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CN101492458B - Method for preparing isosorbide by using tetravalent metal phosphate as catalyst - Google Patents

Method for preparing isosorbide by using tetravalent metal phosphate as catalyst Download PDF

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Publication number
CN101492458B
CN101492458B CN2009100248665A CN200910024866A CN101492458B CN 101492458 B CN101492458 B CN 101492458B CN 2009100248665 A CN2009100248665 A CN 2009100248665A CN 200910024866 A CN200910024866 A CN 200910024866A CN 101492458 B CN101492458 B CN 101492458B
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tetravalent metal
metal phosphate
isosorbide
catalyst
prepared
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CN101492458A (en
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黄和
余定华
顾铭燕
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Qingzhou City Ruixin Renewable Resources Technology Co ltd
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Nanjing Tech University
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Abstract

The invention discloses a method for preparing isosorbide by using tetravalent metal phosphate as a catalyst, which takes sorbitol as a raw material and tetravalent metal phosphate as a catalyst, and directly prepares the isosorbide through dehydration reaction.

Description

A kind of method that adopts tetravalent metal phosphate as catalyst to prepare Isosorbide
Technical field
The present invention relates to chemical technology field, be specifically related to a kind ofly, adopt biomass material to prepare the method for Isosorbide with tetravalent metal phosphate as catalyst.
Background technology
Isosorbide is the anhydro derivatives of D-sorbyl alcohol, sorbyl alcohol is the good depressor and the diuretic(s) of treatment encephalic supercharging disease aspect medical, because dehydration back hydroxyl has become ehter bond, its fat-soluble increase greatly, be different from sorbyl alcohol fully, absorbing immediately after oral is the oral dehydration and diuresis medicine of a kind of effective perviousness.Isosorbide has been applied to clinical abroad, and domestic only as the intermediate that synthesizes antianginal drug sorbide nitrate and isosorbide mononitrate.Isosorbide industrial be the important source material of span and Tween class tensio-active agent and intermediate, because its special chirality feature as intermediate, is applied to the synthetic of liquid crystal material, be widely used in electronics, fields such as national defence.Hot research in recent years then is that it is joined among the PET as polymeric additive, to improve the second-order transition temperature H of polymkeric substance gThereby, the intensity of increase polymkeric substance, the application market of expansion polymkeric substance.
Traditional Isosorbide all is to adopt still reaction production, need carry out a series of separation to product, as as far back as 1964 U.S. Atlas Chemical Industries company (USP 3160641) just proposed with the sorbyl alcohol dewatered product after the compound treatment acid catalysis that contains borate ion, through can obtaining the Isosorbide of purifying behind the underpressure distillation recrystallization, in afterwards several years the said firm to have proposed again to adopt sulfuric acid and tosic acid be the method for Preparation of Catalyst Isosorbide and the method for purification (USP 3454603 and 3484459); 2002 du pont company (USP 6407266) a kind of Isosorbide quantity-produced technology has been proposed, feed carrier gas N 2And replacement organic solvent in the past: feed the solution of sugar alcohol or anhydrosugar alcohol in reactor, carrier gas is fed by the bottom; Solution evaporation is removed most water; Dewater under catalyst action, the water that produces in the reaction is taken in carrier gas out of, derives product from reactor bottom.The raw material that uses is 70% sorbyl alcohol, H 2SO 4Make catalyzer, proposed the reactor of an integrated form.E.I.Du Pont Company is devoted to develop the production separating technology of a complete Isosorbide, after delivered a series of patent in several years, a more complete Isosorbide continuous production processes (USP 6864378) was finally proposed in 2005; Pacific Northwest National Laboratory in 2007 have delivered the relevant patent (USP 0173651～0173654) of the catalyzer that uses in a series of Isosorbide preparations, be converted into solid acid catalyst from the sulfuric acid catalyst that uses in the past, and add some metals as the generation of promotor with the minimizing by product with hydrogenation.All there are some common deficiencies in these production technique: still reaction, need under certain pressure or vacuum condition, dewater, and be not suitable for continuous production; Mineral acid is that catalyzer is had relatively high expectations to catalyticreactor, the long by product that generates dark color easily of life-span, though the by product that ion exchange resin produces is few, but the life-span is shorter; Operating temperature range is narrow, and high temperature causes sorbyl alcohol to decompose or the product carbon distribution easily, and the water that low temperature causes reacting generation easily can not in time be removed and reduce speed of reaction; The separation of product often needs organic solvent such as toluene or dimethylbenzene to participate in distillation, and recrystallization process, and a spot of inorganic acid ion is difficult to remove in the product.Face these difficult problems, we need find a kind of efficient acid catalyst and production technique of suitable continuous production Isosorbide.
The inconvenience that brings aborning along with inorganic acid catalyst, some relevant alternative catalysts have been engendered, the most significant is exactly solid acid catalyst, as HY and HZSM-5 molecular sieve (USP 6013812 and 7420067), but the productive rate of the Isosorbide that obtains under these molecular sieve catalytics is not high.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with the renewable resources, and production cost is low, reaction conditions gentleness, the method for preparing Isosorbide that operating process is simple, product yield is high.
Purpose of the present invention can reach by following measure:
A kind of method that adopts tetravalent metal phosphate as catalyst to prepare Isosorbide is characterized in that with the sorbyl alcohol being raw material, and tetravalent metal phosphate is a catalyzer, prepares Isosorbide by dehydration reaction.
Aforesaid method specifically can may further comprise the steps:
With tetravalent metal phosphate is pack into the constant temperature zone of fixed-bed reactor of catalyzer, preferably uses tubular fixed-bed reactor, at N 2Protection is warmed up to 200～350 ℃ with catalytic bed down, and preferred 250～300 ℃, the reactant Sorbitol Solution USP is added reactor, react by catalytic bed the gasification back, and the mixture after reaction finishes obtains Isosorbide through separating.Described separation can be undertaken by the separation method of routines such as distillation, recrystallization.
The concentration of above-mentioned Sorbitol Solution USP is 8%～15% sorbitol aqueous solution, preferred 10～12%; N 2Volume space velocity be 1～10h -1, preferred 3～6h -1
Described tetravalent metal phosphate can be unbodied tetravalent metal phosphate, a kind of in the tetravalent metal phosphate of the tetravalent metal phosphate of the tetravalent metal phosphate of preparation that refluxes, roasting preparation or hydrothermal preparation.
Tetravalent metal in the tetravalent metal phosphate of the tetravalent metal phosphate of described unbodied tetravalent metal phosphate, the preparation that refluxes, roasting preparation and the tetravalent metal phosphate of hydrothermal preparation is preferably Zr (zirconium), Ti (titanium) or Sn (tin).
Above-mentioned unbodied tetravalent metal phosphate is prepared by following method: with tetravalent metal source ZrOCl 28H 2O, TiCl 4Or SnCl 4With phosphorus source H 3PO 4Or Na 2HPO 4After the dissolving, under 20～30 ℃ of conditions, mix stirring, filter with 1: 6～1: 2 ratio of mol ratio, filter precipitate with deionized water wash to pH 3～3.5, filter cake can obtain unbodied tetravalent metal phosphate at 100～120 ℃ of drying 18～20h.
The tetravalent metal phosphate of above-mentioned backflow preparation is prepared by following method: the unbodied tetravalent metal phosphate that will the prepare according to the method described above 50～100h that refluxes in 10～12M phosphoric acid, filter, deionized water wash is to pH 3～3.5, and 100～110 ℃ are drying to obtain the tetravalent metal phosphates that reflux and prepare.
The tetravalent metal phosphate of above-mentioned roasting preparation is prepared by following method: the amorphous tetravalent metal phosphate that will prepare according to the method described above is at 400～450 ℃ of roasting 8～10h, temperature rise rate is 1 ℃/min, obtains the tetravalent metal phosphate of roasting preparation.
The tetravalent metal phosphate of above-mentioned hydrothermal preparation is prepared by following method: with tetravalent metal source ZrOCl 28H 2O, Ti (SO 4) 2Or SnCl 4With H 3PO 4After the dissolving, stir the formation coagulant liquid with 1: 6～1: 2 mixed of mol ratio, this coagulant liquid is transferred in the reactor, reactor is taken out behind 180 ℃ of reaction 6～48h in thermostat container, be cooled to room temperature, to pH 〉=5, can obtain the tetravalent metal phosphate of hydrothermal preparation with the deionized water thorough washing 50～60 ℃ of following vacuum-dryings.
The dissolving in source metal and phosphorus source comprises that both are dissolved in respectively in water, acid or the aqueous acid, also comprises a side is dissolved in the middle of the opposing party's the solution (aqueous solution, acid solution or aqueous acid).Percentage composition of the present invention is weight percentage.
The catalyzer of preparation Isosorbide of the present invention can be above-mentioned unbodied tetravalent metal phosphate, the tetravalent metal phosphate for preparing, the tetravalent metal phosphate of roasting preparation or the tetravalent metal phosphate of hydrothermal preparation reflux.This tetravalent metal phosphate activity of such catalysts is more than 24 hours.
The present invention is by the preliminary screening to catalyzer, can see tetravalent metal phosphate, Zr particularly, Ti, Sn, this class solid acid uses this class solid super-strong acid can reduce the use and the environmental friendliness of solvent to the good catalytic activity of sorbyl alcohol dehydration preparation Isosorbide, they belong to heterogeneous catalyst, easily separated and recovery.It is catalyzer that the present invention adopts tetravalent metal phosphate, be that reactor carries out sorbyl alcohol dehydration preparation Isosorbide with the fixed bed, and this operational path does not have bibliographical information as yet.Specifically can carry out according to following steps:
Catalyzer is divided into suitable particle (according to the size of reactor used size decision granules of catalyst, in the example of the present invention according to size (the long 16cm of used reactor, internal diameter 7cm), select 30～50 orders for use), get pack into the constant temperature zone of tubular fixed-bed reactor of catalyzer, after the systems inspection sealing, slowly the temperature of rising catalytic bed arrives required value under the N2 that flows purges; Raw material Sorbitol Solution USP (constant flow pump) is squeezed into system, and (mass space velocity is 1.2～8.4h -1, 2.4～3.6h most preferably -1), after gasification, react through catalytic bed, leave the N of catalytic bed 2With reaction mixture after ice-water bath cooling and gas-liquid separation, gas emptying, the liquid collecting sampling, product is qualitative with LC-MS, with HPLC-Dionex U3000 chromatogram, employing Aminex HPX-87H chromatographic column and differential refraction detector analysis are quantitative.
Beneficial effect of the present invention: the production method of Isosorbide of the present invention is to be raw material with the sorbyl alcohol, tetravalent metal phosphate is a catalyzer, the operation process is simple, production cost is low, environmental pollution is little, and the selectivity of Isosorbide is up to 81.30%, and yield is up to 69.80%, and catalyzer is easily separated and recovery, is a kind of very strong novel method of industrialization demand, practicality that satisfies.
Embodiment
Embodiment 1
With 23.3g H 3PO 4Be dissolved in the 476ml water 22.5gZrOCl 28H 2O is dissolved in the 140ml water, and both are stirred in mixed at room temperature, and suction filtration and be precipitated to pH 3 with deionized water wash filters then, and filter cake changes 100 ℃ of oven drying 18h over to, the cooling cooling, and compressing tablet is broken into pieces, and 30～50 orders sieve, and obtain amorphous phosphoric acid Zr catalyst.
With pack into the constant temperature zone of tubular fixed-bed reactor of the amorphous phosphoric acid Zr catalyst of 30～50 purposes 0.5g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 8% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 2
To contain 7.23ml TiCl 4The HCl solution of 215ml 2M slowly join the H of 200ml 1.25M 3PO 4In the solution, stirring at room 24h, suction filtration and be precipitated to pH 3.5 then with deionized water wash, filter cake changes 100 ℃ of oven drying 20h over to, the cooling cooling, compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains amorphous phosphoric acid titanium catalyst.
With pack into the constant temperature zone of tubular fixed-bed reactor of the amorphous phosphoric acid titanium catalyst of 30～50 purposes 0.5g, rest part is filled with quartz sand.After the systems inspection sealing, be 10h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 250 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 3
The Na that will contain 100ml 0.6M 2HPO 4The aqueous solution slowly joins the SnCl of 100ml 0.3M 4In the aqueous solution, stirring at room, then suction filtration and with deionized water wash to pH 3, filter cake changes 120 ℃ of oven drying 18h over to, cooling cooling, compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains amorphous phosphoric acid tin catalyst.
With pack into the constant temperature zone of tubular fixed-bed reactor of the amorphous phosphoric acid tin catalyst of 30～50 purposes 0.5g, rest part is filled with quartz sand.After the systems inspection sealing, be 1h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 350 ℃, then 12% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 4
The amorphous phosphoric acid zirconium 10g that embodiment 1 is obtained is at the H of 500ml 10M 3PO 4The 100h that refluxes in the solution filters, and deionized water wash is to 3.5,110 ℃ of dryings of pH, the cooling cooling, and compressing tablet is broken 30～50 orders into pieces and is sieved, the zirconium phosphate catalyzer that obtains refluxing and prepare.
With 30～50 purposes pack into the constant temperature zone of tubular fixed-bed reactor of the zirconium phosphate 0.5g prepare that refluxes, rest part is filled with quartz sand.After the systems inspection sealing, be 6h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 250 ℃, then 15% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 5
The amorphous phosphoric acid titanium 8g that embodiment 2 is obtained is at the H of 320ml 10M 3PO 4The 50h that refluxes in the solution filters, and deionized water wash is to 3,100 ℃ of dryings of pH, the cooling cooling, and compressing tablet is broken 30～50 orders into pieces and is sieved, the titanium phosphate catalyzer that obtains refluxing and prepare.
With 30～50 purposes pack into the constant temperature zone of tubular fixed-bed reactor of the titanium phosphate 0.5g obtain that refluxes, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 8% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 6
The amorphous phosphoric acid tin 5.4g that embodiment 3 is obtained is at the H of 250ml 12M 3PO 4The 100h that refluxes in the solution filters, and deionized water wash is to 3.5,100 ℃ of dryings of pH, the cooling cooling, and compressing tablet is broken 30～50 orders into pieces and is sieved, the phosphoric acid tin catalyst that obtains refluxing and prepare.
With 30～50 purposes pack into the constant temperature zone of tubular fixed-bed reactor of the phosphoric acid tin 0.5g obtain that refluxes, rest part is filled with quartz sand.After the systems inspection sealing, be 5h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 12% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 7
The amorphous phosphoric acid zirconium 5g that embodiment 1 is obtained is warming up to 400 ℃ and keep 10h with the temperature rise rate of 1 ℃/min in tube furnace, the cooling cooling, and compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains the zirconium phosphate that roasting prepares.
Pack into the constant temperature zone of tubular fixed-bed reactor of the zirconium phosphate 0.5g that 30～50 purpose roastings are obtained, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 8
The amorphous phosphoric acid titanium 5g that embodiment 2 is obtained is warming up to 450 ℃ and keep 8h with the temperature rise rate of 1 ℃/min in tube furnace, the cooling cooling, and compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains the titanium phosphate that roasting prepares.
Pack into the constant temperature zone of tubular fixed-bed reactor of the titanium phosphate 0.5g that 30～50 purpose roastings are obtained, rest part is filled with quartz sand.After the systems inspection sealing, be 5h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 250 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 9
The amorphous phosphoric acid tin 5g that embodiment 3 is obtained is warming up to 400 ℃ and keep 8h with the temperature rise rate of 1 ℃/min in tube furnace, the cooling cooling, and compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains the phosphoric acid tin that roasting prepares.
Pack into the constant temperature zone of tubular fixed-bed reactor of the phosphoric acid tin 0.5g that 30～50 purpose roastings are obtained, rest part is filled with quartz sand.After the systems inspection sealing, be 1h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 10
With 20gZrOCl 28H 2O is dissolved in the 110ml water, adds 85%H in this solution 3PO 47.2ml, stir the formation coagulant liquid in mixed at room temperature, this coagulant liquid is transferred in the reactor, again reactor is taken out behind 180 ℃ of anti-48h in thermostat container, be cooled to room temperature, use the deionized water thorough washing to pH 〉=5,60 ℃ of vacuum-dryings, the cooling cooling, compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains the zirconium phosphate that hydrothermal preparation obtains.
Pack into the constant temperature zone of tubular fixed-bed reactor of the zirconium phosphate 0.5g that 30～50 purpose hydro-thermals are obtained, rest part is filled with quartz sand.After the systems inspection sealing, be 4h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 15% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 11
With 20gTi (SO 4) 2Be dissolved among the 100ml 1M HCl, in this solution, add 85%H 3PO 49.6ml, stir the formation coagulant liquid in mixed at room temperature, this coagulant liquid is transferred in the reactor, in thermostat container, take out behind 180 ℃ of reaction 6h, be cooled to room temperature, use the deionized water thorough washing to pH 〉=5,55 ℃ of vacuum-dryings, the cooling cooling, compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains the titanium phosphate that hydrothermal preparation obtains.
Pack into the constant temperature zone of tubular fixed-bed reactor of the titanium phosphate 0.5g that 30～50 purpose hydro-thermals are obtained, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Embodiment 12
With 18gSnCl 4Be dissolved in the 100ml water, in this solution, add 85%H 3PO 4Solution 6.1ml, stir the formation coagulant liquid in mixed at room temperature, this coagulant liquid is transferred in the reactor, in thermostat container, take out behind 180 ℃ of anti-6h, be cooled to room temperature, use the deionized water thorough washing to pH 〉=5,60 ℃ of vacuum-dryings, the cooling cooling, compressing tablet is broken 30～50 orders into pieces and is sieved, and obtains the phosphoric acid tin that hydrothermal preparation obtains.
Pack into the constant temperature zone of tubular fixed-bed reactor of the phosphoric acid tin 0.5g that 30～50 purpose hydro-thermals are obtained, rest part is filled with quartz sand.After the systems inspection sealing, be 6h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Comparative Examples 1
With pack into the constant temperature zone of tubular fixed-bed reactor of the former powder catalyzer of 30～50 purpose HY 0.5g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Comparative Examples 2
With pack into the constant temperature zone of tubular fixed-bed reactor of the former powder of 30～50 purpose HZSM-5 (Si/Al=100) catalyzer 0.5g, rest part is filled with quartz sand.After the systems inspection sealing, be 3h at volume space velocity -1N 2Under the gas velocity with catalytic bed temperature programming to 300 ℃, then 10% Sorbitol Solution USP is squeezed into system, react by catalytic bed the gasification back, reaction mixture is after ice-water bath cooling and gas-liquid separation, the gas emptying, the liquid sampling of collecting behind the reaction 2h is analyzed, be the results are shown in Table one.
Table one embodiment and Comparative Examples reaction result
Embodiment Sorbyl alcohol transformation efficiency (%) Isosorbide selectivity (%) Isosorbide yield (%)
Embodiment 1 85.64 48.34 41.40
Embodiment 2 81.68 51.84 42.34
Embodiment 3 78.99 45.73 36.12
Embodiment 4 90.33 52.82 47.71
Embodiment 5 92.20 55.84 51.48
Embodiment 6 78.37 53.23 41.72
Embodiment 7 88.09 48.64 42.85
Embodiment 8 90.57 55.66 50.41
Embodiment 9 87.59 46.98 41.45
Embodiment 10 90.34 52.27 47.22
Embodiment 11 97.06 46.39 45.03
Embodiment 12 85.85 81.30 69.80
Comparative Examples 1 100 40.58 40.58
Comparative Examples 2 95.78 30.10 28.83

Claims (8)

1.一种采用四价金属磷酸盐作催化剂制备异山梨醇的方法，其特征在于以山梨醇为原料，四价金属磷酸盐为催化剂，通过脱水反应制备异山梨醇；所述的四价金属磷酸盐为无定形的四价金属磷酸盐、回流制备的四价金属磷酸盐、焙烧制备的四价金属磷酸盐或水热制备的四价金属磷酸盐，其中，四价金属为Zr，Ti或Sn。1. a kind of method that adopts tetravalent metal phosphate to prepare isosorbide as catalyst is characterized in that taking sorbitol as raw material, tetravalent metal phosphate is catalyst, prepares isosorbide by dehydration reaction; described tetravalent metal Phosphate is amorphous tetravalent metal phosphate, tetravalent metal phosphate prepared by reflux, tetravalent metal phosphate prepared by roasting or hydrothermally prepared tetravalent metal phosphate, wherein the tetravalent metal is Zr, Ti or Sn. 2.根据权利要求1所述的制备异山梨醇的方法，其特征在于所述的方法包括以下步骤：2. the method for preparing isosorbide according to claim 1 is characterized in that described method comprises the following steps: 将四价金属磷酸盐为催化剂装入固定床反应器的恒温段，在N2保护下将催化床层升温到200～350℃，将反应物山梨醇溶液加入反应器，气化后通过催化床层进行反应，反应结束后的混合物经分离得到异山梨醇。Put tetravalent metal phosphate as the catalyst into the constant temperature section of the fixed bed reactor, raise the temperature of the catalytic bed to 200-350°C under the protection of N2 , add the reactant sorbitol solution into the reactor, and pass through the catalytic bed after gasification The layer is reacted, and the mixture after the reaction is separated to obtain isosorbide. 3.根据权利要求2所述的采用四价金属磷酸盐作催化剂制备异山梨醇的方法，其特征在于所述的山梨醇溶液的浓度为8％～15％。3. the method for preparing isosorbide using tetravalent metal phosphate as a catalyst according to claim 2, characterized in that the concentration of the sorbitol solution is 8% to 15%. 4.根据权利要求2所述的采用四价金属磷酸盐作催化剂制备异山梨醇的方法，其特征在于N2的体积空速为1～10h-1。4. The method for preparing isosorbide using tetravalent metal phosphate as a catalyst according to claim 2, characterized in that the volumetric space velocity of N 2 is 1-10 h -1 . 5.根据权利要求4所述的采用四价金属磷酸盐作催化剂制备异山梨醇的方法，其特征在于N2的体积空速为3～6h-1。5. The method for preparing isosorbide using tetravalent metal phosphate as a catalyst according to claim 4, characterized in that the volume space velocity of N 2 is 3-6 h -1 . 6.根据权利要求2所述的采用四价金属磷酸盐作催化剂制备异山梨醇的方法，其特征在于所述的固定床反应器为管式固定床反应器。6. adopt tetravalent metal phosphate according to claim 2 as the method for preparing isosorbide as catalyst, it is characterized in that described fixed-bed reactor is a tubular fixed-bed reactor. 7.根据权利要求2所述的采用四价金属磷酸盐作催化剂制备异山梨醇的方法，其特征在于在N2保护下将催化床层升温到250～300℃。7. The method for preparing isosorbide using tetravalent metal phosphate as a catalyst according to claim 2, characterized in that the temperature of the catalytic bed is raised to 250-300° C. under the protection of N . 8.根据权利要求1所述的采用四价金属磷酸盐作催化剂制备异山梨醇的方法，其特征在于所述的无定形的四价金属磷酸盐是由如下方法得到的：将四价金属源ZrOCl2·8H2O、TiCl4或SnCl4与磷源H3PO4或Na2HPO4溶解后，以摩尔比1∶6～1∶2的比例在20～30℃条件下混合搅拌，过滤，滤得的沉淀用去离子水洗涤至pH 3～3.5，滤饼在100～120℃干燥18～20h即可得到无定形的四价金属磷酸盐；8. adopt tetravalent metal phosphate according to claim 1 to make the method for catalyst preparation isosorbide, it is characterized in that described amorphous tetravalent metal phosphate is obtained by following method: the tetravalent metal source After dissolving ZrOCl 2 8H 2 O, TiCl 4 or SnCl 4 and phosphorus source H 3 PO 4 or Na 2 HPO 4 , mix and stir at a molar ratio of 1:6-1:2 at 20-30°C, filter , the filtered precipitate was washed with deionized water to pH 3-3.5, and the filter cake was dried at 100-120°C for 18-20 hours to obtain amorphous tetravalent metal phosphate; 所述的回流制备的四价金属磷酸盐是由如下方法得到的：将上述无定形的四价金属磷酸盐在10～12M磷酸中回流50～100h，过滤，去离子水洗涤至pH 3～3.5，100～110℃干燥即得回流制备的四价金属磷酸盐；The tetravalent metal phosphate prepared by reflux is obtained by the following method: reflux the above-mentioned amorphous tetravalent metal phosphate in 10-12M phosphoric acid for 50-100h, filter, and wash with deionized water to pH 3-3.5 , and dry at 100-110°C to obtain the tetravalent metal phosphate prepared by reflux; 所述的焙烧制备的四价金属磷酸盐是由如下方法得到的：将上述无定形四价金属磷酸盐在400～450℃煅烧8～10h，升温速率为1℃/min，得到焙烧制备的四价金属磷酸盐；The tetravalent metal phosphate prepared by roasting is obtained by the following method: calcining the above-mentioned amorphous tetravalent metal phosphate at 400-450°C for 8-10 hours, and the heating rate is 1°C/min to obtain the tetravalent metal phosphate prepared by roasting. Valence metal phosphates; 所述的水热制备的四价金属磷酸盐是由如下方法得到的：将四价金属源ZrOCl2·8H2O、Ti(SO4)2或SnCl4与H3PO4溶解后，以摩尔比1∶6～1∶2的比例混合搅拌形成凝胶液，将该凝胶液转移入反应釜中，再将反应釜在恒温箱中180℃反应6～48h后取出，冷却至室温，用去离子水充分洗涤至pH≥5，在50～60℃下真空干燥得到水热制备的四价金属磷酸盐。The tetravalent metal phosphate prepared by hydrothermal method is obtained by the following method: after dissolving tetravalent metal source ZrOCl 2 ·8H 2 O, Ti(SO 4 ) 2 or SnCl 4 with H 3 PO 4 , Mix and stir at a ratio of 1:6 to 1:2 to form a gel liquid, transfer the gel liquid into a reaction kettle, then react the reaction kettle in a constant temperature box at 180°C for 6 to 48 hours, take it out, cool to room temperature, and use Fully wash with deionized water until pH ≥ 5, and vacuum dry at 50-60° C. to obtain tetravalent metal phosphate prepared by hydrothermal method.
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