CN102476056A - Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof - Google Patents
Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof Download PDFInfo
- Publication number
- CN102476056A CN102476056A CN2012100472022A CN201210047202A CN102476056A CN 102476056 A CN102476056 A CN 102476056A CN 2012100472022 A CN2012100472022 A CN 2012100472022A CN 201210047202 A CN201210047202 A CN 201210047202A CN 102476056 A CN102476056 A CN 102476056A
- Authority
- CN
- China
- Prior art keywords
- methyl ester
- acid methyl
- fatty alcohol
- oxide
- fatty acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a catalyst used in fatty alcohol production with a fatty acid methyl ester catalyzed hydrogenation technology. The catalyst is composed of, by weight: 18-66% of a mixture of copper oxide and zinc oxide, 0-40% of one or two selected from manganese oxide and nickel oxide, 5-17% of alumina, and 0-45% of a carrier, wherein the carrier is diatomite or calcium carbonate. The catalyst is advantaged in environment friendliness, high activity, good product stability, and the like. The invention also discloses a preparation method of the catalyst used in fatty alcohol production with the fatty acid methyl ester catalyzed hydrogenation technology. The method comprises steps that: at least two soluble salts of copper, zinc, manganese, nickel, and aluminum are dissolved in water, such that a mixed solution is prepared; water, or a mixture of water and the carrier is adopted as a base solution; an aqueous solution of sodium carbonate and the mixed solution are dropped into the base solution with a co-current flow; when dropping is finished, a precipitate is obtained; the precipitate is aged, filtered, washed, dried, roasted, and pressed, such that a finished product is obtained. The preparation method is advantaged in simple technology, high operability, easy industrialization, and the like.
Description
Technical field
The present invention relates to catalyst and preparation field thereof, be specifically related to a kind of Catalysts and its preparation method and application that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol.
Background technology
Fatty alcohol, particularly natural high class fatty alcohol are the basic materials of fine chemical products such as washing agent, surfactant, plastic plasticizer.Fine chemical product by fatty alcohol production has thousands of kinds more than, is widely used in fields such as chemical industry, oil, metallurgy, weaving, machinery, mining, building, plastics, rubber, leather, papermaking, communications and transportation, food, medical and health, daily-use chemical industry and agricultural.
Produce fatty alcohol in the industry and mainly contain two lines: a kind of is to be the raw material production fatty alcohol with alkene; Another kind is to be raw material with the natural oil, makes itself and methyl alcohol generation ester exchange, generates fatty acid methyl ester, and catalytic hydrogenation obtains fatty alcohol again.The fatty alcohol that the former route is produced is on the high side, and synthetic fatty alcohol difficult degradation; And the fatty alcohol of latter's route production have clean result good, can biodegradation etc. characteristics.Thereby the latter's synthesis path has bigger advantage.
In the prior art, the catalyst of fatty acid methyl ester hydrogenation good catalytic activity is mainly contained Pt series catalysts, Pd series catalysts etc.Though Pt series catalysts and Pd series catalysts all have very high activity, advantage such as selectivity preferably, because of costing an arm and a leg of they, its industrial applications is restricted.Although developed the Pd/C catalyst of high catalytic activity, and the use price of Pd/C catalyst is reduced to a certain extent, because the ore resources of Pd is rare, large-scale industrialization is used still unlikely.The main CuCr of employing catalyst is gone up in industry at present, but the Cr that the CuCr catalyst discharges in the preparation process
6+Environment has been caused serious pollution.
Publication number is catalyst and method for making and the application that the one Chinese patent application of CN 101733124A discloses a kind of fixed bed hydrogenation for continuous production of fatty alcohol; Catalyst is a component with copper and zinc, is co-catalyst with one or more of manganese, barium or zirconium, is structural promoter with silicon and aluminium; Measure with oxide; Active component quality percentage composition is 40%～95%, and co-catalyst quality percentage composition is 1%～30%, and structural promoter quality percentage composition is 0.01%～50%; Its preparation method comprises: bialuminate solution and alkaline sodium silicate solution are neutralized into the glue reaction; At 50～80 ℃ of aging 0.5～2h, one or more soluble-salts in the soluble-salt of copper, zinc and manganese, barium, the zirconium are mixed, add with alkaline sedimentation agent solution and stream; Obtain deposition, obtain the catalyst of fixed bed hydrogenation for continuous production of fatty alcohol after washing, drying, the roasting.Though this catalyst has catalytic activity preferably, be the substitute of CuCr catalyst, need be neutralized into the glue reaction in this Preparation of catalysts process, the preparation method is comparatively complicated, and influence factor is many, is not easy to control, the catalyst poor reproducibility.
Summary of the invention
The invention provides a kind of environmental friendliness, active high, the catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that product stability is good.
A kind of catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol, form by following components in weight percentage content:
Cupric oxide or cupric oxide and zinc oxide mixture 18%～55%;
A kind of in manganese oxide, the nickel oxide or two kind 0%～40%;
Aluminium oxide 5%～17%;
Carrier 0%～45%;
Described carrier is diatomite or calcium carbonate.
As preferably, the described catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol, form by following components in weight percentage content:
Cupric oxide or cupric oxide and zinc oxide mixture 18%～55%;
A kind of in manganese oxide, the nickel oxide or two kind 0%～40%;
Aluminium oxide 5%～17%;
Carrier 30 as one kind %～45%.
Carrier can make each component be dispersed on the carrier surface; Obtain higher specific surface area; Improve the catalytic efficiency of unit mass component, the described catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is when containing the carrier of weight percentage 30%～40%, and its catalytic activity obviously improves.
Further preferred, the described catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol, form by following components in weight percentage content:
Cupric oxide or cupric oxide and zinc oxide mixture 18%～55%;
A kind of in manganese oxide, the nickel oxide or two kind 1%～40%;
Aluminium oxide 5%～17%;
Carrier 30 as one kind %～45%.
Under the condition of a kind of or two kinds of existence in manganese oxide, nickel oxide, can together give play to higher catalytic activity with other components.
Further preferred, the described catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol, form by following components in weight percentage content:
Cupric oxide 20%～35%;
Zinc oxide 3%～10%;
Manganese oxide 2%～10%;
Nickel oxide 17%～27%;
Aluminium oxide 5%～17%;
Carrier 30 as one kind %～40%.
When containing above-mentioned components in weight percentage content, particularly exist simultaneously with cupric oxide and zinc oxide, this catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol shows very excellent catalytic activity.
The invention provides a kind of Preparation of catalysts method that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol, preparation is simple, controllability is good, workable.
The described Preparation of catalysts method that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is characterized in that, may further comprise the steps:
(1) at least two kinds in soluble copper salt, soluble zinc salt, soluble manganese salt, soluble nickel salt, the aluminum soluble salt are dissolved in the water, are mixed with that to contain solute gross weight percentage composition be 5%～15% mixed solution;
(2) with carrier and water by weight 0～0.12: 1 obtains base fluid after mixing; Stirring is warming up to 55 ℃～60 ℃; Add the mixed solution in aqueous sodium carbonate and the step (1) to base fluid and drip, the dropping process keeps pH=5～6, after the mixed solution in the step (1) drips off; Regulate pH to 9～10 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃～60 ℃ aging 2h～4h, filter, after the washing, oven dry,, after suppressing, obtain being used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol at 400 ℃～500 ℃ roasting 2h～3h.
In the step (1); The interpolation of soluble copper salt, soluble zinc salt, soluble manganese salt, soluble nickel salt and aluminum soluble salt is selected according to the required catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that obtains; As including the cupric oxide composition, then need add corresponding soluble copper salt at the catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol.Soluble copper salt, soluble zinc salt, soluble manganese salt, soluble nickel salt and aluminum soluble salt are in deposition in step (2) fully; For example; Because the soluble copper salt that adds precipitates in step (2) fully; Generate cupric oxide after being deposited in 400 ℃～500 ℃ roasting 2h～3h, therefore, can be by precipitating the quality of calculating the catalyst cupric oxide that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol fully.
The described catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol can be applicable to the reaction of fatty acid methyl ester catalytic hydrogenation system fatty alcohol; This catalyst has advantages of high catalytic activity in the reaction of fatty acid methyl ester catalytic hydrogenation system fatty alcohol, it specifically may further comprise the steps:
The described catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 230 ℃～280 ℃, and reaction pressure is 6Mpa～10Mpa, and the liquid phase air speed is 0.8～1.2h
-1, add fatty acid methyl ester, at H
2With the fatty acid methyl ester volume ratio be that successive reaction prepares fatty alcohol under 8000～13000: 1 the condition.
As preferably, described fatty acid methyl ester is C
12～C
18Fatty acid methyl ester, then the preparation fatty alcohol be corresponding carbon number C
12～C
18Fatty alcohol, under these conditions, this catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is at C
12～C
18Fatty acid methyl ester catalytic hydrogenation system C
12～C
18The reaction of fatty alcohol in, embody excellent catalytic activity and good stability, through after the use of long period, still have catalytic activity preferably.
Compared with prior art, the present invention has following advantage:
The present invention is used for catalyst cupric oxide or the cupric oxide and the zinc oxide mixture of fatty acid methyl ester catalytic hydrogenation system fatty alcohol; A kind of in manganese oxide, the nickel oxide or two kinds; Produce synergy between each component of aluminium oxide and carrier; Show preferably catalytic activity, selectivity and stability preferably preferably, and the present invention to be used for each component environmental pollution of catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol little, have environmental benefit preferably.The catalyst that the present invention is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is fit to be applied to the reaction of fatty acid methyl ester catalytic hydrogenation system fatty alcohol very much, is easy to the industrialization promotion utilization, has broad application prospects.
The present invention is used for the Preparation of catalysts method of fatty acid methyl ester catalytic hydrogenation system fatty alcohol, and preparation technology is simple, controllability good, workable, is easy to suitability for industrialized production, has favorable economic benefit.
The specific embodiment
Embodiment 1
(1) 31.6g copper nitrate, 5.7g zinc nitrate, 23.9g aluminum nitrate, 4.2g manganese nitrate and 26.7g nickel nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 5% mixed solution, put into dropping funel.The 51.0g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 10% with deionized water, puts into dropping funel.
(2) 16.9g diatomite and 200g deionized water are added in the beaker, obtain base fluid after the mixing, open stirring and be warming up to 55 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 55 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 9 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃ of aging 2h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 450 ℃ of following roasting 2h, is obtained the catalyst that 50.1g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 1 obtains is made up of following components in weight percentage content:
Cupric oxide 26.31%;
Zinc oxide 4.77%;
Manganese oxide 3.27%;
Nickel oxide 21.36%;
Aluminium oxide 11.21%;
Diatomite 33.06%.
The catalyst that the 20mL that embodiment 1 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 240 ℃, and reaction pressure is 6Mpa, and the liquid phase air speed is 0.8h
-1, add methyl laurate, at H
2With the methyl laurate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 9000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl laurate is 99.6%, and the productive rate of fatty alcohol is 99.0%, and the selectivity of fatty alcohol is 99.4%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied excellent stability.
Embodiment 2
(1) 28.5g copper nitrate, 23.6g aluminum nitrate, 15.3g manganese nitrate and 38.8g nickel nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 11% mixed solution, put into dropping funel.The 53.0g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 15% with deionized water, puts into dropping funel.
(2) 22.8g calcium carbonate and 200g deionized water are added in the beaker, obtain base fluid after the mixing, open stirring and be warming up to 55 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=5, and temperature keeps 55 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 9 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃ of aging 4h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 400 ℃ of following roasting 2h, is obtained the catalyst that 61.2g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 2 obtains is made up of following components in weight percentage content:
Cupric oxide 19.40%;
Manganese oxide 9.71%;
Nickel oxide 25.37%;
Aluminium oxide 9.04%;
Calcium carbonate 36.47%.
The catalyst that the 20mL that embodiment 2 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 230 ℃, and reaction pressure is 9Mpa, and the liquid phase air speed is 1.0h
-1, add methyl stearate, at H
2With the methyl stearate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 11000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl stearate is 98.1%, and the productive rate of fatty alcohol is 92.5%, and the selectivity of fatty alcohol is 94.3%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied stability preferably.
Embodiment 3
(1) 35.6g copper nitrate, 28.1g zinc nitrate, 11.7g aluminum nitrate and 2.5g manganese nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 15% mixed solution, put into dropping funel.The 45.2g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 8% with deionized water, puts into dropping funel.
(2) 19.8g calcium carbonate and 200g deionized water are added in the beaker, obtain base fluid after the mixing, open stirring and be warming up to 60 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 60 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 10 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 60 ℃ of aging 3h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 500 ℃ of following roasting 2h, is obtained the catalyst that 49.8g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 3 obtains is made up of following components in weight percentage content:
Cupric oxide 29.83%;
Zinc oxide 23.71%;
Manganese oxide 1.95%;
Aluminium oxide 5.51%;
Calcium carbonate 39%.
The catalyst that the 20mL that embodiment 3 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 260 ℃, and reaction pressure is 10Mpa, and the liquid phase air speed is 1.0h
-1, add methyl stearate, at H
2With the methyl stearate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 8000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl stearate is 99.1%, and the productive rate of fatty alcohol is 94.5%, and the selectivity of fatty alcohol is 95.4%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied stability preferably.
Embodiment 4
(1) 29.9g copper nitrate, 22.4g zinc nitrate, 18.4g aluminum nitrate and 17.2g nickel nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 10% mixed solution, put into dropping funel.The 48.7g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 5% with deionized water, puts into dropping funel.
(2) the 200g deionized water is added in the beaker, obtains base fluid, open stirring and be warming up to 57 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 57 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 9 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 57 ℃ of aging 3h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 400 ℃ of following roasting 3h, is obtained the catalyst that 32.7g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 4 obtains is made up of following components in weight percentage content:
Cupric oxide 37.68%;
Zinc oxide 28.44%;
Nickel oxide 20.82%;
Aluminium oxide 13.06%.
The catalyst that the 20mL that embodiment 4 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 280 ℃, and reaction pressure is 9Mpa, and the liquid phase air speed is 1.2h
-1, add methyl hexadecanoate, at H
2With the methyl hexadecanoate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 10000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl hexadecanoate is 95.3%, and the productive rate of fatty alcohol is 90.3%, and the selectivity of fatty alcohol is 94.8%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied stability preferably.
Embodiment 5
(1) 44.6g copper nitrate, 15.5g zinc nitrate and 30.3g aluminum nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 12% mixed solution, put into dropping funel.The 50.5g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 12% with deionized water, puts into dropping funel.
(2) 14.7g diatomite and 200g deionized water are added in the beaker, obtain base fluid, open stirring and be warming up to 55 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 55 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 9 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃ of aging 3h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 500 ℃ of following roasting 2h, is obtained the catalyst that 46.5g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 5 obtains is made up of following components in weight percentage content:
Cupric oxide 39.84%;
Zinc oxide 13.94%;
Aluminium oxide 15.37%;
Diatomite 30.85%.
The catalyst that the 20mL that embodiment 5 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 250 ℃, and reaction pressure is 7Mpa, and the liquid phase air speed is 1.0h
-1, add methyl laurate, at H
2With the methyl laurate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 13000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl laurate is 99.0%, and the productive rate of fatty alcohol is 95.8%, and the selectivity of fatty alcohol is 96.8%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied stability preferably.
Embodiment 6
(1) 29.8g copper nitrate, 21.5g aluminum nitrate, 5.7g manganese nitrate and 34.7g nickel nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 9% mixed solution, put into dropping funel.The 53.0g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 8% with deionized water, puts into dropping funel.
(2) 19.3g calcium carbonate and 200g deionized water are added in the beaker, obtain base fluid, open stirring and be warming up to 56 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 56 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 10 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 56 ℃ of aging 2h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 400 ℃ of following roasting 3h, is obtained the catalyst that 52.1g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 6 obtains is made up of following components in weight percentage content:
Cupric oxide 23.66%;
Manganese oxide 4.21%;
Nickel oxide 26.50%;
Aluminium oxide 9.61%;
Calcium carbonate 36.01%.
The catalyst that the 20mL that embodiment 6 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 260 ℃, and reaction pressure is 9Mpa, and the liquid phase air speed is 1.2h
-1, add methyl stearate, at H
2With the methyl stearate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 10000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl stearate is 99.5%, and the productive rate of fatty alcohol is 95.1%, and the selectivity of fatty alcohol is 95.6%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied stability preferably.
Embodiment 7
(1) 39.95g copper nitrate, 10.62g zinc nitrate, 13.4g aluminum nitrate, 12.6g manganese nitrate and 26.2g nickel nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 5% mixed solution, put into dropping funel.The 71.0g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 10% with deionized water, puts into dropping funel.
(2) 17.5g calcium carbonate and 200g deionized water are added in the beaker, obtain base fluid after the mixing, open stirring and be warming up to 55 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 55 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 9 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃ of aging 2h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 450 ℃ of following roasting 2h, is obtained the catalyst that 56.8g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 7 obtains is made up of following components in weight percentage content:
Cupric oxide 29.33%;
Zinc oxide 7.85%;
Manganese oxide 8.63%;
Nickel oxide 18.46%;
Aluminium oxide 5.54%;
Calcium carbonate 30.19%.
The catalyst that the 20mL that embodiment 7 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 240 ℃, and reaction pressure is 6Mpa, and the liquid phase air speed is 0.8h
-1, add methyl laurate, at H
2With the methyl laurate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 9000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl laurate is 99.5%, and the productive rate of fatty alcohol is 98.8%, and the selectivity of fatty alcohol is 99.3%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied excellent stability.
Embodiment 8
(1) 31.6g copper nitrate, 5.7g zinc nitrate, 23.9g aluminum nitrate, 4.2g manganese nitrate and 26.7g nickel nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 5% mixed solution, put into dropping funel.The 51.0g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 10% with deionized water, puts into dropping funel.
(2) the 200g deionized water is added in the beaker, obtains base fluid after the mixing, open stirring and be warming up to 55 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 55 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 9 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃ of aging 2h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 450 ℃ of following roasting 2h, is obtained the catalyst that 33.1g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 8 obtains is made up of following components in weight percentage content:
Cupric oxide 39.31%;
Zinc oxide 7.13%;
Manganese oxide 4.88%;
Nickel oxide 31.92%;
Aluminium oxide 16.75%.
The catalyst that the 20mL that embodiment 8 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 240 ℃, and reaction pressure is 6Mpa, and the liquid phase air speed is 0.8h
-1, add methyl laurate, at H
2With the methyl laurate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 9000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl laurate is 98.6%, and the productive rate of fatty alcohol is 96.8%, and the selectivity of fatty alcohol is 98.2%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied stability preferably.
Embodiment 9
(1) 31.6g copper nitrate, 5.7g zinc nitrate and 23.9g aluminum nitrate are dissolved in the deionized water, are mixed with that to contain solute gross weight percentage composition be 5% mixed solution, put into dropping funel.The 51.0g natrium carbonicum calcinatum is mixed with the aqueous sodium carbonate of carbonated sodium weight percentage 10% with deionized water, puts into dropping funel.
(2) 16.9g diatomite and 200g deionized water are added in the beaker, obtain base fluid after the mixing, open stirring and be warming up to 55 ℃; Base fluid in beaker and drip add mixed solution and the aqueous sodium carbonate in the step (1); The dropping process keeps pH=6, and temperature keeps 55 ℃, after the mixed solution in the step (1) drips off; Regulate pH to 9 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃ of aging 2h, after the filtration, filter cake wash to the pH value be 7, filter once more, filter cake oven dry back at 450 ℃ of following roasting 2h, is obtained the catalyst that 37.3g is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol after suppressing.
The catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol that embodiment 9 obtains is made up of following components in weight percentage content:
Cupric oxide 34.92%;
Zinc oxide 6.33%;
Aluminium oxide 14.88%;
Diatomite 43.87%.
The catalyst that the 20mL that embodiment 9 is obtained is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol is contained in fixed bed reactors, and reaction temperature is 240 ℃, and reaction pressure is 6Mpa, and the liquid phase air speed is 0.8h
-1, add methyl laurate, at H
2With the methyl laurate volume ratio be that successive reaction prepares fatty alcohol, moves 40 days continuously and reacts under 9000: 1 the condition.
Move 40 days average result continuously, the conversion ratio of methyl laurate is 99.0%, and the productive rate of fatty alcohol is 97.7%, and the selectivity of fatty alcohol is 98.7%.Simultaneously, this performance that is used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol does not have to descend basically, has embodied stability preferably.
Claims (7)
1. catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol, form by following components in weight percentage content:
Cupric oxide or cupric oxide and zinc oxide mixture 18%～55%;
A kind of in manganese oxide, the nickel oxide or two kind 0%～40%;
Aluminium oxide 5%～17%;
Carrier 0%～45%;
Described carrier is diatomite or calcium carbonate.
2. the catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol according to claim 1 is characterized in that, is made up of following components in weight percentage content:
Cupric oxide or cupric oxide and zinc oxide mixture 18%～55%;
A kind of in manganese oxide, the nickel oxide or two kind 0%～40%;
Aluminium oxide 5%～17%;
Carrier 30 as one kind %～45%.
3. the catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol according to claim 2 is characterized in that, is made up of following components in weight percentage content:
Cupric oxide or cupric oxide and zinc oxide mixture 18%～55%;
A kind of in manganese oxide, the nickel oxide or two kind 1%～40%;
Aluminium oxide 5%～17%;
Carrier 30 as one kind %～45%.
4. the catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol according to claim 3 is characterized in that, is made up of following components in weight percentage content:
Cupric oxide 20%～35%;
Zinc oxide 3%～10%;
Manganese oxide 2%～10%;
Nickel oxide 17%～27%;
Aluminium oxide 5%～17%;
Carrier 30 as one kind %～40%.
5. according to each described Preparation of catalysts method that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol of claim 1～4, it is characterized in that, may further comprise the steps:
(1) at least two kinds in soluble copper salt, soluble zinc salt, soluble manganese salt, soluble nickel salt, the aluminum soluble salt are dissolved in the water, are mixed with that to contain solute gross weight percentage composition be 5%～15% mixed solution;
(2) with carrier and water by weight 0～0.12: 1 obtains base fluid after mixing; Stirring is warming up to 55 ℃～60 ℃; Add the mixed solution in aqueous sodium carbonate and the step (1) to base fluid and drip, the dropping process keeps pH=5～6, after the mixed solution in the step (1) drips off; Regulate pH to 9～10 with aqueous sodium carbonate, obtain precipitated product;
(3) with the precipitated product in the step (2) at 55 ℃～60 ℃ aging 2h～4h, filter, after the washing, oven dry,, after suppressing, obtain being used for the catalyst of fatty acid methyl ester catalytic hydrogenation system fatty alcohol at 400 ℃～500 ℃ roasting 2h～3h.
6. the preparation method of a fatty alcohol; It is characterized in that; May further comprise the steps: each described catalyst that is used for fatty acid methyl ester catalytic hydrogenation system fatty alcohol of claim 1～4 is contained in fixed bed reactors; Reaction temperature is 230 ℃～280 ℃, and reaction pressure is 6Mpa～10Mpa, and the liquid phase air speed is 0.8～1.2h
-1, add fatty acid methyl ester, at H
2With the fatty acid methyl ester volume ratio be that successive reaction prepares fatty alcohol under 8000～13000: 1 the condition.
7. the preparation method of fatty alcohol according to claim 6 is characterized in that, described fatty acid methyl ester is C
12～C
18Fatty acid methyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210047202 CN102476056B (en) | 2012-02-28 | 2012-02-28 | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210047202 CN102476056B (en) | 2012-02-28 | 2012-02-28 | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102476056A true CN102476056A (en) | 2012-05-30 |
| CN102476056B CN102476056B (en) | 2012-12-26 |
Family
ID=46088911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210047202 Active CN102476056B (en) | 2012-02-28 | 2012-02-28 | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102476056B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140172A (en) * | 2015-03-24 | 2016-11-23 | 南京博明科技有限责任公司 | A kind of catalyst pressing liquid-phase hydrogenatin fatty alcohol be applicable to fatty acid methyl ester |
| CN106622379A (en) * | 2016-12-20 | 2017-05-10 | 江苏金马油脂科技发展有限公司 | Preparation method and application of fatty acid methyl ester hydrogenation copper-based catalyst |
| CN106944113A (en) * | 2017-04-07 | 2017-07-14 | 中国科学技术大学 | A kind of preparation method of hydrogenation catalyst and fatty alcohol |
| CN107635660A (en) * | 2015-03-26 | 2018-01-26 | 巴斯夫公司 | Hydrogenolysis catalyst with peracid tolerance |
| CN108144619A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | It is a kind of to be used for catalyst and preparation method of the benzene carboxylic ester Hydrogenation for benzyl alcohol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057407A (en) * | 1990-06-21 | 1992-01-01 | 花王株式会社 | Hydrogenation catalyst and production method thereof |
-
2012
- 2012-02-28 CN CN 201210047202 patent/CN102476056B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057407A (en) * | 1990-06-21 | 1992-01-01 | 花王株式会社 | Hydrogenation catalyst and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUAN PENG ET AL.,: "Cu-Zn/Al2O3 Catalyst for the Hydrogenation of Esters to Alcohols", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140172A (en) * | 2015-03-24 | 2016-11-23 | 南京博明科技有限责任公司 | A kind of catalyst pressing liquid-phase hydrogenatin fatty alcohol be applicable to fatty acid methyl ester |
| CN107635660A (en) * | 2015-03-26 | 2018-01-26 | 巴斯夫公司 | Hydrogenolysis catalyst with peracid tolerance |
| US11077428B2 (en) | 2015-03-26 | 2021-08-03 | Basf Corporation | Hydrogenolysis catalysts with high acid tolerance |
| CN108144619A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | It is a kind of to be used for catalyst and preparation method of the benzene carboxylic ester Hydrogenation for benzyl alcohol |
| CN106622379A (en) * | 2016-12-20 | 2017-05-10 | 江苏金马油脂科技发展有限公司 | Preparation method and application of fatty acid methyl ester hydrogenation copper-based catalyst |
| CN106944113A (en) * | 2017-04-07 | 2017-07-14 | 中国科学技术大学 | A kind of preparation method of hydrogenation catalyst and fatty alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102476056B (en) | 2012-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102476056B (en) | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof | |
| CN100398202C (en) | Process for preparing Cu-Zn-Al vapor hydroformylation catalyst and products therefrom | |
| CN101347737B (en) | Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid | |
| CN102989490B (en) | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof | |
| CN109926040B (en) | Heterogeneous catalyst for preparing isophorone and preparation and application thereof | |
| CN103230810A (en) | Fischer-Tropsch synthetic catalyst for preparing low-carbon olefin by utilizing synthetic gas, modified molecular sieve carrier and preparation method | |
| CN103657658B (en) | Carboxylic ester hydrogenation catalyst and prepare the method for cyclohexanol and ethanol | |
| CN103480377A (en) | Preparation method of copper based catalyst for methanol synthesis | |
| CN102151568A (en) | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof | |
| CN102218320A (en) | Catalyst for hydrogenation, preparation method and application thereof | |
| CN105727962B (en) | Catalyst and its preparation method and application for dimethyl adipate hexylene glycol | |
| CN102974382B (en) | Catalyst for preparing ethanol by virtue of acetate hydrogenation and preparation method thereof | |
| CN101234351A (en) | Catalyst for synthesizing vanillin and derivative and preparation | |
| CN103769148A (en) | Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst | |
| CN103372441B (en) | Preparation method of methanol synthesis catalyst | |
| CN1301984C (en) | Catalysis method for synthesizing gamma butyrolactone | |
| CN105363456A (en) | Copper-based catalyst and preparation method and application thereof | |
| CN104624196A (en) | High-specific-surface-area Fischer-Tropsch synthesis catalyst and preparation method and application of high-specific-surface-area Fischer-Tropsch synthesis catalyst | |
| CN101906038A (en) | Method for preparing ester by catalytic oxidization of 1,3-propanediol | |
| CN105153058A (en) | Synthetic method of benzotriazoles compound | |
| CN110975940B (en) | Composite metal photocatalysis system and preparation method and application thereof | |
| CN103372439B (en) | The preparation method of catalst for synthesis of methanol | |
| CN102976892B (en) | Method for preparing ethanol through acetic ester hydrogenation | |
| CN103372440B (en) | Preparation method of methanol synthesis catalyst | |
| CN103551154B (en) | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |