CN109761746B - Process and system for preparing secondary alcohol by liquid wax oxidation - Google Patents
Process and system for preparing secondary alcohol by liquid wax oxidation Download PDFInfo
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- CN109761746B CN109761746B CN201910153402.8A CN201910153402A CN109761746B CN 109761746 B CN109761746 B CN 109761746B CN 201910153402 A CN201910153402 A CN 201910153402A CN 109761746 B CN109761746 B CN 109761746B
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- 238000000034 method Methods 0.000 title claims abstract description 37
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- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
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- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
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- 229910052697 platinum Inorganic materials 0.000 description 6
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Abstract
The invention relates to the field of preparing secondary alcohol by liquid wax oxidation, in particular to a process and a system for preparing secondary alcohol by liquid wax oxidation. The process comprises the following steps: carrying out liquid phase oxidation on liquid wax, carrying out esterification reaction on an oxidation reaction product and secondary alcohol, recovering crude secondary alcohol boric acid ester in the esterification product, and removing acid and ester substances from the residual substances through alkali washing and water washing to obtain unreacted alkane; more than 25% of unreacted alkane is subjected to hydrogenation reaction, and the obtained product enters a liquid phase oxidation step of liquid wax; and processing the recovered crude secondary alcohol borate to obtain the secondary alcohol. Compared with the process without hydrogenation reaction, the method increases the hydrogenation step, reduces the consumed raw material alkane (unit consumption) from 1.53 ton/ton to 1.25 ton/ton, improves the apparent selectivity of the raw material alkane to the monohydric secondary alcohol from about 70 percent to about 85 percent, greatly improves the economic benefit and reduces the environmental pollution.
Description
Technical Field
The invention relates to the field of preparation of secondary alcohol by liquid wax oxidation, in particular to a process and a system for preparing secondary alcohol by liquid wax oxidation.
Background
The secondary alcohol synthesized by normal liquid wax oxidation method is added with ethylene oxide to obtain high-efficiency surfactant, which is an important component of high-end emulsion and detergent formula. The raw material liquid wax is hydrolyzed in the presence of dehydrated boric acid and an amino base substance cocatalyst to generate secondary alcohol boric acid ester (metaborate, etc.) in an oxygen-containing gas atmosphere to obtain a product, namely, the primary secondary alcohol, wherein the one-way conversion rate of the raw material normal liquid wax is about 10-20%, the selectivity of the primary secondary alcohol is about 70%, and main byproducts are monoketone (about 15%), dihydric alcohol (about 7%), acid, ester, etc.
The prior process for preparing secondary alcohol by liquid wax oxidation mainly separates byproducts by saponification washing, rectification and other processes, and treats the byproducts by incineration or biochemical degradation and other modes. Therefore, not only certain environmental pollution is caused, but also the consumption of the raw material liquid wax is higher, and economic loss is caused. Therefore, the improvement of the selectivity of the monohydric secondary alcohol is the problem which needs to be solved by the process for preparing the secondary alcohol by the liquid wax oxidation method.
Some patents propose (e.g. Texaco) high temperature and high pressure (300-.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a process for preparing secondary alcohol by liquid wax oxidation, which is characterized in that the recovered unreacted alkane after esterification is subjected to hydrogenation reaction, ketone in the unreacted alkane generates monohydric secondary alcohol, alkane containing monohydric secondary alcohol enters the liquid wax oxidation reaction, so that the apparent selectivity of the raw material alkane to the monohydric secondary alcohol is improved from about 70% to about 85%, the consumption (unit consumption) of the raw material alkane for refining the monohydric secondary alcohol is reduced from 1.53 ton/ton to 1.25 ton/ton, the economic benefit is greatly improved, and the environmental pollution is greatly reduced.
The second purpose of the invention is to provide a system for preparing secondary alcohol by liquid wax oxidation, which provides the requirement for the equipment of the process reaction for industrial production.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the process for preparing secondary alcohol by liquid wax oxidation comprises the following steps:
carrying out liquid phase oxidation on liquid wax to obtain an oxidation reaction product, and carrying out esterification reaction on the oxidation reaction product and secondary alcohol to obtain an esterification product;
recovering crude secondary alcohol borate in the esterification product, and removing acid and ester substances from the residual substances through alkaline washing and water washing to obtain unreacted alkane;
carrying out hydrogenation reaction on more than 25% of the unreacted alkane by mass, and taking the obtained product as the raw material of the liquid-phase oxidation to participate in the liquid-phase oxidation;
and processing the recovered crude secondary alcohol borate to obtain the secondary alcohol.
In the present invention, the liquid wax is a saturated aliphatic n-alkane having 8 to 30 carbon atoms.
In the invention, unreacted alkane in the esterification reaction is saponified and washed and then subjected to hydrogenation reaction, part of monohydric ketone is reduced into monohydric secondary alcohol in the process, and the monohydric secondary alcohol enters the liquid wax oxidation reaction, so that compared with the process without hydrogenation reaction, the consumed raw material alkane (unit consumption) is reduced from 1.53 tons/ton to 1.25 tons/ton, the economic benefit is greatly improved, and the environmental pollution is reduced; in addition, from the overall process point of view, the conversion of the monoketone into the product secondary alcohol increases the apparent selectivity of the raw material alkane to the monohydric secondary alcohol from about 70 percent to about 85 percent, thereby realizing the maximum 15 percent increase of the selectivity of the monohydric secondary alcohol, namely the invention adopts selective hydrogenation of the recovered alkane to remarkably improve the apparent selectivity of the monohydric secondary alcohol.
In the step of hydrogenating more than 25% by mass of the unreacted alkane, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% or the like of the unreacted alkane may be hydrogenated.
The recovered crude secondary alcohol borate is processed to obtain secondary alcohol, and the secondary alcohol is washed and rectified according to hydrolysis alkali washing, and the processes are conventional processes and are not described any more.
Further, in the liquid phase oxidation, the reaction temperature is 140-200 ℃, and the reaction pressure is 0-3.0 MPaG.
As in the different embodiments, the reaction temperature can be 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and so on; likewise, in various embodiments, the reaction pressure may be 0.0MPaG, 0.5MPaG, 0.8MPaG, 1.0MPaG, 1.5MPaG, 1.8MPaG, 2.0MPaG, 2.5MPaG, 2.8MPaG, 3.0MPaG, and the like.
Further, the liquid phase oxidation is carried out in a catalyst, a promoter and an oxygen atmosphere.
Furthermore, the catalyst is dehydrated boric acid, and the cocatalyst is an amino alkali substance.
Further, the addition amount of the dehydrated boric acid is 0.5-10% of the weight of the liquid wax, and the addition amount of the amino base substance is 0.001-0.1% of the weight of the liquid wax;
as in various embodiments, the dehydrated boric acid can be added in an amount of 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., by weight of the liquid wax.
The addition amount of the amino alkali substance is 0.001%, 0.005%, 0.008%, 0.01%, 0.05%, 0.09%, 0.1% and the like of the weight of the liquid wax;
further, the aerobic atmosphere is: gas with oxygen content of 2 vol% to 10 vol%.
As in various embodiments, the oxygen content may be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.
That is, it is most preferable to subject the liquid wax to liquid phase oxidation with a gas having an oxygen content of 2 vol% to 10 vol% in the presence of 0.5 wt% to 10 wt% of dehydrated boric acid and 0.001 wt% to 0.1 wt% of an amino base.
Further, the esterification was carried out at 100-200 ℃ under a nitrogen flow or under reduced pressure.
As in the various embodiments, the temperature of the esterification can be 100 deg.C, 120 deg.C, 130 deg.C, 150 deg.C, 170 deg.C, 200 deg.C, and the like.
Further, the hydrogenation reaction is carried out under a hydrogenation catalyst, and the hydrogenation catalyst includes any one or more of Cu-based, Ni-based, Pb-based, Pt-based, and Co-based, and preferably any one or more of Ni-based, Pt-based, Pb-based, and Co-based.
The hydrogenation catalyst used in the present invention is a copper-based catalyst, a nickel-based catalyst, a lead-based catalyst, a platinum-based catalyst, or a cobalt-based catalyst. For example, the copper-based catalyst may be a copper-based catalyst having a copper content of 40%, the nickel-based catalyst may be a nickel-based catalyst having a nickel content of 25%, the lead-based catalyst may be a lead-based catalyst having a lead content of 10%, the platinum-based catalyst may be a platinum-based catalyst having a platinum content of 20%, and the cobalt-based catalyst may be a cobalt-based catalyst having a cobalt content of 30%.
Further, the hydrogenation reaction is carried out at a temperature of 80-200 ℃.
Preferably, the hydrogenation reaction is carried out at a temperature of 130 ℃ and 200 ℃, more preferably at a temperature of 130 ℃ and 160 ℃.
As in the various embodiments, the hydrogenation reaction temperature may be 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 to 20 MPaG.
Preferably, the pressure of the hydrogenation reaction is 1.0 to 3.0 MPaG.
As in the different embodiments, the pressure of the hydrogenation reaction may be 0.5MPaG, 1MPaG, 2MPaG, 3MPaG, 5MPaG, 7MPaG, 8MPaG, 10MPaG, 12MPaG, 15MPaG, 17MPaG, 20MPaG, and the like.
Further, in the hydrogenation reaction, the molar ratio of hydrogen to carbonyl is 10-40: 1, preferably 20 to 40:1, more preferably 30 to 40: 1.
as in the various embodiments, the molar ratio of hydrogen to carbonyl can be 20:1, 25:1, 30:1, 35:1, 40:1, and so forth.
In the invention, unreacted alkane is converted into monohydric secondary alcohol by the selection of the selective hydrogenation catalyst and the limitation of the selective hydrogenation reaction conditions, so that the conversion rate and the selectivity of the monohydric ketone in the monohydric secondary alcohol are both more than 90%.
The invention also provides a system for preparing secondary alcohol by a liquid wax oxidation method, which comprises an oxidation reaction device, an esterification reaction device, an alkane recovery device, an alkali washing device, a water washing device and a hydrogenation reaction device which are sequentially connected by adopting pipelines;
the hydrogenation reaction device is also connected with a feed pipeline of the oxidation reaction device;
and a branch pipe is arranged on a pipeline between the water washing device and the hydrogenation reaction device, and one end of the branch pipe is connected with a feed pipeline of the oxidation reaction device.
The system provided by the invention provides support for the process for preparing the secondary alcohol by the liquid wax oxidation method, so that the system can be used for industrial production.
Furthermore, the oxidation reaction device is more than one.
Further, the oxidation reaction device is a stirring kettle or a bubble column.
Furthermore, the oxidation reaction devices are connected in series.
In addition, the recovered crude secondary alcohol borate is processed to obtain the secondary alcohol by adopting the following devices:
a borate ester hydrolysis device, an alkali washing device, a water washing device, a light weight removal device and a heavy weight removal device.
Namely, after the alkane recovery device is connected with the borate hydrolysis device, the reaction is carried out according to the subsequent devices to obtain the secondary alcohol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention carries out hydrogenation reaction on partial or all unreacted alkane in the esterification reaction to generate monohydric secondary alcohol from the monohydric ketone in the alkane, the alkane containing the monohydric secondary alcohol enters the liquid wax oxidation reaction, so that the apparent selectivity of the raw material alkane to the monohydric secondary alcohol is improved from about 70 percent to about 85 percent, the consumption (unit consumption) of the raw material alkane for refining the monohydric secondary alcohol is reduced from 1.53 ton/ton to 1.25 ton/ton, the economic benefit is greatly improved, and the environmental pollution is reduced.
(2) The invention also selects a selective hydrogenation catalyst and a hydrogenation condition, so that the conversion rate and the selectivity of the monoketone are both over 90 percent.
(3) The invention also provides a system for preparing the secondary alcohol by the liquid wax oxidation method, provides requirements for equipment for the process reaction, and is used for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic diagram of a process flow for preparing secondary alcohol by a liquid wax oxidation method provided by the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The conditions of the hydrogenation reaction are well known
The hydrogenation reaction conditions were carried out using a pilot plant reactor with the following parameters: the reactor length is 3500mm by adopting DN40, and the filling height of the catalyst is about 0.5 m.
1. Influence of hydrogen carbonyl ratio on conversion rate and selectivity of ketone
The reaction was carried out at a reaction temperature of 150 ℃ and a pressure of 2.0MPaG, and the catalyst was a nickel-based catalyst, and the results are shown in Table 1.
TABLE 1 influence of Hydrogen carbonyl ratio on ketone conversion, selectivity
Ratio of hydrogen to carbonyl (mol) | 6:1 | 12:1 | 20:1 | 30:1 | 40:1 |
Percent conversion of ketone (mol) | 75 | 85 | 90 | 98 | 99 |
(mol) Ketone Selectivity | 99.8 | 99.8 | 99.6 | 99 | 99 |
As can be seen from Table 1, the molar ratio of hydrogen to carbonyl is 20 to 40:1 has higher conversion rate and selectivity, wherein the molar ratio of hydrogen to carbonyl is 30-40: 1 the effect is better.
2. Effect of different reaction temperatures on the conversion of ketones
The results of investigating the effect of temperature on ketone conversion at a 40:1 molar ratio of hydrogen to carbonyl, a pressure of 2.0MPaG, and a nickel-based catalyst are shown in Table 2.
TABLE 2 Effect of different reaction temperatures on ketone conversion
Reaction temperature C | 80 | 100 | 130 | 140 | 150 | 160 | 180 | 200 |
Percent conversion of ketone (mol) | 40 | 75 | 90 | 98 | 99 | 99 | 99 | 99 |
(mol) Ketone Selectivity | 95 | 95 | 99.6 | 99 | 99 | 99 | 95 | 90 |
As can be seen from Table 2, the reaction temperature is 130-200 ℃ under the above conditions, wherein the reaction temperature is preferably 130-200 ℃, and more preferably 130-160 ℃.
3. Effect of different reaction pressures on ketone conversion
The results of investigating the effect of the reaction pressure on the conversion of ketone at a molar ratio of 40:1 of carbonyl hydride and a temperature of 150 ℃ using a nickel-based catalyst are shown in Table 3.
TABLE 3 influence of different reaction pressures on the conversion of ketones
Reaction pressure MPaG | 0.5 | 1.0 | 2.0 | 3.0 | 18 |
Percent conversion of ketone (mol) | 75 | 90 | 99 | 99 | 99.5 |
(mol) Ketone Selectivity | 90 | 99 | 99 | 99 | 95 |
As can be seen from Table 3, the ketone conversion and selectivity are both good at reaction pressures of 1.0-3.0 MPaG.
4. Effect of different catalysts on ketone conversion
The effect of different catalysts on ketone conversion was explored at a 40:1 molar ratio of hydrogen to carbonyl, a temperature of 150 ℃, and a reaction pressure of 2.0MPaG, and the results are shown in Table 4.
TABLE 4 Effect of different catalysts on ketone conversion
Catalyst type | 1 | 2 | 3 | 4 | 5 |
Percent conversion of ketone (mol) | 85 | 99 | 99 | 99 | 98 |
(mol) Ketone Selectivity | 90 | 99 | 97 | 99 | 99 |
Wherein, in the catalyst types, 1 is a copper catalyst, 2 is a nickel catalyst, 3 is a platinum catalyst, 4 is a lead catalyst, and 5 is a cobalt catalyst.
As can be seen from Table 4, the catalysts Ni-based catalyst, Pt-based catalyst, Pb-based catalyst and Co-based catalyst are preferably used.
In the above embodiment of the invention, the copper catalyst is Pricat Cu 60/8; the nickel catalyst is HTC Ni 500; the platinum catalyst is Type 73; HTC Co 2000 is selected as the cobalt catalyst; the lead catalyst is HTA 50.
Examples of the experiments
Recovering C by saponification and water washing12-C14Normal alkane, a reactor is filled with nickel catalyst HTC Ni 500, the reaction temperature is 150 ℃, the pressure is 2.0MPaG, the alkane feeding amount is 5kg/h, and the hydrogen amount is 500 NL/h. And (5) detecting the sample. The results obtained by gas chromatography are shown in Table 5.
TABLE 5 comparison of hydrogenation reactant alkanes with hydrogenation product Components
Example 2
The process for preparing secondary alcohol by liquid wax oxidation method, as shown in figure 1, comprises the following steps:
1. in the oxidation reactor, the reaction raw material is 100 wt% hydrogenation recovered alkane.
Recovery of 100% of hydrogenated C12-C14100g of normal liquid wax is put into a four-mouth glass flask, and 4g of metaboric acid and 0.1g of an amino alkali substance cocatalyst are added. Under the action of mechanical stirring, 0.3L of oxygen-deficient oxygen is introduced at the temperature of 170 ℃ per minute, the oxygen concentration is 8 vol%, and the reaction lasts for 2 hours. After the reaction was completed, the reaction product was hydrolyzed with 100g of hot water, and the upper oil phase was examined. The results obtained by gas chromatography are shown in Table 6.
TABLE 6 comparison of reactant and product Components
In addition, counting the values of other aspects, and calculating to obtain the following contents:
the oxidation conversion rate is 18.0 percent;
the oxidation selectivity is 73.3%;
apparent selectivity was 85.5%.
Wherein, the oxidation conversion (%) (mass number of the raw material liquid wax-mass number of the unreacted liquid wax) × 100/mass number of the raw material liquid wax;
oxidation selectivity (%) -, formation of secondary monohydric alcohol liquid wax mass number 100/mass of reaction liquid wax;
apparent selectivity (%). q.secondary monohydric alcohol switched liquid wax mass number 100/reaction liquid wax mass number.
2. Esterifying partial secondary alcohol obtained by an oxidation reaction product and an alcohol recovery tower in an esterification reactor, removing excessive dehydrated boric acid, and changing a small amount of free alcohol in the oxidation reaction product into boric acid ester;
the esterification was carried out at a temperature of 200 ℃ under a nitrogen stream.
3. In an alkane recovery tower, obtaining tower bottom residual liquid containing unreacted hydrocarbon and secondary alcohol borate through distillation separation;
unreacted alkane is subjected to removal of reaction by-product acid and ester impurities through an alkaline washing tower A and a water washing tower A and then enters a hydrogenation reactor;
unreacted alkane is reacted under the action of hydrogenation catalyst Ni and under the conditions of temperature of 150 ℃ and pressure of 2.0MPaG, and the molar ratio of hydrogen to carbonyl is 40:1, reducing the monoketone by-product in the alkane into the product of the monohydric secondary alcohol (the conversion rate is 95-97%, and the selectivity is 97-99%). The obtained secondary alcohol enters into a circulating oxidation and esterification pipeline, enters into subsequent hydrolysis alkali washing rectification from the residual liquid in the hydrocarbon recovery tower kettle and finally enters into a product secondary alcohol.
4. Enabling the tower bottom residual liquid containing the secondary alcohol borate to enter a borate ester hydrolysis tower according to a path, and then sequentially entering an alkaline washing tower B, a water washing tower B, a light component removing tower and a heavy component removing tower to obtain secondary alcohol;
the subsequent hydrolysis, alkali washing, water washing and rectification of the crude secondary alcohol borate are conventional processes and are not described in detail.
Comparative example
The process for preparing secondary alcohol by liquid wax oxidation method, as shown in figure 1, comprises the following steps:
1. in the oxidation reactor, the reaction raw material is 0 wt% of hydrogenation recovered alkane:
recovery of unhydrogenated C12-C14100g of normal liquid wax is put into a four-mouth glass flask, and 4g of metaboric acid and 0.1g of an amino alkali substance cocatalyst are added. Under the action of mechanical stirring, at 170 deg.C, introducing 0.3L of oxygen-poor and oxygen-rich liquid per minuteDegree 8 vol%, and reaction for 2 hours. After the reaction, the reaction product was hydrolyzed with 100g of hot water, and the upper oil phase was taken to examine the sample. The results obtained by gas chromatography are shown in Table 7.
TABLE 7 comparison of reactant and product Components
In addition, counting the values of other aspects, and calculating to obtain the following contents:
the oxidation conversion rate is 16.72 percent;
the oxidation selectivity is 71.3 percent;
apparent selectivity 71.3%.
The flow of other working sections is the same as that of example 2, and is not described again.
From the overall process point of view, about 97% of oxidation by-product monoketone is converted into product secondary alcohol, and the apparent selectivity of the monohydric secondary alcohol is increased by about 15% compared with that of the product without adding a hydrogenation step.
Example 3
The process for preparing secondary alcohol by liquid wax oxidation method, as shown in figure 1, comprises the following steps:
1. in the oxidation reactor, the reaction raw material is 50 wt% of hydrogenation recovered alkane:
50 wt% hydrogenation to recover alkanes, where the hydrogenated normal alkanes, i.e. unreacted alkane hydrogenated product:
50g of unhydrogenated and 50g of hydrogenated C12-C14Normal liquid wax is put into a four-mouth glass flask, and 4g of metaboric acid and 0.1g of an amino base substance cocatalyst are added. Under the action of mechanical stirring, 0.3L of oxygen-deficient oxygen is introduced at the temperature of 170 ℃ per minute, the oxygen concentration is 8 vol%, and the reaction lasts for 2 hours. After the reaction, the reaction product was hydrolyzed with 100g of hot water, and the upper oil phase was taken to examine the sample. The results obtained by gas chromatography are shown in Table 8.
TABLE 8 comparison of reactant and product Components
In addition, counting the values of other aspects, and calculating to obtain the following contents:
the oxidation conversion rate is 17.27%;
the oxidation selectivity is 72.22%;
apparent selectivity 78.42%.
The flow of other working sections is the same as that of example 2, and is not described again.
Example 4
The process for preparing secondary alcohol by liquid wax oxidation method, as shown in figure 1, comprises the following steps:
1. in the oxidation reactor, the reaction raw material is 80 wt% of hydrogenation recovered alkane:
20g of unhydrogenated and 80g of hydrogenated C12-C14Normal liquid wax is put into a four-mouth glass flask, and 4g of metaboric acid and 0.1g of an amino base substance cocatalyst are added. Under the action of mechanical stirring, 0.3L of oxygen-deficient oxygen is introduced at the temperature of 170 ℃ per minute, the oxygen concentration is 8 vol%, and the reaction lasts for 2 hours. After the reaction, the reaction product was hydrolyzed with 100g of hot water, and the upper oil phase was taken to examine the sample. The results obtained by gas chromatography are shown in Table 9.
TABLE 9 comparison of reactants with product Components
In addition, counting the values of other aspects, and calculating to obtain the following contents:
the oxidation conversion rate is 17.9%;
the oxidation selectivity is 71.5 percent;
apparent selectivity 81.0%.
The flow of other working sections is the same as that of example 2, and is not described again.
The hydrogenation of the recovered hydrocarbons at different ratios is compared, and the oxidation products are compared (the oxidation conditions are the same), as shown in Table 10.
TABLE 10 comparison of the effects of hydrogenation of recovered hydrocarbons to produce secondary alcohols in different proportions
The hydrogenation proportion of the recovered hydrocarbons% | Oxidation conversion% | Selectivity for oxidation% | 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 apparent selectivity of the raw material alkane to the monohydric secondary alcohol is improved to different degrees in the liquid phase oxidation step of the obtained product entering the oxidizer after different percentages of unreacted alkane are subjected to hydrogenation reaction, and the apparent selectivity of the raw material alkane to the monohydric secondary alcohol is improved along with the increase of the percentage of the unreacted alkane to be hydrogenated.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (13)
1. The process for preparing the secondary alcohol by the liquid wax oxidation method is characterized by comprising the following steps:
carrying out liquid phase oxidation on liquid wax to obtain an oxidation reaction product, and carrying out esterification reaction on the oxidation reaction product and secondary alcohol to obtain an esterification product;
recovering crude secondary alcohol borate in the esterification product, and removing acid and ester substances from the residual substances through alkaline washing and water washing to obtain unreacted alkane;
carrying out hydrogenation reaction on more than 25% of the unreacted alkane by mass, and taking the obtained product as the raw material of the liquid-phase oxidation to participate in the liquid-phase oxidation;
the hydrogenation reaction is carried out under the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst comprises any one or more of Cu series, Ni series, Pb series, Pt series and Co series;
the hydrogenation reaction is carried out at the temperature of 130 ℃ and 160 ℃; the pressure of the hydrogenation reaction is 1.0-3.0 MPaG;
processing the recovered crude secondary alcohol boric acid ester to obtain secondary alcohol;
in the hydrogenation reaction, the molar ratio of hydrogen to carbonyl is 20-40: 1.
2. the process as claimed in claim 1, wherein the liquid phase oxidation is carried out at a reaction temperature of 140 ℃ to 200 ℃ and a reaction pressure of 0 to 3.0 MPaG.
3. The process of claim 1 wherein the liquid phase oxidation is carried out in an oxygen atmosphere with a catalyst and a promoter.
4. The process according to claim 3, characterized in that the catalyst is dehydrated boric acid and the cocatalyst is an amino base.
5. The process according to claim 4, wherein the dehydrated boric acid is added in an amount of 0.5-10% by weight of the liquid wax, and the amino base substance is added in an amount of 0.001-0.1% by weight of the liquid wax.
6. The process according to claim 3, wherein the aerobic atmosphere is: gas with oxygen content of 2 vol% to 10 vol%.
7. The process as claimed in claim 1, wherein the esterification is carried out at 100-200 ℃ under a nitrogen flow or under reduced pressure.
8. The process of claim 1, wherein the hydrogenation catalyst is any one or more of Ni-based, Pt-based, Pb-based, and Co-based.
9. The device for preparing the secondary alcohol by the liquid wax oxidation method is characterized by comprising an oxidation reaction device, an esterification reaction device, an alkane recovery device, an alkali washing device, a water washing device and a hydrogenation reaction device which are sequentially connected by adopting pipelines;
the hydrogenation reaction device is also connected with a feed pipeline of the oxidation reaction device;
and a branch pipe is arranged on a pipeline between the water washing device and the hydrogenation reaction device, and one end of the branch pipe is connected with a feed pipeline of the oxidation reaction device.
10. The device according to claim 9, wherein valves for controlling the flow of materials are arranged on the pipeline between the water washing device and the hydrogenation reaction device and the branch pipes.
11. The apparatus according to claim 9 or 10, wherein the oxidation reaction apparatus is one or more.
12. The apparatus of claim 11, wherein the oxidation reaction apparatus is a stirred tank or a bubble column.
13. The apparatus according to claim 11, wherein the oxidation reaction apparatus is provided in plurality, and the oxidation reaction apparatuses are connected in series.
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Denomination of invention: Process and system for producing secondary alcohols by liquid wax oxidation Granted publication date: 20220322 Pledgee: Industrial and Commercial Bank of China Limited Lianyungang Lianyun Branch Pledgor: JISANGSU SECOL CHEMICAL Co. Registration number: Y2024980027421 |
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