CN113929559A - Method for synthesizing branched dodecanol from acetone with high yield - Google Patents
Method for synthesizing branched dodecanol from acetone with high yield Download PDFInfo
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- CN113929559A CN113929559A CN202111223645.8A CN202111223645A CN113929559A CN 113929559 A CN113929559 A CN 113929559A CN 202111223645 A CN202111223645 A CN 202111223645A CN 113929559 A CN113929559 A CN 113929559A
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 56
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 16
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 13
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 13
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 13
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009833 condensation Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- VTPOKROHHTWTML-UHFFFAOYSA-N pentacosan-13-one Chemical compound CCCCCCCCCCCCC(=O)CCCCCCCCCCCC VTPOKROHHTWTML-UHFFFAOYSA-N 0.000 claims abstract description 4
- WZCNWCLFWMINNF-UHFFFAOYSA-N dodecane-2,3-dione Chemical compound CCCCCCCCCC(=O)C(C)=O WZCNWCLFWMINNF-UHFFFAOYSA-N 0.000 claims abstract 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000012918 MOF catalyst Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000013177 MIL-101 Substances 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000013206 MIL-53 Substances 0.000 claims description 3
- 239000013132 MOF-5 Substances 0.000 claims description 3
- 239000013118 MOF-74-type framework Substances 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- LSKONYYRONEBKA-UHFFFAOYSA-N 2-Dodecanone Natural products CCCCCCCCCCC(C)=O LSKONYYRONEBKA-UHFFFAOYSA-N 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 8
- 238000000855 fermentation Methods 0.000 abstract description 5
- 230000004151 fermentation Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- UVMPXOYNLLXNTR-UHFFFAOYSA-N butan-1-ol;ethanol;propan-2-one Chemical compound CCO.CC(C)=O.CCCCO UVMPXOYNLLXNTR-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- ILXYCHCYCRZISX-UHFFFAOYSA-N hexacosane-13,14-dione Chemical compound CCCCCCCCCCCCC(=O)C(=O)CCCCCCCCCCCC ILXYCHCYCRZISX-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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Abstract
The invention relates to a method for synthesizing branched dodecanol with high yield from acetone, which is divided into three parts: 1) in a first catalyst bed layer of a fixed bed continuous reactor, preparing MIBK with high selectivity by acetone self-condensation/hydrogenation reaction of a biomass ABE fermentation product acetone under the catalysis of a metal loaded Metal Organic Framework (MOF) material M-MOF; 2) in a second catalyst bed layer of the fixed bed continuous reactor, the first catalyst bed layer generates a product MIBK which is catalyzed by a metal-loaded magnesium-aluminum hydrotalcite catalyst M-MgAl-HT, and self-condensation/hydrogenation generates branched-chain dodecanedione; 3) and in a third catalyst bed layer of the fixed bed continuous reactor, the second catalyst bed layer generates a product branched-chain dodecyl ketone, and the branched-chain dodecyl alcohol is generated by hydrogenation under the catalysis of the Ru/C catalyst. The alcohols can be used for preparing high-performance biomass-based surfactants.
Description
Technical Field
The invention relates to a lignocellulose-based upstream platform compound, in particular to a method for synthesizing branched dodecanol from acetone with high yield.
Background
Due to the characteristics of being renewable and environment-friendly, biomass resources become one of the key ways to solve the problem and are receiving wide attention. As a big agricultural country, China has huge lignocellulose reserves. Therefore, the development of lignocellulose utilization conversion technology to convert the lignocellulose utilization conversion technology into fuel and downstream bulk chemicals has great significance for relieving energy shortage and improving environmental problems. Especially in the aspect of preparing high value-added chemicals, lignocellulose is a powerful competitor to replace the traditional petrochemical route at present due to low cost.
Dodecanol is an important chemical, and is an intermediate for the industrial preparation of surfactants such as Sodium Dodecyl Sulfate (SDS) and Sodium Dodecyl Benzene Sulfonate (SDBS). Currently, the industrial preparation of the dodecanol mainly takes coconut oil and palm oil as raw materials and is obtained by transesterification, hydrogenation and rectification. The dependence of raw materials is strong, and the structural performance of the product is single. In view of the above two points, a technical route for converting lignocellulose into branched dodecanol is developed, which not only can relieve the dependence degree of dodecanol industry on raw oil, but also can prepare a surfactant with high performance and special application.
In this patent we use acetone as the feedstock, which can be directly obtained from biomass lignocellulose by acetone-butanol-ethanol (ABE) fermentation. The process has been over a hundred years old and the technology is mature. Acetone and hydrogen are directly synthesized into the straight-chain dodecanol with high yield through a fixed bed reactor provided with three catalyst bed layers. The method specifically comprises the following three steps: 1) in a first catalyst bed layer of a fixed bed continuous reactor, preparing MIBK with high selectivity by acetone self-condensation/hydrogenation reaction of a biomass ABE fermentation product acetone under the catalysis of a metal-loaded molecular sieve or a metal-loaded Metal Organic Framework (MOF) material catalyst M-MOF; 2) in a second catalyst bed layer of the fixed bed continuous reactor, the first catalyst bed layer generates a product MIBK which is catalyzed by a metal-doped magnesium-aluminum hydrotalcite catalyst M-MgAl-HT, and self-condensation/hydrogenation generates branched chain dodecyl diketone; 3) and in a third catalyst bed layer of the fixed bed continuous reactor, the second catalyst bed layer generates a product branched-chain dodecyl ketone, and the branched-chain dodecyl alcohol is generated by hydrogenation under the catalysis of the Ru/C catalyst. The whole process only uses acetone and hydrogen as raw materials, has low price, avoids the separation of a catalyst and a product, realizes chemical integration, and is beneficial to the continuous production of the product.
Disclosure of Invention
The invention aims to provide a novel, simple and efficient synthetic route for synthesizing branched dodecanol from a lignocellulose derivative compound acetone with high selectivity and high yield.
The invention is realized by the following technical scheme:
the branched dodecanol is directly synthesized by using three catalyst beds of a continuous reactor.
1) In a first catalyst bed layer of a fixed bed continuous reactor, preparing MIBK with high selectivity by acetone self-condensation/hydrogenation reaction of a biomass ABE fermentation product acetone under the catalysis of a metal loaded Metal Organic Framework (MOF) material catalyst M-MOF;
in this patent we use acetone as the feedstock, which can be directly obtained from biomass lignocellulose by acetone-butanol-ethanol (ABE) fermentation.
2) In a second catalyst bed layer of the fixed bed continuous reactor, the first catalyst bed layer generates a product MIBK which is catalyzed by a metal-doped magnesium-aluminum hydrotalcite catalyst M-MgAl-HT, and self-condensation/hydrogenation generates branched chain dodecyl diketone; 3) and in a third catalyst bed layer of the fixed bed continuous reactor, the second catalyst bed layer generates a product branched-chain dodecyl ketone, and the branched-chain dodecyl alcohol is generated by hydrogenation under the catalysis of the Ru/C catalyst.
The first catalyst bed layer is a supported metal bifunctional M-MOF catalyst, and the supported MOF material is one or a mixture of more than two of the following substances: ZIF-8, MIL-53, MIL-101, MOF-5, MOF-74; the metal M is one or a mixture of more than two of cobalt, nickel, copper, palladium, platinum, ruthenium and iridium, and the mass doping amount of the metal in the metal-doped M-MOF catalyst is more than 0-20% (preferably more than 0-5%);
the second catalyst bed layer is a metal-doped magnesium-aluminum hydrotalcite catalyst M-MgAl-HT, the doped metal is one or a mixture of more than two of cobalt, nickel, copper, palladium, platinum, ruthenium and iridium-doped magnesium-aluminum hydrotalcite, and the mass doping amount of metal in the metal-doped solid alkali is more than 0-20% (preferably more than 0-5%);
the third catalyst bed layer is a Ru/C catalyst, and the mass doping amount of Ru is more than 0-20% (preferably more than 0-5%);
the conditions of the fixed bed reactor were: the temperature is between 100 and 500 ℃ (preferably 100 and 300 ℃), the pressure of reaction hydrogen is between 0.1 and 10.0MPa (preferably 0.1 and 1.0MPa), and the mass space velocity of raw materials is between 0.1 and 10.0h-1(preferably 0.1-5 h)-1)，H2The molar ratio to the substrate starting material is from 1 to 800 (preferably from 1 to 200).
Through the steps, the branched dodecanol can be directly obtained with high selectivity by taking acetone and hydrogen as raw materials, the yield is over 80 percent, and the method is a green and simple new synthesis route for preparing the surfactant precursor by taking a platform compound derived from lignocellulose as a raw material.
Drawings
FIG. 1 reaction route for preparing branched dodecanol by acetone condensation/hydrogenation
FIG. 2 GC-MS spectrum of MIBK
FIG. 3 GC-MS spectrum of branched dodecanol
Detailed Description
The invention will now be illustrated by means of specific examples, without restricting its scope to these examples.
Examples 1 to 14
1. Preparation of the catalyst:
1) supported M-MOF catalyst: MOF supports ZIF-8, MIL-53, MIL-101, MOF-5, MOF-74 are commercial catalyst products purchased directly. Respectively preparing 0-5 wt% of metal salt solution (one or more than two of cobalt nitrate, nickel nitrate, copper nitrate, palladium nitrate, platinum chloride, ruthenium chloride, iridium chloride and the like), diluting according to the saturated water absorption capacity of the carrier, adding one or more of the metal salt solution into the carrier for soaking in a medium volume, standing overnight, drying at 80 ℃, and reducing the calcined catalyst in situ for 2 hours by using hydrogen at 100-500 ℃ in a fixed bed. (see Table 1, examples 1-7)
2) Preparation of metal-doped magnesium aluminum hydrotalcite: the metal-doped magnalium hydrotalcite is prepared by mixing 0.093mol M of magnesiumg(NO3)2·6H2O，0.0465mol Al(NO3)3·9H2Dissolving O and 0.01mol metal salt solution (one or more of cobalt nitrate, nickel nitrate, copper nitrate, palladium nitrate, platinum chloride, ruthenium chloride, iridium chloride, etc.) in 100ml water, and dissolving the solution in 0.219mol NaOH and 0.0565mol Na under 70 deg.C water bath condition2CO3Adding 100ml of the aqueous solution dropwise, continuing stirring and aging overnight after the dropwise addition is finished, filtering and washing, drying overnight at 80 ℃, and calcining for 8 hours at 450 ℃ to obtain the metal-doped magnesium-aluminum hydrotalcite. The calcined catalyst was reduced in situ in a fixed bed at 500 ℃ for 2h with hydrogen. (see Table 1, examples 8-14)
3) The Ru/C catalyst was a commercial catalyst product purchased directly.
TABLE 1 Supported Metal A/X type bifunctional catalyst
2. Condensation and hydrogenation of acetone to prepare branched dodecanol: in a fixed bed reactor, 1.0g of first, second and third bed catalysts are sequentially loaded into a reaction tube, the hydrogen pressure in the reactor is kept at 0.3MPa, the hydrogen flow rate is 150mL/min, and acetone is pumped into the reactor by a high performance liquid chromatography pump at 0.05 mL/min. The reaction results are shown in tables 2 and 3.
TABLE 2 acetone Autocondensation reaction results
It can be seen from table 2 that acetone can be condensed/hydrogenated to branched dodecanol with high selectivity and high yield under the combined action of the three-bed catalyst. For the second bed catalyst M-MgAl-HT (examples 16-19), Pd and Pt doped magnesium aluminum hydrotalcite has better activity; for the first bed catalyst M-MOF, when different metals are matched with the MOF carrier (examples 20-27), the combined activity of the supported metal Pd and the carrier MIL-101 is better; the reactivity is optimum when the temperature for the first bed is 120 ℃ for 100 ℃ and the temperature for the second bed is 250 ℃ and the temperature for the third catalyst bed is 80 ℃ (examples 29-33).
By way of the above examples, a series of detailed procedures for catalyst preparation (examples 1-14) are detailed and their activities in the condensation/hydrogenation of acetone to branched dodecanol are fully discussed. Under the conditions given above (examples 16-33), a yield of branched dodecanol of about 95% overall was obtained. The branched dodecanol can be used for preparing a high-performance biomass-based surfactant.
Claims (6)
1. A method for synthesizing branched dodecanol with high yield from acetone is characterized in that:
reacting in a fixed bed continuous reactor filled with three catalyst bed layers at one time, and synthesizing branched dodecanol by one step with acetone under the catalysis of the three catalyst bed layers;
1) in a first catalyst bed layer of a fixed bed continuous reactor, acetone is catalyzed by a Metal Organic Framework (MOF) material M-MOF catalyst loaded with metal, and MIBK is prepared at high selectivity through acetone self-condensation/hydrogenation reaction;
2) in a second catalyst bed layer of the fixed bed continuous reactor, the first catalyst bed layer generates a product MIBK which is catalyzed by a metal-loaded magnesium-aluminum hydrotalcite catalyst M-MgAl-HT, and self-condensation/hydrogenation generates branched-chain dodecanedione;
3) and in a third catalyst bed layer of the fixed bed continuous reactor, the second catalyst bed layer generates a product branched-chain dodecyl ketone, and the branched-chain dodecyl alcohol is generated by hydrogenation under the catalysis of the Ru/C catalyst.
2. The method of claim 1, wherein:
in the step 1), a supported metal bifunctional M-MOF catalyst is used as a first catalyst bed layer to carry out self-condensation/hydrogenation reaction of acetone; the carrier MOF material is one or a mixture of more than two of the following substances: ZIF-8, MIL-53, MIL-101, MOF-5, MOF-74; the metal M is one or a mixture of more than two of cobalt, nickel, copper, palladium, platinum, ruthenium and iridium, and the mass doping amount of the metal in the metal-doped M-MOF catalyst is more than 0-20% (preferably more than 0-5%).
3. The method of claim 1, wherein:
in the step 2), the metal-loaded magnesium-aluminum hydrotalcite M-MgAl-HT is one or a mixture of more than two of cobalt, nickel, copper, palladium, platinum, ruthenium and iridium-doped magnesium-aluminum hydrotalcite, and the mass doping amount of metal in the metal-doped solid base is more than 0-20% (preferably more than 0-5%).
4. The method of claim 1, wherein:
in step 3), the mass doping amount of Ru in the Ru/C catalyst is more than 0-20% (preferably more than 0-5%).
5. The method of claim 1, wherein:
a fixed bed continuous reactor is adopted in the steps 1) to 3); the supported metal bifunctional M-MOF catalyst is used as a first catalyst bed layer to catalyze the self-condensation/hydrogenation of acetone into MIBK; the metal-loaded magnesium-aluminum hydrotalcite catalyst M-MgAl-HT is used as a second catalyst bed layer to catalyze the MIBK to carry out self-condensation/hydrogenation to generate branched-chain dodecanedione; the Ru/C catalyst is used as a third catalyst bed layer to catalyze the hydrogenation of the branched dodecanone into branched dodecanol; the conditions of the fixed bed reactor were: the temperature is between 100 ℃ and 500 ℃ (preferably 60-300 ℃), the pressure of reaction hydrogen is between 0.1-10.0MPa (preferably 0.1-1.0MPa), and the mass space velocity of raw materials is between 0.1-10.0h-1(preferably 0.1-5 h)-1)，H2The molar ratio to the substrate starting material is from 1 to 800 (preferably from 1 to 200).
6. The method of claim 1, wherein:
MIBK, branched dodecanedione, branched dodecanol refers to the product of FIG. 1 and one or a mixture of two or more of its isomers and homologs.
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