CN109761746A - Liquid wax aoxidizes the technique and system of secondary alcohol processed - Google Patents
Liquid wax aoxidizes the technique and system of secondary alcohol processed Download PDFInfo
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Abstract
The present invention relates to liquid waxes to aoxidize secondary alcohol field processed, the in particular to technique and system of liquid wax oxidation secondary alcohol processed.For the technique the following steps are included: liquid wax carries out liquid phase oxidation, oxidation reaction product and secondary alcohol carry out esterification, and the thick secondary alcohol borate recycling being esterified in product, surplus materials removes acids and Ester through alkali cleaning, water elution, obtains unreacted alkane；25% or more unreacted alkane carries out hydrogenation reaction, and obtained product enters in the liquid phase oxidation step of liquid wax progress；The thick secondary alcohol borate of recycling obtains secondary alcohol through processing.The present invention increases hydrogenation step, for the process for not carrying out hydrogenation reaction, it consumes starting alkane (unit consumption) and is reduced to 1.25 tons/ton from 1.53 tons/ton, so that starting alkane is increased to about 85% from about 70% to the apparent selectivity of unitary secondary alcohol, greatly improves economic benefit and reduce environmental pollution.
Description
Technical field
The present invention relates to liquid waxes to aoxidize secondary alcohol field processed, aoxidizes the technique of secondary alcohol processed in particular to liquid wax and is
System.
Background technique
The secondary alcohol ethane via epoxyethane addition of positive structure liquid wax oxidizing process synthesis, obtains efficient surfactant, is high-end cream
The important component of liquid and detergent compositions.Raw material liquid wax is oxygen-containing under dehydration boric acid and amino alkaloids co-catalyst
The secondary alcohol borate (metaboric acid ester etc.) that atmosphere generates obtains product unitary secondary alcohol, the list of the positive structure liquid wax of raw material by hydrolysis
Journey conversion ratio about 10-20%, unitary secondary alcohol selectivity about 70%, Main By product be monoketone (about 15%), dihydric alcohol (about
7%), acid, ester etc..
Current liquid wax oxidation legal system secondary alcohol technique mainly passes through the techniques separating by-products such as saponification washing and rectifying, and
It is handled by modes such as burning or biochemical degradations.Certain environmental pollution, and raw material liquid wax comparatively high consumption are not only caused in this way,
Cause economic loss.So the selectivity for improving unitary secondary alcohol is that liquid wax oxidation legal system secondary alcohol technique must solve the problems, such as.
There is partial monopoly to propose (300-500 DEG C, 20-100MPaG) of (such as Texaco) high temperature and pressure plus hydrogen retrieval alkane
So that wherein monoketone is converted into alkane, but process dangerous is high, at high cost, and selectivity is low.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide the technique that liquid wax oxidizing process prepares secondary alcohol, by returning after esterification
It receives unreacted alkane and carries out hydrogenation reaction, the ketogenesis unitary secondary alcohol in unreacted alkane enters liquid containing unitary secondary alcohol alkane
In wax oxidation reaction, so that starting alkane is increased to about 85% from about 70% to the apparent selectivity of unitary secondary alcohol, purification unitary is secondary
Alcohol consumes starting alkane (unit consumption) and is reduced to 1.25 tons/ton from 1.53 tons/ton, greatly improves economic benefit and reduces environment
Pollution.
The second object of the present invention is to provide the system that liquid wax oxidizing process prepares secondary alcohol, provide for above-mentioned technological reaction
Equipment provides demand, to be used for industrialization production.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The technique that liquid wax oxidizing process prepares secondary alcohol, comprising the following steps:
Liquid wax carries out the oxidation reaction product that liquid phase oxidation obtains and secondary alcohol carries out esterification, obtains esterification and generates
Object；
Thick secondary alcohol borate recycling in the esterification product, surplus materials remove acids and esters through alkali cleaning, water elution
Substance obtains unreacted alkane；
25% or more of the unreacted alkane quality carries out hydrogenation reaction, and obtained product is as the liquid phase oxidation
Raw material participate in the liquid phase oxidation；
The thick secondary alcohol borate of recycling obtains secondary alcohol through processing.
In the present invention, liquid wax refers to the representative examples of saturated aliphatic n-alkane of carbon number 8-30.
In the present invention, hydrogenation reaction is carried out after saponification washing by the unreacted alkane to esterification, which makes
Part monoketone is reduced to unitary secondary alcohol, which enters in liquid wax oxidation reaction, compared to not carrying out hydrogenation reaction
Process for, consume starting alkane (unit consumption) and from 1.53 tons/ton be reduced to 1.25 tons/ton, greatly improve economic benefit and
Reduce environmental pollution；In addition, monoketone is converted into product secondary alcohol from the point of view of integrated artistic, so that starting alkane is secondary to unitary
The apparent selectivity of alcohol is increased to about 85% from about 70%, thus realize that unitary secondary alcohol selectivity highest increases by 15%, i.e., it is of the invention
The apparent selectivity for adding hydrogen to significantly improve unitary secondary alcohol using paraffin selectivity is recycled.
25% or more of unreacted alkane quality carried out in the step of hydrogenation reaction, can for 25%, 30%, 40%,
50%, 60%, 70%, 80%, 90%, 100% etc. unreacted alkane carries out hydrogenation reaction.
The thick secondary alcohol borate of recycling obtains secondary alcohol through processing and washes rectifying progress according to hydrolysis soda-wash water, is conventional work
Skill repeats no more.
Further, in the liquid phase oxidation, reaction temperature is 140-200 DEG C, reaction pressure 0-3.0MPaG.
As in various embodiments, reaction temperature can for 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C,
200 DEG C etc.；Similarly, in various embodiments, reaction pressure can for 0.0MPaG, 0.5MPaG, 0.8MPaG,
1.0MPaG, 1.5MPaG, 1.8MPaG, 2.0MPaG, 2.5MPaG, 2.8MPaG, 3.0MPaG etc..
Further, the liquid phase oxidation carries out under oxygen atmosphere in catalyst, co-catalyst and having.
Further, the catalyst is dehydration boric acid, and co-catalyst is amino alkaloids.
Further, the additive amount of the dehydration boric acid is the 0.5%-10% of the liquid wax weight, amino alkaloids
Additive amount be the liquid wax weight 0.001%-0.1%；
As in various embodiments, be dehydrated boric acid additive amount can for liquid wax weight 0.5%, 0.8%, 1%,
1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% etc..
The additive amount of amino alkaloids be the liquid wax weight 0.001%, 0.005%, 0.008%, 0.01%,
0.05%, 0.09%, 0.1% etc.；
Further, described to have oxygen atmosphere are as follows: the gas of oxygen content 2vol%-10vol%.
As in various embodiments, oxygen content can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% etc.
Deng.
That is to say, being most preferably dehydrated boric acid and 0.001wt%-0.1wt% amino bases object in 0.5wt%-10wt%
Liquid phase oxidation is carried out to the liquid wax with the gas of oxygen content 2vol%-10vol% in the presence of matter.
Further, it under nitrogen stream or decompression, is esterified at 100-200 DEG C.
As in various embodiments, the temperature of esterification can be 100 DEG C, 120 DEG C, 130 DEG C, 150 DEG C, 170 DEG C, 200
DEG C etc..
Further, the hydrogenation reaction carries out under hydrogenation catalyst, the hydrogenation catalyst include Cu system, Ni system,
Pb system, Pt system, Co system are any one or more of, and preferably Ni system, Pt system, Pb system and Co system are any one or more of.
It should be noted that hydrogenation catalyst used in the present invention is Cu-series catalyst, nickel catalyst, the catalysis of lead system
Agent, platinum group catalyst, cobalt series catalyst.If Cu-series catalyst can be the Cu-series catalyst that copper content is 40%, the catalysis of nickel system
Agent can be the nickel catalyst that nickel content is 25%, and lead series catalysts can be the lead series catalysts of the lead containing 10%, platinum group
Catalyst can be the platinum group catalyst of the platinum containing 20%, and cobalt series catalyst can be the cobalt series catalyst of the cobalt containing 30%.
Further, the hydrogenation reaction carries out under the conditions of 80-200 DEG C of temperature.
Preferably, the hydrogenation reaction carries out under the conditions of 130-200 DEG C of temperature, and more preferably 130-160 DEG C.
As in various embodiments, the temperature of hydrogenation reaction can for 80 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C,
150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 200 DEG C etc..
Further, the pressure of the hydrogenation reaction is 0.5-20MPaG.
Preferably, the pressure of the hydrogenation reaction is 1.0-3.0MPaG.
As in various embodiments, the pressure of hydrogenation reaction can for 0.5MPaG, 1MPaG, 2MPaG, 3MPaG,
5MPaG, 7MPaG, 8MPaG, 10MPaG, 12MPaG, 15MPaG, 17MPaG, 20MPaG etc..
Further, in the hydrogenation reaction, hydrogen carbonyl molar ratio is 10-40:1, preferably 20-40:1, more preferably 30-
40:1.
As in various embodiments, hydrogen carbonyl molar ratio can be 20:1,25:1,30:1,35:1,40:1 etc..
In the present invention, unreacted alkane is bright anti-by the selection and limitation selective hydrogenation of selective hydrocatalyst
Condition is answered, so that monoketone therein is converted into the conversion ratio of unitary secondary alcohol and selectivity reaches 90% or more.
The present invention also provides the systems that liquid wax oxidizing process prepares secondary alcohol, including use the sequentially connected oxidation reaction of pipeline
Device, esterification device, alkane recyclable device, alkaline cleaner, water washing device, hydrogenation reaction device；
The hydrogenation reaction device is also connect with the feed pipe of the oxidation reaction apparatus；
Pipeline between the water washing device and the hydrogenation reaction device, which is provided with, to be in charge of, described one end being in charge of and institute
State the feed pipe connection of oxidation reaction apparatus.
System provided by the invention, the technique for preparing secondary alcohol for liquid wax oxidizing process provide support, to be used for industrialization production.
Further, the oxidation reaction apparatus is more than one.
Further, the oxidation reaction apparatus is stirred tank or bubble tower.
Further, the oxidation reaction apparatus is multiple, is connected between the oxidation reaction apparatus.
It is realized in addition, the thick secondary alcohol borate of recycling obtains secondary alcohol through processing using following device:
Borate hydrolysis device, alkaline cleaner, water washing device, take off it is with light packs set, de- refitting sets to obtain.
It is reacted, is obtained secondary by subsequent above-mentioned apparatus after alkane recyclable device connection borate hydrolysis device
Alcohol.
Compared with prior art, the invention has the benefit that
(1) present invention is by carrying out hydrogenation reaction to some or all of esterification unreacted alkane, by alkane one
First ketogenesis unitary secondary alcohol enters in liquid wax oxidation reaction containing unitary secondary alcohol alkane, so that starting alkane is to unitary secondary alcohol table
It sees selectivity and is increased to about 85% from about 70%, purification unitary secondary alcohol consumption starting alkane (unit consumption) is reduced to from 1.53 tons/ton
1.25 tons/ton greatly improve economic benefit and reduce environmental pollution.
(2) present invention also selects selective hydrocatalyst and hydroconversion condition so that the conversion ratio of monoketone and
Selectivity is 90% or more.
(3) the present invention also provides the systems that liquid wax oxidizing process prepares secondary alcohol, provide equipment for above-mentioned technological reaction and mention
For demand, to be used for industrialization production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the process flow diagram that liquid wax oxidizing process provided by the invention prepares secondary alcohol.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The condition of hydrogenation reaction is groped
The condition of hydrogenation reaction is carried out using pilot scale, pilot reactor parameter: being used DN40 reactor length 3500mm, is urged
The filling height of agent is 0.5m or so.
1, hydrogen carbonyl compares the influence of ketone conversion ratio, selectivity
At 150 DEG C of reaction temperature, pressure is to be reacted under 2.0MPaG, and catalyst is nickel catalyst, as a result such as table 1
It is shown.
1 hydrogen carbonyl of table compares the influence of ketone conversion ratio, selectivity
| Hydrogen carbonyl ratio (mol) | 6:1 | 12:1 | 20:1 | 30:1 | 40:1 |
| Ketone conversion ratio % (mol) | 75 | 85 | 90 | 98 | 99 |
| Ketone selectivity % (mol) | 99.8 | 99.8 | 99.6 | 99 | 99 |
As it can be seen from table 1 hydrogen carbonyl molar ratio is that 20-40:1 all has higher conversion ratio and selectivity, wherein with hydrogen
Carbonyl molar ratio is 30-40:1 better effect.
2, differential responses temperature influences ketone conversion ratio
It is 40:1 in hydrogen carbonyl molar ratio, pressure 2.0MPaG, catalyst is nickel catalyst, explores temperature and converts to ketone
The influence of rate, the results are shown in Table 2.
2 differential responses temperature of table influences ketone conversion ratio
| Reaction temperature DEG C | 80 | 100 | 130 | 140 | 150 | 160 | 180 | 200 |
| Ketone conversion ratio % (mol) | 40 | 75 | 90 | 98 | 99 | 99 | 99 | 99 |
| Ketone selectivity % (mol) | 95 | 95 | 99.6 | 99 | 99 | 99 | 95 | 90 |
From table 2 it can be seen that reaction temperature, which is 130-200 DEG C, preferable effect under above-mentioned condition, wherein preferably
It is 130-200 DEG C, more preferably 130-160 DEG C.
3, differential responses pressure influences ketone conversion ratio
It is 40:1 in hydrogen carbonyl molar ratio, temperature is 150 DEG C, and catalyst is nickel catalyst, explores reaction pressure and turns to ketone
The influence of rate, the results are shown in Table 3.
3 differential responses pressure of table influences ketone conversion ratio
| Reaction pressure MPaG | 0.5 | 1.0 | 2.0 | 3.0 | 18 |
| Ketone conversion ratio % (mol) | 75 | 90 | 99 | 99 | 99.5 |
| Ketone selectivity % (mol) | 90 | 99 | 99 | 99 | 95 |
From table 3 it can be seen that reaction pressure is under 1.0-3.0MPaG, ketone conversion ratio and selectivity are preferable.
4, different catalysts influence ketone conversion ratio
It is 40:1 in hydrogen carbonyl molar ratio, temperature is 150 DEG C, and reaction pressure is that different catalysts are explored under 2.0MPaG to ketone
The influence of conversion ratio, the results are shown in Table 4.
4 different catalysts of table influence ketone conversion ratio
| Catalyst type | 1 | 2 | 3 | 4 | 5 |
| Ketone conversion ratio % (mol) | 85 | 99 | 99 | 99 | 98 |
| Ketone selectivity % (mol) | 90 | 99 | 97 | 99 | 99 |
Wherein, in catalyst type, 1 is Cu-series catalyst, and 2 be nickel catalyst, and 3 be platinum group catalyst, and 4 urge for lead system
Agent, 5 be cobalt series catalyst.
From table 4, it can be seen that selecting catalyst n i series catalysts, Pt series catalysts, Pb series catalysts and Co series catalysts
Preferably.
In the above embodiment of the present invention, Cu-series catalyst selects Pricat Cu 60/8；Nickel catalyst selects HTC Ni
500；Platinum group catalyst selects Type 73；Cobalt series catalyst selects HTC Co 2000；Lead series catalysts select HTA 50.
Experimental example
Recycling C is washed through saponification12-C14N-alkane, reactor load nickel catalyst trade mark HTC Ni 500, reaction
150 DEG C of temperature, pressure 2.0MPaG, alkane inlet amount 5kg/h, amounts of hydrogen 500NL/h.Test sample.According to gas chromatographic analysis
Method is obtained a result as shown in table 5.
5 hydrogenation reaction object alkane of table and hydrogenation products Comparative
Embodiment 2
Liquid wax oxidizing process prepares the technique of secondary alcohol, as shown in Figure 1, comprising the following steps:
1. reaction raw materials are that 100wt% adds hydrogen retrieval alkane in oxidation reactor.
Recycling 100% plus hydrogen C12-C14Positive structure liquid wax 100g, is put into four mouthfuls of glass flasks, and 4g metaboric acid is added, and
0.1g amino alkaloids co-catalyst.Under mechanical agitation, 170 DEG C of temperature, it is passed through 0.3L oxygen deprivation, oxygen concentration per minute
8vol%, it reacts 2 hours.After the reaction was completed, reaction product is hydrolyzed with 100g hot water, upper oil phase, test sample.According to gas
Chromatography analysis method is obtained a result as shown in table 6.
6 reactant of table and product component compare
In addition, counting otherwise numerical value, calculates, obtains the following contents:
Conversion rate of oxidation 18.0%；
Aoxidize selection rate 73.3%；
Apparent selectivity 85.5%.
Wherein, conversion rate of oxidation (%)=(mass number of raw material liquid wax-unreacted liquid wax mass number) * 100/ material liquid
The mass number of wax；
Oxidation selectivity (%)=generation unitary secondary alcohol liquid wax mass number * 100/ reacts the mass number of liquid wax；
Apparent selectivity (%)=unitary secondary alcohol conversion liquid wax mass number * 100/ reacts the mass number of liquid wax.
2. the part secondary alcohol obtained through peroxidization product with alcohol recovery tower is esterified in esterifier,
Except dissociating on a small quantity present in excessive dehydration boric acid and oxidation reaction product, alcohols will become borate；
Under nitrogen flowing, 200 DEG C at a temperature of be esterified.
3. in alkane recovery tower, it is separated by distillation to obtain the tower bottom containing unreacting hydrocarbon and containing secondary alcohol borate ester residual
Liquid；
Unreacted alkane is after caustic wash tower A and water scrubber A elimination reaction by-product acids and ester impurities, into adding hydrogen
Reactor；
Unreacted alkane reacts, hydrogen under hydrogenation catalyst Ni effect under the conditions of 150 DEG C of temperature and pressure 2.0MPaG
Carbonyl molar ratio is 40:1, and the monoketone by-product in alkane is reduced to product unitary secondary alcohol (conversion ratio 95-97%, selective 97-
99%).This obtained part secondary alcohol enters cyclic oxidation, esterification by pipeline, recycles in bottom product from hydrocarbon into subsequent water
Solution alkali cleaning rectifying etc. eventually enters into product secondary alcohol.
4. the tower bottoms containing secondary alcohol borate ester enters borate hydrolysis tower according to path, alkali cleaning is then sequentially entered
Tower B, water scrubber B, lightness-removing column, weight-removing column, obtain secondary alcohol；
Washing rectifying from the hydrolysis soda-wash water of thick secondary alcohol borate backward is common process, is repeated no more.
Comparative example
Liquid wax oxidizing process prepares the technique of secondary alcohol, as shown in Figure 1, comprising the following steps:
1. reaction raw materials are that 0wt% adds hydrogen retrieval alkane in oxidation reactor:
Recycling does not add hydrogen C12-C14Positive structure liquid wax 100g, is put into four mouthfuls of glass flasks, and 4g metaboric acid and 0.1g ammonia is added
Base alkaloids co-catalyst.Under mechanical agitation, 170 DEG C of temperature, it is passed through 0.3L oxygen deprivation, oxygen concentration per minute
8vol%, it reacts 2 hours.After the reaction was completed, reaction product is hydrolyzed with 100g hot water, takes upper oil phase, test sample.According to
Gas chromatography is obtained a result as shown in table 7.
7 reactant of table and product component compare
In addition, counting otherwise numerical value, calculates, obtains the following contents:
Conversion rate of oxidation 16.72%；
Oxidation selectivity 71.3%；
Apparent selectivity 71.3%.
Other workshop section's processes are repeated no more with 2 part of embodiment.
From the point of view of integrated artistic, oxidized byproduct monoketone 97% or so is converted into product secondary alcohol, adds compared to being added without
Hydrogen step, unitary secondary alcohol apparently selectively increase by 15% or so.
Embodiment 3
Liquid wax oxidizing process prepares the technique of secondary alcohol, as shown in Figure 1, comprising the following steps:
1. reaction raw materials are that 50wt% adds hydrogen retrieval alkane in oxidation reactor:
50wt% adds hydrogen retrieval alkane, herein plus n-alkane namely unreacted alkane add the product after hydrogen after hydrogen:
50g does not add hydrogen and 50g to add hydrogen retrieval C12-C14Positive structure liquid wax, is put into four mouthfuls of glass flasks, and 4g metaboric acid is added,
And 0.1g amino alkaloids co-catalyst.Under mechanical agitation, 170 DEG C of temperature, it is passed through 0.3L oxygen deprivation per minute, oxygen is dense
8vol% is spent, it reacts 2 hours.After the reaction was completed, reaction product is hydrolyzed with 100g hot water, takes upper oil phase, test sample.Root
It obtains a result as shown in table 8 according to gas chromatography.
8 reactant of table and product component compare
In addition, counting otherwise numerical value, calculates, obtains the following contents:
Conversion rate of oxidation 17.27%；
Oxidation selectivity 72.22%；
Apparent selectivity 78.42%.
Other workshop section's processes are repeated no more with 2 part of embodiment.
Embodiment 4
Liquid wax oxidizing process prepares the technique of secondary alcohol, as shown in Figure 1, comprising the following steps:
1. reaction raw materials are that 80wt% adds hydrogen retrieval alkane in oxidation reactor:
20g does not add hydrogen and 80g to add hydrogen retrieval C12-C14Positive structure liquid wax, is put into four mouthfuls of glass flasks, and 4g metaboric acid is added,
And 0.1g amino alkaloids co-catalyst.Under mechanical agitation, 170 DEG C of temperature, it is passed through 0.3L oxygen deprivation per minute, oxygen is dense
8vol% is spent, it reacts 2 hours.After the reaction was completed, reaction product is hydrolyzed with 100g hot water, takes upper oil phase, test sample.Root
It obtains a result as shown in table 9 according to gas chromatography.
9 reactant of table and product component compare
In addition, counting otherwise numerical value, calculates, obtains the following contents:
Conversion rate of oxidation 17.9%；
Oxidation selectivity 71.5%；
Apparent selectivity 81.0%.
Other workshop section's processes are repeated no more with 2 part of embodiment.
Comparison different proportion recycling hydrocarbon adds hydrogen, and oxidation product compares (oxidizing condition is identical), is specifically shown in Table 10.
The effect that 10 different proportion of table recycling hydrocarbon adds hydrogen to prepare secondary alcohol compares
| Recycling hydrocarbon adds hydrogen ratio % | Conversion rate of oxidation % | Oxidation selectivity % | Apparent selectivity % |
| 0 | 16.72 | 71.3 | 71.3 |
| 50 | 17.27 | 72.22 | 78.42 |
| 80 | 17.9 | 71.5 | 81.0 |
| 100 | 18.0 | 73.3 | 85.5 |
The unreacted alkane of different weight percentage carries out hydrogenation reaction, and obtained product enters the Oxygen in Liquid of oxidator progress
Change in step, starting alkane apparently selectively has different degrees of raising to unitary secondary alcohol, also, with unreacted alkane
The percentage of hydrogen is added to increase, starting alkane increases the raising of the apparent selectivity of unitary secondary alcohol.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. the technique that liquid wax oxidizing process prepares secondary alcohol, which comprises the following steps:
Liquid wax carries out the oxidation reaction product that liquid phase oxidation obtains and secondary alcohol carries out esterification, obtains esterification product；
Thick secondary alcohol borate recycling in the esterification product, surplus materials remove acids and Ester through alkali cleaning, water elution,
Obtain unreacted alkane；
25% or more of the unreacted alkane quality carries out hydrogenation reaction, original of the obtained product as the liquid phase oxidation
Material participates in the liquid phase oxidation；
The thick secondary alcohol borate of recycling obtains secondary alcohol through processing.
2. technique according to claim 1, which is characterized in that in the liquid phase oxidation, reaction temperature is 140-200 DEG C,
Reaction pressure 0-3.0MPaG.
3. technique according to claim 1, which is characterized in that the liquid phase oxidation is in catalyst and co-catalyst and aerobic
It is carried out under atmosphere；
Further, the catalyst is dehydration boric acid, and co-catalyst is amino alkaloids.
4. technique according to claim 3, which is characterized in that the additive amount of the dehydration boric acid is the liquid wax weight
0.5%-10%, the additive amount of amino alkaloids are the 0.001%-0.1% of the liquid wax weight；
Further, described to have oxygen atmosphere are as follows: the gas of oxygen content 2vol%-10vol%.
5. technique according to claim 1, which is characterized in that under nitrogen stream or decompression, ester is carried out at 100-200 DEG C
Change.
6. technique according to claim 1-5, which is characterized in that the hydrogenation reaction under hydrogenation catalyst into
Row, the hydrogenation catalyst include Cu system, Ni system, Pb system, Pt system, Co system it is any one or more, preferably Ni system, Pt system,
Pb system and Co system are any one or more of.
7. technique according to claim 5, which is characterized in that the hydrogenation reaction under the conditions of 80-200 DEG C of temperature into
Row；
Preferably, the hydrogenation reaction carries out under the conditions of 80-200 DEG C of temperature, and more preferably 130-160 DEG C；
Further, the pressure of the hydrogenation reaction is 0.5-20MPaG；
Preferably, the pressure of the hydrogenation reaction is 1.0-3.0MPaG；
Further, in the hydrogenation reaction, hydrogen carbonyl molar ratio is 10-40:1, preferably 20-40:1.
8. the system that liquid wax oxidizing process prepares secondary alcohol, which is characterized in that including using the sequentially connected oxidation reaction apparatus of pipeline,
Esterification device, alkane recyclable device, alkaline cleaner, water washing device, hydrogenation reaction device；
The hydrogenation reaction device is also connect with the feed pipe of the oxidation reaction apparatus；
Pipeline between the water washing device and the hydrogenation reaction device, which is provided with, to be in charge of, described one end being in charge of and the oxygen
Change the feed pipe connection of reaction unit.
9. system according to claim 8, which is characterized in that between the water washing device and the hydrogenation reaction device
Pipeline and it is described be in charge of be provided with control Flow of Goods and Materials valve.
10. system according to claim 8 or claim 9, which is characterized in that the oxidation reaction apparatus is more than one；
Further, the oxidation reaction apparatus is stirred tank or bubble tower；
Further, the oxidation reaction apparatus is multiple, is connected between the oxidation reaction apparatus.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503322A (en) * | 2018-12-10 | 2019-03-22 | 沈阳化工大学 | A kind of process preparing higher alcohols by paraffin |
| CN110240538A (en) * | 2019-06-27 | 2019-09-17 | 万华化学集团股份有限公司 | A method of preparing high-carbon branched secondary alcohol |
| CN117550954A (en) * | 2023-11-09 | 2024-02-13 | 江苏赛科化学有限公司 | Processing technology for preparing secondary alcohol by oxidation of alkane |
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| CN117550954A (en) * | 2023-11-09 | 2024-02-13 | 江苏赛科化学有限公司 | Processing technology for preparing secondary alcohol by oxidation of alkane |
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