CN109608305A - A kind of synthesis preparation method of multi-joint alcohol - Google Patents
A kind of synthesis preparation method of multi-joint alcohol Download PDFInfo
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- CN109608305A CN109608305A CN201811362409.2A CN201811362409A CN109608305A CN 109608305 A CN109608305 A CN 109608305A CN 201811362409 A CN201811362409 A CN 201811362409A CN 109608305 A CN109608305 A CN 109608305A
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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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a kind of synthesis preparation methods of multi-joint alcohol to include the following steps, S1, and raw material liquid-phase hydrogenatin reaction carries out in 60mL high pressure fixed bed, to every layer of addition catalyst 0.1~50g catalyst of reactor, remaining section is filled with quartz sand, with hydrogen displacement apparatus, is restored to catalyst；S2, make system temperature reach 110 DEG C~270 DEG C, pressure reach 1.6MPa~10.0MPa, 14~26g lipid reactant is added and boosts through pump, is mixed with the hydrogen of 200~260 times of amount of substance, into hydrogenator, obtains product A.Catalyst of the present invention can be repeatedly used for a long, and catalyst service life reaches as high as 1.5 years, be a kind of environment amenable multicomponent, heterogeneous, continuous, three section multistage catalyst to catalyzing hydrogenating technology of fixed bed.
Description
Technical field
The present invention relates to multi-joint alcohol synthesis technical field more particularly to a kind of synthesis preparation methods of multi-joint alcohol.
Background technique
Multi-joint alcohol possesses 2-12 multidigit in the hydroxyl of more carbochain end positions, activity with higher, with organic acid,
The reaction of isocyanates, acid anhydrides can form different types of derivative.Multi-joint alcohol is a kind of emerging fine chemical material, property
Can be unique, it is non-corrosive, and the fine chemicals of a series of new can be produced, in UV coating, polyurethane, polyester, plasticizer, agriculture
The fields such as medicine, medicine, dyestuff are in an increasingly wide range of applications, are mainly used for improving mechanical strength, the toughness etc. of product, improve
Many performances such as product resistant to hydrolysis, heat-resisting, chemical-resistant reagent.
There are many kinds of production methods, such as: reaction production alkynol sylvite, warp can be carried out by benzene, alkynes, ketone and sodium hydroxide
It crosses and neutralizes, separates to obtain alkynol benzole soln, then obtain alkynol solution after distillation, crystallization, centrifuge separation, de- benzene, alkynol solution adds
After hydrogen multi-joint alcoholic solution, finally crystallize, filter to obtain multi-joint alcohol finished product, this process route is longer, and the production cost is very high, can also be with
Poly- first using acrylate, then repeated hydrogenation obtains multi-joint alcohol route, and this method is at present also in using autoclave interval plus hydrogen
Exploratory stage.
Offshore company develops a kind of process that multi-joint alcohol is prepared from epoxy alkene, but the technique will in terms of industrialization
Facing the less problem of epoxy alkene resource can be used the method for hydroformylation also to prepare multi-joint alcohol, but this method produces multi-joint alcohol
Selectivity it is very low.
More mature multi-joint alcohol production method is hydrogenation method in the world at present, with aliphatic polyol acid or cycloaliphatic polyols acid warp
It crosses and generates ester with alcohol ester hydroxylating, then the multi-joint alcohol of repeated hydrogenation system, obtains pure multi-joint alcohol eventually by rectification and purification, this technique can
It effectively improves the purity of product and reduces the generation of byproduct, the three wastes are seldom, and raw material is easy to get, and production cost is relatively low.
Domestic some companies it is proposed that polynary more carbon carboxylic acids are reduced into the technical solution of alcohol without over-churning direct hydrogenation, and
The research work of the polynary carbonic acid of some mixing or direct hydrogenation is made respectively, which theoretically opens a technique
Simply, the low-cost variation route for preparing first alcohol.But the key of the technology be develop it is a kind of direct by polynary more carbon carboxylic acids
Hydrogenating reduction at alcohol raw catelyst, and this catalyst be will not be by carboxylic acid fouled catalyst, although there is some correlations
Patent, but still without the industrial production device or pilot-plant that use the technical solution, this technology is also in exploration
Among, the research work of domestic direct hydrogenation synthol is underway always, but up to the present using polynary more carbonic acid as raw material
The commercial plant that direct hydrogenation generates alcohol has not been reported.
There are also R&D institutions to have carried out the research work of this respect for the country, once developed a kind of chromium-free cupro-nickel system
Catalyst, the catalyst can be used for mixing carbon oxygenatedchemicals containing aldehyde, acid esters and acetic acid preparation of ethanol by hydrogenating in the gaseous state
In reaction, catalyst is demonstrated by good catalytic hydrogenation activity, and acetaldehyde, ethyl acetate and most acetic acid are converted into second
Alcohol.But since the catalyst contains crome metal, important threat is constituted to environment.
In Sinopec Group；Shang Petrochemical Inst., SINOPEC
The main solution of catalyst of description production trans-1,4-cyclohexane dimethanol and preparation method thereof in the patent of 103878003 A of CN
Trans-1,4-cyclohexane dimethanol is received when terephthalyl alcohol certainly existing in the prior art adds hydrogen to prepare 1,4 cyclohexane dimethanol
The not high problem of rate, for the patent using active carbon as carrier, at least one of Ni2P and MoP are auxiliary agent, and Pd and Pt are active group
Point, in catalyst the content (w) of Ni or Mo or (Ni+Mo) be 0.1% 1,0%, Pd content (w) be 0.1%-1.0%, Pd with
The molar ratio 1:1 of Pt, the catalyst metal component price used are higher.
Summary of the invention
The purpose of the present invention is to solve disadvantages existing in the prior art, and a kind of synthesis system of the multi-joint alcohol proposed
Preparation Method.
To achieve the goals above, present invention employs following technical solutions:
A kind of synthesis preparation method of multi-joint alcohol, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction is carried out in 60mL high pressure fixed bed, to every layer of addition catalyst 0.1 of reactor~
50g catalyst, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 110 DEG C~270 DEG C, pressure reach 1.6MPa~10.0MPa, 14~26g lipid is added
Reactant boosts through pump, mixes with the hydrogen of 200~260 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 8~11 hours, obtains qualified multi-joint alcohol.
Preferably, the catalyst includes copper, zinc, aluminium and zr element, and copper, zinc, aluminium and zr element are with oxide weight calculation amount
20-60% is accounted in total catalyst weight than are as follows: copper oxide, zinc oxide accounts for 5-45%, and aluminium oxide accounts for 5-33%, manganese dioxide,
Zirconium dioxide metal oxide accounts for 0-35%, the catalyst be by copper, zinc, aluminium, manganese, zirconium solubility salt such as nitrate or
The shared weight ratio of hydrochloride, zirconium oxychloride based on respective metal oxides is dissolved with water, and mixed solution is made, and then will
Mixed solution caustic soda, potassium hydroxide, sodium carbonate or ammonium hydroxide, ammonium hydrogen carbonate, urea neutralization to pH value are 4.5-9.5 or so, raw
Washed at precipitating, dry, high-temperature roasting, molding are made.
Preferably, the catalyst uses hydrogen as reducing agent before using, and reduction temperature is 110~270 DEG C, catalyst
The maturing temperature of preparation is at 250 DEG C~550 DEG C, and calcining time is 2~12 hours.
Preferably, in the S1, the catalyst in hydrogenation plant is added to point three layers of addition, remaining section quartz sand or an oxygen
Change aluminium, zeolite, active carbon filling.
Preferably, the raw material includes esters, ketone or alcohols, the esters include glycerine, ethyl acetate, acetone,
Dimethyl adipate, dimethyl glutarate, dimethyl malenate, diethyl malonate, isopropylidene ketone, amino butanol, 2,2,4,
4- dimethyl -1,3- ring diacetyl, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, 2- aminopropanol, L- aminopropanol, D- aminopropan
Alcohol, DL- aminopropanol, 2,2,6- trimethyl -4- hydroxy-cyclohexan alcohol/ketone mixtures.
Preferably, there are three catalyst layers altogether from top to bottom in the reactor.
Preferably, the maturing temperature of the hydrogenation catalyst preparation is at 350 DEG C to 530 DEG C, and calcining time is 12-36 small
When.
Preferably, the lipid reactant includes 1, 4- succinic acid methyl esters, 1,5- glutaric acid methyl esters, 1,6- adipic acid first
Ester, 1,7- pimelic acid methyl esters, 1,8- suberic acid methyl esters, 1,9- azelaic acid methyl esters and 1,4- decanedioic acid methyl esters.
Preferably, in the S2, when hydrogenation reaction, reaction velocity 1-7 hours -1, hydrogen ester molar ratio 25-475, preferably
It is 2.5Mpa for reaction pressure, temperature is 150 DEG C to 160 DEG C, and reaction velocity 4-5 hours -1, hydrogen ester molar ratio is 125-275.
Preferably, reaction dissolvent is methanol, ethyl alcohol, propyl alcohol, n-butyl alcohol, ethylene glycol, third in the catalyst preparation process
Glycol, glycerine, ethyl acetate and its mixture, methanol, ethyl alcohol are as solvent.
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, catalyst can be repeatedly used for a long, and catalyst uses
Service life reaches as high as 1.5 years, is that a kind of environment amenable multicomponent, heterogeneous, continuous, three section multistage catalyst of fixed bed are urged
Change hydrogen addition technology, the invention discloses a kind of multicomponents, heterogeneous, continuous, three section multistage catalyst to catalyzing hydrogenating skill of fixed bed
Art, liquid-phase hydrogenatin reaction carry out in high pressure fixed bed, than nitro compounds plus hydrogen, do not have dinitro security risk, reaction mitigates steady
Fixed, no vigorous reaction factor is substantially excellent without waste water or biodegradability, and environmental protection aspect has the advantage that can not be substituted.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.
Embodiment one
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 160 DEG C, pressure reach 2.5MPa, 14.6g1 is added, 4- succinic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 200 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 8 hours, obtains the qualified multi-joint alcohol of 11.1g.
Embodiment two
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction carries out in 60mL high pressure fixed bed, to every layer of addition catalyst 0.1g of reactor
Catalyst, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 250 DEG C, pressure reach 2.5MPa, 16.0g1 is added, 5- glutaric acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 250 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 8.5 hours, obtains the qualified multi-joint alcohol of 12.15g.
Embodiment three
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 50g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 260 DEG C, pressure reach 2.5MPa, 17.4g1 is added, 6- adipic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 210 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 9 hours, obtains the qualified multi-joint alcohol of 13.4g.
Example IV
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 180 DEG C, pressure reach 3.5MPa, 18.8g1 is added, 7- pimelic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 240 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 9.5 hours, obtains the qualified multi-joint alcohol of 15g.
Embodiment five
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 230 DEG C, pressure reach 3.5MPa, 20.2g1 is added, 8- suberic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 230 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 9.5 hours, obtains the qualified multi-joint alcohol of 16.8g.
Embodiment six
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 130 DEG C, pressure reach 3.5MPa, 21.6g1 is added, 9- azelaic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 210 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 10 hours, obtains the qualified multi-joint alcohol of 18g.
Embodiment seven
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 240 DEG C, pressure reach 2.5MPa, 23.0g1 is added, 4- decanedioic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 220 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 11 hours, obtains the qualified multi-joint alcohol of 18.3g.
Embodiment eight
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 130 DEG C, pressure reach 2.5MPa, 16.1g1 is added, 4- succinic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 250 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 8 hours, obtains the qualified multi-joint alcohol of 13g.
Embodiment nine
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 130 DEG C, pressure reach 2.5MPa, 17.1g1 is added, 5- glutaric acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 250 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 8.5 hours, obtains the qualified multi-joint alcohol of 13g.
Embodiment ten
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 130 DEG C, pressure reach 3.5MPa, 19.1g1 is added, 6- adipic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 220 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 9 hours, obtains the qualified multi-joint alcohol of 14.9g.
Embodiment 11
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 220 DEG C, pressure reach 3.5MPa, 20.7g1 is added, 7- pimelic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 220 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 9.5 hours, obtains the qualified multi-joint alcohol of 16g.
Embodiment 12
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 230 DEG C, pressure reach 3.5MPa, 22.2g1 is added, 8- suberic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 250 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 9.5 hours, obtains the qualified multi-joint alcohol of 17.7g.
Embodiment 13
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 130 DEG C, pressure reach 4.5MPa, 23.8g1 is added, 9- azelaic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 210 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 10 hours, obtains the qualified multi-joint alcohol of 18.7g.
Embodiment 14
A kind of synthesis preparation method of multi-joint alcohol proposed by the present invention, includes the following steps,
S1, raw material liquid-phase hydrogenatin reaction are carried out in 60mL high pressure fixed bed, are urged to every layer of addition catalyst 20g of reactor
Agent, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 240 DEG C, pressure reach 6.5MPa, 25.3g1 is added, 4- decanedioic acid methyl esters rises through pump
Pressure, mixes with the hydrogen of 260 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is through following
Ring compressor is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid point into low pressure separator
From；
S4, the gas a part discharge reaction system isolated, a part enters its composition of line chromatography, after separation
Liquid enters fractionation refining plant and carries out refinement treatment, reacts 11 hours, obtains the qualified multi-joint alcohol of 20.8g.
Line chromatograph is added in the multi-joint alcohol that above-mentioned 14 groups of embodiments are produced, and counts, obtains to HPLC
Following result out:
By above table it is found that the multi-joint alcohol prepared through the invention, improves HPLC purity, react more mild
Under the conditions of carry out, the conventional process techniques of ratio, reaction pressure reduce, temperature reduce, especially substantially increase reaction yield, receive
Rate can reach 95.5%-99.5% or more, avoid using expensive rhodium ruthenium noble metal catalyst, then use inexpensively
Base metal catalyst has saved cost, establishes the composition that a kind of novel on-line chromatograph tests and analyzes intermediate and product
Middle control data feedback system eventually, not only increases efficiency using ternary to the four-way catalyst of heterogeneous metallic copper zinc-containing alloy,
It reduces costs, it is more main to greatly reduce reaction pressure, the safety of reaction is increased, the heterogeneous metal hydrogenation catalysis
Reaction is more suitable for large-scale industrial production, has Commercial Prospect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to should be covered by the protection scope of the present invention with replacing or changing.
Claims (10)
1. a kind of synthesis preparation method of multi-joint alcohol, which is characterized in that include the following steps,
S1, raw material liquid-phase hydrogenatin reaction carries out in 60mL high pressure fixed bed, to every layer of 0.1~50g of addition catalyst of reactor
Catalyst, remaining section are filled with quartz sand, with hydrogen displacement apparatus, are restored to catalyst；
S2, make system temperature reach 110 DEG C~270 DEG C, pressure reach 1.6MPa~10.0MPa, the reaction of 14~26g lipid is added
Object boosts through pump, mixes with the hydrogen of 200~260 times of amount of substance, into hydrogenator, obtains product A；
S3, product A is cooling through heat exchanger, into high-pressure separator, make gas-liquid separation, the high pressure hydrogen isolated is pressed through circulation
Contracting machine is sent into reactor cycles and is used, and the highly pressurised liquid containing a small amount of gas carries out further gas-liquid separation into low pressure separator；
S4, the gas a part discharge reaction system isolated, a part enter its composition of line chromatography, the liquid after separation
Refinement treatment is carried out into fractionation refining plant, reacts 8~11 hours, obtains qualified multi-joint alcohol.
2. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that the catalyst includes
Copper, zinc, aluminium and zr element, copper, zinc, aluminium and the zr element weight ratio in terms of oxide are as follows: copper oxide accounts in total catalyst weight
20-60%, zinc oxide account for 5-45%, and aluminium oxide accounts for 5-33%, and manganese dioxide, zirconium dioxide metal oxide account for 0-35%, institute
Stating catalyst is by copper, zinc, aluminium, manganese, the solubility salt such as nitrate or hydrochloride of zirconium, zirconium oxychloride by respective metallic element
The shared weight ratio of oxide meter is dissolved with water, and mixed solution is made, then by mixed solution caustic soda, potassium hydroxide, carbonic acid
It is 4.5-9.5 or so that sodium or ammonium hydroxide, ammonium hydrogen carbonate, urea, which are neutralized to pH value, generates precipitating, washed, dry, high-temperature roasting,
Molding is made.
3. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that the catalyst is using
Preceding to use hydrogen as reducing agent, reduction temperature is 110~270 DEG C, the maturing temperature of catalyst preparation be at 250 DEG C~550 DEG C,
Calcining time is 2~12 hours.
4. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that in the S1, hydrogen is added to set
Catalyst in standby is added to point three layers of addition, remaining section quartz sand or aluminium oxide, zeolite, active carbon filling.
5. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that the raw material includes ester
Class, ketone or alcohols, the esters include glycerine, ethyl acetate, acetone, dimethyl adipate, dimethyl glutarate, the third two
Dimethyl phthalate, diethyl malonate, isopropylidene ketone, amino butanol, 2,2,4,4- dimethyl -1,3- ring diacetyl, Isosorbide-5-Nitrae-hexamethylene
Alkane dicarboxylic acid dimethyl ester, 2- aminopropanol, L- aminopropanol, D- aminopropanol, DL- aminopropanol, 2,2,6- trimethyl -4- hydroxyl
Base-cyclohexanone mixture.
6. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that from upper in the reactor
To lower altogether there are three catalyst layer.
7. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that the hydrogenation catalyst system
Standby maturing temperature is at 350 DEG C to 530 DEG C, and calcining time is 12-36 hours.
8. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that the lipid reactant packet
Include 1,4- succinic acid methyl esters, 1,5- glutaric acid methyl esters, 1,6- adipic acid methyl esters, 1,7- pimelic acid methyl esters, 1,8- suberic acid methyl esters,
1,9- azelaic acid methyl esters and 1,4- decanedioic acid methyl esters.
9. a kind of synthesis preparation method of multi-joint alcohol according to claim 1, which is characterized in that in the S2, add hydrogen anti-
At once, reaction velocity 1-7 hours -1, hydrogen ester molar ratio 25-475, reaction pressure 2.5Mpa, temperature is 150 DEG C to 160 DEG C,
Reaction velocity 4-5 hours -1, hydrogen ester molar ratio are 125-275.
10. a kind of synthesis preparation method of multi-joint alcohol according to claim 2, which is characterized in that the catalyst preparation
Reaction dissolvent is methanol, ethyl alcohol, propyl alcohol, n-butyl alcohol, ethylene glycol, propylene glycol, glycerine, ethyl acetate and its mixing in the process
Object, methanol, ethyl alcohol are as solvent.
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