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, at mobile N
2Purging down, the temperature of slow rising catalytic bed arrives required value; 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 |