CN103949266B - Take isopropanolamine as catalyst and the preparation method of Material synthesis 2,5-dimethyl pyrazine - Google Patents
Take isopropanolamine as catalyst and the preparation method of Material synthesis 2,5-dimethyl pyrazine Download PDFInfo
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Abstract
The invention discloses the catalyst that one take isopropanolamine as Material synthesis 2,5-dimethyl pyrazine, comprise carrier and be carried on the active component on carrier, described active component is cupric oxide, zinc oxide and other metal oxides; The load capacity of described cupric oxide is 5% ~ 15% of catalyst quality, and the load capacity of zinc oxide is 5% ~ 15% of catalyst quality; Other metal oxides described are silver oxide and/or chromium oxide, and the load capacity of other metal oxides is 4% ~ 8% of catalyst quality; Described carrier is Al
2o
3carrier or silica-alumina supports, in described silica-alumina supports, the mass percentage of silica is not more than 20%.The present invention adopts cupric oxide and zinc oxide, and one or both in silver oxide and chromium oxide are as active component, the activity and selectivity of catalyst can be significantly improved, the catalyst of preparation has that reaction condition gentleness, isopropanolamine conversion ratio are high, the selective high feature of 2,5-dimethyl pyrazine.
Description
Technical field
The invention belongs to catalyst preparation technical field, being specifically related to a kind of is Material synthesis 2 with isopropanolamine, the catalyst of 5-dimethyl pyrazine and preparation method.
Background technology
2,5-dimethyl pyrazine (2,5-dimethylpyrazine) be a kind of important medicine chemical material, it is synthesis Glipizide, the key intermediate of the newtype drugs such as acipimox, 5-Methylpyrazine-2-carboxylic acid methyl esters, specifies the flavorant of use simultaneously, adds in the food such as baked goods, cocoa, coffee, meat, nut in it or GB GB2760-1996, produce pleasant fragrance, have important use in the food industry.At present, 2, the typical synthetic technology circuit of 5-dimethyl pyrazine has: the ketone 1) containing active methylene group with nitrous acid process, then be reduced into, two molecule alphas-amino ketones again cyclodehydration obtains dihydro pyrazine, changes into alkyl pyrazine because strong aromatisation trend makes dihydro pyrazine be easy to dehydrogenation.Need to carry out being oxidized with mercury chloride just can obtain 2,5-dimethyl pyrazine after the dehydration of alpha-amido ketone self-condensation.This method process route is complicated, and mercury chloride is easily to environment, and production cost is high, is not suitable for large-scale industrial production; 2) methacrylaldehyde and ammonia are under ammonium salt exists, and in glycerine, add thermal response, the raw materials used methacrylaldehyde of this method has severe toxicity, and easily blasts, and has very large potential safety hazard; 3) prepare 2,5-dimethyl pyrazine by alpha-amido acetone oxidation, the method needs high-temperature catalytic, and accessory substance is many, and separation and purification causes difficulty; 4) preparation is synthesized by alpha-halogen MIBK.Alpha-halogen MIBK and ammonia, in autoclave, react under high temperature, and halogen is first obtained alpha-amido ketone by amino replacement, and the further condensation closed loop of alpha-amido ketone obtains dihydro pyrazine, is then oxidized to stable pyrazine.Due to the reaction needed HTHP with ammonia, operating condition is harsh.In recent years, take isopropanolamine as raw material, catalyst carries out gas-solid phase reaction continuous seepage 2 under existing, 5-dimethyl pyrazine technology is extensive with its raw material sources, production cost is low, working condition is gentle, and product yield high obtains and develops rapidly, and the key of this technique is exactly catalyst technology.
It is that the method for 2,5-dimethyl pyrazine produced by raw material and 2,5-dimethyl pyrazine is separated, purification process that Chinese patent CN03143258.X and CN03143258.1 describes respectively with isopropanolamine, but does not relate to the preparation method of catalyst.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and providing a kind of take isopropanolamine as the catalyst of Material synthesis 2,5-dimethyl pyrazine.This catalyst adopts cupric oxide and zinc oxide, and one or both in silver oxide and chromium oxide are as active component, the activity and selectivity of catalyst can be significantly improved, the catalyst of preparation has that reaction condition gentleness, isopropanolamine conversion ratio are high, the selective high feature of 2,5-dimethyl pyrazine.Adopt this catalyst isopropanolamine to synthesize 2,5-dimethyl pyrazine, the molar yield of isopropanolamine can reach more than 84.7%, and the molar yield of 2,5-dimethyl pyrazine can reach more than 73.2%.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of is Material synthesis 2 with isopropanolamine, the catalyst of 5-dimethyl pyrazine, comprise carrier and be carried on the active component on carrier, it is characterized in that, described active component is cupric oxide, zinc oxide and other metal oxides; The load capacity of described cupric oxide is 5.0% ~ 15.0% of catalyst quality, and the load capacity of zinc oxide is 5.0% ~ 15.0% of catalyst quality; Other metal oxides described are silver oxide and/or chromium oxide, and the load capacity of other metal oxides is 4.0% ~ 8.0% of catalyst quality; Described carrier is Al
2o
3carrier or silica-alumina supports, in described silica-alumina supports, the mass percentage of silica is not more than 20%.
Above-mentioned take isopropanolamine as Material synthesis 2, the catalyst of 5-dimethyl pyrazine, the load capacity of described cupric oxide is 8% ~ 14% of catalyst quality, and the load capacity of zinc oxide is 9% ~ 15% of catalyst quality, and the load capacity of other metal oxides is 4% ~ 7% of catalyst quality.
Above-mentioned take isopropanolamine as Material synthesis 2, the catalyst of 5-dimethyl pyrazine, the load capacity of described cupric oxide is 10% of catalyst quality, and the load capacity of zinc oxide is 13% of catalyst quality, and the load capacity of other metal oxides is 5.5% of catalyst quality.
The catalyst of above-mentioned with isopropanolamine is Material synthesis 2,5-dimethyl pyrazine, also comprise the auxiliary agent be carried on carrier, described auxiliary agent is iron oxide and/or manganese oxide, and the load capacity of auxiliary agent is 0.5% ~ 1% of catalyst quality.
The catalyst of above-mentioned with isopropanolamine is Material synthesis 2,5-dimethyl pyrazine, the specific area of described carrier is 200m
2g
-1~ 350m
2g
-1, the pore volume of carrier is 0.45mLg
-1~ 0.60mLg
-1.
In addition, present invention also offers a kind of method preparing above-mentioned catalyst, it is characterized in that, the method comprises the following steps:
Step one, by nitrate deionized water dissolving corresponding for active component, obtain dipping solution, then adopt equi-volume impregnating that carrier is placed in dipping solution and flood 1h ~ 4h;
Step 2, by step one dipping after carrier dry 6h ~ 10h at 100 DEG C ~ 120 DEG C, then roasting 2h ~ 6h at 300 DEG C ~ 500 DEG C, obtains catalyst.
Further, present invention also offers the method that the second prepares above-mentioned catalyst, it is characterized in that, the method comprises the following steps:
Step one, active component and carrier are carried out cal rolling mixing, obtain mixed material;
Step 2, in mixed material described in step one, add bonding agent and deionized water, mix to be placed on double screw extruder and extrude, obtain strip-shaped materials; Described binding agent is one or more in sodium carboxymethylcellulose, starch and sesbania powder; The quality of described binding agent is 0.5% ~ 2% of mixed material quality, and the quality of deionized water is 50% ~ 80% of mixed material quality;
Step 3, by the dry 6h ~ 8h at 100 DEG C ~ 120 DEG C of strip-shaped materials described in step 2, then roasting 2h ~ 6h at 300 DEG C ~ 500 DEG C, obtains catalyst.
Further, present invention also offers the method that the third prepares above-mentioned catalyst, it is characterized in that, the method comprises the following steps:
Step one, nitrate deionized water dissolving corresponding for active component is mixed with solution A;
Step 2, precipitating reagent deionized water dissolving is mixed with solution B; Described precipitating reagent is Na
2cO
3and/or NaHCO
3;
Step 3, solution A and solution B are heated to 60 DEG C ~ 85 DEG C respectively, then add in the solution B after heating by the solution A after heating under agitation, the pH value to solution B is 7.0 ~ 8.0, obtains the slip containing precipitation;
Step 4, by slip described in step 3 stir 0.5h ~ 2h, then under 65 DEG C ~ 90 DEG C conditions leave standstill 1h ~ 4h, discard the upper clear supernate of slip, spend deionized water discard upper clear supernate after slip be not more than 0.1% to the sodium ions content in slip;
Step 5, add carrier in step 4 after washing slip, filter after stirring 0.5h ~ 2h, obtain filter cake, by described filter cake dry 8h ~ 12h at 100 DEG C ~ 120 DEG C, then roasting 4h ~ 8h at 300 DEG C ~ 500 DEG C, obtains catalyst powder;
Step 6, in catalyst powder described in step 5, add bonding agent and deionized water, mix to be placed on double screw extruder and extrude, obtain strip-shaped materials; Described binding agent is one or more in sodium carboxymethylcellulose, starch and sesbania powder; The quality of described binding agent is 0.5% ~ 2% of catalyst powder weight, and the quality of deionized water is 50% ~ 80% of catalyst powder weight;
Step 7, by the dry 6h ~ 8h at 100 DEG C ~ 120 DEG C of strip-shaped materials described in step 6, then roasting 2h ~ 6h at 300 DEG C ~ 500 DEG C, obtains catalyst.
The present invention compared with prior art has the following advantages:
1, the present invention adopts cupric oxide and zinc oxide, and one or both in silver oxide and chromium oxide are as active component, the activity and selectivity of catalyst can be significantly improved, the catalyst of preparation has that reaction condition gentleness, isopropanolamine conversion ratio are high, the selective high feature of 2,5-dimethyl pyrazine.
2, the present invention adopts Al
2o
3carrier or silica content are not more than the silica-alumina supports of 20%, preferential oxidation silicone content is not more than the silica-alumina supports of 20%, silica-alumina supports containing certain proportion silica effectively can improve the specific area of carrier, modulation can also be carried out to the Acidity of Aikalinity of carrier simultaneously, improve the anti-carbon deposition ability of catalyst, make the performance of catalyst more stable.
3, method for preparing catalyst of the present invention is simple, and Catalyst Production does not limit by equipment, is easy to industrial-scale production.
4, adopt catalyst isopropanolamine of the present invention to synthesize 2,5-dimethyl pyrazine, the molar yield of isopropanolamine can reach more than 84.7%, and the molar yield of 2,5-dimethyl pyrazine can reach more than 73.2%.
Below by embodiment, technical solution of the present invention is described in further detail.
Detailed description of the invention
The quality purity of the nitrate adopted in the embodiment of the present invention all >=98%, calculates according to 98%.
Embodiment 1
The catalyst of the present embodiment, comprise carrier and be carried on the active component on carrier, described active component is cupric oxide, zinc oxide and chromium oxide; The load capacity of described cupric oxide is 9.71% of catalyst quality, and the load capacity of zinc oxide is 11.56% of catalyst quality, and the load capacity of chromium oxide is 3.36% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 10%, and the specific area of described silica-alumina supports is 200m
2g
-1, the pore volume of carrier is 0.45mLg
-1.
The preparation method of the present embodiment is:
Step one, by 30.1gCu (NO
3)
23H
2o, 43.11gZn (NO
3)
26H
2o and 18.05gCr (NO
3)
39H
2o deionized water dissolving, is mixed with dipping solution, then adopts equi-volume impregnating to be that the spherical silica-alumina supports of 1mm ~ 3mm is placed in dipping solution and floods 2h by 75.4g diameter;
Step 2, by step one dipping after silica-alumina supports dry 8h at 120 DEG C, then roasting 5h at 450 DEG C, obtains catalyst after cooling.
Embodiment 2
The catalyst of the present embodiment, comprise carrier and be carried on the active component on carrier, described active component is cupric oxide, zinc oxide and silver oxide; The load capacity of described cupric oxide is 10.71% of catalyst quality, and the load capacity of zinc oxide is 9.35% of catalyst quality, and the load capacity of silver oxide is 5.67% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 15%, and the specific area of described silica-alumina supports is 225m
2g
-1, the pore volume of carrier is 0.47mLg
-1.
The preparation method of the present embodiment is:
Step one, by 53.64gCu (NO
3)
23H
2o, 56.35gZn (NO
3)
26H
2o and 13.70gAgNO
3with deionized water dissolving, be mixed with dipping solution, then adopt equi-volume impregnating to be that the spherical silica-alumina supports of 1mm ~ 3mm is placed in dipping solution and floods 4h by 120g diameter;
Step 2, by step one dipping after silica-alumina supports dry 10h at 100 DEG C, then roasting 6h at 300 DEG C, obtains catalyst after cooling.
Embodiment 3
The catalyst of the present embodiment, comprise carrier and be carried on the active component on carrier, described active component is cupric oxide, zinc oxide, chromium oxide and silver oxide; The load capacity of described cupric oxide is 14% of catalyst quality, and the load capacity of zinc oxide is 15% of catalyst quality, and the load capacity of chromium oxide is 4% of catalyst quality, and the load capacity of silver oxide is 3% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 20%, and the specific area of described silica-alumina supports is 245m
2g
-1, the pore volume of carrier is 0.51mLg
-1.
The preparation method of the present embodiment is:
Step one, 14g cupric oxide, 15g zinc oxide, 4g chromium oxide, 3g silver oxide and 64g silica-alumina supports are carried out cal rolling mixing 0.5h, obtain mixed material;
Step 2, in mixed material described in step one, add 1.5g sodium carboxymethylcellulose and 75mL deionized water, mix to be placed on double screw extruder and extrude, obtain the strip-shaped materials that diameter is 1.5mm;
Step 3, by the dry 8h at 120 DEG C of strip-shaped materials described in step 2, then roasting 6h at 450 DEG C, obtains catalyst.
Embodiment 4
The catalyst of the present embodiment, comprise carrier and be carried on the active component on carrier, described active component is cupric oxide, zinc oxide and chromium oxide; The load capacity of described cupric oxide is 10% of catalyst quality, and the load capacity of zinc oxide is 13% of catalyst quality, and the load capacity of chromium oxide is 5.5% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 10%, and the specific area of described silica-alumina supports is 260m
2g
-1, the pore volume of carrier is 0.50mLg
-1.
The preparation method of the present embodiment is:
Step one, by 43.39gCu (NO
3)
23H
2o, 67.89gZn (NO
3)
26H
2o and 41.37gCr (NO
3)
39H
2o deionized water dissolving is mixed with the solution A that concentration is 1mol/L;
Step 2, by 70gNa
2cO
3the solution B that concentration is 1mol/L is mixed with deionized water dissolving;
Step 3, solution A and solution B are heated to 70 DEG C respectively, then add in the solution B after heating by the solution A after heating under agitation, the pH value to solution B is 7.2, obtains the slip containing precipitation;
Step 4, slip described in step 3 is stirred 2h, under 85 DEG C of conditions, then leaves standstill the upper clear supernate discarding slip after 2h, spend deionized water discard upper clear supernate after slip be not more than 0.1% to the sodium ions content in slip;
Step 5, add 100g silica-alumina supports in step 4 after washing slip, filter after stirring 0.5h, obtain filter cake, by described filter cake dry 10h at 120 DEG C, then roasting 4h at 500 DEG C, obtains catalyst powder 140g;
Step 6, in catalyst powder described in step 5, add 1g starch, 1g sesbania powder and 100mL deionized water, mix to be placed on double screw extruder and extrude, obtain the strip-shaped materials that diameter is 1.5mm;
Step 7, by the dry 6h at 120 DEG C of strip-shaped materials described in step 6, then roasting 4h at 500 DEG C, obtains catalyst.
Embodiment 5
The catalyst of the present embodiment, comprise carrier and the active component be carried on carrier and auxiliary agent, described active component is cupric oxide, zinc oxide and silver oxide; The load capacity of described cupric oxide is 13.33% of catalyst quality, and the load capacity of zinc oxide is 14.53% of catalyst quality, and the load capacity of silver oxide is 6.27% of catalyst quality; Described auxiliary agent is manganese oxide, and the load capacity of auxiliary agent is 0.5% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 20%, and the specific area of described silica-alumina supports is 350m
2g
-1, the pore volume of carrier is 0.60mLg
-1.
The preparation method of the present embodiment is:
Step one, 13.33g cupric oxide, 14.53g zinc oxide, 6.27g silver oxide, 0.5g manganese oxide and 65.37g silica-alumina supports are carried out cal rolling mixing 0.5h, obtain mixed material;
Step 2, in mixed material described in step one, add 0.5g sodium cellulose glycolate, 0.5g starch and 1g sesbania powder and 50mL deionized water, mix to be placed on double screw extruder and extrude, obtain the strip-shaped materials that diameter is 1.5mm;
Step 3, by the dry 6h at 100 DEG C of strip-shaped materials described in step 2, then roasting 5h at 300 DEG C, obtains catalyst.
Embodiment 6
The catalyst of the present embodiment, comprise carrier and the active component be carried on carrier and auxiliary agent, described active component is cupric oxide, zinc oxide, silver oxide and chromium oxide; The load capacity of described cupric oxide is 8% of catalyst quality, and the load capacity of zinc oxide is 9% of catalyst quality, and the load capacity of silver oxide is 2.0% of catalyst quality, and the load capacity of chromium oxide is 2.0% of catalyst quality; Described auxiliary agent is iron oxide, and the load capacity of auxiliary agent is 1.0% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 20%, and the specific area of described silica-alumina supports is 300m
2g
-1, the pore volume of carrier is 0.55mLg
-1.
The preparation method of the present embodiment is:
Step one, by 24.79gCu (NO
3)
23H
2o, 33.57gZn (NO
3)
26H
2o, 2.99gAgNO
3, 10.74gCr (NO
3)
39H
2o and 5.16gFe (NO
3)
39H
2o deionized water dissolving is mixed with the solution A that concentration is 2mol/L;
Step 2, by 80gNaHCO
3the solution B that concentration is 2mol/L is mixed with deionized water dissolving;
Step 3, solution A and solution B are heated to 60 DEG C respectively, then add in the solution B after heating by the solution A after heating under agitation, the pH value to solution B is 7.0, obtains the slip containing precipitation;
Step 4, slip described in step 3 is stirred 1h, under 90 DEG C of conditions, then leaves standstill the upper clear supernate discarding slip after 4h, spend deionized water discard upper clear supernate after slip be not more than 0.1% to the sodium ions content in slip;
Step 5, add 78g silica-alumina supports in step 4 after washing slip, filter after stirring 2h, obtain filter cake, by described filter cake dry 8h at 100 DEG C, then roasting 8h at 300 DEG C, obtains catalyst powder 100g;
Step 6, in catalyst powder described in step 5, add 0.5g sodium cellulose glycolate and 80mL deionized water, mix to be placed on double screw extruder and extrude, obtain the strip-shaped materials that diameter is 1.5mm;
Step 7, by the dry 8h at 100 DEG C of strip-shaped materials described in step 6, then roasting 6h at 300 DEG C, obtains catalyst.
Embodiment 7
The catalyst of the present embodiment, comprise carrier and be carried on the active component on carrier, described active component is cupric oxide, zinc oxide and silver oxide; The load capacity of described cupric oxide is 5% of catalyst quality, and the load capacity of zinc oxide is 15% of catalyst quality, and the load capacity of silver oxide is 8% of catalyst quality; Described carrier is Al
2o
3carrier, described Al
2o
3the specific area of carrier is 200m
2g
-1, the pore volume of carrier is 0.45mLg
-1.
The preparation method of the present embodiment is:
Step one, by 15.5gCu (NO
3)
23H
2o, 55.95gZn (NO
3)
26H
2o and 11.97gAgNO
3with deionized water dissolving, be mixed with dipping solution, then adopt equi-volume impregnating to be that the spherical silica-alumina supports of 1mm ~ 3mm is placed in dipping solution and floods 1h by 72g diameter;
Step 2, by step one dipping after silica-alumina supports dry 6h at 110 DEG C, then roasting 2h at 500 DEG C, obtains catalyst after cooling.
Embodiment 8
The catalyst of the present embodiment, comprise carrier and be carried on the active component on carrier, described active component is cupric oxide, zinc oxide and chromium oxide; The load capacity of described cupric oxide is 15% of catalyst quality, and the load capacity of zinc oxide is 5% of catalyst quality, and the load capacity of chromium oxide is 4% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 20%, and the specific area of described silica-alumina supports is 245m
2g
-1, the pore volume of carrier is 0.51mLg
-1.
The preparation method of the present embodiment is:
Step one, 15g cupric oxide, 5g zinc oxide, 4g chromium oxide and 76g silica-alumina supports are carried out cal rolling mixing 0.5h, obtain mixed material;
Step 2, in mixed material described in step one, add 0.4g sodium carboxymethylcellulose, 0.1g sesbania powder and 80mL deionized water, mix to be placed on double screw extruder and extrude, obtain the strip-shaped materials that diameter is 1.5mm;
Step 3, by the dry 7h at 110 DEG C of strip-shaped materials described in step 2, then roasting 2h at 500 DEG C, obtains catalyst.
Embodiment 9
The catalyst of the present embodiment, comprise carrier and the active component be carried on carrier and auxiliary agent, described active component is cupric oxide, zinc oxide and chromium oxide; The load capacity of described cupric oxide is 10% of catalyst quality, and the load capacity of zinc oxide is 13% of catalyst quality, and the load capacity of chromium oxide is 5.5% of catalyst quality; Described auxiliary agent is iron oxide and manganese oxide, and the load capacity of iron oxide is 0.4% of catalyst quality, and the load capacity of manganese oxide is 0.3% of catalyst quality; Described carrier is the mass percentage of silica is the silica-alumina supports of 20%, and the specific area of described silica-alumina supports is 300m
2g
-1, the pore volume of carrier is 0.55mLg
-1.
The preparation method of the present embodiment is:
Step one, by 30.99gCu (NO
3)
23H
2o, 48.49gZn (NO
3)
26H
2o, 29.55gCr (NO
3)
39H
2o, 2.07gFe (NO
3)
39H
2o and 1.08gMn (NO
3)
24H
2o deionized water dissolving is mixed with the solution A that concentration is 0.8mol/L;
Step 2, by 40gNa
2cO
3and 20gNaHCO
3the solution B that concentration is 0.8mol/L is mixed with deionized water dissolving;
Step 3, solution A and solution B are heated to 85 DEG C respectively, then add in the solution B after heating by the solution A after heating under agitation, the pH value to solution B is 8.0, obtains the slip containing precipitation;
Step 4, slip described in step 3 is stirred 0.5h, under 65 DEG C of conditions, then leaves standstill the upper clear supernate discarding slip after 1h, spend deionized water discard upper clear supernate after slip be not more than 0.1% to the sodium ions content in slip;
Step 5, add 70.8g silica-alumina supports in step 4 after washing slip, filter after stirring 1h, obtain filter cake, by described filter cake dry 12h at 110 DEG C, then roasting 6h at 400 DEG C, obtains catalyst powder 100g;
Step 6, in catalyst powder described in step 5, add 1g sodium cellulose glycolate, 0.5g starch, 0.5g sesbania powder and 50mL deionized water, mix to be placed on double screw extruder and extrude, obtain the strip-shaped materials that diameter is 1.5mm;
Step 7, by the dry 7h at 110 DEG C of strip-shaped materials described in step 6, then roasting 2h at 450 DEG C, obtains catalyst.
The catalyst of embodiment 1 ~ 9 is made respectively the particle of 1mm ~ 2mm, then get 30mL and be seated in
fixed bed reactors in, system nitrogen leak test, replace qualified after, pass into the nitrogen of 75mL/min, the hydrogen of 100mL/min, be warmed up to 350 DEG C ~ 500 DEG C with the speed of 2 DEG C/min and carry out activation process, after activation terminates, reaction bed temperature is controlled at 250 DEG C ~ 450 DEG C, in feedstock quality than isopropanolamine: nitrogen: the ratio of hydrogen=1:4:6 is to continuous feed in reactor, Deng metering, sampling analysis after system stability, and calculate the conversion ratio of isopropanolamine and the yield of 2,5-dimethyl pyrazine.The reactivity worth of catalyst is in table 1.
Wherein the computing formula of the conversion ratio of isopropanolamine and the yield of 2,5-dimethyl pyrazine is as follows:
Table 1 catalyst sample performance
| Catalyst | Isopropanolamine conversion ratio/% | 2,5-dimethyl pyrazine yield/% |
| Embodiment 1 | 84.7 | 76.3 |
| Embodiment 2 | 90.2 | 82.1 |
| Embodiment 3 | 84.7 | 74.5 |
| Embodiment 4 | 92.8 | 85.4 |
| Embodiment 5 | 87.8 | 73.2 |
| Embodiment 6 | 92.3 | 86.2 |
| Embodiment 7 | 90.4 | 74.8 |
| Embodiment 8 | 87.2 | 73.6 |
| Embodiment 9 | 93.2 | 83.1 |
As can be seen from Table 1, it is high that catalyst of the present invention has isopropanolamine conversion ratio, and 2, the selective high feature of 5-dimethyl pyrazine, and catalytic reaction condition is gentle, the molar yield of isopropanolamine can reach more than 84.7%, the molar yield of 2,5-dimethyl pyrazine can reach more than 73.2%.
The above; it is only preferred embodiment of the present invention; not any restriction is done to the present invention, every above embodiment is done according to invention technical spirit any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (7)
1. one kind take isopropanolamine as the catalyst of Material synthesis 2,5-dimethyl pyrazine, and comprise carrier and be carried on the active component on carrier, it is characterized in that, described active component is cupric oxide, zinc oxide and other metal oxides; The load capacity of described cupric oxide is 5% ~ 15% of catalyst quality, and the load capacity of zinc oxide is 5% ~ 15% of catalyst quality; Other metal oxides described are silver oxide and/or chromium oxide, and the load capacity of other metal oxides is 4% ~ 8% of catalyst quality; Described carrier is Al
2o
3carrier or silica-alumina supports, in described silica-alumina supports, the mass percentage of silica is not more than 20%; The specific area of described carrier is 200m
2g
-1~ 350m
2g
-1, the pore volume of carrier is 0.45mLg
-1~ 0.60mLg
-1.
2. according to claim 1 take isopropanolamine as Material synthesis 2, the catalyst of 5-dimethyl pyrazine, it is characterized in that, the load capacity of described cupric oxide is 8% ~ 14% of catalyst quality, the load capacity of zinc oxide is 9% ~ 15% of catalyst quality, and the load capacity of other metal oxides is 4% ~ 7% of catalyst quality.
3. according to claim 2 take isopropanolamine as Material synthesis 2, the catalyst of 5-dimethyl pyrazine, it is characterized in that, the load capacity of described cupric oxide is 10% of catalyst quality, the load capacity of zinc oxide is 13% of catalyst quality, and the load capacity of other metal oxides is 5.5% of catalyst quality.
4. take isopropanolamine as Material synthesis 2 according to claim 1,2 or 3, the catalyst of 5-dimethyl pyrazine, is characterized in that, also comprises the auxiliary agent be carried on carrier, described auxiliary agent is iron oxide and/or manganese oxide, and the load capacity of auxiliary agent is 0.5% ~ 1% of catalyst quality.
5. prepare a method for catalyst as described in claim 1,2 or 3, it is characterized in that, the method comprises the following steps:
Step one, by nitrate deionized water dissolving corresponding for active component, obtain dipping solution, then adopt equi-volume impregnating that carrier is placed in dipping solution and flood 1h ~ 4h;
Step 2, by step one dipping after carrier dry 6h ~ 10h at 100 DEG C ~ 120 DEG C, then roasting 2h ~ 6h at 300 DEG C ~ 500 DEG C, obtains catalyst.
6. prepare a method for catalyst as described in claim 1,2 or 3, it is characterized in that, the method comprises the following steps:
Step one, active component and carrier are carried out cal rolling mixing, obtain mixed material;
Step 2, in mixed material described in step one, add bonding agent and deionized water, mix to be placed on double screw extruder and extrude, obtain strip-shaped materials; Described binding agent is one or more in sodium carboxymethylcellulose, starch and sesbania powder; The quality of described binding agent is 0.5% ~ 2% of mixed material quality, and the quality of deionized water is 50% ~ 80% of mixed material quality;
Step 3, by the dry 6h ~ 8h at 100 DEG C ~ 120 DEG C of strip-shaped materials described in step 2, then roasting 2h ~ 6h at 300 DEG C ~ 500 DEG C, obtains catalyst.
7. prepare a method for catalyst as described in claim 1,2 or 3, it is characterized in that, the method comprises the following steps:
Step one, nitrate deionized water dissolving corresponding for active component is mixed with solution A;
Step 2, precipitating reagent deionized water dissolving is mixed with solution B; Described precipitating reagent is Na
2cO
3and/or NaHCO
3;
Step 3, solution A and solution B are heated to 60 DEG C ~ 85 DEG C respectively, then add in the solution B after heating by the solution A after heating under agitation, the pH value to solution B is 7.0 ~ 8.0, obtains the slip containing precipitation;
Step 4, by slip described in step 3 stir 0.5h ~ 2h, then under 65 DEG C ~ 90 DEG C conditions leave standstill 1h ~ 4h, discard the upper clear supernate of slip, spend deionized water discard upper clear supernate after slip be not more than 0.1% to the sodium ions content in slip;
Step 5, add carrier in step 4 after washing slip, filter after stirring 0.5h ~ 2h, obtain filter cake, by described filter cake dry 8h ~ 12h at 100 DEG C ~ 120 DEG C, then roasting 4h ~ 8h at 300 DEG C ~ 500 DEG C, obtains catalyst powder;
Step 6, in catalyst powder described in step 5, add bonding agent and deionized water, mix to be placed on double screw extruder and extrude, obtain strip-shaped materials; Described binding agent is one or more in sodium carboxymethylcellulose, starch and sesbania powder; The quality of described binding agent is 0.5% ~ 2% of catalyst powder weight, and the quality of deionized water is 50% ~ 80% of catalyst powder weight;
Step 7, by the dry 6h ~ 8h at 100 DEG C ~ 120 DEG C of strip-shaped materials described in step 6, then roasting 2h ~ 6h at 300 DEG C ~ 500 DEG C, obtains catalyst.
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| CN106582672B (en) * | 2016-11-29 | 2019-08-30 | 西安凯立新材料股份有限公司 | A kind of preparation method and application synthesizing 2,5-dimethyl pyrazine catalyst |
| CN116371417B (en) * | 2023-03-06 | 2023-10-03 | 济南悟通生物科技有限公司 | Catalyst for synthesizing 3, 4-dimethyl pyrrole and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105846A (en) * | 1985-07-31 | 1986-07-09 | 化学工业部化肥工业研究所 | The manufacture method of pyrazine compounds |
| CN1513846A (en) * | 2003-08-18 | 2004-07-21 | 淄博正存化工有限公司 | Method of preparing 2,5-dimethyl pyrazine using gas solid contact catalytic process |
| CN103691443A (en) * | 2013-12-13 | 2014-04-02 | 广西大学 | Catalyst for synthesizing 2,5-dimethylpyrazine and preparation method of catalyst |
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| JPH0674254B2 (en) * | 1986-06-13 | 1994-09-21 | 広栄化学工業株式会社 | Process for producing pyrazine derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105846A (en) * | 1985-07-31 | 1986-07-09 | 化学工业部化肥工业研究所 | The manufacture method of pyrazine compounds |
| CN1513846A (en) * | 2003-08-18 | 2004-07-21 | 淄博正存化工有限公司 | Method of preparing 2,5-dimethyl pyrazine using gas solid contact catalytic process |
| CN103691443A (en) * | 2013-12-13 | 2014-04-02 | 广西大学 | Catalyst for synthesizing 2,5-dimethylpyrazine and preparation method of catalyst |
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