CN102350321B - Resin ball capable of selectively adsorbing aromatic hydrocarbon component of hydrocarbon mixture, and preparation method thereof - Google Patents
Resin ball capable of selectively adsorbing aromatic hydrocarbon component of hydrocarbon mixture, and preparation method thereof Download PDFInfo
- Publication number
- CN102350321B CN102350321B CN 201110204328 CN201110204328A CN102350321B CN 102350321 B CN102350321 B CN 102350321B CN 201110204328 CN201110204328 CN 201110204328 CN 201110204328 A CN201110204328 A CN 201110204328A CN 102350321 B CN102350321 B CN 102350321B
- Authority
- CN
- China
- Prior art keywords
- synthetic
- resin ball
- resin balls
- resin
- reaction
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of adsorption and separation, and specifically, relates to a resin ball capable of preferential adsorption of an aromatic hydrocarbon component of a hydrocarbon mixture, and a preparation method thereof. The resin ball is a styrene resin ball which has a certain crosslinking degree and is subjected to copolymerization modification by polar monomers. Through the difference of swelling adsorption capacities of the resin ball on aromatic hydrocarbons and non-aromatic hydrocarbons, an aromatic hydrocarbon component of a hydrocarbon mixture can be adsorbed conveniently by the resin ball so that an aromatic hydrocarbon component separation effect is realized. The resin ball is a random copolymer, wherein styrene is utilized as a main monomer, and various polar monomers and different cross-linking agents are utilized to modify styrene. The resin ball is prepared from easily available raw materials, is easy for synthesis, can be recycled, is convenient for operation and aftertreatment, simplifies a process flow, and reduces an operation cost and energy consumption. In application, through a gradient centrifugation method, the resin ball provides a novel and simple approach for high-efficiency separation of aromatic hydrocarbons and non-aromatic hydrocarbons.
Description
Technical field
The invention belongs to the adsorption separation technology field, be specifically related to resin balls of aromatic component in a kind of alternative adsorbs hydrocarbons mixture and preparation method thereof.
Background technology
In recent years, the oil product development is swift and violent, and its application constantly enlarges, and product variety continues to increase.Based on the enhancing of health of people consciousness, the quality index of various oil products also is improved.Simultaneously, along with the development of petrochemical industry and textile industry, the demand of aromatic hydrocarbon product also constantly increases.Preparation low arene content, high-octane high-quality gasoline, solvent naphtha is used in the eco-friendly edible oil extraction of extremely low aromatic hydrocarbons and sulfur content, and the hydrocarbon products of producing high arene content becomes the matter of utmost importance that petroleum industrial circle faces.
At present, the main source of aromatic hydrocarbons is catalytic reforming gasoline or hydrogenated pyrolysis gasoline, and the method for aromatics separation is mainly liquid liquid extraction process and extractive distillation method from this kind hydrocarbon mixture.
Liquid liquid extraction process is the method for utilizing solvent that the difference of each components dissolved degree of hydro carbons is separated aromatic hydrocarbons with non-aromatics.Solvent is to the solvability of aromatic hydrocarbons and selectively higher, and separating effect is better.This method can obtain with higher yield highly purified BTX product (benzene,toluene,xylene).It is 30～70% raw material that existing liquid liquid extraction process is suitable for processing the aromatic hydrocarbons mass content, when arene content is higher than this scope, then needs convert with non-aromatics is mixed first, so just so that energy consumption increases the unit efficiency reduction.
The extractive distillation method is the method for utilizing solvent that the difference of each component relative volatility impact of hydro carbons is separated with non-aromatics aromatic hydrocarbons.Compare with liquid liquid extraction process, this method has flow process and easy and simple to handle, and equipment investment is low, low power consumption and other advantages, can be used for processing the raw material of high arene content, be suitable for reclaiming single aromatic hydrocarbon product from narrow fraction oil, its shortcoming is to be difficult to obtain simultaneously highly purified BTX product.
Two kinds of techniques have his own strong points, and have certain complementarity.
At present, being used for solvent that aromatic hydrocarbons separates has six kinds of sulfolane, tetraethylene glycol, triethylene glycol, dimethyl sulfoxide (DMSO), N-formyl-morpholine and 1-METHYLPYRROLIDONEs, and front four kinds are usually used in liquid liquid extraction process, and rear two kinds are usually used in extractive distillation technique.Realized that in the world industrialized Aromatic Extraction Process has Udex method, Sulfolane method, IFP method, Arosolvan method and Formex method Lung biopsy, first three kind belongs to liquid liquid extraction process, and rear two kinds belong to extractive distillation technique.Wherein, the Sulfolane method take sulfolane as solvent with its solvability by force, selectively good, separate easily, few, the nontoxic cheapness of solvent loss, and technology maturation is reliable, installs stablely, is widely adopted in the world.At home, the advantage such as ripe by the liquid liquid extraction technique of petrochemical industry academy of sciences research and development, it is high to have the benzene,toluene,xylene product purity, and solvent consumption is few, most widely used.But the method need to be washed processing for reclaiming sulfolane, consumes a large amount of water and energy, produces thus a large amount of waste water, and production cost is increased.
At solvent naphtha and edible oil manufacture field, take off the aromatic hydrocarbons technology and mainly contain hydrogenation method, adsorption method of separation, sulfonation method and extraction fractional distillation.Hydrogenation method is under catalyst action, and unsaturated hydrocarbons is converted into the method for saturated hydrocarbons, and it is effective that this method is taken off aromatic hydrocarbons, but only be suitable for having the occasion of sufficient hydrogen source, and be difficult to make aromatic hydrocarbons particularly heavy aromatics content drop to 100,000/below.Sulfonation method is to make aromatic hydrocarbons and sulfuric acid, oleum or sulfur trioxide reaction be converted into sulfonic acid, and the method for further separating is again used this method gained liquid waste processing difficulty, and acid sludge is difficult to effective utilization, and the loss of the solvent naphtha of the especially high arene content of solvent naphtha is larger.Extraction fractional distillation is only limited to the 6# removing aromatic hydrocarbons by using solvent naphtha at present.Absorption method is that these adsorbent adsorbances are less, can not be used for the higher solvent naphtha of arene content with the method for polar adsorbent (such as silica gel, zeolite, aluminium oxide etc.) aromatics separation and non-aromatics.
Defective based on prior art, we invented a kind of novel can swelling adsorbs hydrocarbons mixture in the resin balls of aromatic component, use this kind resin balls, adopt the gradient separations method, for efficiently aromatics separation and non-aromatics provide a new easier approach.
Summary of the invention
The invention provides a kind of can swelling adsorbs hydrocarbons mixture in the resin balls of aromatic component, this resin balls adds in addition various polar monomers and crosslinking agent it is carried out modification take styrene (St) as main monomer.Based on aromatic hydrocarbons and the non-aromatics swelling ability different to resin balls, resin balls has higher adsorptive selectivity to aromatic component.
Of the present invention can swelling adsorbs hydrocarbons mixture in the resin balls of aromatic component be random copolymer, formed by styrene monomer, polar monomer and crosslinking agent, wherein the mol ratio of styrene monomer and polar monomer is 100: 2～50, the total amount of styrene monomer and polar monomer and the mol ratio of crosslinking agent are 100: 1～30, and the particle diameter of resin balls is in 0.45～2mm scope.
Such resin balls contains a plurality of phenyl ring take styrene as main monomer, has strengthened significantly its adsorption capacity to aromatic hydrocarbons; When certain degree of cross linking makes resin balls obtain than the high swelling property energy, also keeping stability, such as heat endurance, solvent resistance etc.; Introduce polar monomer, when increasing resin balls polarity, reduced the swelling adsorption capacity of resin balls to non-aromatics, improved the adsorptive selectivity of resin balls to aromatic component.
Polar monomer used in the technique scheme has acrylic ester monomer, such as ethyl acrylate, butyl acrylate, the first class ethyl acrylate, acrylonitrile etc., and the acrylic ester monomer that contains sulfuryl, such as 4-hydroxyl-4 '-first class acryloxy diphenyl sulphone (DPS) (SDPMA), 4-hydroxyl-4 '-acryloxy diphenyl sulphone (DPS) (SDPA), 4-methacryloxy-4 '-acetoxyl group diphenyl sulphone (DPS) (SDPMAEA), 4-acryloxy-4 '-acetoxyl group diphenyl sulphone (DPS)s (SDPAEA) etc. can select one or more polar monomers and styrene to carry out modification by copolymerization during polymerization; The structural formula of acrylic ester monomer that wherein contains sulfuryl is as follows:
R
1For-H or-CH
3
R
2For-H or-COCH
3
Used crosslinking agent has nonpolar crosslinking agent such as divinylbenzene (DVB), and the polarity crosslinking agent is such as 4,4 '-dimethyl allene acyloxy diphenyl sulphone (DPS) (SDPDMA), 4,4 '-two propylene acyloxy diphenyl sulphone (DPS)s (SDPDA) etc. can select one or more crosslinking agents to carry out cross-linking modified to resin balls during polymerization.The structural formula of its Semi-polarity crosslinking agent is as follows:
R
3For-H or-CH
3
Compare with existing solvent segregation, Adsorption Phase of the present invention changes solid into, does not have the problems such as the stripping loss of usual vehicle partition method and recovery, more is conducive to the simplification of flow process, and then improves separating technology, improves and separates benefit.Easy and simple to handle when using this kind resin balls handle hydrocarbon mixture, only need make hydrocarbon mixture to be separated at a certain temperature slowly by a series of pillars that resin balls is housed, after multiple adsorb, get final product to get the extremely low efflux of arene content, and used resin balls reusable edible after taking off the aromatic hydrocarbons processing, this is just so that cost has improved productivity effect.
Since the resin balls swelling ability of high-crosslinking-degree a little less than, but the adsorption ability is stronger, the resin balls of low crosslinking degree then in contrast, for this kind character, we have proposed the gradient separations method, the liquid to be separated that is variable concentrations separates with the resin balls of different model, and the resin balls of the mixed liquor of high arene content than low crosslinking degree mainly carried out the swelling adsorbing separation; The resin balls of the mixed liquor of low arene content than high-crosslinking-degree strengthens its adsorption ability in swelling absorption.
Resin balls for swelling adsorbs hydrocarbons mixture aromatic component of the present invention, its preparation method is as follows:
One, polar monomer is synthetic
SDPMA's is synthetic: add 5.01g (20mmol) SDP, 2.08mL (15mmol) triethylamine and 20mL dimethyl formamide in two mouthfuls of flasks of 50mL, mix and be placed in the cryosel bath the slow mixed liquor that contains 1.45mL (15mmol) methacrylic chloride and 14.5mL dimethyl formamide that drips in nitrogen atmosphere.Drip and finish rear filtering solid, gained filtrate dropwise splashes in the 400mL distilled water, stirs and separates out precipitation, and room temperature oven dry in vacuum drying oven namely gets crude product behind the suction filtration, and crude product is through the column chromatography separating-purifying;
During synthetic SDPA the methacrylic chloride in the SDPMA synthetic reaction being changed to acryloyl chloride gets final product; During synthetic SDPMAEA the SDP in the SDPMA synthetic reaction is changed to SDPMA, methacrylic chloride is changed to chloroacetic chloride and gets final product; During synthetic SDPAEA the SDP in the SDPMA synthetic reaction is changed to SDPA, methacrylic chloride is changed to chloroacetic chloride and gets final product.
Two, the polarity crosslinking agent is synthetic
SDPDMA's is synthetic: add 5.01g (20mmol) SDP, 5.56mL (40mmol) triethylamine and 20mL dimethyl formamide in two mouthfuls of flasks of 100mL, mix and be placed in the cryosel bath the slow mixed liquor that contains 5.81mL (60mmol) methacrylic chloride and 25mL dimethyl formamide that drips in nitrogen atmosphere.Drip and finish rear filtering solid, gained filtrate dropwise splashes in the 500mL distilled water, stirs and separates out precipitation, and room temperature oven dry in vacuum drying oven namely gets crude product behind the suction filtration, and crude product is through the column chromatography separating-purifying.
During synthetic SDPDA the methacrylic chloride in the SDPDMA synthetic reaction being changed to acryloyl chloride gets final product.
Three, resin balls is synthetic
The resin balls of aromatic component is random copolymer in the alternative adsorbs hydrocarbons mixture, take dibenzoyl peroxide (BPO) as initator, polyvinyl alcohol (PVA) is the water dispersant, methylene blue is the water polymerization inhibitor, the employing suspension polymerization is synthetic, wherein oil phase contains initiator B PO, styrene monomer, polar monomer, crosslinking agent and cosolvent (toluene, atoleine, dimethyl formamide etc.), and water is comprised of PVA solution and methylene blue solution.Wherein the mol ratio of styrene monomer and polar monomer is 100: 2～50, the total amount of styrene monomer and polar monomer and the mol ratio of crosslinking agent are 100: 1～30, the consumption of initator be styrene monomer, polar monomer and crosslinking agent gross mass 0.5～1.5%, the consumption of cosolvent be styrene monomer, polar monomer and crosslinking agent cumulative volume 0～150%; The concentration of PVA solution is to contain 3g PVA and 3g sodium chloride in every 100mL distilled water, and the volume of PVA solution is 3～5 times of oil phase cumulative volume; Methylene blue solution is that mass fraction is the aqueous solution of 1～3% methylene blue, and consumption is 0.02～0.06mL methylene blue solution/10mL PVA solution.
During polymerization, after oil phase, water mixed respectively, pour in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h, then be put in adjusting rotary speed to 130 in the water bath with thermostatic control～350rpm, at 70～90 ℃ of reaction 9～12h; Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 12～36h, dries the resin balls of rear collection cut size in 0.45～2mm scope, namely prepares the resin balls of aromatic component in the alternative adsorbs hydrocarbons mixture of the present invention.
Four, the mensuration of absorption property
1. get an amount of gained resin balls, put into drier behind 70 ℃ of baking 2h and be cooled to room temperature, for subsequent use.
2. in measuring cup, take by weighing 1. middle gained resin balls of 0.5g step, add 10mL toluene, room temperature swelling a period of time after the sealing, then absorb toluene, and dry the toluene that is not adsorbed with filter paper, the quality of resin balls after the weighing swelling.Resin balls is as follows to the adsorbance computing formula of toluene:
Q
Toluene=(m
2-m
1)/m
1
Q wherein
TolueneBe the adsorbance of resin balls to toluene, unit is g/g;
m
1Be the quality of resin balls before the swelling, unit is g;
m
2Be the quality of resin balls after the swelling, unit is g.
3. in measuring cup, take by weighing the 0.5g step 1. in the gained resin balls, add the 5mL benzinum, room temperature swelling a period of time after the sealing, then absorb benzinum, dry the benzinum that is not adsorbed with filter paper, and the quality of resin balls after the weighing swelling.Resin balls is as follows to the adsorbance computing formula of benzinum:
Q
Benzinum=(m
4-m
3)/m
3
Q wherein
BenzinumBe the adsorbance of resin balls to benzinum, unit is g/g;
m
3Be the quality of resin balls before the swelling, unit is g;
m
4Be the quality of resin balls after the swelling, unit is g.
Resin balls is as follows to the adsorptive selectivity coefficient formulas of toluene:
β=Q
Toluene/ Q
Benzinum
Wherein β is that resin balls is to the adsorptive selectivity coefficient of toluene, dimensionless;
Q
TolueneBe the adsorbance of resin balls to toluene, unit is g/g;
Q
BenzinumBe the adsorbance of resin balls to benzinum, unit is g/g.
4. recycling of resin balls: the resin balls heating desorption after the swelling absorption is attached, then proceed the operations such as preliminary treatment, swelling absorption.
Description of drawings
The absorption property of the different degree of cross linking resin balls of Fig. 1: embodiment 3 preparations.
As shown in Figure 1, under this experiment condition, 1～No. 5 ball is along with the increase of the degree of cross linking, resin balls reduces gradually to the adsorption capacity of toluene, ease up at last, this is because toluene is stronger to the swelling ability of resin balls, and swelling absorption is occupied an leading position, so along with the increase of the degree of cross linking, resin balls shows monotonicity to the adsorption capacity of toluene; Resin balls increases first the adsorption capacity of benzinum and subtracts afterwards and increase, this be because benzinum to the swelling ability of resin balls a little less than, along with the increase of the degree of cross linking, swelling absorption and adsorption are alternately occupied an leading position, so resin balls shows fluctuation to the adsorption capacity of benzinum.No. 6 the ball degree of cross linking is larger, and toluene and benzinum are all shown preferably adsorption capacity, causes it selectively relatively poor, and it does not have the good of low crosslinking degree resin balls to the adsorption capacity of toluene.
The specific embodiment
In order to be illustrated more clearly in the present invention, be listed below embodiment, but its to scope of the present invention without any restriction.
Embodiment 1:SDPDMA's is synthetic
In two mouthfuls of flasks of 100mL, add 5.01g (20mmol) SDP, 5.56mL (40mmol) triethylamine and 20mL dimethyl formamide, mix and be placed in the cryosel bath the slow mixed liquor that contains 5.81mL (60mmol) methacrylic chloride and 25mL dimethyl formamide that drips in nitrogen atmosphere.Drip and finish rear filtering solid, gained filtrate dropwise splashes in the 500mL distilled water, stirs and separates out precipitation, and room temperature oven dry in vacuum drying oven namely gets crude product behind the suction filtration, and crude product is through the column chromatography separating-purifying.
1H?NMR(500MHz，CDCl
3，TMS)：δ(ppm)7.98(4H，d，-Ph)，7.28(4H，d，-Ph)，6.35(2H，s，＝CH
2)，5.80(2H，s，＝CH
2)，2.04(6H，s，-CH
3).IR(KBr，cm
-1)：1742(C＝O)，2924(-CH
3)，1635(C＝C)，1323-1290(＝SO
2)。Show and prepared SDPDMA.
Embodiment 2:SDPMA's is synthetic
In two mouthfuls of flasks of 50mL, add 5.01g (20mmol) SDP, 2.08mL (15mmol) triethylamine and 20mL dimethyl formamide, mix and be placed in the cryosel bath the slow mixed liquor that contains 1.45mL (15mmol) methacrylic chloride and 14.5mL dimethyl formamide that drips in nitrogen atmosphere.Drip and finish rear filtering solid, gained filtrate dropwise splashes in the 400mL distilled water, stirs and separates out precipitation, and room temperature oven dry in vacuum drying oven namely gets crude product behind the suction filtration, and crude product is through the column chromatography separating-purifying.
1H?NMR(300MHz，CDCl
3，TMS)：δ(ppm)7.93(2H，d，-Ph)，7.76(2H，d，-Ph)，7.25(2H，d，-Ph)，6.85(2H，d，-Ph)，6.51(1H，s，-OH)，6.36(1H，s，＝CH
2)，5.81(1H，s，＝CH
2)，2.04(3H，s，-CH
3).IR(KBr，cm
-1)：1738(C＝O)，2927(-CH
3)，1636(C＝C)，1315-1289(＝SO
2)。Show and prepared SDPMA.
Embodiment 3: different degree of cross linking resin balls synthetic
After by the prescription of table 1 oil phase and water being mixed respectively, pour in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under the 225rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The absorption property to toluene, benzinum of resin balls is seen Fig. 1 (annotate: adsorption conditions is room temperature absorption 48h).
Table 1: the raw material proportioning of different degree of cross linking resin balls
Embodiment 4: butyl acrylate (Ba) modified resin ball synthetic
After by the prescription of table 2 oil phase and water being mixed respectively, add in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under 180～190rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The modified resin ball sees Table 9 (annotate: adsorption conditions is room temperature absorption 48h) to the swelling absorption property of toluene, benzinum.
Table 2: the raw material proportioning of butyl acrylate (Ba) modified resin ball
Embodiment 5: EMA (EMA) modified resin ball synthetic
After by the prescription of table 3 oil phase and water being mixed respectively, add in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under 175～185rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The modified resin ball sees Table 9 (annotate: adsorption conditions is room temperature absorption 48h) to the swelling absorption property of toluene, benzinum.
Table 3: the raw material proportioning of EMA (EMA) modified resin ball
Embodiment 6: acrylonitrile (AN) modified resin ball synthetic
After by the prescription of table 4 oil phase and water being mixed respectively, add in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under 195～205rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The modified resin ball sees Table 9 (annotate: adsorption conditions is room temperature absorption 48h) to the swelling absorption property of toluene, benzinum.
Table 4: the raw material proportioning of acrylonitrile (AN) modified resin ball modified resin ball
Synthesizing of embodiment 7:SDPMA modified resin ball
After by the prescription of table 5 oil phase and water being mixed respectively, add in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under 200～210rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The modified resin ball sees Table 9 (annotate: adsorption conditions is room temperature absorption 48h) to the swelling absorption property data of pure solution.
The raw material proportioning of table 5:SDPMA modified resin ball modified resin ball
Synthesizing of embodiment 8:Ba, SDPMA modified resin ball
After by the prescription of table 6 oil phase and water being mixed respectively, add in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under 220～230rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The modified resin ball sees Table 9 (annotate: adsorption conditions is room temperature absorption 48h) to the swelling absorption property data of pure solution.
The raw material proportioning of table 6:Ba, SDPMA modified resin ball
Synthesizing of embodiment 9:SDPDMA modified resin ball
After by the prescription of table 7 oil phase and water being mixed respectively, add in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under 250～260rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The modified resin ball sees Table 9 (annotate: adsorption conditions is room temperature absorption 48h) to the swelling absorption property data of pure solution.
The raw material proportioning of table 7:SDPDMA modified resin ball
Synthesizing of embodiment 10:Ba, SDPDMA modified resin ball
After by the prescription of table 8 oil phase and water being mixed respectively, add in the lump N is housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h after, put into and be preheated to 70 ℃ water bath with thermostatic control, under 250～260rpm rotating speed, then reaction 1.5h is warming up to 85 ℃ of reaction 4h, continues to be warming up to 90 ℃ of reaction 5h.Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 24h, dries the resin balls of rear collection cut size in 0.45～2mm scope, and is for subsequent use.The modified resin ball sees Table 9 (annotate: adsorption conditions is room temperature absorption 48h) to the swelling absorption property data of pure solution.
The raw material proportioning of table 8:Ba, SDPDMA modified resin ball
Table 9: the absorption property of modified resin ball
As shown in Table 9, under this experiment condition, compare with the non-polar resin ball, the modified resin ball reduces the adsorption capacity of benzinum, the adsorption capacity of toluene is improved, so the increase of β value, illustrate that being introduced in of polar monomer or polarity crosslinking agent improved the adsorptive selectivity to aromatic hydrocarbons of resin balls to a certain extent, and the increase of polarity is effectively in the raising of adsorptive selectivity, and is wherein best with the performance of the polar monomer that contains sulfuryl or polarity crosslinking agent.
Different material forms or other model resin balls of different ratios of raw materials also all shows preferably adsorptive selectivity.
Claims (2)
1. the resin balls of aromatic component in the alternative adsorbs hydrocarbons mixture, it is characterized in that: this resin balls is random copolymer, be polymerized by styrene monomer, polar monomer and crosslinking agent, wherein the mol ratio of styrene monomer and polar monomer is 100: 2～50, the total amount of styrene monomer and polar monomer and the mol ratio of crosslinking agent are 100: 1～30, and the particle diameter of resin balls is in 0.45～2mm scope; Polar monomer is one or more among 4-hydroxyl-4 '-first class acryloxy diphenyl sulphone (DPS) SDPMA, 4-hydroxyl-4 '-acryloxy diphenyl sulphone (DPS) SDPA, 4-methacryloxy-4 '-acetoxyl group diphenyl sulphone (DPS) SDPMAEA, 4-acryloxy-the 4 '-acetoxyl group diphenyl sulphone (DPS) SDPAEA; Crosslinking agent is 4, one or more among 4 '-dimethyl allene acyloxy diphenyl sulphone (DPS) SDPDMA, 4,4 '-two propylene acyloxy diphenyl sulphone (DPS) SDPDA;
The synthetic of SDPMA is to add 5.01g SDP, 2.08mL triethylamine and 20mL dimethyl formamide in two mouthfuls of flasks of 50mL, mix and be placed in the cryosel bath the slow mixed liquor that contains 1.45mL methacrylic chloride and 14.5mL dimethyl formamide that drips in nitrogen atmosphere; Drip and finish rear filtering solid, gained filtrate dropwise splashes in the 400mL distilled water, stirs and separates out precipitation, and room temperature oven dry in vacuum drying oven namely gets crude product behind the suction filtration, and crude product obtains SDPMA behind the column chromatography separating-purifying; The synthetic of SDPA is the methacrylic chloride in the above-mentioned SDPMA synthetic reaction to be changed to acryloyl chloride get final product; The synthetic of SDPMAEA is that the SDP in the above-mentioned SDPMA synthetic reaction is changed to SDPMA, and methacrylic chloride is changed to chloroacetic chloride and gets final product; The synthetic of SDPAEA is that the SDP in the above-mentioned SDPMA synthetic reaction is changed to SDPA, and methacrylic chloride is changed to chloroacetic chloride and gets final product;
The synthetic of SDPDMA is to add 5.01g SDP, 5.56mL triethylamine and 20mL dimethyl formamide in two mouthfuls of flasks of 100mL, mix and be placed in the cryosel bath the slow mixed liquor that contains 5.81mL methacrylic chloride and 25mL dimethyl formamide that drips in nitrogen atmosphere; Drip and finish rear filtering solid, gained filtrate dropwise splashes in the 500mL distilled water, stirs and separates out precipitation, and room temperature oven dry in vacuum drying oven namely gets crude product behind the suction filtration, and crude product obtains SDPDMA behind the column chromatography separating-purifying; The synthetic of SDPDA is the methacrylic chloride in the above-mentioned SDPDMA synthetic reaction to be changed to acryloyl chloride get final product.
2. the preparation method of the resin balls of aromatic component in a kind of alternative adsorbs hydrocarbons mixture claimed in claim 1, its step is as follows:
1) adopt suspension polymerization synthetic, wherein oil phase contains initator dibenzoyl peroxide, styrene monomer, polar monomer, crosslinking agent and cosolvent, and water is comprised of poly-vinyl alcohol solution and methylene blue solution; Cosolvent is toluene, atoleine or dimethyl formamide;
2) mol ratio of styrene monomer and polar monomer is 100: 2～50, the total amount of styrene monomer and polar monomer and the mol ratio of crosslinking agent are 100: 1～30, the consumption of initator be styrene monomer, polar monomer and crosslinking agent gross mass 0.5～1.5%, the consumption of cosolvent be styrene monomer, polar monomer and crosslinking agent cumulative volume 0～150%; The concentration of poly-vinyl alcohol solution is to contain 3g polyvinyl alcohol and 3g sodium chloride in every 100ml distilled water, and the volume of poly-vinyl alcohol solution is 3～5 times of oil phase cumulative volume; Methylene blue solution is that mass fraction is the aqueous solution of 1～3% methylene blue, and consumption is 0.02～0.06mL methylene blue solution/10mL poly-vinyl alcohol solution;
3) oil phase, water are mixed respectively after, pour in the lump N be housed
2In the there-necked flask of ingress pipe, reflux condensing tube, mechanical agitator, logical N
20.5h, then be put in adjusting rotary speed to 130 in the water bath with thermostatic control～350rpm, at 70～90 ℃ of reaction 9～12h; Reaction is filtered to get resin microsphere after finishing, and with carrene extracting 12～36h, dries the resin balls of rear collection cut size in 0.45～2mm scope, namely prepares the resin balls of aromatic component in the alternative adsorbs hydrocarbons mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110204328 CN102350321B (en) | 2011-07-21 | 2011-07-21 | Resin ball capable of selectively adsorbing aromatic hydrocarbon component of hydrocarbon mixture, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110204328 CN102350321B (en) | 2011-07-21 | 2011-07-21 | Resin ball capable of selectively adsorbing aromatic hydrocarbon component of hydrocarbon mixture, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102350321A CN102350321A (en) | 2012-02-15 |
| CN102350321B true CN102350321B (en) | 2013-03-13 |
Family
ID=45574029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110204328 Expired - Fee Related CN102350321B (en) | 2011-07-21 | 2011-07-21 | Resin ball capable of selectively adsorbing aromatic hydrocarbon component of hydrocarbon mixture, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102350321B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974324B (en) * | 2012-11-22 | 2014-11-26 | 中蓝晨光化工研究设计院有限公司 | Strong-polarity macroporous adsorption resin |
| CN106084130B (en) * | 2016-07-06 | 2018-06-29 | 吉林建筑大学 | A kind of preparation method of Porous deproteinized bone resin balls |
| CN107082837B (en) * | 2017-05-12 | 2019-11-22 | 山东大学 | A kind of preparation method of partial size and the controllable monodisperse polystyrene microsphere of surface charge |
| CN108587573A (en) * | 2018-05-15 | 2018-09-28 | 辽宁大学 | A kind of synthetic method of phase-changing energy storage material |
| CN109115929B (en) * | 2018-10-30 | 2021-03-02 | 兰州东立龙信息技术有限公司 | Polar porous polymer coating capillary chromatographic column and preparation and application methods thereof |
| CN111675781B (en) * | 2020-07-16 | 2022-09-20 | 万华化学集团股份有限公司 | Styrene-acrylonitrile copolymer with improved silver streaks and preparation method and device thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215355A (en) * | 2008-01-09 | 2008-07-09 | 苏州大学 | High oil absorption resin and synthetic method thereof |
| CN101314624A (en) * | 2008-05-21 | 2008-12-03 | 安徽省电力公司合肥供电公司 | High oil suction resin and uses thereof |
| CN101716493A (en) * | 2009-11-26 | 2010-06-02 | 中蓝晨光化工研究院有限公司 | Macroporous adsorptive resin for processing phenol and phenylamine in wastewater and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060183812A1 (en) * | 2005-02-16 | 2006-08-17 | Miller James R | Adsorptive coating formulation |
-
2011
- 2011-07-21 CN CN 201110204328 patent/CN102350321B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215355A (en) * | 2008-01-09 | 2008-07-09 | 苏州大学 | High oil absorption resin and synthetic method thereof |
| CN101314624A (en) * | 2008-05-21 | 2008-12-03 | 安徽省电力公司合肥供电公司 | High oil suction resin and uses thereof |
| CN101716493A (en) * | 2009-11-26 | 2010-06-02 | 中蓝晨光化工研究院有限公司 | Macroporous adsorptive resin for processing phenol and phenylamine in wastewater and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102350321A (en) | 2012-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102350321B (en) | Resin ball capable of selectively adsorbing aromatic hydrocarbon component of hydrocarbon mixture, and preparation method thereof | |
| CN101987291B (en) | Macropore adsorption resin as well as preparation method and application thereof | |
| CN1022621C (en) | Adsorptive separation of para-xylene using 1,2,3,4-tetralin desorbent | |
| KR101620117B1 (en) | Improved extractive distillation processes using water-soluble extractive solvents | |
| CN100467120C (en) | Macroporous adsorption resin special used for separating antibiotic and its preparation method | |
| CN109776764B (en) | Super-crosslinked organic polymer material, preparation method and application | |
| CN104781218A (en) | Polymerizable spirobisindane monomers and polymers prepared therefrom | |
| JP2004115515A (en) | Method for simultaneously synthesizing paraxylene and styrene | |
| TW201202183A (en) | Ethylene production by steam cracking of normal paraffins | |
| Zhu et al. | Highly selective removal of heterocyclic impurities from toluene by nonporous adaptive crystals of perethylated pillar [6] arene | |
| CN110237823B (en) | Metal organic framework material with ethane preferential adsorption function and preparation method thereof | |
| CN103059190B (en) | Resin ball capable of swelling and adsorbing aromatic hydrocarbon in hydrocarbon mixture and preparation method of resin ball | |
| CN101186719B (en) | Composite function resin, preparation method thereof, and method for treating phthalate pollution of water body | |
| CN109836304B (en) | Method for separating cyclopentane/2, 2-dimethylbutane | |
| CN104403045A (en) | Preparation method of chlorogenic acid uniformly-imprinted microspheres | |
| CN104418687B (en) | Adsorption stripping dimethyl benzene and the method for ethylbenzene from C8 aromatic component | |
| CN102146297B (en) | Method for producing environmental-friendly aromatic oil | |
| CN106925213A (en) | For n-alkane adsorbing separation adsorbent and preparation method thereof | |
| CN106943994A (en) | A kind of n-alkane adsorbing separation adsorbent and preparation method thereof | |
| CN106084130B (en) | A kind of preparation method of Porous deproteinized bone resin balls | |
| Robinson et al. | Adsorption of fatty acids from solvents-duolite AZ anion exchange resin | |
| JPH07100375A (en) | High-density large surface area adsorbent | |
| CN102491946A (en) | Method for separating and purifying huperzine by molecular imprinting technology | |
| CN109317092B (en) | Modified zeolite molecular sieve and preparation method and application thereof | |
| CN110713429A (en) | Method for purifying chromatographically pure hexane |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130313 Termination date: 20150721 |
|
| EXPY | Termination of patent right or utility model |