CN101020627A - Process of synthesizing 1,4-cyclohexyl dione - Google Patents
Process of synthesizing 1,4-cyclohexyl dione Download PDFInfo
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- CN101020627A CN101020627A CN 200710061447 CN200710061447A CN101020627A CN 101020627 A CN101020627 A CN 101020627A CN 200710061447 CN200710061447 CN 200710061447 CN 200710061447 A CN200710061447 A CN 200710061447A CN 101020627 A CN101020627 A CN 101020627A
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Abstract
The present invention relates to environment friendly process of synthesizing 1, 4-cyclohexyl dione. The process includes the following steps: 1. preparing skeleton nickel catalyst; 2. preparing 1, 4-cyclohexyl diol with hydroquinone as material and through catalytic hydrogenation under the action of the skeleton nickel catalyst in a high pressure reactor; and 3. oxidizing with hydrogen peroxide or catalytic dehydrogenation to prepare 1, 4-cyclohexyl dione. The present invention is significant in industrial production of 1, 4-cyclohexyl dione, and has the advantages of easy-to-control mild reaction, low cost, environment friendship, easy-to-prepare catalyst with high stability and reusability, and high product yield.
Description
Technical field
The present invention relates to a kind of eco-friendlyly 1, the synthetic method of 4-cyclohexanedione belongs to chemosynthesis technical field.
Background technology
Bibliographical information be feedstock production 1 with the Resorcinol, a kind of method of 4-cyclohexanedione is at first shortening generation 1 in water or alcoholic solution of Resorcinol, the 4-cyclohexanediol, the latter is generated 1 by oxidations such as chromic acid, bromate, hydrogen peroxide, oxygen in acetone or acetic acid solution, 4-cyclohexanedione product.Having proposed in 50% the Resorcinol aqueous solution of alkalescence as, RObertJ., is that catalyzer carries out shortening with the skeleton nickel, after intermediate separates, at RuCl
3Under the catalyzer, obtain 1, the 4-cyclohexanedione through hypochlorite oxidation.In addition, patent DE19541262 has reported by the Resorcinol single stage method and has produced 1, the method for 4-cyclohexanedione, and in this method, autoclave is made reactor, under the hydrogen condition, palladium-carbon and ten hydration Na
2B
4O
7Make catalyzer, diglyme is made solvent, and feed stock conversion is 86.5%, and product selectivity is 46.1%, and product yield is lower.More than these methods use expensive chemical oxidizing agent or organic solvent more, pollute easily.
Summary of the invention
The objective of the invention is to solve existing 1, use a large amount of poisonous chemical oxidizing agents or organic solvent to the problem that environment pollutes easily in the 4-cyclohexanedione production process, provide a kind of new eco-friendly 1,4-cyclohexanedione preparation method, improve product yield simultaneously, reduce production costs.
The object of the present invention is achieved like this: this eco-friendly 1, the synthetic method of 4-cyclohexanedione is characterized in that: described 1, the 4-cyclohexanedione prepares according to following steps:
A, preparation skeletal nickel catalyst: in the 200ml beaker of agitator and thermometer is housed, add 16gNaOH and 60ml water, be cooled to 50 ℃ under the vigorous stirring, with the under agitation a small amount of one by one adding of 12.5g alumel wherein, regulate alloy adding speed and make solution temperature remain on 50 ± 2 ℃.Add finish after, under slowly stirring,, wash through washing and alcohol then and obtain skeletal nickel catalyst in 50 ± 2 ℃ of following water-baths one hour;
B, preparation 1, the 4-cyclohexanediol: with the Resorcinol be raw material under the skeletal nickel catalyst effect that steps A obtains, shortening generates 1 in autoclave, the 4-cyclohexanediol, hydrogen pressure 0.5-10MPa, the reaction times is 2-10 hour;
C1, hydrogen peroxide oxidation method preparation 1, the 4-cyclohexanedione:
With sodium wolframate, ten poly-wolframic acid quaternary ammonium salt or FeBr
3Be catalyzer, with oxalic acid, oxine, Whitfield's ointment or o-phenanthroline is ligand, with water is solvent, with hydrogen peroxide oxidation step B obtain 1,4-cyclohexanediol preparation 1,4-cyclohexanedione, temperature of reaction is controlled at 40-120 ℃, reaction times is 2-48 hour, and distillation obtains 1, the 4-cyclohexanedione;
Perhaps C2, catalytic dehydrogenation legal system are equipped with 1, the 4-cyclohexanedione:
C2-1, preparation metal oxide catalyst: by weight percentage,, be dissolved in wiring solution-forming in the 1-3 deionized water doubly, add 1-3 powdery γ-Al doubly 30-70% cupric nitrate and 10-35% zinc nitrate and 0-15% magnesium nitrate or Xiao Suangu mixing
2O
3Or molecular sieve is as carrier, fully stirs it is mixed and to become the jelly shape, is extruded into bar shaped then, places baking oven fully to be cut into 5mm length after the oven dry for 110～120 ℃, and high-temperature calcination promptly got required oxidation catalyst in 3～6 hours in retort furnace;
C2-2, catalytic dehydrogenation legal system are equipped with 1,4-cyclohexanedione: in fixed-bed reactor, add the oxidation catalyst 10g that step C2-1 obtains, reduce down at 280-330 ℃ earlier and obtain composite metal catalyst, then with 20% 1, the 4-cyclohexanediol aqueous solution feeds reactor with the speed of 1000-3000/h, and reaction obtains product 1,4-cyclohexanedione under 200-350 ℃ and 0.1-1MPa.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described hydrogenation reaction preparation 1 of step B, the method of 4-cyclohexanediol comprises: get 56g Resorcinol and 6g skeletal nickel catalyst and 250ml water and add together in the autoclave, add 50%NaOH solution 1ml again, charge into hydrogen 1-5MPa then, reacted 3-5 hour down at 150-200 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1,4-cyclohexanediol behind the reaction solution dephlegmate.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method for 4-cyclohexanedione comprises: earlier with 5.9g FeBr
3And 11.6g1, the 4-cyclohexanediol joins respectively in the three-necked bottle of 250ml, at ice bath with under stirring the 30ml hydrogen peroxide slowly is added drop-wise in the reaction flask then, stirs reaction 24h down, distill product 1, the 4-cyclohexanedione.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: earlier 0.66g sodium wolframate, 0.25g oxalic acid and 30ml hydrogen peroxide are added in the three-necked bottle, stir 5min, again 11.6g 1,4 one cyclohexanediol is added in the three-necked bottle, temperature is set at 80 ℃, the reaction 24h, distill product 1, the 4-cyclohexanedione.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method for 4-cyclohexanedione comprises: with 0.6g ten poly-wolframic acid quaternary ammonium salt and 11.6g 1, the 4--cyclohexanediol joins respectively in the three-necked bottle of 250mL earlier, slowly be added drop-wise to the hydrogen peroxide of 60ml in the reaction flask at ice bath and under stirring then, stir reaction 12h down, distill product 1, the 4-cyclohexanedione.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: the hydrogen peroxide with 0.66g sodium wolframate, 0.29g8-hydroxyquinoline and 50ml adds in the three-necked bottle earlier, stir 5min, again with 11.6g1, the 4-cyclohexanediol adds in the three-necked bottle, temperature is set at 90 ℃, the reaction 12h, distill product 1, the 4-cyclohexanedione.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: earlier 0.66g sodium wolframate, 0.27g Whitfield's ointment and 30ml hydrogen peroxide are added in the three-necked bottle, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, temperature is set at 80 ℃, the reaction 24h, distill product 1, the 4-cyclohexanedione.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: earlier 0.66g sodium wolframate, 0.45g o-phenanthroline and 60ml hydrogen peroxide are added in the three-necked bottle, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, temperature is set at 80 ℃, the reaction 12h, distill product 1, the 4-cyclohexanedione.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, the described method for preparing metal catalyst of step C2-1 comprises: 20g cupric nitrate, 10g zinc nitrate and 5g magnesium nitrate are dissolved in wiring solution-forming in the 30ml deionized water, add 50g powdery γ-Al
2O
3Carrier, abundant stirring mixes it and becomes the jelly shape, and extrusion is shaped then, places baking oven fully to be cut into 5mm length after the oven dry for 110～120 ℃, and high-temperature calcination promptly got required oxidation catalyst in 3～6 hours in retort furnace at last.
Described eco-friendly 1, the synthetic method of 4-cyclohexanedione, step C2-2 catalytic dehydrogenation legal system is equipped with 1, and the method for 4-cyclohexanedione comprises: in fixed-bed reactor, add the 10g oxidation catalyst, reduce down at 330 ℃ earlier and obtain composite metal catalyst, then with 20% 1, the 4-cyclohexanediol aqueous solution feeds reactor with the speed of 1000/h, 250 ℃ of temperature, pressure 0.2MPa reaction down obtains product 1,4-cyclohexanedione.
Provided by the invention 1, preparation method's technical progress effect of 4-cyclohexanedione shows:
1, reaction temperature and easily control have been avoided the use of expensive chemical oxidizing agent and organic solvent, and environmentally safe is a kind of green environment close friend's a route of synthesis;
2, raw material is cheap and easy to get among the present invention, and the simple and good stability of Preparation of Catalyst can also be used by recovery set;
3, product yield height.
Embodiment
Embodiment 1
A, in the 200ml beaker of agitator and thermometer is housed, add 16g NaOH and 60ml water, be cooled to 50 ℃ under the vigorous stirring, wherein the under agitation a small amount of one by one adding of 12.5g alumel (Jinan Xin Hai lead to special alloy company limited).Regulating alloy adding speed makes solution temperature remain on 50 ± 2 ℃.Add finish after, under slowly stirring,, wash through repeatedly washing and alcohol then and obtain skeletal nickel catalyst in 50 ± 2 ℃ of following water-baths one hour.
B, the 6g skeletal nickel catalyst of getting the 56g Resorcinol and preparing previously, add in the autoclave together with 250ml water, add 50%NaOH solution 1ml again, charge into hydrogen pressure 1.5MPa then, reacted 3 hours down at 200 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 92%.
C1, elder generation are with 5.9g FeBr
3With 11.6g 1, the 4-cyclohexanediol joins respectively in the three-necked bottle of 250ml, at ice bath with under stirring the 30ml hydrogen peroxide slowly is added drop-wise in the reaction flask then, stirs reaction 24h down, and distillation can get product 1,4-cyclohexanedione, yield 81%.
Embodiment 2
A, with embodiment 1
B, the 6g skeletal nickel catalyst of getting the 56g Resorcinol and preparing previously, add in the autoclave together with 250ml water, add 50%NaOH solution 1ml again, charge into hydrogen pressure 1.2MPa then, reacted 3 hours down at 150 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 90%.
C1, elder generation add 0.66g sodium wolframate, 0.25g oxalic acid and 30ml hydrogen peroxide in the three-necked bottle, stir 5min, and again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, and temperature is set at 80 ℃, reaction 24h, and distillation can get product 1,4-cyclohexanedione, yield 78%.
Embodiment 3
A, with embodiment 1
B, get the 5.8g skeletal nickel catalyst and the freshly prepd 0.3g skeletal nickel catalyst of A step that reclaim after the B step reaction among 56g Resorcinol and the embodiment 2, add in the autoclave together with 250ml water, add 50%NaOH solution 1ml again, charge into hydrogen pressure 1.8MPa then, reacted 5 hours down at 180 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 93%.
C1, elder generation are with 0.6g ten poly-wolframic acid quaternary ammonium salt and 11.6g 1, and the 4-cyclohexanediol joins respectively in the three-necked bottle of 250ml, slowly is added drop-wise to the 60ml hydrogen peroxide in the reaction flask under ice bath and stirring then, stir reaction 12h down, distillation can get product 1,4-cyclohexanedione, yield 79%.
Embodiment 4
A, with embodiment 1
B, the 6g skeletal nickel catalyst of getting the 56g Resorcinol and preparing previously, add in the autoclave together with 250ml water, add 50%NaOH solution 2ml again, charge into hydrogen pressure 1MPa then, reacted 3 hours down at 150 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 85%.
C1, elder generation add the hydrogen peroxide of 0.66g sodium wolframate, 0.29g oxine and 50ml in the three-necked bottle, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, and temperature is set at 90 ℃, reaction 12h, distillation can get product 1,4-cyclohexanedione, yield 80%.
Embodiment 5
A, with embodiment 1
B, the 6g skeletal nickel catalyst of getting the 56g Resorcinol and preparing previously, add in the autoclave together with 250ml water, add 50%NaOH solution 1ml again, charge into hydrogen pressure 4MPa then, reacted 3 hours down at 180 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 93%.
C1, elder generation add 0.66g sodium wolframate, 0.27g Whitfield's ointment and 30ml hydrogen peroxide in the three-necked bottle, stir 5min, and again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, and temperature is set at 80 ℃, reaction 24h, and distillation can get product 1,4-cyclohexanedione, yield 78%.
Embodiment 6
A, with embodiment 1
B, get the 5.8g skeletal nickel catalyst and the freshly prepd 0.2g skeletal nickel catalyst of A step that reclaim after the B step reaction among 56g Resorcinol and the embodiment 5, add in the autoclave together with 250ml water, add 50%NaOH solution 1ml again, charge into hydrogen pressure 2.0MPa then, reacted 3 hours down at 180 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 91%.
C1, elder generation add 0.66g sodium wolframate, 0.45g o-phenanthroline and 60ml hydrogen peroxide in the three-necked bottle, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, and temperature is set at 80 ℃, reaction 12h, distillation can get product 1,4-cyclohexanedione, yield 83%.
Embodiment 7
A, with embodiment 1
B, the 6g skeletal nickel catalyst of getting the 56g Resorcinol and preparing previously, add in the autoclave together with 250ml water, add 50%NaOH solution 1ml again, charge into hydrogen pressure 2MPa then, reacted 3 hours down at 180 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 88%.
C2-1,20g cupric nitrate, 10g zinc nitrate and 5g magnesium nitrate be dissolved in wiring solution-forming in the deionized water of 30ml, add 50g powdery γ-Al
2O
3Carrier, abundant stirring mixes it and becomes the jelly shape, and extrusion is shaped then, places baking oven fully to be cut into 5mm left and right sides suitable length after the oven dry for 110～120 ℃, and high-temperature calcination promptly got required oxidation catalyst in 3～6 hours in retort furnace at last.
C2-2, in fixed-bed reactor, add the 10g oxidation catalyst, reduce down at 280 ℃ earlier and obtain composite metal catalyst, then with 20% 1, the 4-cyclohexanediol aqueous solution feeds reactor with the speed of 3000/h, reaction can obtain product 1,4-cyclohexanedione, yield 62% under 200 ℃ and 0.1MPa.Measure the activity of such catalysts site of using through methods such as TEM, XRD and be nano level.
Embodiment 8
A, with embodiment 1
B, the 6g skeletal nickel catalyst of getting the 56g Resorcinol and preparing previously, in a 250ml water-adding autoclave, add 50%NaOH solution 1ml again, charge into hydrogen pressure 3MPa then, reacted 6 hours down at 150 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1 behind the reaction solution dephlegmate, the 4-cyclohexanediol, yield 91%.
C2-1,30g cupric nitrate, 10g zinc nitrate and 5g Xiao Suangu be dissolved in wiring solution-forming in the deionized water of 30ml, add 50g mealy molecular sieve carrier, fully stirring mixes it and becomes the jelly shape, extrusion is shaped then, place baking oven fully to be cut into 5mm left and right sides suitable length after the oven dry for 110～120 ℃, high-temperature calcination promptly got required oxidation catalyst in 3～6 hours in retort furnace at last.
C2-2, in fixed-bed reactor, add the 10g oxidation catalyst, reduce down at 330 ℃ earlier and obtain composite metal catalyst, then with 20% 1, the 4-cyclohexanediol aqueous solution feeds reactor with the speed of 1000/h, reaction can obtain product 1,4-cyclohexanedione, yield 71% under 250 ℃ and 0.2MPa.
Listed examples of the present invention is intended to further illustrate this 1 of the harmful organic solvent of avoiding using, the preparation method of 4-cyclohexanedione, and protection scope of the present invention is not constituted any restriction.All can obtain 1 with the embodiment of the invention with via claims 1-10 of the present invention, 4-cyclohexanedione product.
Claims (10)
1, a kind of eco-friendly 1, the synthetic method of 4-cyclohexanedione is characterized in that: described 1, the 4-cyclohexanedione prepares according to following steps:
A, preparation skeletal nickel catalyst: in the 200ml beaker of agitator and thermometer is housed, add 16g NaOH and 60ml water, be cooled to 50 ℃ under the vigorous stirring, with the under agitation a small amount of one by one adding of 12.5g alumel wherein, regulate alloy adding speed and make solution temperature remain on 50 ± 2 ℃.Add finish after, under slowly stirring,, wash through washing and alcohol then and obtain skeletal nickel catalyst in 50 ± 2 ℃ of following water-baths one hour;
B, preparation 1, the 4-cyclohexanediol: with the Resorcinol be raw material under the skeletal nickel catalyst effect that steps A obtains, shortening generates 1 in autoclave, the 4-cyclohexanediol, hydrogen pressure 0.5-10MPa, the reaction times is 2-10 hour;
C1, hydrogen peroxide oxidation method preparation 1, the 4-cyclohexanedione:
With sodium wolframate, ten poly-wolframic acid quaternary ammonium salt or FeBr
3Be catalyzer, with oxalic acid, oxine, Whitfield's ointment or o-phenanthroline is ligand, with water is solvent, with hydrogen peroxide oxidation step B obtain 1,4-cyclohexanediol preparation 1,4-cyclohexanedione, temperature of reaction is controlled at 40-120 ℃, reaction times is 2-48 hour, and distillation obtains 1, the 4-cyclohexanedione;
Perhaps C2, catalytic dehydrogenation legal system are equipped with 1, the 4-cyclohexanedione:
C2-1, preparation metal oxide catalyst: by weight percentage,, be dissolved in wiring solution-forming in the 1-3 deionized water doubly, add 1-3 powdery γ-Al doubly 30-70% cupric nitrate and 10-35% zinc nitrate and 0-15% magnesium nitrate or Xiao Suangu mixing
2O
3Or molecular sieve is as carrier, fully stirs it is mixed and to become the jelly shape, is extruded into bar shaped then, places baking oven fully to be cut into 5mm length after the oven dry for 110～120 ℃, and high-temperature calcination promptly got required oxidation catalyst in 3～6 hours in retort furnace;
C2-2, catalytic dehydrogenation legal system are equipped with 1,4-cyclohexanedione: in fixed-bed reactor, add the oxidation catalyst 10g that step C2-1 obtains, reduce down at 280-330 ℃ earlier and obtain composite metal catalyst, then with 20% 1, the 4-cyclohexanediol aqueous solution feeds reactor with the speed of 1000-3000/h, and reaction obtains product 1,4-cyclohexanedione under 200-350 ℃ and 0.1-1MPa.
2, described eco-friendly 1 according to claim 1, the synthetic method of 4-cyclohexanedione is characterized in that:
The described hydrogenation reaction preparation 1 of step B, the method of 4-cyclohexanediol comprises: get 56g Resorcinol and 6g skeletal nickel catalyst and 250ml water and add in the autoclave together, add 50%NaOH solution 1ml again, charge into hydrogen 1-5MPa then, reacted 3-5 hour down at 150-200 ℃, reaction removes by filter skeletal nickel catalyst earlier with recovery set usefulness after finishing, and promptly gets product 1,4-cyclohexanediol behind the reaction solution dephlegmate.
3, described eco-friendly 1 according to claim 1, the synthetic method of 4-cyclohexanedione is characterized in that: the described hydrogen peroxide oxidation 1 of step C1, and 4-cyclohexanediol preparation 1, the method for 4-cyclohexanedione comprises: earlier with 5.9g FeBr
3With 11.6g 1, the 4-cyclohexanediol joins respectively in the three-necked bottle of 250mL, the hydrogen peroxide of 30ml slowly is added drop-wise in the reaction flask at ice bath and under stirring then, stirs reaction 24h down, distill product 1, the 4-cyclohexanedione.
4, according to claim 1 described eco-friendly 1, the synthetic method of 4-cyclohexanedione is characterized in that: the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: earlier 0.66g sodium wolframate, 0.25q oxalic acid and 30ml hydrogen peroxide are added in the three-necked bottle, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, temperature is set at 80 ℃, the reaction 24h, distill product 1, the 4-cyclohexanedione.
5, according to claim 1 described eco-friendly 1, the synthetic method of 4-cyclohexanedione, it is characterized in that: the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method for 4-cyclohexanedione comprises: with 0.6g ten poly-wolframic acid quaternary ammonium salt and 11.6g 1, the 4-cyclohexanediol joins respectively in the three-necked bottle of 250mL earlier, slowly be added drop-wise to the hydrogen peroxide of 60ml in the reaction flask at ice bath and under stirring then, stir reaction 12h down, distill product 1, the 4-cyclohexanedione.
6, according to claim 1 described eco-friendly 1, the synthetic method of 4-cyclohexanedione is characterized in that: the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: the hydrogen peroxide with 0.66g sodium wolframate, 0.29g oxine and 50ml adds in the three-necked bottle earlier, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, temperature is set at 90 ℃, the reaction 12h, distill product 1, the 4-cyclohexanedione.
7, according to claim 1 described eco-friendly 1, the synthetic method of 4-cyclohexanedione is characterized in that: the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: earlier 0.66g sodium wolframate, 0.27g Whitfield's ointment and 30ml hydrogen peroxide are added in the three-necked bottle, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, temperature is set at 80 ℃, the reaction 24h, distill product 1, the 4-cyclohexanedione.
8, according to claim 1 described eco-friendly 1, the synthetic method of 4-cyclohexanedione is characterized in that: the described hydrogen peroxide oxidation 1 of step C1,4-cyclohexanediol preparation 1, the method of 4-cyclohexanedione comprises: earlier 0.66g sodium wolframate, 0.45g o-phenanthroline and 60ml hydrogen peroxide are added in the three-necked bottle, stir 5min, again with 11.6g 1, the 4-cyclohexanediol adds in the three-necked bottle, temperature is set at 80 ℃, the reaction 12h, distill product 1, the 4-cyclohexanedione.
9, according to claim 1 described eco-friendly 1, the synthetic method of 4-cyclohexanedione, it is characterized in that: the described method for preparing metal catalyst of step C2-1 comprises: 20g cupric nitrate, 10g zinc nitrate and 5g magnesium nitrate are dissolved in wiring solution-forming in the 30ml deionized water, add 50g powdery γ-Al
2O
3Carrier, abundant stirring mixes it and becomes the jelly shape, and extrusion is shaped then, places baking oven fully to be cut into 5mm length after the oven dry for 110～120 ℃, and high-temperature calcination promptly got required oxidation catalyst in 3～6 hours in retort furnace at last.
10, according to claim 1 described eco-friendly 1, the synthetic method of 4-cyclohexanedione, it is characterized in that: step C2-2 catalytic dehydrogenation legal system is equipped with 1, and the method for 4-cyclohexanedione comprises: in fixed-bed reactor, add the 10g oxidation catalyst, reduce down at 330 ℃ earlier and obtain composite metal catalyst, then with 20% 1, the 4-cyclohexanediol aqueous solution feeds reactor with the speed of 1000/h, 250 ℃ of temperature, pressure 0.2MPa reaction down obtains product 1,4-cyclohexanedione.
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| US4229364A (en) * | 1979-05-14 | 1980-10-21 | The Procter & Gamble Company | Synthesis of 1,4-bis(dicyanomethylene) cyclohexane |
| CN1156425C (en) * | 2001-04-18 | 2004-07-07 | 中国石油化工股份有限公司 | Process for preparing cyclohexanone by dehydrogenating cyclohexanol |
| JP2004525986A (en) * | 2001-04-27 | 2004-08-26 | ロンザ ア−ゲ− | Method for producing ketone |
| CN1275922C (en) * | 2005-01-12 | 2006-09-20 | 浙江工业大学 | Preparation of hydroresorcinol |
| CN100344597C (en) * | 2005-12-28 | 2007-10-24 | 浙江工业大学 | Process for preparing cyclohexone by catalyzing oxidating cyclohexol |
| CN1847206A (en) * | 2006-05-10 | 2006-10-18 | 浙江工业大学 | Synthesis process of cyclohexanone and cyclohexanol |
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Assignee: Hebei Tonghua Chemical Co., Ltd. Assignor: Hebei University Contract record no.: 2010130000088 Denomination of invention: Method for preparing 1,1,1-trifluoroethane Granted publication date: 20090513 License type: Exclusive License Open date: 20070822 Record date: 20100827 |
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