CN116041142A - Process for preparing 2-propyl-1-heptanol - Google Patents
Process for preparing 2-propyl-1-heptanol Download PDFInfo
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- CN116041142A CN116041142A CN202111264935.7A CN202111264935A CN116041142A CN 116041142 A CN116041142 A CN 116041142A CN 202111264935 A CN202111264935 A CN 202111264935A CN 116041142 A CN116041142 A CN 116041142A
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- Prior art keywords
- propyl
- nitrogen
- heptenal
- containing polymer
- catalyst
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- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004005 microsphere Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 27
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 26
- 238000005470 impregnation Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- GADNZGQWPNTMCH-CSKARUKUSA-N (e)-2-propylhept-2-enal Chemical compound CCCC\C=C(C=O)/CCC GADNZGQWPNTMCH-CSKARUKUSA-N 0.000 claims 7
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- GADNZGQWPNTMCH-NTMALXAHSA-N (z)-2-propylhept-2-enal Chemical compound CCCC\C=C(C=O)\CCC GADNZGQWPNTMCH-NTMALXAHSA-N 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 150000001299 aldehydes Chemical class 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- MMFCJPPRCYDLLZ-CMDGGOBGSA-N (2E)-dec-2-enal Chemical compound CCCCCCC\C=C\C=O MMFCJPPRCYDLLZ-CMDGGOBGSA-N 0.000 description 18
- MMFCJPPRCYDLLZ-UHFFFAOYSA-N dec-2-enal Natural products CCCCCCCC=CC=O MMFCJPPRCYDLLZ-UHFFFAOYSA-N 0.000 description 17
- 238000009826 distribution Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 7
- 238000004846 x-ray emission Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 5
- 239000004440 Isodecyl alcohol Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WDMOXLRWVGEXJV-UHFFFAOYSA-N 8-methylnonanal Chemical compound CC(C)CCCCCCC=O WDMOXLRWVGEXJV-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- -1 copper-zinc-aluminum Chemical compound 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of alkanol preparation by olefine aldehyde hydrogenation, and discloses a method for preparing 2-propyl-1-heptanol, which comprises the following steps: in the presence of a catalyst, 2-propyl-2-heptenal is contacted with hydrogen to carry out hydrogenation reaction; the preparation method of the catalyst comprises the following steps: the alumina microsphere is contacted with a nitrogen-containing polymer solution, then the contact product is subjected to first roasting under inert atmosphere to obtain a carrier, and then the metal active component is loaded on the carrier. The method can improve the selectivity of the 2-propyl-1-heptanol on the premise of ensuring the conversion rate of the 2-propyl-2-heptenal.
Description
Technical Field
The invention relates to the technical field of alkanol preparation by olefine aldehyde hydrogenation, in particular to a method for preparing 2-propyl-1-heptanol.
Background
In recent years, the industry began to use higher carbon number alcohols to produce plasticizers, one of which is decanol, for reasons of safety and environmental protection of plasticized products. 2-propyl-1-heptanol is one of the important representatives of decanol. The existing routes for producing 2-propyl-1-heptanol mainly include: (1) The trimerization of propylene or the oligomerization and the cutting of propylene and butene are carried out to obtain C9 olefin, and then 2-propyl-1-heptanol is produced through oxo synthesis and hydrogenation; (2) Synthesizing valeraldehyde by hydroformylation of butene, condensing to generate 2-propyl-2-heptenal, and hydrogenating to obtain 2-propyl-1-heptanol.
CN101185893a discloses a catalyst for preparing isodecyl alcohol by gas phase hydrogenation of decenal and a preparation method thereof. The catalyst is prepared by adopting a coprecipitation method and consists of copper oxide, zinc oxide, aluminum oxide and active auxiliary agent; the active auxiliary agent is one or more of metal element compounds of Na, K, ni, co, mg, ca, ba; the molar contents of copper oxide, zinc oxide and aluminum oxide are respectively 20-70%, 28-70% and 1-10%, and the active auxiliary agent is 0.1-2.0%. The catalyst is used for preparing the isodecyl alcohol by gas-phase hydrogenation of the decenal, and has higher decenal conversion rate and isodecyl alcohol selectivity. However, the gas phase hydrogenation reaction needs to be carried out at 140-180 ℃, and the subsequent condensation separation is needed, so that the energy consumption is high and the process is complex.
CN1883795A discloses a preparation method of copper-zinc-aluminum gas phase aldehyde hydrogenation catalyst, the active components of which are 10-60% of CuO,20-80% of ZnO and 0.1-20% of Al 2 O 3 And tabletting and forming graphite serving as a carrier to obtain the catalyst. The method of stepwise continuous coprecipitation is adopted, the intermittent feeding mode which is carried out stepwise is changed into the continuous feeding mode, the prepared catalyst has large specific surface area and pore volume, the dispersity of active metal copper is high, and the activity of the catalyst is greatly improved. However, the raw material aldehyde is gasified in a gas phase reaction mode, and the decenal is gasified in the phase change processIs easy to polymerize and reduces the selectivity of the target product alcohol.
CN102666455a process for the preparation of decanol by hydrogenation of decenal. The process requires at least two reactors, wherein the first reactor uses a copper-based and/or nickel-based catalyst and the second reactor uses a palladium or ruthenium catalyst, all in the liquid phase over a solid catalyst. The process enables high yields of decenal to be hydrogenated to decanol with less than 1500ppm of unsaturated decenal in the hydrogenation effluent. The hydrogenation process of this invention is relatively complex, employing multiple reactors in series, and the second reactor uses an expensive noble metal catalyst.
CN104513131B discloses a process for preparing decanol by liquid phase hydrogenation of decenal. The method uses an organic polymer supported Raney nickel catalyst, and decenal flows through a catalyst bed layer in a liquid state under a hydrogen atmosphere, so that decanol can be obtained with high yield and high selectivity. However, the catalyst is Raney nickel, the price is high, and a certain combustion danger exists in the using process.
CN106179373a proposes a catalyst for liquid phase hydrogenation of decenal to isodecyl alcohol and a preparation method thereof. The three active components of nickel, copper and chromium are loaded on an alumina carrier by adopting a precipitation method, and the prepared catalyst has higher isodecyl aldehyde conversion rate and isodecyl alcohol selectivity. However, the presence of chromium can pose a significant environmental and health hazard.
CN113019378A discloses an enal hydrogenation catalyst which can be used for the hydrogenation of decenal to make decanol, comprising: niO 5-50%, cuO 5-25%, mgO 0.1-10%, and gamma-Al 2O3 in balance. The catalyst is prepared by mixing gamma-alumina powder, a magnesium source and a water-soluble organic matter, performing solid-liquid separation, and sequentially performing first drying and first roasting to obtain a product serving as an intermediate carrier; mixing the obtained intermediate carrier, an alumina precursor and an additive, and then sequentially carrying out molding, second drying and second roasting to obtain a carrier; and (3) carrying out impregnation treatment on the carrier by using a mixed solution containing nickel and copper, carrying out solid-liquid separation, and sequentially carrying out third drying and third roasting to obtain the olefine aldehyde hydrogenation catalyst. Has good coking resistance and catalytic activity, and can prolong the service life of the catalyst. However, the catalyst belongs to the traditional forming method, the particle size distribution of the obtained catalyst is wide, the particle spacing is large when the catalyst is filled, and hot spots are easy to occur in the reaction process.
Disclosure of Invention
In order to solve the problems of high catalyst cost caused by noble metal and environmental pollution caused by metal chromium used in the catalyst for preparing alkanol by hydrogenating olefine aldehyde in the prior art, and the complex process route of a multi-step hydrogenation method is not suitable for industrial application. The invention provides a method for preparing 2-propyl-1-heptanol.
For 10 ten thousand tons of decanol produced annually, the selectivity can be improved by about 200 ten thousand per 1% under the condition of unchanged conversion rate, and the annual economic benefit can be improved; in addition, the reduction of byproducts can reduce the energy consumption of the rectification separation of the subsequent products, thereby achieving the purposes of energy conservation, emission reduction and synergy. Thus, in order to increase decanol selectivity, the present invention provides a process for preparing 2-propyl-1-heptanol, the process comprising: in the presence of a catalyst, 2-propyl-2-heptenal is contacted with hydrogen to carry out hydrogenation reaction;
the preparation method of the catalyst comprises the following steps: the alumina microsphere is contacted with a nitrogen-containing polymer solution, then the contact product is subjected to first roasting under inert atmosphere to obtain a carrier, and then the metal active component is loaded on the carrier.
The catalyst is prepared by carrying out carbon-nitrogen doping on specific alumina microspheres to obtain a carrier and then loading a metal active component. The catalyst of the invention adopts a one-step hydrogenation method to hydrogenate 2-propyl-2-heptenal to prepare 2-propyl-1-heptanol under the condition of not using noble metals and metallic chromium, thus obtaining higher conversion rate of 2-propyl-2-heptenal and selectivity of 2-propyl-1-heptanol.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the diameter of alumina microspheres refers to the average diameter of alumina microspheres.
The present invention provides a process for preparing 2-propyl-1-heptanol, the process comprising: in the presence of a catalyst, 2-propyl-2-heptenal is contacted with hydrogen to carry out hydrogenation reaction;
the preparation method of the catalyst comprises the following steps: the alumina microsphere is contacted with a nitrogen-containing polymer solution, then the contact product is subjected to first roasting under inert atmosphere to obtain a carrier, and then the metal active component is loaded on the carrier.
According to the present invention, preferably, the alumina microspheres have a particle diameter of 200 to 800 μm and a coefficient of variation of 3 to 8%.
According to the present invention, the source of the alumina microspheres is not particularly limited as long as the particle diameter and the coefficient of variation of the alumina microspheres satisfy the defined ranges. The alumina microspheres can be prepared by the method described in CN110203953B or CN 110282642B. Preferably, the preparation method of the alumina microsphere comprises the following steps: the preparation method comprises the steps of taking aluminum sol as a disperse phase, taking an organic solvent as a continuous phase, enabling the disperse phase to form liquid drops under the shearing action of the continuous phase, solidifying to obtain gel microspheres, and drying and roasting to obtain the aluminum oxide microspheres.
In the method for preparing alumina microspheres according to the present invention, preferably, the alumina sol has a solid content of 5 to 8wt%.
In the method for preparing alumina microspheres according to the present invention, preferably, a monohydric saturated alcohol having an organic solvent of C1 to C10, preferably octanol, is used in the preparation of alumina microspheres.
In the method for preparing alumina microspheres according to the present invention, the drying temperature may be 100 to 120 ℃ and the drying time may be 3 to 15 hours.
In the method for preparing alumina microspheres according to the present invention, the firing temperature may be 550 to 1200 ℃ and the firing time may be 4 to 10 hours.
According to the present invention, preferably, the alumina microspheres are prepared in a microchannel reactor. The type of the microchannel reactor is not particularly limited, and the microchannel reactor may be a single-channel reactor and/or a multi-channel reactor.
According to a further preferred embodiment of the present invention, the multi-channel reactor is an eight-channel reactor. Describing the structure of the eight-channel reactor, wherein the eight-channel reactor comprises a continuous phase distribution layer, a first liquid drop generation layer, a second liquid drop generation layer and a disperse phase distribution layer, the continuous phase distribution layer consists of petal-shaped resistance distribution channels, eight fluid outlets at the tail ends of the petal-shaped resistance distribution channels, a continuous vertical inlet and four positioning holes, fluid is called one stage after each branch, a certain resistance is added before each stage of fluid branch, and the width of the channels is reduced along with the increase of the radius of the circumference where the starting end of each stage is positioned; the first liquid drop generation layer is provided with eight T-shaped channels, four positioning holes and eight through holes so as to meet the requirement of continuous phase flowing from the distribution layer to the generation layer, the second liquid drop generation layer is similar to the first liquid drop generation layer in structure, and eight liquid drop outlets are distributed at the tail end of a main channel of the T-shaped channel; the disperse phase distribution layer has a similar structure to the continuous phase distribution layer, and besides petal-shaped resistance distribution channels and eight disperse phase outlets at the tail end of the petal-shaped resistance distribution channels, the disperse phase distribution layer also has a disperse phase fluid inlet and 8 product outlets.
According to the present invention, the process of preparing alumina microspheres of the present invention is preferably illustrated with an eight-pass reactor. The preparation method comprises the steps of taking aluminum sol as a disperse phase, taking an organic solvent as a continuous phase, adjusting the flow rate of the continuous phase, enabling the continuous phase to be full of a continuous phase distribution layer and flow into a liquid drop generation layer, then flowing out from an outlet, enabling the flow rate of the continuous phase to be stabilized at 6-10mL/min, adjusting the flow rate of the disperse phase to be 1-4mL/min, enabling the disperse phase to be full of the disperse phase distribution layer and flow into the liquid drop generation layer, further generating liquid drops under the shearing action of the continuous phase, solidifying the liquid drops in an oil column to obtain gel microspheres, drying, and roasting to obtain the aluminum oxide microspheres with the diameters of 200-800 mu m and the variation coefficients of 3-8%.
The amount of the nitrogen-containing polymer used according to the present invention may be selected within a wide range, and preferably the amount of the nitrogen-containing polymer solution used in terms of the nitrogen-containing polymer is 0.1 to 1g relative to 100g of the alumina microspheres.
According to the present invention, the conditions for contacting the alumina microspheres with the nitrogen-containing polymer solution may be selected within a wide range, and preferably, the contacting is performed at a temperature of 100 to 120℃for a period of 4 to 10 hours.
According to the present invention, the kind of the nitrogen-containing polymer may be selected within a wide range, and preferably, the nitrogen-containing polymer in the nitrogen-containing polymer solution is a polymer containing nitrogen heterocycle, preferably at least one of polyvinylimidazole, polyvinylpyridine and polyvinylpyrrolidone, and more preferably polyvinylimidazole.
According to the present invention, the concentration of the nitrogen-containing polymer in the nitrogen-containing polymer solution is not particularly limited, and preferably the concentration of the nitrogen-containing polymer in the nitrogen-containing polymer solution is 0.1 to 1wt%. (e.g., may be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1 wt%).
According to the present invention, preferably, the solvent used in the preparation of the nitrogen-containing polymer solution is an alcohol, preferably a saturated alcohol of C1-C4, more preferably methanol and/or ethanol.
According to the present invention, the conditions of the first firing may be selected within a wide range, and preferably, the temperature of the first firing is 400 to 800 ℃ for 2 to 10 hours.
According to the present invention, preferably, the method for preparing the catalyst further comprises a step of first drying the product of the contact of the alumina microspheres with the nitrogen-containing polymer solution, and then, a step of first firing, more preferably, the first drying temperature is 60-80 ℃ for 4-12 hours.
According to the present invention, preferably, the metal active component is Ni.
According to the present invention, it is preferable that the metal active component is used in an amount of 5 to 20g in terms of metal element relative to 20g of the carrier.
According to the present invention, it is preferable that the metal active component is used in such an amount that the content of the metal active component in terms of metal element in the resultant catalyst is 15 to 50wt%.
According to the present invention, preferably, the metal active component is supported on the carrier in such a manner that the carrier is impregnated with the impregnation liquid containing the metal active component, and then subjected to the second calcination under an inert atmosphere.
According to the present invention, preferably, the impregnation liquid containing the metal active component is prepared by dissolving a water-soluble salt of a metal in water, and more preferably, the mass percentage of the metal in the impregnation liquid containing the metal active component is 10 to 15wt%.
According to the invention, the conditions of impregnation with the impregnation liquid can be chosen within wide limits, preferably at a temperature of 30-40℃for a time of 1-5 hours.
In the present invention, the impregnation may be performed by any one of impregnation methods commonly used in the art, for example, an isovolumetric impregnation method and an overdose impregnation method, and may be performed by one impregnation or a plurality of impregnation, as long as the amount of the metal active component supported is allowed to satisfy the requirement.
According to the invention, the conditions of the second calcination may be selected within a wide range, preferably the temperature of the second calcination is 300-600 ℃ for 4-8 hours.
According to the present invention, preferably, the preparation method of the catalyst further comprises performing the first calcination after performing the second drying of the impregnated support, more preferably, the second drying is performed at a temperature of 80 to 120 ℃ for a time of 4 to 12 hours.
According to the present invention, preferably, the hydrogenation reaction conditions include: the temperature is 50-200deg.C, preferably 90-150deg.C, the hydrogen pressure is 0.5-8MPa, preferably 3-5MPa, and the liquid hourly space velocity of 2-propyl-2-heptenal is 0.01-5h -1 Preferably 0.02-0.1h -1 。
According to the present invention, preferably, the 2-propyl-2-heptenal is contacted with hydrogen in the form of a 2-propyl-2-heptenal solution, and the solvent in the 2-propyl-2-heptenal solution is a saturated alcohol having 1 to 10 carbon atoms.
According to the present invention, preferably, the molar ratio of the 2-propyl-2-heptenal to hydrogen is 1:50-100.
According to the present invention, preferably, the weight ratio of the 2-propyl-2-heptenal to the saturated alcohol of C1-C10 is 1:5-10.
Preferably, according to the present invention, the C1-C10 saturated alcohol is decanol.
The present invention will be described in detail by examples. In the following examples of the present invention,
decenal conversion = (moles of decenal in starting material-moles of unreacted decenal)/(moles of decenal in starting material x 100%).
Decanol selectivity = moles of decanol in the product/(moles of decenal in the feed-moles of unreacted decenal) x 100%.
The diameter of the alumina microsphere is tested by adopting a scanning electron microscope.
The method for testing the variation coefficient comprises the following steps: the number of the alumina microspheres in the unit area is measured by a scanning electron microscope, the diameter of each alumina microsphere is measured, and then the alumina microspheres are calculated according to a formula of a variation coefficient.
The coefficient of variation is calculated according to the following formula:
CV: coefficient of variation, n: counting alumina microsphere particles, X i : the particle diameter of the single alumina microsphere is equal to that of the single alumina microsphere,
all alumina microsphere particle diameters average.
Preparation example
The preparation of alumina microsphere is carried out by adopting a microstructure reactor, wherein the dispersed phase adopts alumina sol with 7.5wt% of solid content, the continuous phase and liquid in an oil column adopt organic solvent octanol, the flow rate of the continuous phase is firstly regulated to ensure that the continuous phase is full of the continuous phase distribution layer and flows into the liquid drop generation layer, then flows out from an outlet, and the flow rate of the continuous phase is finally stabilized at 6-10mL/min. And then adjusting the flow rate of the disperse phase to be 1-4mL/min, so that the disperse phase is filled in the disperse phase distribution layer and flows into the liquid drop generation layer, and further liquid drops are generated under the shearing action of the continuous phase. The droplets are solidified in an oil column to obtain gel microspheres, and the gel microspheres are dried at 120 ℃ for 12 hours and baked at 600 ℃ for 4 hours to obtain alumina microspheres with diameter of 345 mu m and variation coefficient of 7.2 percent.
Example 1
(1) 100g of the alumina microspheres obtained in the preparation example were immersed in an ethanol solution of polyvinyl imidazole having a concentration of 1wt% (wherein the amount of polyvinyl imidazole used was 1 g), then transferred to a hydrothermal kettle, reacted at 100℃for 10 hours, cooled and filtered, dried at 80℃for 4 hours, and then placed in a nitrogen atmosphere, and calcined at 400℃for 10 hours to obtain a support (carbon-doped alumina microspheres).
(2) 20g of the carrier was put in a 15wt% nickel nitrate aqueous solution (wherein the amount of nickel nitrate is 5g in terms of metal element), immersed at 30℃for 5 hours, then taken out of the carrier, drained, dried at 80℃for 12 hours, and calcined at 600℃for 4 hours in a nitrogen atmosphere to obtain a catalyst.
The nickel loading in the catalyst was 18.9wt% as characterized by X-ray fluorescence spectroscopy (XRF).
Example 2
Step (1) is the same as in example 1.
(2) 20g of the support was placed in a 15wt% nickel nitrate aqueous solution (wherein the amount of nickel nitrate as a metal element was 5 g), immersed at 30℃for 5 hours, then taken out of the support, drained, dried at 80℃for 12 hours, and calcined at 600℃for 4 hours in a nitrogen atmosphere.
(3) Repeating the operation of the step (2) for 3 times to obtain the catalyst.
The nickel loading in the catalyst was 43.7wt% as characterized by XRF.
Example 3
(1) 100g of the alumina microspheres obtained in the preparation example were immersed in an ethanol solution of polyvinylimidazole having a concentration of 0.1wt% (wherein the amount of polyvinylimidazole used was 0.1 g), then transferred to a hydrothermal kettle, reacted at 120℃for 4 hours, cooled and filtered, dried at 60℃for 12 hours, and then placed in a nitrogen atmosphere, and calcined at 800℃for 2 hours to obtain a support (carbon-doped alumina microspheres).
(2) 20g of the support was placed in a 15wt% nickel nitrate aqueous solution (wherein the amount of nickel nitrate as a metal element was 5 g), immersed at 40℃for 1 hour, then taken out, drained, dried at 120℃for 4 hours, and calcined at 300℃for 8 hours in a nitrogen atmosphere.
(3) Repeating the operation of the step (2) for 3 times to obtain the catalyst.
The nickel loading in the catalyst was 44.7wt% as characterized by XRF.
Comparative example 1
The catalyst preparation was carried out as in example 1, except that the support was replaced with alumina dental spheres (purchased from enoki biotechnology ltd, particle size 3-4 mm).
The nickel loading in the catalyst was 19.5wt% as characterized by XRF.
Comparative example 2
The catalyst preparation was carried out as in example 2, except that the support was replaced with alumina dental spheres (purchased from enoki biotechnology ltd, particle size 3-4 mm).
The nickel loading in the catalyst was 45.3wt% as characterized by XRF.
Comparative example 3
The catalyst preparation was carried out as in example 1, except that the procedure of preparation of the support of step (1), i.e., directly using alumina microspheres as a support, was not included.
The nickel loading in the catalyst was 19.7wt% as characterized by XRF.
Test case
The catalysts of the above examples and comparative examples were tested for the performance of liquid phase hydrogenation of 2-propyl-2-heptenal to produce 2-propyl-1-heptanol, 20mL of the catalyst was charged into a reactor, and after reduction at 450℃for 4 hours in a hydrogen atmosphere, hydrogen, liquid 2-propyl-2-heptenal and solvent (2-propyl-1-heptanol) were continuously fed, and the reaction temperature, pressure of hydrogen, liquid hourly space velocity of 2-propyl-2-heptenal and weight ratio of 2-propyl-2-heptenal to solvent were as shown in Table 1, and the test results were shown in Table 1.
TABLE 1
Note that: decenal refers to 2-propyl-2-heptenal in table 1.
As can be seen from the results in Table 1, the catalyst prepared by the method of the present invention has a higher conversion rate of 2-propyl-2-heptenal and a higher selectivity of 2-propyl-1-heptanol in the preparation of 2-propyl-1-heptanol by liquid phase hydrogenation of 2-propyl-2-heptenal. Compared with the catalyst in the embodiment 1-2, the catalyst in the embodiment 1-3 has basically equivalent metal active component content, and under the same hydrogenation test condition, the selectivity of 2-propyl-1-heptanol can be further improved by more than 1% on the premise of ensuring the conversion rate of 2-propyl-2-heptenal by adopting the catalyst in the embodiment 1-3.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for preparing 2-propyl-1-heptanol, the process comprising: in the presence of a catalyst, 2-propyl-2-heptenal is contacted with hydrogen to carry out hydrogenation reaction;
the preparation method of the catalyst comprises the following steps: the alumina microsphere is contacted with a nitrogen-containing polymer solution, then the contact product is subjected to first roasting under inert atmosphere to obtain a carrier, and then the metal active component is loaded on the carrier.
2. The method of claim 1, wherein the nitrogen-containing polymer solution is used in an amount of 0.1 to 1g, calculated as nitrogen-containing polymer, relative to 100g of alumina microspheres.
3. The method of claim 1, wherein the alumina microspheres are contacted with the nitrogen-containing polymer solution at a temperature of 100-120 ℃ for a period of 4-10 hours.
4. The method of claim 1, wherein the alumina microspheres have a diameter of 200-800 μm and a coefficient of variation of 3-8%;
and/or the nitrogen-containing polymer in the nitrogen-containing polymer solution is a polymer containing nitrogen heterocycle, preferably at least one of polyvinylimidazole, polyvinylpyridine and polyvinylpyrrolidone, more preferably polyvinylimidazole;
and/or the concentration of the nitrogen-containing polymer in the nitrogen-containing polymer solution is 0.1-1wt%;
and/or the solvent used in the preparation of the nitrogen-containing polymer solution is an alcohol, preferably a saturated alcohol of C1-C4, more preferably methanol and/or ethanol.
5. The method of claim 1, wherein the first firing is at a temperature of 400-800 ℃ for a time of 2-10 hours.
6. The method according to claim 1, wherein the metal active component is used in an amount of 5 to 20g in terms of metal element relative to 20g of carrier;
and/or, the metal active component is Ni.
7. The method according to claim 1, wherein the metal active component is supported on the carrier by impregnating the carrier with an impregnation liquid containing the metal active component, followed by a second calcination under an inert atmosphere;
preferably, the temperature of the impregnation is 30-40 ℃ and the time is 1-5h;
preferably, the temperature of the second roasting is 300-600 ℃ and the time is 4-8h.
8. The process of claim 1, wherein the hydrogenation reaction conditions comprise: the temperature is 50-200deg.C, preferably 90-150deg.C, the hydrogen pressure is 0.5-8MPa, preferably 3-5MPa, and the liquid hourly space velocity of 2-propyl-2-heptenal is 0.01-5h -1 Preferably 0.02-0.1h -1 。
9. The process of claim 8 wherein the 2-propyl-2-heptenal is contacted with hydrogen as a 2-propyl-2-heptenal solution, the solvent in the 2-propyl-2-heptenal solution being a C1-C10 saturated alcohol;
and/or, the molar ratio of the 2-propyl-2-heptenal to the hydrogen is 1:50-100.
10. The method of claim 9, wherein the weight ratio of 2-propyl-2-heptenal to C1-C10 saturated alcohol is 1:5-10;
and/or, the saturated C1-C10 alcohol is decyl alcohol.
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