CN103708998B - Process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with solid catalyst - Google Patents
Process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with solid catalyst Download PDFInfo
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- CN103708998B CN103708998B CN201310666164.3A CN201310666164A CN103708998B CN 103708998 B CN103708998 B CN 103708998B CN 201310666164 A CN201310666164 A CN 201310666164A CN 103708998 B CN103708998 B CN 103708998B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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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
- C07C29/14—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
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- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
The invention relates to a process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with a solid catalyst. The method comprises the following steps of adding the solid catalyst and a raw material aldehyde into an autoclave, wherein an addition amount of the catalyst is 1-25% by mass that of the raw material aldehyde; reacting for 4-20 h at a temperature of 80-240 DEG C and under a hydrogen pressure of 0.5-8 MPa; and finally obtaining the long-chain alcohol. The raw material aldehyde is n-butyl aldehyde or n-valeraldehyde; the long-chain alcohol is octanol or decanol; the solid catalyst is a metal-solid acid (alkali) catalyst and comprises a metal, an auxiliary agent and a solid acid (alkali), wherein a mass percentage of the metal is the catalyst is 0.5-40%; the mass percentage of the auxiliary agent is 0-10%; and the balance being the solid acid (alkali). The provided environment-friendly novel process for the one-step synthesis of the long-chain alcohol by catalyzing the aldehydes with the solid catalyst can greatly shorten a process flow for synthesizing the long-chain alcohol and reduces equipment cost and operation cost.
Description
Technical field
The present invention relates to Green Chemical Technology field, be specially a kind of solid catalyst respectively catalysis butyraldehyde-n and valeraldehyde one-step synthesis octanol and decyl alcohol, and obtain the processing method of propyl carbinol and Pentyl alcohol simultaneously.
Background technology
Octanol (2-Ethylhexyl Alcohol) is important Organic Chemicals, as a kind of important plasticizer alcohol, for the synthesis of softening agent such as Octyl acrylate, dioctyl sebacate, dioctyl phthalate (DOP)s (DOP).In addition, octanol as excellent property solvent, petroleum additive etc. and be widely used.
Decyl alcohol (2-propyl enanthol) is also a kind of important plasticizer alcohol.Compared to DOP, adopt the polrvinyl chloride product of Di Iso Decyl Phthalate (DIDP) plasticizer production of being synthesized by decyl alcohol to have better electrical insulating property, low volatility, to human body and environment safer, become the ideal substitute of DOP.
Octanol is substantially identical with the technological process of production of decyl alcohol, all adopts that low-carbon alkene obtains corresponding low-carbon (LC) aldehyde through low pressure oxo process, low-carbon (LC) aldehyde obtains high-carbon aldehyde, high-carbon aldehyde through aldol condensation and obtains product alcohol three reaction process through hydrogenation again.Aldol reaction wherein, industrially use liquid base (dilute NaOH solution) as catalyzer more, though higher feed stock conversion and product yield can be obtained, but catalyzer can not reuse, serious to equipment corrosion, wastewater discharge is large, and environmental pollution is serious.Solid catalyst not only has high reactivity and highly selective but also reusable, also be beneficial to and be bonded dual-function catalyst with hydrogenation active component, catalysis aldehydes one step obtains long-chain alcohol, thus reaches the object of simplification of flowsheet, reduction cost of equipment and process cost, raising process economics.
The present invention adopts metal-solids acid (alkali) catalyzer, respectively catalysis butyraldehyde-n and valeraldehyde one-step synthesis octanol and decyl alcohol, and obtains propyl carbinol and Pentyl alcohol simultaneously.
Summary of the invention
The invention provides a kind of novel environment-friendly process by metal-solids acid (alkali) catalyst aldehydes one-step synthesis long-chain alcohol.Have that technical process is short, cost of equipment and process cost is low, advantages of environment protection, metal-solids acid (alkali) catalyzer simultaneously designing preparation has high reactivity, stability and optionally feature.
The concrete technical scheme of the present invention is as follows:
A kind of processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol, comprise the following steps: in autoclave, add solid catalyst and raw material aldehyde, wherein the add-on of catalyzer is 1 ~ 25% of raw material aldehyde quality, temperature of reaction 80 ~ 240 DEG C, hydrogen pressure is 0.5 ~ 8MPa, reaction times 4 ~ 20h, finally obtains long-chain alcohol.
Described raw material aldehyde is: butyraldehyde-n or valeraldehyde, and what described long-chain alcohol generated when raw material aldehyde is butyraldehyde-n is octanol (2-Ethylhexyl Alcohol); What generate when raw material aldehyde is valeraldehyde is decyl alcohol (2-propyl enanthol);
Described solid catalyst is metal-solids acid (alkali) catalyzer, its composition comprises metal, auxiliary agent and solid acid (alkali), and wherein, metal massfraction is in the catalyst 0.5 ~ 40%, the massfraction of auxiliary agent is 0 ~ 10%, and all the other are solid acid (alkali).
The mass percentage of described auxiliary agent is preferably 0% or 0.1 ~ 6.5%.
Metal in described metal-solids acid (alkali) catalyzer is: Cu, Ni, Co, Pt, Pd, Ru or Rh.
Solid acid in described metal-solids acid (alkali) catalyzer or solid alkali are: HY, HZSM-5, USY, H β, AlPO
4-5, SAPO-34, Al
2o
3, MgO-Al
2o
3, TiO
2, MgO, ZrO
2or ZnO.
Auxiliary agent in described metal-solids acid (alkali) catalyzer is: Cr, Ce, Mo, K, Mn, V, La, Zn or Fe.
The add-on of described catalyzer is preferably 5 ~ 20% of raw material aldehyde quality.
Beneficial effect of the present invention is as follows:
1. industrial be Material synthesis octanol with butyraldehyde, take valeral as the technological process of Material synthesis decyl alcohol, comprise aldol condensation, hydrogenation two-step reaction, the long increase causing cost of equipment and process cost of technical process, and the sig water catalytic erosion equipment that aldol condensation is used, produce a large amount of contaminated wastewater environment.The novel environment-friendly process of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol provided by the present invention, substantially reduces the technical process of synthetic long chain alcohol, reduces cost of equipment and process cost.For metal-solids acid (alkali) catalyzer that this process exploitation goes out, overcome the not easily separated and reusable problem that sig water catalyzer exists.
2. processing method provided by the present invention is while synthesis octanol or decyl alcohol, also obtains propyl carbinol or the important Organic chemical products of Pentyl alcohol two kinds.
3. adopt metal-solids acid (alkali) catalyst low-carbon (LC) aldehyde one-step synthesis long-chain alcohol, the transformation efficiency of low-carbon (LC) aldehyde can reach 100%, and the yield of long-chain alcohol reaches as high as 80%.
Embodiment
The catalyst preparation process that metal-solids acid (alkali) catalyzer that the present invention adopts can provide in reference literature (Applied Catalysis A:General, 2009,367:93 – 98):
Example is prepared as, its preparation process with Ni-Ce-HY catalyzer
By for subsequent use for solid acid HY 500 DEG C of roasting 4h in retort furnace.First, metal component precursor Ni (NO is taken
3)
26H
2o2.664g and auxiliary agent precursor Ce (NO
3)
36H
2o0.543g is made into the 15mL aqueous solution, by solid acid HY after 10g thermal treatment of the salt solution impregnation that is made into; After ageing 24h, 110 DEG C of dry 10h, then, 450 DEG C of roasting 4h in retort furnace, finally, 450 DEG C of reduction 4h in reducing furnace hydrogen gas atmosphere, can obtain 5wt.%Ni-Ce-HY catalyzer, wherein the massfraction of Ni is 5%, and the massfraction of auxiliary agent is 2%.
Embodiment 1
Add in 100mL autoclave 30g valeraldehyde and be equivalent to valeraldehyde quality 10% Ni-Ce-HY catalyzer, first use N
2displaced air, then use H
2displacement, under the temperature of reaction of 160 DEG C, is filled with H
2maintain pressure 2.0MPa, magnetic agitation 6h.Reaction terminates to carry out gas chromatographic analysis to production fluid afterwards, and the transformation efficiency of valeraldehyde is 89.2%, and decyl alcohol yield is 75.0%.Have a small amount of valeraldehyde direct hydrogenation to generate Pentyl alcohol, the yield of Pentyl alcohol is 11.8% simultaneously.
Embodiment 2-17 according to the operation steps of embodiment 1, reaction conditions and the results are shown in summary sheet.
Embodiment 18-38 is according to the operation steps of embodiment 1, and raw material aldehyde selects butyraldehyde-n, reaction conditions and the results are shown in summary sheet.
Embodiment 39
In 100mL autoclave, put into 32g butyraldehyde-n, and then add the 15wt.%Cu-Cr-MgO catalyzer of butyraldehyde-n quality 10%, first use N
2purge and use H again three times
2purge three times.H is poured at 200 DEG C
2maintain reaction pressure 4.5MPa, magnetic agitation 8h.After reaction terminates, filtration under diminished pressure, carries out gas chromatographic analysis to filtrate, and the transformation efficiency of butyraldehyde-n is 100%, and the yield of 2-Ethylhexyl Alcohol is 78.1%.By reacted catalyzer absolute ethanol washing three times, 110 DEG C of dry 8h.Roasting 4h in 500 DEG C of retort furnaces, then use H
24h is reduced at 200 DEG C.Then under identical reaction conditions, that investigates catalyzer reuses effect, the results are shown in following table.Along with the increase of reaction times, the activity of catalyzer slightly declines, and after use 3 times, the yield of 2-Ethylhexyl Alcohol have dropped 5.4%.Catalyzer still has very high activity.
Number of times reused by catalyzer | Butyraldehyde-n transformation efficiency/% | 2-Ethylhexyl Alcohol yield/% |
1 | 100 | 78.1 |
2 | 98.5 | 73.4 |
3 | 96.8 | 72.7 |
Claims (3)
1. the processing method of a catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol, it is characterized by and comprise the following steps: in autoclave, add solid catalyst and raw material aldehyde, wherein the add-on of catalyzer is 1 ~ 25% of raw material aldehyde quality, temperature of reaction 80 ~ 240 DEG C, hydrogen pressure is 0.5 ~ 8MPa, reaction times 4 ~ 20h, finally obtains long-chain alcohol;
Described raw material aldehyde is: butyraldehyde-n or valeraldehyde, and what described long-chain alcohol generated when raw material aldehyde is butyraldehyde-n is 2-Ethylhexyl Alcohol; What generate when raw material aldehyde is valeraldehyde is 2-propyl enanthol;
Described solid catalyst is metal-solids acid catalyst or metal-solids alkaline catalysts, and the composition of metal-solids acid catalyst comprises metal, auxiliary agent and solid acid, and the composition of metal-solids alkaline catalysts comprises metal, auxiliary agent and solid alkali; Wherein, metal massfraction is in the catalyst 0.5 ~ 40%, and the massfraction of auxiliary agent is 0 ~ 10%, and all the other are solid acid or solid alkali;
Metal in described metal-solids acid catalyst or metal-solids alkaline catalysts is: Cu, Ni, Co, Pt, Pd, Ru or Rh;
Described solid acid or solid alkali are: HY, HZSM-5, USY, H β, AlPO
4-5, SAPO-34, Al
2o
3, MgO-Al
2o
3, TiO
2, MgO, ZrO
2or ZnO;
Auxiliary agent in described metal-solids acid catalyst or metal-solids alkaline catalysts is: Cr, Ce, Mo, K, Mn, V, La, Zn or Fe.
2. the processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol as claimed in claim 1, the mass percentage that it is characterized by described auxiliary agent is 0% or 0.1 ~ 6.5%.
3. the processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol as claimed in claim 1, the add-on that it is characterized by described catalyzer is 5 ~ 20% of raw material aldehyde quality.
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