CN103708998A - 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 PDF

Info

Publication number
CN103708998A
CN103708998A CN201310666164.3A CN201310666164A CN103708998A CN 103708998 A CN103708998 A CN 103708998A CN 201310666164 A CN201310666164 A CN 201310666164A CN 103708998 A CN103708998 A CN 103708998A
Authority
CN
China
Prior art keywords
chain alcohol
long
alkali
catalyzer
solid catalyst
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
Application number
CN201310666164.3A
Other languages
Chinese (zh)
Other versions
CN103708998B (en
Inventor
赵新强
梁宁
安华良
王延吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Technology
Original Assignee
Hebei University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hebei University of Technology filed Critical Hebei University of Technology
Priority to CN201310666164.3A priority Critical patent/CN103708998B/en
Publication of CN103708998A publication Critical patent/CN103708998A/en
Application granted granted Critical
Publication of CN103708998B publication Critical patent/CN103708998B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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

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

A kind of processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol
Technical field
The present invention relates to Green Chemical Technology field, be specially a kind of solid catalyst catalysis butyraldehyde-n and valeraldehyde one-step synthesis octanol and decyl alcohol respectively, 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 is as the solvent of excellent property, petroleum additive etc. and be widely used.
Decyl alcohol (2-propyl enanthol) is also a kind of important plasticizer alcohol.Compared to DOP, the polrvinyl chloride product of Di Iso Decyl Phthalate (DIDP) plasticizer production that employing is synthesized by decyl alcohol has better electrical insulating property, low volatility, safer to human body and environment, has become the ideal substitute of DOP.
The technological process of production of octanol and decyl alcohol is basic identical, all adopts low-carbon alkene to obtain corresponding low-carbon (LC) aldehyde, low-carbon (LC) aldehyde through low pressure oxo process and through aldol condensation, obtains high-carbon aldehyde, high-carbon aldehyde and through hydrogenation, obtain three reaction process of product alcohol again.Aldol reaction wherein, the industrial liquid bases (dilute NaOH solution) that use are as catalyzer more, though can obtain higher feed stock conversion and product yield, 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 be combined with hydrogenation activity component and form dual-function catalyst, catalysis aldehydes one step obtains long-chain alcohol, thereby reaches the object of simplification of flowsheet, reduction cost of equipment and process cost, raising process economy.
The present invention adopts metal-solid acid (alkali) catalyzer, difference catalysis butyraldehyde-n and valeraldehyde one-step synthesis octanol and decyl alcohol, and obtain propyl carbinol and Pentyl alcohol simultaneously.
Summary of the invention
The invention provides a kind of novel environment-friendly process by metal-solid 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-solid acid (alkali) catalyzer of design preparation simultaneously has high reactivity, stability and feature optionally.
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, 80～240 ℃ of temperature of reaction, 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 when raw material aldehyde is valeraldehyde, generate is decyl alcohol (2-propyl enanthol);
Described solid catalyst is metal-solid acid (alkali) catalyzer, its composition comprises metal, auxiliary agent and solid acid (alkali), and wherein, the massfraction of metal in catalyzer is 0.5～40%, the massfraction of auxiliary agent is 0～10%, and all the other are solid acid (alkali).
The quality percentage composition of described auxiliary agent is preferably 0% or 0.1～6.5%.
Metal in described metal-solid acid (alkali) catalyzer is: Cu, Ni, Co, Pt, Pd, Ru or Rh.
Solid acid or solid alkali in described metal-solid acid (alkali) catalyzer 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-solid 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. industrially take butyraldehyde as the synthetic octanol of raw material, the technological process of valeral as the synthetic decyl alcohol of raw material of take, comprise aldol condensation, hydrogenation two-step reaction, technical process length causes the increase of cost of equipment and process cost, and aldol condensation sig water catalytic erosion equipment 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, has shortened the technical process of synthetic long chain alcohol greatly, has reduced cost of equipment and process cost.Metal-the solid acid going out for this process exploitation (alkali) catalyzer, has overcome the not easily separated and reusable problem that sig water catalyzer exists.
2. processing method provided by the present invention, in synthetic octanol or decyl alcohol, also obtains two kinds of important Organic chemical products of propyl carbinol or Pentyl alcohol.
3. adopt metal-solid 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-solid acid (alkali) catalyzer that the present invention adopts provides in can reference literature (Applied Catalysis A:General, 2009,367:93 – 98):
With the example that is prepared as of Ni-Ce-HY catalyzer, its preparation process
Solid acid HY 500 ℃ of roasting 4h in retort furnace are standby.First, take metal component precursor Ni (NO 3) 26H 2o2.664g and auxiliary agent precursor Ce (NO 3) 36H 2o0.543g is made into the 15mL aqueous solution, on the solid acid HY by the salt solution impregnation being made into after 10g thermal treatment; After ageing 24h, 110 ℃ of dry 10h, then, and 450 ℃ of roasting 4h in retort furnace, last, in reducing furnace hydrogen gas atmosphere, 450 ℃ of reduction 4h, can obtain 5wt.%Ni-Ce-HY catalyzer, and wherein the massfraction of Ni is 5%, and the massfraction of auxiliary agent is 2%.
Embodiment 1
To adding 30g valeraldehyde in 100mL autoclave and being equivalent to 10% Ni-Ce-HY catalyzer of valeraldehyde quality, first use N 2displaced air, then use H 2displacement, under the temperature of reaction of 160 ℃, is filled with H 2maintain pressure 2.0MPa, magnetic agitation 6h.Reaction finishes rear production fluid to be carried out to gas chromatographic analysis, 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 is according to the operation steps of embodiment 1, reaction conditions and the results are shown in summary sheet.
Figure BDA0000433361750000031
Embodiment 18-38 is according to the operation steps of embodiment 1, and raw material aldehyde is selected butyraldehyde-n, reaction conditions and the results are shown in summary sheet.
Figure BDA0000433361750000032
Figure BDA0000433361750000041
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 again H three times 2purge three times.At 200 ℃, pour H 2maintain reaction pressure 4.5MPa, magnetic agitation 8h.After reaction finishes, 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 absolute ethanol washing three times of reacted catalyzer, 110 ℃ of dry 8h.Roasting 4h in 500 ℃ of retort furnaces, then use H 2at 200 ℃, reduce 4h.Then under identical reaction conditions, investigate the effect of reusing of catalyzer, the results are shown in following table.Along with the increase of reaction times, the activity of catalyzer slightly declines, and is using the yield of 2-Ethylhexyl Alcohol after 3 times to decline 5.4%.Catalyzer still has very high activity.
Catalyzer is reused number of times Butyraldehyde-n transformation efficiency/% 2-Ethylhexyl Alcohol yield/%
1 100 78.1
2 98.5 73.4
3 96.8 72.7

Claims (6)

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, 80 ~ 240 ℃ of temperature of reaction, 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 when raw material aldehyde is valeraldehyde, generate is decyl alcohol (2-propyl enanthol);
Described solid catalyst is metal-solid acid (alkali) catalyzer, and its composition comprises metal, auxiliary agent and solid acid (alkali), and wherein, the massfraction of metal in catalyzer is 0.5 ~ 40%, and the massfraction of auxiliary agent is 0 ~ 10%, and all the other are solid acid (alkali).
2. the processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol, the quality percentage composition that it is characterized by described auxiliary agent is preferably 0% or 0.1 ~ 6.5%.
3. the processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol, the metal it is characterized by described metal-solid acid (alkali) catalyzer is: Cu, Ni, Co, Pt, Pd, Ru or Rh.
4. the processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol, the solid acid or the solid alkali that it is characterized by described metal-solid acid (alkali) catalyzer 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.
5. the processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol, the auxiliary agent it is characterized by described metal-solid acid (alkali) catalyzer is: Cr, Ce, Mo, K, Mn, V, La, Zn or Fe.
6. the processing method of catalysis of solid catalyst aldehydes one-step synthesis long-chain alcohol, the add-on that it is characterized by described catalyzer is preferably 5 ~ 20% of raw material aldehyde quality.
CN201310666164.3A 2013-12-09 2013-12-09 Process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with solid catalyst Active CN103708998B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310666164.3A CN103708998B (en) 2013-12-09 2013-12-09 Process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with solid catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310666164.3A CN103708998B (en) 2013-12-09 2013-12-09 Process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with solid catalyst

Publications (2)

Publication Number Publication Date
CN103708998A true CN103708998A (en) 2014-04-09
CN103708998B CN103708998B (en) 2015-02-04

Family

ID=50402391

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310666164.3A Active CN103708998B (en) 2013-12-09 2013-12-09 Process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with solid catalyst

Country Status (1)

Country Link
CN (1) CN103708998B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112961031A (en) * 2021-02-23 2021-06-15 河北工业大学 Method for preparing high-carbon alcohol based on low-carbon alcohol and acetal compound
CN114805021A (en) * 2022-04-27 2022-07-29 中国科学院青岛生物能源与过程研究所 Preparation method of 2-propyl-1-heptanol

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103351277A (en) * 2013-06-28 2013-10-16 万华化学集团股份有限公司 Neopentyl glycol preparation method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103351277A (en) * 2013-06-28 2013-10-16 万华化学集团股份有限公司 Neopentyl glycol preparation method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112961031A (en) * 2021-02-23 2021-06-15 河北工业大学 Method for preparing high-carbon alcohol based on low-carbon alcohol and acetal compound
CN112961031B (en) * 2021-02-23 2022-03-29 河北工业大学 Method for preparing high-carbon alcohol based on low-carbon alcohol and acetal compound
CN114805021A (en) * 2022-04-27 2022-07-29 中国科学院青岛生物能源与过程研究所 Preparation method of 2-propyl-1-heptanol
CN114805021B (en) * 2022-04-27 2023-09-19 中国科学院青岛生物能源与过程研究所 Preparation method of 2-propyl-1-heptanol

Also Published As

Publication number Publication date
CN103708998B (en) 2015-02-04

Similar Documents

Publication Publication Date Title
CN107304367B (en) Preparation method of branched alkane in range of gasoline, aviation kerosene or diesel oil
CN103506123B (en) A kind of preparation method of aldehyde liquid phase hydrogenating catalyst
CN108102683B (en) Preparation method of branched alkane in range of renewable dodecyl alcohol and aviation kerosene
CN105315130A (en) Method used for preparing 1,3-dihydric alcohol via Prins condensation reaction
CN104725229A (en) Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate
CN106238051A (en) Catalyst for ethyl acetate preparation of ethanol by hydrogenating and its preparation method and application
CN105561997A (en) Preparation method of nickel liquid phase hydrogenation catalyst
CN107794074A (en) A kind of preparation method of branched paraffin in gasoline, aviation kerosine or diesel range
CN105669456A (en) Method for preparing valerate from levulinic acid
CN103708998B (en) Process method for one-step synthesis of long-chain alcohol by catalyzing aldehydes with solid catalyst
KR100335516B1 (en) Process for the hydroformylation of 1,3-butadiene
CN102249854B (en) Two-step-method hydrogenation process for preparing neopentyl glycol
CN111215138A (en) catalyst, preparation method and application of catalyst in preparation of β -isophorone
CN106179373A (en) A kind of catalyst for decenal liquid-phase hydrogenatin isodecanol and preparation method thereof
CN104190401A (en) Molybdenum-based composite metal oxide catalyst for synthesizing propenyl alcohol by glycerol and preparation method of molybdenum-based composite metal oxide catalyst
CN105622336A (en) Method for preparing 1,4-butynediol
CN105080548B (en) A kind of method for improving nickel system liquid phase hydrogenating catalyst selectivity and stability
CN111215079B (en) Method for preparing alcohol by hydrogenation of aldehydes by adopting nickel-based heterogeneous catalyst
CN103864587A (en) Method for synthesizing 2-ethyl-2-hexenal
CN102924251B (en) Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid
CN101781171A (en) Preparation method of dihydric alcohol
CN104788408A (en) Method for producing gamma-valerolactone from hemicellulose
CN104387233A (en) Method for synthesizing tricyclodecanedimethanol
CN103896989B (en) Method for synthesizing di(ethylene) chlorine rhodium (I) dimer
CN106632370A (en) Method for preparing isosorbide through glucose

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