CN102527412A - Synthetic soybean oil-based polyol catalyst, preparation method and application thereof - Google Patents

Synthetic soybean oil-based polyol catalyst, preparation method and application thereof Download PDF

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CN102527412A
CN102527412A CN2011104315384A CN201110431538A CN102527412A CN 102527412 A CN102527412 A CN 102527412A CN 2011104315384 A CN2011104315384 A CN 2011104315384A CN 201110431538 A CN201110431538 A CN 201110431538A CN 102527412 A CN102527412 A CN 102527412A
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catalyst
soybean oil
base polyol
oil base
alcohol
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亢茂青
李楠
王军威
赵雨花
殷宁
李其峰
冯月兰
董振
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a synthetic soybean oil-based polyol catalyst with a composition of SO4<2->/ZrO2-MOx, wherein MOx is one or two of oxides of silicon, aluminum, lanthanum, zinc, nickel, iron, cobalt, titanium, chromium, manganese, tungsten, copper, vanadium and molybdenum, and SO4<2-> is sulfate radical. The molar ratio of Zr and M is 1:X, when M is an element, the range of X is from 0.01 to 0.4; and when M is two elements, the range of X is from 0.01 to 0.6, and the content of SO4<2-> accounts for 1-5% of the total weight of the catalyst. The catalyst of the invention has the advantages easy recycling and reutilization, high catalyst activity, high product selectivity, and good reutilization performance.

Description

A kind of synthetic soybean oil base polyol catalyst and preparation method and application
Technical field
The invention belongs to a kind of catalyst and preparation method and application, relate to a kind of synthetic soybean oil base polyol catalyst and preparation method and application specifically.
Background technology
Polyurethane is made the diversity of prescription and good mechanics, acoustics, electricity and chemical-resistance because of it; Be widely used in foam, elastomer, coating, adhesive, fiber and synthetic leather industry, become people's clothing, food, live, one of row and the requisite synthetic material of high-technology field.Soybean oil is as being easy to get the most and cheap vegetable oil; Can be used as the synthetic potential source of polyurethane, not only help to reduce dependence, can also improve agricultural product added value oil product with raw polyol; Promote agricultural development, have good economy and social effect.
Research epoxidized soybean oil open loop addition at present generates the catalyst of soybean oil base polyol and obtained certain progress: Petrovic Z adopts fluoboric acid to make catalyst, synthesizes the soybean oil base polyol (U.S. Pat 6107433) with higher hydroxyl value; Andrew Guo etc. in acetone with HBr, HCl as catalyst and open loop addition reagent; Prepare the soybean oil base polyol (Andrew Guo, YoungjinCho, the ZoranS.Petrovic.J PolymSci Part A:Polym Chem.2000 that contain halogen; 38,3900-3910); Yantao Li etc. are catalyst with the triphenyl phosphite, and acrylic acid is made solvent and open loop reagent, the reaction 8h obtain the target product polyalcohol (Yantao Li, LiyuFu, Shufen Lai, et al.Eur J LipidSciTechnol, 2010,112:511-516).U.S. Pat 6573354B1 and US6433121B1 are with epoxidized soybean oil, H 2O, CH 3The mixture of OH is via the synthetic polyalcohol of HBF4 catalysis.The homogeneous catalyst that these reports are adopted is difficult to separate with product, and last handling process is complicated, is difficult to reuse, and with an organic solvent also can cause environmental pollution in addition.Chinese patent CN101397251A adopts solid super acid catalyst SO 4 2-/ ZrO 2The opening of catalysis epoxidized soybean oil preferably, this heterogeneous catalyst separates with product easily, and small molecule alcohol had both been made reactant simultaneously, made solvent again, had avoided the use of other organic solvent, can separated and recycling after the reaction.But exist catalyst activity and selectivity of product low, reusability is low.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst and be easy to synthetic soybean oil base polyol catalyst and preparation method and the application that recycling, catalyst activity are high, selectivity of product is high, reuse is good.Catalyst of the present invention consists of:
SO 4 2-/ ZrO 2-MO x, auxiliary agent MO wherein xBe one or both the mixture in the oxide of silicon, aluminium, lanthanum, zinc, nickel, iron, cobalt, titanium, chromium, manganese, tungsten, copper, vanadium, molybdenum, SO 4 2-Be sulfate radical.
The mol ratio of described zirconium and auxiliary agent M is Zr: M=1: X, and when M was a kind of element, the span of X was 0.01～0.4; When M was two kinds of elements, the span of X was 0.01～0.6, SO 4 2-Content accounts for 1%～5% of total catalyst weight.
Catalyst of the present invention is prepared by following method:
(1) water soluble salt with water-soluble zirconates and one or both auxiliary agents adds in the deionized water jointly, and preparation zirconates concentration is the solution of 0.05～0.75mol/L, adds the alkaline sedimentation agent solution again, and regulator solution pH value is 8～11, obtains the hydroxide hydrogel;
(2) hydrogel is left standstill aging 2～48h, be preferably 10～24h; Filter, washing, dry 4～24h under 80～120 ℃ of conditions, be 6～12h preferred drying time, processes the hydroxide xerogel;
(3) the hydroxide xerogel floods 10～120min in aqueous sulfuric acid, and sulfuric acid concentration is 0.2～5mol/L, is preferably 1～3mol/L, the ratio of the aqueous sulfuric acid that uses and hydroxide xerogel be 1～7mL/g, be preferably 2～5mL/g; Xerogel behind the absorption sulfuric acid is filtered out, in 80～120 ℃ of drying 4～24h; After high-temperature roasting obtains solid super acid catalyst, sintering temperature is 350～850 ℃, is preferably 400～700 ℃, and roasting time is 1～10h, is preferably 2～6h.
Aforesaid solubility zirconates can be zirconium nitrate, zirconyl nitrate or zirconium oxychloride.
Aforesaid auxiliary agent, when auxiliary agent was silica, soluble silicon salt was alumina silicate, sodium metasilicate or sodium metasilicate; When auxiliary agent was aluminium oxide, aluminum soluble salt was aluminum nitrate, oxalic acid aluminium, aluminium chloride or alumina silicate; Select nitrate, acetate, oxalates or the chloride of transition metal during for transition metal oxide when auxiliary agent, be preferably nitrate, acetate or the chloride of lanthanum, zinc, nickel, iron, titanium, chromium, manganese, tungsten.
Aforesaid precipitating reagent can be ammoniacal liquor, sodium carbonate, sodium acid carbonate, potash, urea, ammonium carbonate, sodium hydroxid or potassium hydroxide, is preferably ammoniacal liquor or sodium carbonate.
Aforesaid washing spends deionised water to there not being Cl when adopting chloride raw material -, spend deionised water when adopting alumina silicate, sodium metasilicate, sodium metasilicate, oxalic acid aluminium, nitrate, acetate to neutral.
The application of catalyst of the present invention in synthetic soybean oil polyalcohol comprises the steps:
Epoxidized soybean oil, small molecular alcohol, catalyst are joined in the reactor, and wherein the mol ratio of small molecular alcohol and epoxidized soybean oil is 10～100: 1, is preferably 30～80: 1; The use amount of catalyst is 0.5～20% of an epoxidized soybean oil mass fraction, is preferably 1～10%, charges into the air in the nitrogen replacement reactor earlier; Closed reactor afterwards, under stirring condition with reaction mass heated to 70～170 ℃, preferred 80～150 ℃; Reaction time is 1～8h, is preferably 1.5～5h, after question response finishes; Be cooled to room temperature, filter out catalyst, filtrating is vacuumized under the temperature 40～120 ℃ remove remove unreacted small molecular alcohol; Removing temperature is 50～130 ℃, is preferably 70～100 ℃; The time of removing is 20～120min, is preferably 40～80min, to react the isolated catalyst in back according to the ratio of 5～30mL/g with acetone 2～5 times, the catalyst after the cleaning is under 80～120 ℃, drying 4～24h reuses again.
Aforesaid small molecular alcohol is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, n-hexyl alcohol; Particular methanol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol.
The present invention compared with prior art has following advantage
1, can catalyst be separated with product through simple filtering, process is simple;
2, catalyst is easy to recycling;
3, catalyst preparation process is simple, and active height and reaction condition are gentle, and side reaction is few, non-environmental-pollution.
The specific embodiment
Following embodiment adopts hydrochloric acid-acetone method to measure the epoxide group conversion ratio, and the product hydroxyl value is measured according to HG/T2709-1995.
Embodiment 1:
With 8.06gZrOCl 28H 2O, 0.68gLaCl 37H 2O joins in the 150mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, La, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, and Cake Wash (is not used AgNO to there being Cl- 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3.5h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-La 2O 3Solid acid catalyst, ZrO in the catalyst 2With La 2O 3Mol ratio be 25: 1, SO 4 2-Account for the 4wt% of total catalyst.
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 30g absolute methanol, the above-mentioned catalyst S O of 0.5g successively 4 2-/ ZrO 2-La 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 110 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 70 ℃ and removes unreacted methanol, promptly gets weak yellow liquid product soybean oil base polyol.It is 97.8% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 196.5mgKOH/g.
Embodiment 2:
With 12.89gZrOCl 28H 2O and 1.53gNi (NO 3) 26H 2O joins in the 200mL deionized water, except that sintering temperature is that 600 ℃, roasting time are the 3h, according to making SO with embodiment 1 identical condition and step 4 2-/ ZrO 2-NiO solid acid catalyst.ZrO in the catalyst 2With the mol ratio of NiO be 6: 1, SO 4 2-Account for the 3wt% of total catalyst.
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 46g absolute ethyl alcohol, 0.5g solid acid catalyst SO successively 4 2-/ ZrO 2-NiO, closed reactor, logical N 2Air in the displacement still is warming up to 120 ℃ afterwards under stirring condition, behind the reaction 3h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 80 ℃ and removes ethanol, promptly gets weak yellow liquid product soybean oil base polyol.It is 95.1% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 191.4mgKOH/g.
Embodiment 3:
With 8.25g ZrOCl 28H 2O, 2.83gNa 2SiO 39H 2O joins in the 150mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 10, obtains the hydroxide hydrogel of Zr, Si, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3.5h under 500 ℃ of conditions at last, make SO 4 2-/ ZrO 2-SiO 2The doping solid acid catalyst.ZrO in the catalyst 2With SiO 2Mol ratio be 3: 1, SO 4 2-Account for the 5wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 60g anhydrous isopropyl alcohol, 0.6g solid acid catalyst SO successively 4 2-/ ZrO 2-SiO 2, closed reactor, logical N 2Air in the displacement still is warming up to 125 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 80 ℃ and removes isopropyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 96.3% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 191.9mgKOH/g.
Embodiment 4:
With 8.05gZrOCl 28H 2O, 1.65g Zn (CH 3COO) 28H 2O joins in the 125mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Si, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3.5h under 500 ℃ of conditions at last, make SO 4 2-/ ZrO 2-ZnO doping solid acid catalyst.ZrO in the catalyst 2With the mol ratio of ZnO be 6: 1, SO 4 2-Account for the 2.5wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), the anhydrous normal propyl alcohol of 60g, 0.6g solid acid catalyst SO successively 4 2-/ ZrO 2-ZnO, closed reactor, logical N 2Air in the displacement still is warming up to 125 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 90 ℃ and removes normal propyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 97.2% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 195.7mgKOH/g.
Embodiment 5:
With 8.06gZrOCl 28H 2O and 1.13gAl (NO 3) 39H 2O joins in the 125mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Al, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Al 2O 3Solid acid catalyst.ZrO in the catalyst 2With Al 2O 3Mol ratio be 20: 1, SO 4 2-Account for the 3.2wt% of total catalyst
In the 100mL agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 30g absolute methanol, 0.5g solid acid catalyst SO successively 4 2-/ ZrO 2-Al 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 110 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 70 ℃ and removes methyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 99.1% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 201.1mgKOH/g.
Embodiment 6:
With 9.52gZr (NO 3) 45H 2O, 1.06gAl 2(C 2O 4) 34H 2O joins in the 150mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor; The regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Al, and hydrogel is left standstill aging 12h; Remove by filter the aqueous solution; And spend deionised water 5 times, and transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Al 2O 3The doping solid acid catalyst.ZrO in the catalyst 2With Al 2O 3Mol ratio be 4: 1, SO 4 2-Account for the 3.0wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 46g absolute ethyl alcohol, 0.5g solid acid catalyst SO successively 4 2-/ ZrO 2-Al 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 110 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 80 ℃ and removes ethanol, promptly gets weak yellow liquid product soybean oil base polyol.It is 96.2% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 193.1mgKOH/g.
Embodiment 7:
With 5.80gZrO (NO 3) 2, 1.85gAl (NO 3) 39H 2O joins in the 150mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor; The regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Al, and hydrogel is left standstill aging 12h; Remove by filter the aqueous solution; And spend deionised water 5 times, and transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Al 2O 3The doping solid acid catalyst.ZrO in the catalyst 2With Al 2O 3Mol ratio be 10: 1, SO 4 2-Account for the 3.0wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), the anhydrous normal propyl alcohol of 60g, 0.6g solid acid catalyst SO successively 4 2-/ ZrO 2-Al 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 125 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 90 ℃ and removes normal propyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 93.9% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 189.2mgKOH/g.
Embodiment 8:
With 6.45gZrOCl 28H 2O, 1.74gAl (NO 3) 39H 2O, 0.95gFe 2(NO 3) 39H 2O joins in the 120mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Al, Fe, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Al 2O 3-Fe 2O 3The doping solid acid catalyst.ZrO in the catalyst 2, Al 2O 3, Fe 2O 3Mol ratio be 10: 2.5: 1, SO 4 2-Account for the 3.0wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 30g absolute methanol, 0.5g solid acid catalysis SO successively 4 2-/ ZrO 2-Al 2O 3-Fe 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 110 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 70 ℃ and removes methyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 98.7% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 198.5mgKOH/g.
Embodiment 9:
With 6.95g ZrO (NO 3) 2, 1.35gCrCl 36H 2O, 0.88gNi (NO 3) 26H 2O joins in the 150mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Cr, Ni, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 600 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Cr 2O 3-NiO doping solid acid catalyst.ZrO in the catalyst 2, Cr 2O 3, NiO mol ratio be 6: 1: 0.6, SO 4 2-Account for the 2.5wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 46g absolute ethyl alcohol, 0.5g solid acid catalyst SO successively 4 2-/ ZrO 2-Cr 2O 3-NiO, closed reactor, logical N 2Air in the displacement still is warming up to 120 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 80 ℃ and removes ethanol, promptly gets weak yellow liquid product soybean oil base polyol.It is 96.3% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 193.7mgKOH/g.
Embodiment 10:
With 8.14gZrOCl 28H 2O, 1.88gFe 2(NO 3) 39H 2O, 0.85gNa 2SiO 39H 2O joins in the 120mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Fe, Si, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 600 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Fe 2O 3-SiO 2The doping solid acid catalyst.ZrO in the catalyst 2: Fe 2O 3: SiO 2Mol ratio be 25: 4: 3, SO 4 2-Account for the 3.5wt% of total catalyst.
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), the anhydrous normal propyl alcohol of 60g, 0.5g solid acid catalyst SO successively 4 2-/ ZrO 2-Fe 2O 3-SiO 2, closed reactor, logical N 2Air in the displacement still is warming up to 125 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 90 ℃ and removes normal propyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 96.5% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 194.8mgKOH/g.
Embodiment 11:
With 8.03gZrOCl 28H 2O, 0.55gNa 2WO 42H 2O, 2.78gLaCl 37H 2O joins in the 125mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, W, La, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 500 ℃ of conditions at last, make SO 4 2-/ ZrO 2-WO 3-La 2O 3The doping solid acid catalyst.ZrO in the catalyst 2: WO 3: La 2O 3Mol ratio be 25: 2: 4, SO 4 2-Account for the 3.0wt% of total catalyst.
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 60g anhydrous isopropyl alcohol, 0.6g solid acid catalyst SO successively 4 2-/ ZrO 2-WO 3-La 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 125 ℃ afterwards under stirring condition, behind the reaction 2h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 80 ℃ and removes isopropyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 94.6% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 189.9mgKOH/g.
Embodiment 12:
With 8.05gZrOCl 28H 2O, 1.39gNa 2SiO 39H 2O, 1.96gCrCl 36H 2O joins in the 120mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Si, Cr, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-SiO 2-Cr 2O 3The doping solid acid catalyst.ZrO in the catalyst 2: SiO 2: Cr 2O 3Mol ratio be 20: 4: 3, SO 4 2-Account for the 2.8wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 74g anhydrous normal butyl alcohol, 0.7g solid acid catalyst SO successively 4 2-/ ZrO 2-SiO 2-Cr 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 130 ℃ afterwards under stirring condition, behind the reaction 3h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 110 ℃ and removes n-butanol, promptly gets weak yellow liquid product soybean oil base polyol.It is 96.8% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 194.2mgKOH/g.
Embodiment 13:
With 8.59gZr (NO 3) 45H 2O, 1.36gFe 2(NO 3) 39H 2O, 0.72gMnC 2O 42H 2O joins in the 110mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor; The regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Fe, Mn, and hydrogel is left standstill aging 12h; Remove by filter the aqueous solution; And spend deionised water 5 times, and transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Fe 2O 3-MnO 2The doping solid acid catalyst.ZrO in the catalyst 2: Fe 2O 3: MnO 2Mol ratio be 20: 3: 4, SO 4 2-Account for the 2.4wt% of total catalyst.
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 30g absolute methanol, 0.4g solid acid catalyst SO successively 4 2-/ ZrO 2-Fe 2O 3-MnO 2, closed reactor, logical N 2Air in the displacement still is warming up to 110 ℃ afterwards under stirring condition, behind the reaction 3h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 70 ℃ and removes methyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 94.1% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 188.2mgKOH/g.
Embodiment 14:
With 8.59gZr (NO 3) 45H 2O, 1.03g (CH 3COO) 2Zn8H 2O, 1.76gAl (NO 3) 39H 2O joins in the 120mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor; The regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Zn, Al, and hydrogel is left standstill aging 12h; Remove by filter the aqueous solution; And spend deionised water 5 times, and transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 600 ℃ of conditions at last, make SO 4 2-/ ZrO 2-ZnO-Al 2O 3The doping solid acid catalyst.ZrO in the catalyst 2: ZnO: Al 2O 3Mol ratio be 40: 6: 5, SO 4 2-Account for the 3.0wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 46g absolute ethyl alcohol, 0.5g solid acid catalyst SO successively 4 2-/ ZrO 2-ZnO-Al 2O 3, closed reactor, logical N 2Air in the displacement still is warming up to 120 ℃ afterwards under stirring condition, behind the reaction 3h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 80 ℃ and removes ethanol, promptly gets weak yellow liquid product soybean oil base polyol.It is 98.2% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 197.8mgKOH/g.
Embodiment 15:
With 8.05gZrOCl 28H 2O, 1.27gAl 2(C 2O 4) 34H 2O, 2.21gNa 2SiO 39H 2O joins in the 120mL deionized water, under stirring condition, adds 1mol/L ammoniacal liquor, and the regulator solution pH value is 9, obtains the hydroxide hydrogel of Zr, Al, Si, and hydrogel is left standstill aging 12h, removes by filter the aqueous solution, with Cake Wash to there not being Cl -(use AgNO 3Solution detects), transfer to again in the baking oven in 110 ℃ of dry 12h, grind to form powdery; With the liquid-solid ratio dipping 30min of 2mol/L sulfuric acid solution, filter, with 100mL deionized water washing 3 times according to 5mL/g; Macerate at 110 ℃ of dry 12h, is put into Muffle furnace roasting 3h under 550 ℃ of conditions at last, make SO 4 2-/ ZrO 2-Al 2O 3-SiO 2The doping solid acid catalyst.ZrO in the catalyst 2: Al 2O 3: SiO 2Mol ratio be 25: 3: 8, SO 4 2-Account for the 3.5wt% of total catalyst
In agitated reactor, add 20g epoxidized soybean oil (epoxy group content is 3.8mol/kg), 30 absolute methanols, 0.5g solid acid catalyst SO successively 4 2-/ ZrO 2-Al 2O 3-SiO 2, closed reactor, logical N 2Air in the displacement still is warming up to 110 ℃ afterwards under stirring condition, behind the reaction 3h, stop reaction, adopts water-bath to be cooled to room temperature, filters out catalyst, vacuumizes under 70 ℃ and removes methyl alcohol, promptly gets weak yellow liquid product soybean oil base polyol.It is 98.6% that reaction finishes back measurement ring oxygen groups conversion ratio, and the product hydroxyl value is 198.3mgKOH/g.

Claims (13)

1. synthetic soybean oil base polyol catalyst is characterized in that catalyst consists of:
SO 4 2-/ ZrO 2-MO x, auxiliary agent MO wherein xBe one or both the mixture in the oxide of silicon, aluminium, lanthanum, zinc, nickel, iron, cobalt, titanium, chromium, manganese, tungsten, copper, vanadium, molybdenum, SO 4 2-Be sulfate radical.
The mol ratio of described zirconium and auxiliary agent M is Zr: M=1: X, and when M was a kind of element, the span of X was 0.01～0.4; When M was two kinds of elements, the span of X was 0.01～0.6, SO 4 2-Content accounts for 1%～5% of total catalyst weight.
2. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 1 is characterized in that comprising the steps:
(1) water soluble salt with water-soluble zirconates and one or both auxiliary agents adds in the deionized water jointly, and preparation zirconates concentration is the solution of 0.05～0.75mol/L, adds the alkaline sedimentation agent solution again, and regulator solution pH value is 8～11, obtains the hydroxide hydrogel;
(2) hydrogel is left standstill aging 2～48h, filter, washing, dry 4～24h processes the hydroxide xerogel under 80～120 ℃ of conditions;
(3) the hydroxide xerogel floods 10～120min in aqueous sulfuric acid; Sulfuric acid concentration is 0.2～5mol/L; The ratio of the aqueous sulfuric acid that uses and hydroxide xerogel be 1～7mL/g, the xerogel behind the absorption sulfuric acid is filtered out, in 80～120 ℃ of drying 4～24h; After high-temperature roasting obtains solid super acid catalyst, sintering temperature is 350～850 ℃, and roasting time is 1～10h.
3. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 2 is characterized in that described solubility zirconates is zirconium nitrate, zirconyl nitrate or zirconium oxychloride.
4. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 2 is characterized in that the water soluble salt of described auxiliary agent, and when auxiliary agent was silica, soluble silicon salt was alumina silicate, sodium metasilicate or sodium metasilicate; When auxiliary agent was aluminium oxide, aluminum soluble salt was aluminum nitrate, oxalic acid aluminium, aluminium chloride or alumina silicate; When auxiliary agent was transition metal oxide, soluble transition metal salt was nitrate, acetate, oxalates or chloride.
5. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 4 is characterized in that described soluble transition metal salt is the nitrate of lanthanum, zinc, nickel, iron, titanium, chromium, manganese, tungsten, acetate or chloride.
6. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 2 is characterized in that described precipitating reagent is ammoniacal liquor, sodium carbonate, sodium acid carbonate, potash, urea, ammonium carbonate, sodium hydroxid or potassium hydroxide,
7. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 6 is characterized in that described precipitating reagent is ammoniacal liquor or sodium carbonate.
8. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 1 is characterized in that described washing, spends deionised water to there not being Cl when adopting chloride raw material -, spend deionised water when adopting alumina silicate, sodium metasilicate, sodium metasilicate, oxalic acid aluminium, nitrate, acetate to neutral.
9. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 1 is characterized in that the ageing time in the described step (2) is 10～24h, and be 6～12h drying time.
10. a kind of synthetic soybean oil base polyol Preparation of catalysts method as claimed in claim 1 is characterized in that the sulfuric acid concentration in the described step (3) is 1～3mol/L, the ratio of the aqueous sulfuric acid that uses and hydroxide xerogel be 2～5mL/g; Sintering temperature is 400～700 ℃, and roasting time is 2～6h.
11. a kind of synthetic soybean oil base polyol Application of Catalyst as claimed in claim 1 is characterized in that comprising the steps:
Epoxidized soybean oil, small molecular alcohol, catalyst are joined in the reactor, and wherein the mol ratio of small molecular alcohol and epoxidized soybean oil is 10～100: 1, and the use amount of catalyst is 0.5～20% of an epoxidized soybean oil mass fraction; Charge into the air in the nitrogen replacement reactor earlier, closed reactor afterwards, under stirring condition with reaction mass heated to 70～170 ℃; Reaction time is 1～8h, and question response is cooled to room temperature after finishing; Filter out catalyst, filtrating is vacuumized under the temperature 40～120 ℃ remove remove unreacted small molecular alcohol, removing temperature is 50～130 ℃; The time of removing is 20～120min, to react the isolated catalyst in back according to the ratio of 5～30mL/g with acetone 2～5 times, the catalyst after the cleaning is under 80～120 ℃; Dry 4～24h reuses again.
12. a kind of synthetic soybean oil base polyol Application of Catalyst as claimed in claim 11 is characterized in that described small molecular alcohol is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, n-hexyl alcohol; Particular methanol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol.
13. a kind of synthetic soybean oil base polyol Application of Catalyst as claimed in claim 11; The mol ratio that it is characterized in that described small molecular alcohol and epoxidized soybean oil is 30～80: 1; The use amount of catalyst is 1～10% of an epoxidized soybean oil mass fraction; Reaction temperature is 80～150 ℃, and the reaction time is 1.5～5h, and removing temperature is 70～100 ℃; The time of removing is 40～80min.
CN2011104315384A 2011-12-14 2011-12-14 Synthetic soybean oil-based polyol catalyst, preparation method and application thereof Pending CN102527412A (en)

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CN103772165A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Method for preparing polyoxymethylene dimethyl ether from paraformaldehyde
CN106582814A (en) * 2016-12-20 2017-04-26 福州大学 Epoxide ring-opening reaction catalyst and preparation method thereof
CN109746004A (en) * 2017-11-07 2019-05-14 万华化学集团股份有限公司 A kind of catalyst and its preparing the application in 2,2,6,6- tetramethyl -4- piperidones
CN110787801A (en) * 2019-11-05 2020-02-14 江南大学 Synthetic method and application of magnetic solid acid catalyst
CN112705230A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Catalyst for condensation reaction and preparation method thereof
CN116731764A (en) * 2023-06-28 2023-09-12 孚迪斯石油化工科技(葫芦岛)股份有限公司 Preparation method of modified polyol ester aviation lubricating oil

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CN101397251A (en) * 2008-10-08 2009-04-01 中国科学院山西煤炭化学研究所 Method for synthesizing epoxy soybean oil base polyol under heterogenous catalysis system
CN102172534A (en) * 2011-03-17 2011-09-07 湘潭大学 Nitration catalyst and preparation method and application thereof

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CN103772165A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Method for preparing polyoxymethylene dimethyl ether from paraformaldehyde
CN103772165B (en) * 2012-10-25 2016-05-18 中国石油化工股份有限公司 By the method for paraformaldehyde polyoxymethylene dimethyl ethers processed
CN106582814A (en) * 2016-12-20 2017-04-26 福州大学 Epoxide ring-opening reaction catalyst and preparation method thereof
CN106582814B (en) * 2016-12-20 2019-02-22 福州大学 A kind of epoxy ring opening reaction catalyst and preparation method thereof
CN109746004A (en) * 2017-11-07 2019-05-14 万华化学集团股份有限公司 A kind of catalyst and its preparing the application in 2,2,6,6- tetramethyl -4- piperidones
CN112705230A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Catalyst for condensation reaction and preparation method thereof
CN112705230B (en) * 2019-10-25 2023-06-06 中国石油化工股份有限公司 Catalyst for condensation reaction and preparation method thereof
CN110787801A (en) * 2019-11-05 2020-02-14 江南大学 Synthetic method and application of magnetic solid acid catalyst
CN110787801B (en) * 2019-11-05 2021-10-01 江南大学 Synthetic method and application of magnetic solid acid catalyst
CN116731764A (en) * 2023-06-28 2023-09-12 孚迪斯石油化工科技(葫芦岛)股份有限公司 Preparation method of modified polyol ester aviation lubricating oil
CN116731764B (en) * 2023-06-28 2023-11-24 孚迪斯石油化工科技(葫芦岛)股份有限公司 Preparation method of modified polyol ester aviation lubricating oil

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