9 and the mass parts of dichloroethanes 8 takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be any of calcium phosphate, magnesium carbonate, sodium chloride and calcium hydroxy phosphate；
B, the crude product of styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts and 12
Sodium alkyl benzene sulfonate (abbreviation SDBS) be added to reaction vessel (such as：Three-necked flask) in, 32 DEG C are heated under stirring, treats solid
After thing (whole) dissolving, then by the styrene mixed, divinylbenzene, benzoyl peroxide, toluene, normal heptane and two chloroethenes
The mixture of alkane is added in reaction vessel, is heated to temperature as 80 DEG C, stirs lower progress suspension polymerization, reaction time 8h
Afterwards (to hardening, aging), filtering, solids is the crude product of styrene diethylene benzene copoly mer；
C, styrene diethylene benzene copoly mer hydrophobic catalyst carrier is prepared：Solids (the i.e. benzene that will be obtained after reaction
The crude product of ethene-divinyl benzene copolymer) sequentially washed with deionized water, absolute ethyl alcohol, to remove responseless benzene
The impurity such as ethene and divinylbenzene monomers and organic matter solubility dispersant；Use the acetone of 6 times of quality of solids quality will again
Solids is after apparatus,Soxhlet's (can industrially use the existing equipment with identical function effect) middle extracting 30h, filtering, with
The organic impurities such as toluene and normal heptane mixing pore-foaming agent and dichloroethanes is removed, pore structure is formed, then sequentially uses solids
Methanol, deionized water washing, are fixed pore structure；Again by (the porous small ball shape after purification) solids is dry, screening, i.e.,
(white) styrene diethylene benzene copoly mer (abbreviation SDB) hydrophobic catalyst carrier is made.
Embodiment 26：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
A, dispensing：By the mass parts of deionized water 100, the mass parts of organic matter 0.1, the mass parts of inorganic salts 0.1, detergent alkylate
The mass parts of sodium sulfonate 0.01, the mass parts of styrene 2,2.6 parts of divinylbenzene, the mass parts of benzoyl peroxide 0.02, the matter of toluene 8
The mass ratio of amount part, the mass parts of normal heptane 6 and the mass parts of dichloroethanes 5 takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be any of calcium phosphate, magnesium carbonate, sodium chloride and calcium hydroxy phosphate；
B, the crude product of styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts and 12
Sodium alkyl benzene sulfonate (abbreviation SDBS) be added to reaction vessel (such as：Three-necked flask) in, 25 DEG C are heated under stirring, treats solid
After thing (whole) dissolving, then by the styrene mixed, divinylbenzene, benzoyl peroxide, toluene, normal heptane and two chloroethenes
The mixture of alkane is added in reaction vessel, is heated to temperature as 70 DEG C, stirs lower progress suspension polymerization, reaction time 9h
Afterwards (to hardening, aging), filtering, solids is the crude product of styrene diethylene benzene copoly mer；
C, styrene diethylene benzene copoly mer hydrophobic catalyst carrier is prepared：Solids (the i.e. benzene that will be obtained after reaction
The crude product of ethene-divinyl benzene copolymer) sequentially washed with deionized water, absolute ethyl alcohol, to remove responseless benzene
The impurity such as ethene and divinylbenzene monomers and organic matter solubility dispersant；Use the acetone of 3 times of quality of solids quality will again
Solids is after apparatus,Soxhlet's (can industrially use the existing equipment with identical function effect) middle extracting 48h, filtering, with
The organic impurities such as toluene and normal heptane mixing pore-foaming agent and dichloroethanes is removed, pore structure is formed, then sequentially uses solids
Methanol, deionized water washing, are fixed pore structure；Again by (the porous small ball shape after purification) solids is dry, screening, i.e.,
(white) styrene diethylene benzene copoly mer (abbreviation SDB) hydrophobic catalyst carrier is made.
Embodiment 27：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
A, dispensing：By the mass parts of deionized water 200, the mass parts of organic matter 0.5, the mass parts of inorganic salts 0.5, detergent alkylate
The mass parts of sodium sulfonate 0.06, the mass parts of styrene 10, the amount part of divinylbenzene 13, the mass parts of benzoyl peroxide 0.6, toluene 16
The mass ratio of mass parts, the mass parts of normal heptane 13 and the mass parts of dichloroethanes 12 takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be any of calcium phosphate, magnesium carbonate, sodium chloride and calcium hydroxy phosphate；
B, the crude product of styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts and 12
Sodium alkyl benzene sulfonate (abbreviation SDBS) be added to reaction vessel (such as：Three-necked flask) in, 40 DEG C are heated under stirring, treats solid
After thing (whole) dissolving, then by the styrene mixed, divinylbenzene, benzoyl peroxide, toluene, normal heptane and two chloroethenes
The mixture of alkane is added in reaction vessel, is heated to temperature as 90 DEG C, stirs lower progress suspension polymerization, reaction time 7h
Afterwards (to hardening, aging), filtering, solids is the crude product of styrene diethylene benzene copoly mer；
C, styrene diethylene benzene copoly mer hydrophobic catalyst carrier is prepared：Solids (the i.e. benzene that will be obtained after reaction
The crude product of ethene-divinyl benzene copolymer) sequentially washed with deionized water, absolute ethyl alcohol, to remove responseless benzene
The impurity such as ethene and divinylbenzene monomers and organic matter solubility dispersant；Use the acetone of 8 times of quality of solids quality will again
After solids extracts 12h in apparatus,Soxhlet's (can industrially use the existing equipment with identical function effect), filtering, with
The organic impurities such as toluene and normal heptane mixing pore-foaming agent and dichloroethanes is removed, pore structure is formed, then sequentially uses solids
Methanol, deionized water washing, are fixed pore structure；Again by (the porous small ball shape after purification) solids is dry, screening, i.e.,
(white) styrene diethylene benzene copoly mer (abbreviation SDB) hydrophobic catalyst carrier is made.
Embodiment 28~34：
The preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier, step are：
A, dispensing：By the mass parts of deionized water 100~200, the mass parts of organic matter 0.1~0.5, the matter of inorganic salts 0.1~0.5
Measure part, the mass parts of neopelex 0.01~0.06, the mass parts of styrene 2~10, the mass of divinylbenzene 2~13
Part, the mass parts of benzoyl peroxide 0.02~0.6, the mass parts of toluene 8~16, the mass parts of normal heptane 6~13 and dichloroethanes
The mass ratio of 5~12 mass parts takes each component raw material；
The organic matter can be polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -
2699th, any of hydroxyethyl cellulose, gelatin and sodium carboxymethylcellulose；
The inorganic salts can be any of calcium phosphate, magnesium carbonate, sodium chloride and calcium hydroxy phosphate；
The specific mass parts dosage of each component raw material see the table below in each embodiment：
B, the crude product of styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts and 12
Sodium alkyl benzene sulfonate (abbreviation SDBS) be added to reaction vessel (such as：Three-necked flask) in, 25~40 DEG C are heated under stirring, is treated
After solids (whole) dissolving, then by the styrene mixed, divinylbenzene, benzoyl peroxide, toluene, normal heptane and two
The mixture of chloroethanes is added in reaction vessel, is heated to temperature as 70~90 DEG C, stirs lower progress suspension polymerization, instead
Between seasonable after 7~9h (to hardening, aging), filtering, solids is the crude product of styrene diethylene benzene copoly mer；
C, styrene diethylene benzene copoly mer hydrophobic catalyst carrier is prepared：Solids (the i.e. benzene that will be obtained after reaction
The crude product of ethene-divinyl benzene copolymer) sequentially washed with deionized water, absolute ethyl alcohol, to remove responseless benzene
The impurity such as ethene and divinylbenzene monomers and organic matter solubility dispersant；The acetone of 3~8 times of quality of solids quality is used again
By solids apparatus,Soxhlet's (industrially can use it is existing with identical function effect equipment) in extracting 12~48h after,
Filtering, to remove the organic impurities such as toluene and normal heptane mixing pore-foaming agent and dichloroethanes, pore structure is formed, then by solids
Sequentially washed with methanol, deionized water, be fixed pore structure；Again by (the porous small ball shape after purification) solids it is dry,
Screening, that is, (white) styrene diethylene benzene copoly mer (abbreviation SDB) hydrophobic catalyst carrier is made.
In above-described embodiment 25~34：It is that agitator speed is 10 that the lower suspension polymerization that carries out is stirred described in step b
Suspension polymerization is carried out under conditions of~300rpm/min, preferable agitator speed is 85~125rpm/min, best
Agitator speed is 100rpm/min.
In above-described embodiment 28~34：Temperature is heated to described in step b and preferably replaces with heating for 70~90 DEG C
It it is 80~85 DEG C to temperature.
In above-described embodiment：It is that solids is suitable that the solids is sequentially washed with deionized water, absolute ethyl alcohol (in step c)
Secondary to be washed 2~4 times with deionized water, absolute ethyl alcohol respectively, each washing is solids with deionized water, the quality of absolute ethyl alcohol
3~8 times of quality.
In above-described embodiment：It is that solids sequentially divides that the solids is sequentially washed with methanol, deionized water (in step c)
Do not washed 2~4 times with methanol, deionized water, each washing is with deionized water, 3 that the quality of absolute ethyl alcohol is solids quality
~8 times.
In above-described embodiment：The drying (in step c), screening be by solids temperature be 50~60 DEG C, pressure be
12~36h is dried under conditions of 0.1MPa, then sieves and (crosses 2~5mm sieves), that is, white, 2~5mm of particle diameter φ big particle diameter is made
Styrene diethylene benzene copoly mer hydrophobic catalyst carrier.The ratio of the big particle diameter is up to 35%~40%.
In above-described embodiment：The each component raw material used can first carry out refinement treatment：The commercial styrene of purchase
It is refined that distillation is carried out before the use, and step is as follows：1. 500mL styrene (abbreviation St) monomer is added to 1000mL point
In liquid funnel, washed three times with the 150mL5% NaOH aqueous solution；2. repeatedly washed with deionized water until neutral (pH is 7~
8), it is put into a little anhydrous MgSO4It is drying to liquid clarification；3. the styrene rectification under vacuum after above-mentioned drying, collect and steam
Cut after evaporating, it is standby.The still-process of divinylbenzene (abbreviation DVB) monomer is as styrene monomer.Benzoyl peroxide first
Acyl (abbreviation BPO) uses chloroform as solvent, CH3OH makees precipitating reagent, handled using recrystallizing and refining etc..
In above-described embodiment：Used each raw material is commercially available prod.
In above-described embodiment：It is especially not dated in used percentage, be quality (weight) percentage or
Well known to a person skilled in the art percentage；Described quality (weight) part can be gram.
In above-described embodiment：Technological parameter (temperature, time etc.) and each component numerical quantity in each step etc. are scope
, any point is applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment are compared with technology.
It can implement the invention is not restricted to above-described embodiment, described in present invention and there is the good result.
Claims (5)
1. the preparation method of the styrene diethylene benzene copoly mer hydrophobic catalyst carrier for Pt Metal Supporteds, its feature
It is that step is：
A, dispensing：By the mass parts of deionized water 100~200, the mass parts of organic matter 0.1~0.5, the mass of inorganic salts 0.1~0.5
Part, the mass parts of neopelex 0.01~0.06, the mass parts of styrene 2~10, the mass parts of divinylbenzene 2~13,
The mass parts of benzoyl peroxide 0.1~0.6, the mass parts of toluene 8~16, the mass parts of normal heptane 6~13 and dichloroethanes 5~
The mass ratio of 12 mass parts takes each component raw material；
The organic matter is polyvinyl alcohol -1799, polyvinyl alcohol -2099, polyvinyl alcohol -2499, polyvinyl alcohol -2699, hydroxyl second
Any of base cellulose and sodium carboxymethylcellulose；
The inorganic salts are any of calcium phosphate, magnesium carbonate, sodium chloride and calcium hydroxy phosphate；
The organic matter and the dosage mass ratio of inorganic salts mass parts are 1:1；
The styrene and the dosage mass ratio of divinylbenzene mass parts are 1:1.3；
B, the crude product of styrene diethylene benzene copoly mer is prepared：By deionized water, organic matter, inorganic salts and dodecyl
Benzene sulfonic acid sodium salt is added in reaction vessel, and temperature is heated under stirring as 25~40 DEG C, then by the styrene mixed, divinyl
Base benzene, benzoyl peroxide, toluene, the mixture of normal heptane and dichloroethanes are added in reaction vessel, and being heated to temperature is
70~90 DEG C, stir and carry out suspension polymerization down, after 7~9h of reaction time, filtering, solids is stryrene divinyl
The crude product of base benzene copolymer；
It is that the suspension polymerisation carried out under the conditions of agitator speed is 10~300rpm is anti-that suspension polymerization is carried out under the stirring
Should；
C, styrene diethylene benzene copoly mer hydrophobic catalyst carrier is prepared：The solids obtained after reaction is sequentially spent
Ionized water, absolute ethyl alcohol washing, then extracted in apparatus,Soxhlet's solids with the acetone of 3~8 times of quality of solids quality
After 12~48h, filtering, then solids sequentially wash with methanol, deionized water, then by solids it is dry, sieve, i.e., it is obtained
2~5mm of particle diameter φ big particle diameter styrene diethylene benzene copoly mer hydrophobic catalyst carrier.
2. the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier as described in claim 1, its feature
It is：The lower suspension polymerization that carries out is stirred described in step b to be suspended under conditions of agitator speed is 85~125rpm
Polymerisation.
3. the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier as described in claim 1, its feature
It is：It is heated to temperature described in step b and is 70~90 DEG C replacing with that to be heated to temperature be 80~85 DEG C.
4. the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier as described in claim 1, its feature
It is：It is that solids sequentially uses deionized water, nothing respectively that solids described in step c is sequentially washed with deionized water, absolute ethyl alcohol
Water-ethanol washs 2~4 times, and each washing is with deionized water, 3~8 times that the quality of absolute ethyl alcohol is solids quality.
5. the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier as described in claim 1, its feature
It is：Drying, sieving described in step c is that solids is dried into 12 under conditions of temperature is 50~60 DEG C, pressure is 0.1MPa
~36h, then sieve.
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| CN107973872B (en) * | 2017-12-11 | 2020-12-22 | 西南科技大学 | Preparation method of nano ferroferric oxide doped styrene-divinylbenzene copolymer hydrophobic catalyst carrier |
| CN107973873B (en) * | 2017-12-11 | 2020-06-19 | 西南科技大学 | Preparation method of super-hydrophobic high-compression-resistance styrene-divinylbenzene copolymer catalyst carrier |
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| CN113019464B (en) * | 2021-03-11 | 2022-12-13 | 哈尔滨工程大学 | Preparation method of spherical SDB hydrophobic carrier with controllable size and Pt/SDB hydrophobic catalyst |
| CN113234187A (en) * | 2021-05-17 | 2021-08-10 | 西南科技大学 | Preparation method of nano-silica hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier material |
| CN115888820A (en) * | 2022-11-10 | 2023-04-04 | 广州启轩新材料科技有限公司 | Method for preparing Pt/SDB hydrophobic catalyst by sodium borohydride reduction |
| CN115672409A (en) * | 2022-11-10 | 2023-02-03 | 广州启轩新材料科技有限公司 | Method for preparing Pt/SDB hydrophobic catalyst by hydrazine hydrate reduction |
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