CN101338217A - Method of preparing composite membrane for gasoline desulphurization - Google Patents
Method of preparing composite membrane for gasoline desulphurization Download PDFInfo
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Abstract
The present invention provides a method for manufacturing a composite membrane for gasoline desulfurization. The composite membrane is manufactured by compounding an epidermal layer membrane material and a support layer membrane material. The epidermal layer membrane material is polyethylene glycol or polyethylene oxide, which has strong permselectivity of sulfide in the gasoline; the support layer adopts a sodium polyimide filter membrane or an ultrafiltration membrane with temperature resistance and organic solvent resistance, which can resist complicated components of the gasoline and 150 DEG C high temperature. Adopting the appropriate composite membrane preparation can prepare a composite membrane with ultrathin epidermal layer and no defect which can resist high temperature and hydrocarbon. The composite membrane can be used to for gasoline desulfurization. Under the condition of 110 DEG C feeding temperature and 1.5KPa membrane posterior pressure, the sulfur enrichment factor of the prepared composite membrane for the gasoline with 1000 Mu g/g sulfur content is larger than 4 and the permeation flux is larger than 40kg.Mu m /m< 2 >h.
Description
Technical field
The present invention relates to a kind of manufacture method of composite membrane for gasoline desulphurization, this method belongs to selection and the composite membrane technology of preparing and the application direction thereof of infiltration evaporation mould material.Its major technology characteristics are to test by infiltration evaporation mould material Choice Theory and infiltration evaporation to screen epidermal area mould material and supporting layer mould material, select suitable composite membrane preparation technology, prepare the heatproof with the ultra-thin cortex of zero defect, the composite membrane of anti-hydro carbons.The prepared composite membrane of the present invention can be used for gasoline desulfur, and particularly sulfide in petrol removes.
Background technology
Along with the mankind improve constantly the requirement of living environment quality, more and more stricter oil fuel sulfur-bearing standard has been formulated because of the demand of environmental protection in countries in the world.Europe will be from the 150 μ gg of calendar year 2001 to the restriction of content of sulfur in gasoline
-1Be reduced to 50 μ gg in 2005
-1, Canada then requires content of sulfur in gasoline in 2005 to be not more than 30 μ gg
-1Thereby, gasoline high-efficiency desulfurization Research on New is received various countries scientific worker's concern.In addition, along with accession to WTO, the trend that the oriented international standard of the gasoline standard of China is drawn close finally may limit sulphur content in the gasoline by 800 present μ gg
-1To 50-200 μ gg
-1Scope in.Therefore, must develop a kind of economically viable catalytically cracked gasoline desulfurization new technology, make the sulphur content in the gasoline meet domestic, international new gasoline standard, to improve the market competitiveness of gasoline.
About 50%～60% sulfocompound is thiophene and alkyl derivative thereof in the gasoline, and all the other are mercaptan and other sulfide.Gasoline is adopted direct hydrotreatment, make C-S bond rupture in the thiophene, and be converted into H
2S is the effective ways that reduce sulfide in petrol content.Mainly contain fixed bed, suspension bed and 3 kinds of hydrogenation technique technology of ebullated bed.Under 6～20MPa, 380～480 ℃, 0.2～3.0h reaction conditions, the decreasing ratio of sulfide is 40%～90%.Though hydrogenating desulfurization can remove effectively as difficult sulfide that removes such as thiophene-based, the following shortcoming of ubiquity: (1) RON reduces by 7～10 units; (2) MON reduces by 3～4 units; (3) the alkene addition reaction taking place, needs a large amount of hydrogen of consumption.The facility investment of this process and process cost are all very expensive in addition, and domestic refinery generally lacks hydrogenation unit, so very difficultly generally adopted.Therefore press for other deep desulfurization of gasoline technology cheaply
[5-7]
Those of skill in the art's method by membrane sepn of attempting is the new way that gasoline desulfur is opened up efficient a, less energy-consumption.External Gray Si (Grace)-Dai Weixun (Davison Catalyst) company and Suhl longevity chemical technology company (Sulzer ChemTech) have developed a kind of embrane method desulfurization process of gasoline of the S-Brane of being called as technology jointly, investment cost that can be lower and process cost are directly handled the gasoline of light and middle boiling range scope, obtain sulphur content less than 30 μ gg
-1Super low-sulfur oil.Set up a demo plant that throughput is 100-300BPD the end of the year 2002, just be in operation at present
[8-9]The S-Brane technology has the following advantages: investment that (1) is lower and process cost.According to measuring and calculating, embrane method sulfur removal technology plant investment is $100～500/BPD, and process cost is 0.5～1.5 cent/gallon.(2) working temperature is low, and system works need not process furnace under low temperature (90～120 ℃).(3) process does not produce H
2S, and can obtain the following low-sulphur oil of sulfur-bearing 30 μ g/g.(4), therefore there is not loss of octane number because sepn process does not have chemical reaction, and high-octane number component is kept in the gasoline.(5) can carry out modular design, be easy to amplification, extendible capacity and construction, runtime while is long, for ease of maintenaince.(6) can cooperate with desulfurization technology such as HDS and reach of the requirement of each stage gasoline standard, obtain optimum economic benefit (7) and can partly remove aromatic hydrocarbons, for the following standard that satisfies the low benzene concentration of gasoline is carried out tachnical storage to sulphur content.
The present domestic report that does not still have embrane method gasoline desulfur technology.Also less with the document and the patent of separatory membrane to gasoline desulfur abroad, by retrieval, Gray Si has announced its S-Brane embrane method gasoline desulfur Progress in technique situation in its company's site.In addition, the document of embrane method gasoline desulfur only limits to patent, and the patent of application seldom.(the W.R.Grace﹠amp of W. R. Grace ﹠ Co only at present; Co.-Conn.), three families of Exxon-Mobile company (ExxonMobilResearch and Engineering Company) and company of Marathon Oil (Marathon 0ilCompany) have all applied for the patent aspect the relevant embrane method desulfurization process of gasoline after in October, 2003.For secret reason, above company only to the application of embrane method desulfurization process of gasoline process patent, and to relevant gasoline desulfur with separation membrane and the still unexposed report of membrane prepare technology thereof.
Summary of the invention
Purpose of the present invention is exactly to avoid above-mentioned the deficiencies in the prior art part and manufacture method that a kind of composite membrane for gasoline desulphurization is provided.The technical characterstic of this method is to test by infiltration evaporation mould material Choice Theory and infiltration evaporation to screen epidermal area mould material and supporting layer mould material, select suitable composite membrane preparation technology, prepare the heatproof with the ultra-thin cortex of zero defect, the composite membrane of anti-hydro carbons.This composite membrane is the sulfide in the gasoline is had the polyoxyethylene glycol of selecting perviousness more by force or polyoxyethylene to be composited as supporting tunic as the polyimide filtering membranes of epidermal area mould material and heatproof, organic solvent-resistant by selecting for use, its major technology characteristics are at first to produce support membrane, and then carry out support membrane and epidermis tunic compound, thereby produce the composite membrane that is used for gasoline desulfur, its concrete making step is as follows.
1. the preparation method of support membrane
Composite membrane of the present invention is characterised in that supporting layer is polyimide filtering membranes or ultra-filtration membrane.Concrete preparation method is: aromatic diamine is dissolved in the polar aprotic solvent, under nitrogen protection, in solution, add the aromatic series dianhydride, the add-on of aromatic series dianhydride is the equal molar quantities of aromatic diamine, stirring reaction promptly obtained polyamic acid solution in 6～12 hours under the room temperature, and the polar aprotic solvent consumption is the consumption that the polyimide acid concentration that will generate is controlled at 10～20wt% scope; Under agitation add chemical imidization reagent and carry out chemical imidization, the consumption of chemistry imidization reagent is: every mole of monomer aromatic dianhydride adds 100～800mL, imidization reagent is that triethylamine and diacetyl oxide were by 3: 2 volume ratio blended solution, the imidization time is 6 hours, solution after the imidization reaction is precipitated in water, obtain flaxen product, the washing after drying promptly obtains dissolving in the polyimide film material of polar aprotic solvent; With gained polyimide, additive and polar aprotic solvent by weight 25～35: 5～12: 100 proportional places container, and induction stirring makes it dissolving evenly under the room temperature, removes by filter insoluble impurities, and filtrate is left standstill the degassing; Under 10～40 ℃, above-mentioned gained film-casting liquid is coated on the perforated bottom supporter, after 10～150 seconds volatilization time of control, freezing film obtains polyimide filtering membranes in immersion water or the ethanol; After 24 hours, film soaked 12 hours in ethanol, Virahol, hexane and glycerol successively with the film rinsing, took out to handle under 100～150 ℃ to obtain polyimide filtering membranes or ultra-filtration membrane in 30～600 seconds.
Aromatic diamine is a diphenylmethane diamine (MDA), 4, and 4 '-diamines yl diphenyl ether (ODA) or 3,3 ' dimethyl diphenyl methane diamines (DMMDA) are the aromatic diamine monomers with following structure:
The aromatic series dianhydride is pyromellitic acid dianhydride (PMDA), hexafluorodianhydride (6-FDA) or benzophenone tetracarboxylic dianhydride (BTDA), is the aromatic dianhydride monomer with following structure:
Polar aprotic solvent is N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl formamide or methyl-sulphoxide.
Additive is polyvinyl alcohol, polyoxyethylene glycol or polyvinylpyrrolidone.
2. the preparation method of composite membrane
Epidermal area mould material, linking agent, catalyzer are dissolved in the solvent according to a certain ratio, and the control solid content is 10%-16% (Wt%).Induction stirring, stirring reaction is 24 hours under the room temperature, obtains the preparation liquid of homogeneous transparent.Then preparation liquid is filtered and leaves standstill the degassing 2 days with 300 order stainless (steel) wires.In dry, clean system film chamber, with clean glass stick with film-casting liquid equably dip-coating on polyimide filtering membranes or ultra-filtration membrane as supporting layer.This composite membrane that coats is placed system film chamber 12 hours under 40-50 ℃, make solvent evaporates.Handled 60-100 minute down in 80-120 ℃ then, carry out the esterification and crosslinking reaction.90 ℃ of following drying treatment 12 hours in vacuum drying oven promptly get composite membrane for gasoline desulphurization at last, and the epidermis separating layer thickness of film can be regulated by the concentration or the dip-coating number of times of preparation liquid less than 10 μ m.
The epidermal area mould material is polyoxyethylene glycol (PEG) or polyoxyethylene (PEO).
Solvent is ethanol, Virahol or ethyl acetate.
Linking agent is poly carboxylic acids such as maleic acid (toxilic acid), citric acid or BTCA.
Catalyzer is sodium dihydric hypophosphite (NaH
2PO
2) or sodium hydroxide.
Embodiment
Below in conjunction with specific embodiment in detail technical characterstic of the present invention is described in detail:
Embodiment 1:
1.. the preparation method of support membrane:
The diphenylmethane diamine (MDA) of 4.95g (0.025mol) is dissolved in the N of 80mL; in the N-N,N-DIMETHYLACETAMIDE; induction stirring; add the pyromellitic acid dianhydride (PMDA) of 5.45g (0.025mol) under nitrogen protection in solution, stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature in batches.Add the diacetyl oxide of 6mL and the triethylamine of 9mL under stirring fast, stir under room temperature and finished the part imidization in 6 hours, reaction soln precipitates in water, obtains flaxen product, after washing with water, is dried to constant weight under 50 ℃.Get the dried polyimide 10g of above-mentioned synthetic, induction stirring makes it to be dissolved in 20mL N under the room temperature, in the mixed solvent of N-N,N-DIMETHYLACETAMIDE and 16mL acetone, add 2.2g polyvinylpyrrolidone additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, it is standby that filtrate is left standstill the degassing 24 hours.Under dustless, 25 ℃, relative humidity 50% condition, above-mentioned gained film-casting liquid is coated on sheet glass or the porous bottom, film forming thickness is controlled at about 25 μ m, the 30 seconds volatilization time of control, immerses film forming in water or the alcoholic acid precipitation bath then.The film rinsing after 24 hours, was respectively soaked in ethanol, Virahol, hexane and glycerol 12 hours successively, and taking-up is handled down at 100 ℃ and was obtained polyimide filtering membranes in 300 seconds.
2.. the preparation method of composite membrane:
Epidermal area mould material polyoxyethylene glycol-20000, linking agent maleic acid, catalyzer sodium dihydric hypophosphite are dissolved in the ethyl acetate solvent, and wherein content of crosslinking agent is 15.6% (Wt%), and catalyst content is 2.5% (Wt%), and total solid content is 14%.Induction stirring, stirring reaction is 24 hours under the room temperature, obtains the preparation liquid of homogeneous transparent.Then preparation liquid is filtered and leaves standstill the degassing 2 days with 300 order stainless (steel) wires.In dry, clean system film chamber, with clean glass stick with film-casting liquid equably dip-coating on polyimide filtering membranes as supporting layer.This composite membrane that coats is placed system film chamber 12 hours under 50 ℃, make solvent evaporates.Handled 80 minutes down in 110 ℃ then, carry out the esterification and crosslinking reaction.90 ℃ of following drying treatment 12 hours in vacuum drying oven promptly get composite membrane for gasoline desulphurization at last.
3.. implementation result:
The separation performance of made film is as follows: adopting gasoline cut below 160 ℃ is separate object, wherein feed sulphur content 820 μ g/g, aromaticity content are 13.642% (Wt%), olefin(e) centent is 44.480% (Wt%), normal paraffin content is 3.653% (Wt%), isoparaffin content is 25.318% (Wt%), and naphthene content is 10.227% (Wt%).At feeding temperature is 110 ℃, film backside pressure 0.5KPa, and when the feed liquid flow was 20ml/h, prepared gasoline desulfur was 4.2 with the sulfur enrichment factor of separatory membrane, permeation flux is 70.8kg μ m/m
2H, aromaticity content is 22.651% (Wt%) in the penetrating fluid, and olefin(e) centent is 37.884% (Wt%), and normal paraffin content is 3.523% (Wt%), and isoparaffin content is 20.671% (Wt%), naphthene content is 8.852% (Wt%).
Embodiment 2:
1. the preparation method of support membrane:
With 3 of 5.658g (0.025mol); 3 ' dimethyl diphenyl methane diamines (DMMDA) is dissolved in the dimethyl formamide of 80_mL; induction stirring; the hexafluorodianhydride (6FDA) that under nitrogen protection, in solution, in batches adds 11.106g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 17.32wt%.Add the diacetyl oxide of 6mL and the triethylamine of 9mL under stirring fast, under room temperature, stir
6Hour finish the part imidization, reaction soln precipitates in water, obtains flaxen product, after washing with water, is dried to constant weight under 50 ℃.Get the dried polyimide 10g of above-mentioned synthetic, induction stirring makes it to be dissolved in the mixed solvent of 20mL N,N-dimethylacetamide and 16mL acetone under the room temperature, add 2.7g polyoxyethylene glycol additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, filtrate leave standstill outgas 24 hours standby.Under dustless, 25 ℃, relative humidity 50% condition, above-mentioned gained film-casting liquid is coated on sheet glass or the porous bottom, film forming thickness is controlled at about 25 μ m, the 40 seconds volatilization time of control, immerses film forming in water or the alcoholic acid precipitation bath then.The film rinsing after 24 hours, was respectively soaked in ethanol, Virahol, hexane and glycerol 12 hours successively, and taking-up is handled down at 100 ℃ and was obtained lubricating oil benzol-kentone dewaxing solvent recuperation polyimide filtering membranes in 300 seconds.
2. the preparation method of composite membrane:
Epidermal area mould material polyoxyethylene glycol-2000, linking agent citric acid, catalyzer sodium dihydric hypophosphite are dissolved in the ethyl acetate solvent, and wherein content of crosslinking agent is 17.1% (Wt%), and catalyst content is 3.5% (Wt%), and total solid content is 13%.Induction stirring, stirring reaction is 24 hours under the room temperature, obtains the preparation liquid of homogeneous transparent.Then preparation liquid is filtered and leaves standstill the degassing 2 days with 300 order stainless (steel) wires.In dry, clean system film chamber, with clean glass stick with film-casting liquid equably dip-coating on polyimide filtering membranes as supporting layer.This composite membrane that coats is placed system film chamber 12 hours under 50 ℃, make solvent evaporates.Handled 90 minutes down in 90 ℃ then, carry out the esterification and crosslinking reaction.90 ℃ of following drying treatment 12 hours in vacuum drying oven promptly get composite membrane for gasoline desulphurization at last.
3. implementation result:
The separation performance of made film is as follows: employing gasoline is separate object, and its sulphur content is 1100 μ g/g.At feeding temperature is 105 ℃, film backside pressure 1.5KPa, and when the feed liquid flow was 20ml/h, prepared gasoline desulfur was 4.7 with the sulfur enrichment factor of separatory membrane, permeation flux is 62.5kg μ m/m
2H.
Embodiment 3:
1. the preparation method of support membrane:
With 4 of 5g (0.025mol); 4 '-diamines yl diphenyl ether (ODA) is dissolved in the methyl-sulphoxide of 80_mL; induction stirring; the benzophenone tetracarboxylic dianhydride (BTDA) that under nitrogen protection, in solution, in batches adds 8.0558g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 14.03wt%.Add the diacetyl oxide of 6mL and the triethylamine of 9mL under stirring fast, under room temperature, stir
6Hour finish the part imidization, reaction soln precipitates in water, obtains flaxen product, after washing with water, is dried to constant weight under 50 ℃.Get the dried polyimide 10g of above-mentioned synthetic, induction stirring makes it to be dissolved in the mixed solvent of 20mL N,N-dimethylacetamide and 16mL acetone under the room temperature, add 1.6g polyvinyl alcohol additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, filtrate leave standstill outgas 24 hours standby.Under dustless, 25 ℃, relative humidity 50% condition, above-mentioned gained film-casting liquid is coated on sheet glass or the porous bottom, film forming thickness is controlled at about 25 μ m, the 100 seconds volatilization time of control, immerses film forming in water or the alcoholic acid precipitation bath then.The film rinsing after 24 hours, was respectively soaked in ethanol, Virahol, hexane and glycerol 12 hours successively, and taking-up is handled down at 100 ℃ and was obtained the polyimide ultra-filtration membrane in 500 seconds.
2. the preparation method of composite membrane:
Epidermal area mould material polyoxyethylene, linking agent BTCA, catalyzer time sodium hydroxide are dissolved in the isopropanol solvent, and wherein content of crosslinking agent is 15.3% (Wt%), and catalyst content is 2.1% (Wt%), and total solid content is 12%.Induction stirring, stirring reaction is 24 hours under the room temperature, obtains the preparation liquid of homogeneous transparent.Then preparation liquid is filtered and leaves standstill the degassing 2 days with 300 order stainless (steel) wires.In dry, clean system film chamber, with clean glass stick with film-casting liquid equably dip-coating on polyimide filtering membranes as supporting layer.This composite membrane that coats is placed system film chamber 12 hours under 40 ℃, make solvent evaporates.Handled 85 minutes down in 85 ℃ then, carry out the esterification and crosslinking reaction.90 ℃ of following drying treatment 12 hours in vacuum drying oven promptly get composite membrane for gasoline desulphurization at last.
3. implementation result:
The separation performance of made film is as follows: adopting thiophene, normal heptane, toluene, hexanaphthene, 1-hexene model compound system is separate object, wherein feed sulphur content 1000 μ g/g, toluene level are 16.41% (Wt%), 1-hexene content is 34.085% (Wt%), normal heptane content is 36.474% (Wt%), and hexanaphthene content is 11.733% (Wt%).At feeding temperature is 110 ℃, film backside pressure 1KPa, and when the feed liquid flow was 20ml/h, prepared gasoline desulfur was 5.7 with the sulfur enrichment factor of separatory membrane, permeation flux is 43.4kg μ m/m
2H, toluene level is 33.11% (Wt%) in the penetrating fluid, and 1-hexene content is 26.83% (Wt%), and normal heptane content is 32.27% (Wt%), and hexanaphthene content is 6.27% (Wt%).
Embodiment 4:
1. the preparation method of support membrane:
With 4 of 5g (0.025mol); 4 '-diamines yl diphenyl ether (ODA) is dissolved in the methyl-sulphoxide of 80_mL; induction stirring; the benzophenone tetracarboxylic dianhydride (BTDA) that under nitrogen protection, in solution, in batches adds 8.0558g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 14.03wt%.Add the diacetyl oxide of 6mL and the triethylamine of 9mL under stirring fast, under room temperature, stir
6Hour finish the part imidization, reaction soln precipitates in water, obtains flaxen product, after washing with water, is dried to constant weight under 50 ℃.Get the dried polyimide 10g of above-mentioned synthetic, induction stirring makes it to be dissolved in the mixed solvent of 20mL N,N-dimethylacetamide and 16mL acetone under the room temperature, add 1.6g polyvinyl alcohol additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, filtrate leave standstill outgas 24 hours standby.Under dustless, 25 ℃, relative humidity 50% condition, above-mentioned gained film-casting liquid is coated on sheet glass or the porous bottom, film forming thickness is controlled at about 25 μ m, the 120 seconds volatilization time of control, immerses film forming in water or the alcoholic acid precipitation bath then.The film rinsing after 24 hours, was respectively soaked in ethanol, Virahol, hexane and glycerol 12 hours successively, and taking-up is handled down at 120 ℃ and was obtained the polyimide ultra-filtration membrane in 400 seconds.
2. the preparation method of composite membrane:
Epidermal area mould material polyoxyethylene, linking agent maleic acid, catalyzer sodium dihydric hypophosphite are dissolved in the alcohol solvent, and wherein content of crosslinking agent is 15.3% (Wt%), and catalyst content is 2.1% (Wt%), and total solid content is 12%.Induction stirring, stirring reaction is 24 hours under the room temperature, obtains the preparation liquid of homogeneous transparent.Then preparation liquid is filtered and leaves standstill the degassing 2 days with 300 order stainless (steel) wires.In dry, clean system film chamber, with clean glass stick with film-casting liquid equably dip-coating on polyimide filtering membranes as supporting layer.This composite membrane that coats is placed system film chamber 12 hours under 50 ℃, make solvent evaporates.Handled 100 minutes down in 100 ℃ then, carry out the esterification and crosslinking reaction.90 ℃ of following drying treatment 12 hours in vacuum drying oven promptly get composite membrane for gasoline desulphurization at last.
3. implementation result:
The separation performance of made film is as follows: adopting thiophene, normal heptane model compound system is separate object, and the control feed sulphur content is 900 μ g/g.At feeding temperature is 90 ℃, film backside pressure 0.8KPa, and when the feed liquid flow was 20ml/h, prepared gasoline desulfur was 9.2 with the sulfur enrichment factor of separatory membrane, permeation flux is 46.3kg μ m/m
2H.
Claims (3)
1. the manufacture method of a composite membrane for gasoline desulphurization, this composite membrane is the sulfide in the gasoline is had the polyoxyethylene glycol of selecting perviousness more by force or polyoxyethylene to be composited as supporting tunic as the polyimide filtering membranes of epidermal area mould material and heatproof, organic solvent-resistant by selecting for use, it is characterized in that at first producing support membrane, and then carry out support membrane and epidermis tunic compound, thereby produce the composite membrane that is used for gasoline desulfur, its concrete making step is as follows:
(1) preparation of support membrane
1. aromatic diamine is dissolved in the polar aprotic solvent
Promptly under nitrogen protection, in solution, add the aromatic series dianhydride, the add-on of aromatic series dianhydride is the equal molar quantities of aromatic diamine, stirring reaction promptly obtained polyamic acid solution in 6～12 hours under the room temperature, and the polar aprotic solvent consumption is the consumption that the polyimide acid concentration that will generate is controlled at 10～20wt% scope;
2. under agitation add chemical imidization reagent and carry out chemical imidization
The consumption of chemistry imidization reagent is: every mole of monomer aromatic dianhydride adds 100～800mL, imidization reagent is that triethylamine and diacetyl oxide were by 3: 2 volume ratio blended solution, the imidization time is 6 hours, solution after the imidization reaction is precipitated in water, obtain flaxen product, the washing after drying promptly obtains dissolving in the polyimide film material of polar aprotic solvent;
3. the preparation of polyimide filtering membranes
With gained polyimide, additive and polar aprotic solvent by weight 25～35: 5～12: 100 proportional places container, and induction stirring makes it dissolving evenly under the room temperature, removes by filter insoluble impurities, and filtrate is left standstill the degassing; Under 10～40 ℃, above-mentioned gained film-casting liquid is coated on the perforated bottom supporter, after 10～150 seconds volatilization time of control, freezing film obtains polyimide filtering membranes in immersion water or the ethanol; After 24 hours, film soaked 12 hours in ethanol, Virahol, hexane and glycerol successively with the film rinsing, took out to handle under 100～150 ℃ to obtain polyimide filtering membranes or ultra-filtration membrane in 30～600 seconds;
(2) preparation of composite membrane
1. epidermal area mould material, linking agent, catalyzer are dissolved in the solvent according to a certain ratio, the weight percent of control solid content is 10%-16%; Induction stirring, stirring reaction is 24 hours under the room temperature, obtains the preparation liquid of homogeneous transparent;
2. then preparation liquid is filtered and leaves standstill the degassing 2 days with 300 order stainless (steel) wires, with clean glass stick with preparation liquid equably dip-coating on polyimide filtering membranes or ultra-filtration membrane as supporting layer, this composite membrane that coats is placed system film chamber 12 hours under 40-50 ℃, make solvent evaporates;
3. handled 60-100 minute down in 80-120 ℃ then, carry out the esterification and crosslinking reaction; 90 ℃ of following drying treatment 12 hours in vacuum drying oven promptly get composite membrane for gasoline desulphurization at last.
2. the manufacture method of composite membrane for gasoline desulphurization according to claim 1 is characterized in that the starting material that use are in the support membrane preparation:
Aromatic diamine is a diphenylmethane diamine, 4,4 '-diamines yl diphenyl ether or 3, and 3 ' dimethyl diphenyl methane diamines is the aromatic diamine monomers with following structure:
The aromatic series dianhydride is pyromellitic acid dianhydride, hexafluorodianhydride or benzophenone tetracarboxylic dianhydride, is the aromatic dianhydride monomer with following structure:
Polar aprotic solvent is: N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl formamide or methyl-sulphoxide; Additive is: polyvinyl alcohol, polyoxyethylene glycol or polyvinylpyrrolidone.
3. the manufacture method of composite membrane for gasoline desulphurization according to claim 1 is characterized in that employed starting material are in the composite membrane preparation:
The epidermal area mould material is: polyoxyethylene glycol (PEG) or polyoxyethylene;
Solvent: be ethanol, Virahol or ethyl acetate;
Linking agent is: poly carboxylic acids such as maleic acid, citric acid or BTCA;
Catalyzer is: sodium dihydric hypophosphite or sodium hydroxide.
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| CN102302904A (en) * | 2011-05-17 | 2012-01-04 | 清华大学 | Method for preparing polystyrene maleimide membrane for gasoline desulfurization by pervaporation |
| CN103797092A (en) * | 2011-06-03 | 2014-05-14 | 韩国能源技术研究院 | Hydrocarbon advancement method |
| CN105566907A (en) * | 2016-03-22 | 2016-05-11 | 天津工业大学 | Polyimide nanofiltration membrane prepared on basis of synergic imidization and method thereof |
| CN107602857A (en) * | 2017-09-11 | 2018-01-19 | 中国石油大学(华东) | The preparation method and application of polyimides |
| CN110964492A (en) * | 2018-09-29 | 2020-04-07 | 中国石油化工股份有限公司 | Sulfur dissolving agent and preparation method and application thereof |
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| US4931181A (en) * | 1989-06-02 | 1990-06-05 | Membrane Technology & Research, Inc. | Composite membranes for fluid separations |
| US5098569A (en) * | 1990-12-13 | 1992-03-24 | Monsanto Company | Surface-modified support membrane and process therefor |
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