CN117229133A - Octenal preparation process - Google Patents
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- CN117229133A CN117229133A CN202311525127.0A CN202311525127A CN117229133A CN 117229133 A CN117229133 A CN 117229133A CN 202311525127 A CN202311525127 A CN 202311525127A CN 117229133 A CN117229133 A CN 117229133A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000006482 condensation reaction Methods 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 91
- 239000003513 alkali Substances 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 53
- 238000004587 chromatography analysis Methods 0.000 claims description 18
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
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- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 238000011210 chromatographic step Methods 0.000 claims description 3
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- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 22
- 239000012071 phase Substances 0.000 description 18
- 230000005494 condensation Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- 238000005882 aldol condensation reaction Methods 0.000 description 4
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- 238000012544 monitoring process Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- PYLMCYQHBRSDND-SOFGYWHQSA-N (E)-2-ethyl-2-hexenal Chemical compound CCC\C=C(/CC)C=O PYLMCYQHBRSDND-SOFGYWHQSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
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- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a preparation process of octenal, which comprises a first self-condensation reaction stage and a second self-condensation reaction stage from bottom to top; in the first self-condensation reaction stage, raw material n-butyraldehyde undergoes self-condensation reaction under the catalysis of alkali liquor; the materials after the reaction in the first self-condensation reaction stage are subjected to heat exchange by a primary heat exchange procedure and then are input into a second self-condensation reaction stage to continue the reaction; the material after the reaction in the second self-condensation reaction stage is subjected to secondary heat exchange and then automatically flows into a chromatographic procedure to obtain octenal products; wherein the concentration of the alkali liquor is 6-11 wt%. The preparation process can realize accurate control of temperature, reduces operation difficulty, simplifies process flow and saves process cost; meanwhile, side reactions are reduced, and the product yield is improved.
Description
Technical Field
The application relates to the technical field of chemical synthesis, in particular to a preparation process of octenal.
Background
Octanol is an important basic organic chemical raw material and is widely used for producing plasticizers, solvents, dehydrating agents, defoamers, dispersants, flotation agents, petroleum additives, synthetic fragrances and the like. The industrial production process of octanol takes propylene, synthetic gas and hydrogen as raw materials, and comprises 3 main process links of preparing n-butyraldehyde by propylene hydroformylation, generating octenal (namely 2-ethyl-2-hexenal, which is abbreviated as EPA) by self-condensation and dehydration of n-butyraldehyde, synthesizing octanol by hydrogenation of octenal, and the like, wherein the reaction of synthesizing octenal by self-condensation of n-butyraldehyde is one of important steps of industrial production of octanol.
N-butyraldehyde is a compound with extremely reactive activity, the aldol condensation reaction (also called aldol condensation reaction) is a highly exothermic reaction, firstly, two molecules of n-butyraldehyde are subjected to aldol condensation reaction under the conditions of 0.5-2% (wt) of alkaline solution, 120 ℃ and 0.4MPa to generate aldol, and then the aldol removes one molecule of water to generate more stable octenal, wherein the reaction formula is as follows:
2CH 3 CH 2 CH 2 CHO→CH 3 CH(OH)CH 2 CH 2 CHO
CH 3 CH(OH)CH 2 CH 2 CHO→CH 3 CH=CHCH 2 CHO+H 2 O
based on the characteristics of the process flow, the preparation of the n-butyraldehyde by self-condensation can be divided into two processes: one is to adopt two kettle reactors to operate in series, as shown in figure 1, n-butyraldehyde and NaOH alkali liquor feed enter a first kettle reactor through a heater, self-condensation reaction is carried out at the temperature of 120 ℃, then the reaction mixture further completes the condensation reaction through a second kettle reactor, the reaction product is cooled and then subjected to chromatography, and alkali-containing aqueous solution is removed, so that octenal is obtained; the other is to use a reactor to operate in series with an aldol condensation circulating tower, as shown in figure 2, and the n-butyraldehyde is condensed and dehydrated under the catalysis of sodium hydroxide to generate octenal.
In the process of synthesizing octenal by self-condensation of n-butyraldehyde, the reaction temperature needs to be controlled at 120-125 ℃ in the prior art, because of the characteristic of high heat release of the reaction, if no heat exchange measure is adopted in the condensation process, when the temperature of the reaction feed fluctuates, the temperature in the condensation reactor is easy to be overtemperature, so that the byproducts in the whole process flow are increased, the selectivity of the product is reduced, and the yield is low. In addition, no matter what kind of process is adopted, at least 2 reactors, heat exchangers and other equipment are needed for reaction preparation, and the whole process flow comprises more equipment, is complex to operate and has high cost.
Disclosure of Invention
Aiming at the defects in the prior art, the application discloses a preparation process of octenal, which combines the staged self-condensation reaction distributed up and down with the heat exchange procedure, realizes the accurate control of key parameters (reaction temperature), reduces the occurrence of side reaction, improves the octenal yield, reduces the operation difficulty and saves the process cost.
In order to achieve the technical aim, the application provides a preparation process of octenal, which comprises a first self-condensation reaction stage and a second self-condensation reaction stage from bottom to top; in the first self-condensation reaction stage, raw material n-butyraldehyde undergoes self-condensation reaction under the catalysis of alkali liquor; the materials after the reaction in the first self-condensation reaction stage are subjected to heat exchange by a primary heat exchange procedure and then are input into a second self-condensation reaction stage to continue the reaction; the material after the reaction in the second self-condensation reaction stage is subjected to heat exchange in a secondary heat exchange process and then automatically flows into a chromatography process to obtain octenal products; wherein the concentration of the alkali liquor is 6-11 wt%.
According to the technical scheme, the staged reaction sections and the staged heat exchange procedures are innovatively combined together, in the specific process, sodium hydroxide solution (alkali liquor) and raw material n-butyraldehyde from an upstream butyraldehyde preparation unit are input into a first self-condensation reaction stage at the lower part to react and release heat, and then materials generated in the first self-condensation reaction stage flow from bottom to top under the pushing of an input stream strand and are input into a primary heat exchange procedure to exchange heat, so that the reaction heat can be timely output in the initial stage of the n-butyraldehyde self-condensation reaction, namely, in a severe reaction stage with higher raw material concentration and alkali liquor concentration, the temperature of a reactant system is effectively controlled, the occurrence of overtemperature caused by reaction heat release is prevented, and the occurrence of side reaction is reduced.
In the technical scheme, the reactant system flows from bottom to top and reacts and releases heat, sequentially passes through the first self-condensation reaction stage, the primary heat exchange process, the second self-condensation reaction stage and the secondary heat exchange process, and finally automatically flows into the subsequent chromatography process, so that a logistics flow system similar to plug flow is formed, the process flow is simplified, the occurrence of a back mixing condition can be effectively avoided, and the reaction process and the temperature of the reaction system are effectively controlled. In addition, based on a special logistics flow system, the concentration of the alkali liquor is set to be 6-11 wt%, namely, the concentration of the alkali liquor is set to be higher than that of the prior art, so that the raw material conversion rate is improved and ensured to be higher.
According to the technical scheme, the material after the reaction in the first self-condensation reaction stage is provided with a primary heat exchange procedure, so that the first self-condensation reaction stage is prevented from being overtemperature, and the initial temperature of the material input into the second self-condensation reaction stage can be controlled through heat exchange, so that the temperature of the second self-condensation reaction stage is regulated and controlled, and the overtemperature of the reaction stage is prevented.
In the technical scheme, in order to reduce the saturated vapor pressure of the n-butyraldehyde self-condensation reaction stage, the material reacted in the second self-condensation reaction stage is subjected to heat exchange in a secondary heat exchange process and then cooled, and the self-flow enters a chromatography process to carry out oil-water separation, so that an EPA product of an oil phase is obtained; the EPA product is input into the subsequent hydrogenation process to prepare octanol.
Therefore, the technical scheme of the application innovatively integrates the staged self-condensation reaction stage of the n-butyraldehyde and the staged heat exchange procedure, and simultaneously realizes accurate temperature control and improves the conversion rate and the selectivity of the whole process by controlling the concentration of the alkali liquor catalyst.
In a further example of the application, the lye concentration is 7wt% to 10wt%, still further alternative 8wt% to 9wt%.
Based on the technical scheme, the application explores and optimizes the control temperature and the reaction residence time of each reaction section.
In a further example of the application, the reaction temperature of the first self-condensation reaction stage may be selected from 90 to 120 ℃, and the reaction residence time may be selected from 3.5 to 20min; the reaction temperature of the second self-condensation reaction stage can be selected to be 100-120 ℃, and the reaction residence time can be selected to be 25-55min. Compared with the prior art of n-butyraldehyde self-condensation reaction in a reactor or a reaction kettle with stirring, the technical scheme of the application can more effectively control the reaction process by controlling the residence time of materials in different reaction sections, and further control the reaction temperature by combining the heat exchange amount of different heat exchange sections, thereby improving the selectivity and the yield of the product.
It should be noted that, in the technical scheme of the present application, the specific operation of controlling the residence time of the material in the stages of different reaction stages is not limited, and those skilled in the art can adjust the residence time by adjusting the material input flow, controlling the stage heights of different reaction stages, or adding liquid distributors or fillers, etc. based on the technical scheme of the present application, so that the formed technical scheme is within the scope of the present application.
In a further embodiment of the application, the reaction temperature in the first self-condensation stage is further selected to be in the range of from 90 to 115℃in view of the fact that the higher concentration of n-butyraldehyde and the higher concentration of lye in the feed to the first self-condensation stage are critical for the temperature control in the first self-condensation stage.
In a further embodiment of the application, the reaction temperature of the second self-condensation reaction stage is further selected to be in the range of 105 to 115℃in view of the reduced concentration of n-butyraldehyde and the reduced concentration of lye in the second self-condensation reaction stage relative to the first self-condensation reaction stage.
In a further example of the present application, the feed mass ratio of raw n-butyraldehyde to lye may be selected to be (5-12.1): 1, a step of; further alternatively (5.8-11): 1, according to the characteristics of condensation reaction, the mass ratio of the feeding mass of the n-butyraldehyde to the input alkali liquor in the range can meet the material composition required by normal condensation reaction, and the conversion rate of raw material n-butyraldehyde and the yield of octenal are higher.
In a further example of the application, the temperature of the output material after reaction in the second self-condensation reaction stage after heat exchange is 80-90 ℃.
In a further example of the present application, the method further comprises preheating the raw material n-butyraldehyde at a temperature of 85-95 ℃ to improve the reaction efficiency. Notably, because of the exothermic characteristic of the self-condensation reaction of the n-butyraldehyde, alkali liquor used in the process can be input into the lower part of the condensation comprehensive tower without preheating, and the raw material n-butyraldehyde is mixed and then subjected to catalytic reaction; however, in a specific process, in order to improve the production efficiency, the alkali liquor initially input into the condensation comprehensive tower can be preheated to about 85-95 ℃, so that the working condition of the process in the starting period can be completed as soon as possible, and stable EPA production can be carried out.
It should be noted that the technical characteristics of promoting the self-flowing of the material after the reaction in the second self-condensation reaction stage, which is outputted after heat exchange, to the chromatography process are not limited in the present application, and those skilled in the art can set the technical characteristics of promoting the self-flowing of the material after the reaction in the second self-condensation reaction stage, which is outputted after heat exchange, based on the technical scheme of the present application, through non-creative work, so that the formed technical scheme is within the scope of the present application. Optionally, in a further embodiment of the present application, a n-butyraldehyde self-condensation reaction stage is also provided in communication with the chromatography process. In the actual technical process, the chromatography process is carried out under the nitrogen sealing piece, and the n-butyraldehyde self-condensation reaction stage and the chromatography process can share a nitrogen sealing system by arranging the gas phase communication, so that the gravity self-flowing output effect of the material after the reaction in the second self-condensation reaction stage is ensured.
In a further example of the present application, the method further includes inputting the aqueous phase output from the chromatography step into an upstream alkali liquor preparation step for recycling, or dividing the aqueous phase into two paths, one path being input into the upstream alkali liquor preparation step for recycling and the other path being input into a subsequent sodium hydroxide product preparation step. The self-condensation reaction of n-butyraldehyde produces water, the concentration of the alkali liquor with the concentration of about 2wt% is reduced to about 1wt% after the reaction in the prior art, and part of the alkali liquor can be used for preparing 2wt% alkali liquor, and the other part is input into a subsequent wastewater treatment procedure, so that the process treatment cost is increased. The concentration of the alkali liquor used in the application is 6-11 wt%, the concentration of sodium hydroxide in the water phase extracted from the chromatography process is about 4-5.1 wt%, part of the water phase can be used for preparing 6-11 wt% of alkali liquor for cyclic application, the other part of the water phase can be used for preparing sodium hydroxide products, for example, the water phase can be input into a subsequent triple-effect evaporation module, and part of the water phase can be used for preparing alkali liquor with other concentrations in a specific process flow, thereby avoiding complex wastewater treatment process, simplifying the process flow and saving the process cost.
Compared with the prior art, the octenal preparation process provided by the application realizes accurate control of temperature by integrating a plurality of self-condensation reaction stages and staged heat exchange procedures, reduces the operation difficulty, simplifies the process flow and saves the process cost; the application adopts alkali liquor with the concentration of 6-11 wt% to catalyze the self-condensation reaction of the n-butyraldehyde and set lower reaction temperature, thereby reducing side reaction and improving the product yield.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 illustrates a prior art n-butyraldehyde self-condensation process;
FIG. 2 illustrates another prior art n-butyraldehyde self-condensation process;
FIG. 3 shows a block diagram of an alternative system for octenal preparation in accordance with the present application.
Wherein the following reference numerals are included in fig. 3:
the device comprises a 1-condensation comprehensive tower, 11-first self-condensation reaction stage, 12-primary heat exchange working procedure stage, 13-second self-condensation reaction stage, 14-secondary heat exchange working procedure stage, 15-temperature remote transmission point, 16-heat exchange device, 2-chromatograph, 31-first branch, 32-second branch, 33-high-concentration alkali liquor input pipe and 34-communicating pipe.
Detailed Description
In order that the application may be understood more fully, a more particular description of the application will be rendered by reference to preferred embodiments thereof. It should be understood that these examples are for the purpose of more detailed description only and should not be construed as limiting the application in any way, i.e., not intended to limit the scope of the application.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains. Relational terms such as "first," "second," and the like may be used solely to distinguish one element from another element having the same name in the present embodiments without necessarily requiring or implying any actual such relationship or order between such elements. Features defining "first," "second," etc. may explicitly or implicitly include one or more such features.
Example 1
A process for producing octenal, which comprises a first self-condensation reaction stage and a second self-condensation reaction stage from bottom to top; in the first self-condensation reaction stage, raw material n-butyraldehyde undergoes self-condensation reaction under the catalysis of alkali liquor; the materials after the reaction in the first self-condensation reaction stage are subjected to heat exchange in a primary heat exchange working procedure section and then are input into a second self-condensation reaction stage to continue the reaction; the materials after the reaction in the second self-condensation reaction stage are subjected to a secondary heat exchange process section and then automatically flow into a chromatographic process to obtain octenal products; wherein the concentration of the alkali liquor is 6-11 wt%.
Fig. 3 shows a system structure of the octenal preparation process of the present embodiment, based on which the n-butyraldehyde self-condensation reaction is performed in a condensation integrated tower 1, wherein the condensation integrated tower 1 comprises a first self-condensation reaction stage 11, a primary heat exchange process stage 12, a second self-condensation reaction stage 13 and a secondary heat exchange process stage 14 from bottom to top; raw materials n-butyraldehyde and alkali liquor are respectively input from the lower part of the condensation comprehensive tower 1, and condensation reaction is carried out in a first self-condensation reaction stage 11; the materials after the reaction in the first self-condensation reaction stage are subjected to heat exchange by the primary heat exchange process section 12 and then are input into the second self-condensation reaction stage 13 for continuous reaction; after the material after the reaction in the second self-condensation reaction stage is subjected to heat exchange by the secondary heat exchange working procedure section 14, the material is automatically fed into the chromatograph 2 from the side surface of the top of the condensation comprehensive tower 1 to carry out a chromatography working procedure; the oil phase obtained from the chromatograph 2 is octenal product.
Optionally, the concentration of the alkali liquor is 7wt% to 10wt%, and even more optionally 8wt% to 9wt%.
Optionally, the reaction temperature of the first self-condensation reaction stage 11 is 90-120 ℃, and the reaction residence time is 3.5-20min; the reaction temperature of the second self-condensation reaction stage 13 is 100-120 ℃, and the reaction residence time is 25-55min.
Further alternatively, the reaction temperature of the first self-condensation reaction stage 11 is 90-115 ℃.
Further alternatively, the reaction temperature of the second self-condensation reaction stage is 105-115 ℃.
Optionally, the feed mass ratio of the raw material n-butyraldehyde to the alkali liquor is (5-12.1): 1, a step of; further alternatively (5.8-11): 1.
optionally, the temperature of the material after the reaction in the second self-condensation reaction stage is 80-90 ℃ after heat exchange. It should be noted that the optional operation temperature of the chromatography process of the application is 40-45 ℃, so that a person skilled in the art can choose a suitable method and the heat exchange device 16 to regulate the temperature of the second material before inputting the chromatography process by non-creative labor, and the technical scheme formed by the method is within the protection scope of the application.
It should be noted that, in order to facilitate monitoring the temperature of the condensation complex 1 and other equipment, a person skilled in the art can set the temperature remote transmission point 15 at a suitable position of the condensation complex 1 and other equipment by non-creative labor; in addition, the device can be used for heat exchange, liquid level monitoring, regulation and control and promotion of circulating fluid conveying equipment or devices in a proper link of the preparation process through non-creative labor, and the formed technical scheme is within the protection scope of the application.
Optionally, the preparation process of the embodiment further comprises inputting the aqueous phase output by the chromatography step into an upstream alkali liquor preparation step for cyclic utilization, or dividing the aqueous phase into two paths, one path is input into the upstream alkali liquor preparation step for cyclic utilization, and the other path is input into a subsequent sodium hydroxide product preparation step.
The concentration of alkali liquor used in the preparation process for catalyzing the self-condensation reaction of the n-butyraldehyde is 6-11 wt%, after the reaction is finished, the concentration of aqueous sodium hydroxide extracted from a chromatography process is about 4-5.1 wt%, as shown in figure 3, the aqueous phase outlet of the chromatograph 2 is connected with a high-concentration alkali liquor (the concentration of sodium hydroxide is about 30 wt%) input pipe 33 through a first branch 31, thereby the alkali liquor with the concentration of 6-11 wt% can be obtained through the combination of alkali liquor with different concentrations, and the recycling is realized; in addition, the water phase outlet of the chromatograph 2 is connected with the subsequent sodium hydroxide product preparation procedure through a second branch 32, and sodium hydroxide products are prepared by adopting processes and equipment such as a triple effect evaporation module and the like; during the actual process, the aqueous phase output from the chromatograph 2 may be distributed to the first branch 31 and the second branch 32 according to specific conditions.
Optionally, the preparation process of the application further comprises preheating the raw material n-butyraldehyde at a temperature of 85-95 ℃, thereby providing process preparation efficiency.
Further optionally, the method further comprises preheating the alkali liquor at the initial stage of the starting period, wherein the preheating temperature is 85-90 ℃, and in the specific process operation, the preheated alkali liquor is firstly input and then the preheated raw material n-butyraldehyde is introduced during the preparation of the starting period, so that the rapid reaction is promoted, and the reaction efficiency is improved. Because the self-condensation reaction of the n-butyraldehyde is exothermic, after the process is stable, the preheating of alkali liquor can be stopped, and the alkali liquor at normal temperature can be input to meet the requirement of the reaction temperature.
Optionally, a n-butyraldehyde self-condensation reaction stage is also arranged to be communicated with the chromatography process, and a communicating pipe 34 is arranged between the top of the condensation comprehensive tower 1 and the top of the chromatograph 2 as shown in fig. 3, so that a common nitrogen sealing system is realized, and the gravity self-flowing effect is ensured.
Based on the preparation process shown in example 1, examples 2-4 show the process flow for preparing octenal under specific conditions, and it should be noted that these examples are only preferred and are not intended to limit the scope of the present application.
Example 2
An octenal preparation process, wherein n-butyraldehyde with the temperature of about 90 ℃ and alkali liquor with the concentration of 6-7wt% at normal temperature from an upstream butyraldehyde unit are respectively input into the lower part of a condensation comprehensive tower 1 through pipelines, two streams are respectively input into a first self-condensation reaction stage 11 through the lower part of the condensation comprehensive tower 1, and the n-butyraldehyde undergoes condensation reaction in the first self-condensation reaction stage 11. Wherein the feeding mass ratio of raw material n-butyraldehyde to alkali liquor is 5.5-7; the reaction temperature of the first self-condensation reaction stage 11 is about 90-113℃and the reaction residence time is about 19 minutes.
The temperature of the material after the reaction in the first self-condensation reaction stage is 107-110 ℃ after the heat exchange in the primary heat exchange process section 12, and part of the material is input into the second self-condensation reaction stage 13 for continuous reaction. Wherein the reaction temperature of the second self-condensation reaction stage 13 is about 110-118 ℃ and the reaction residence time is about 55min.
The temperature of the material after the reaction in the second self-condensation reaction stage which is output after heat exchange is about 84-88 ℃, the part of the material is input into a chromatography process and separated in a chromatograph 2 to obtain an EPA product of an oil phase, and a sampling detection site is arranged at a proper position of an oil phase outlet of the chromatograph 2 to obtain the raw material conversion rate of 98.2%, the product selectivity of 98.3% and the yield of 96.53%. The water phase separated by the chromatographic apparatus 2 is alkali liquor with the concentration of 3.6wt% -4wt%, one path of the alkali liquor returns to the alkali liquor preparation process, and the alkali liquor catalyst used in the embodiment is prepared with the alkali liquor with the concentration of 30wt% for recycling, and one path of the alkali liquor is input into the subsequent sodium hydroxide product preparation process.
Example 3
The n-butyraldehyde with the temperature of about 90 ℃ and alkali solution with the concentration of 8-9 wt% at normal temperature from an upstream butyraldehyde unit are respectively input into the lower part of a condensation comprehensive tower 1 through pipelines, two streams are respectively input into a first self-condensation reaction stage 11 through the lower part of the condensation comprehensive tower 1, and the n-butyraldehyde undergoes condensation reaction in the first self-condensation reaction stage 11 to obtain a first material. Wherein the feeding mass ratio of raw material n-butyraldehyde to alkali liquor is 7.5-8.5; the reaction temperature of the first self-condensation reaction stage 11 is about 90-115℃and the reaction residence time is about 17 minutes.
The temperature of the material after the reaction in the first self-condensation reaction stage is 105-108 ℃ after the heat exchange in the primary heat exchange working procedure section 12, and the partial material is input into the second self-condensation reaction stage 13 for continuous reaction. Wherein the reaction temperature of the second self-condensation reaction stage 13 is about 108-115 ℃ and the reaction residence time is about 50min.
The temperature of the material after the reaction in the second self-condensation reaction stage which is output after heat exchange is about 84-88 ℃, the part of the material is input into a chromatography process and separated in a chromatograph 2 to obtain an EPA product of an oil phase, and a sampling detection site is arranged at a proper position of an oil phase outlet of the chromatograph 2 to obtain the raw material conversion rate of the implementation is 99.3%, the product selectivity is 98.5%, and the yield is 97.81%. The water phase separated by the chromatographic apparatus 2 is alkali liquor with the concentration of 4.2-4.5 wt%, one path of the alkali liquor is returned to the alkali liquor preparation process, and the alkali liquor catalyst used in the embodiment is circularly reused with the alkali liquor with the concentration of 30wt%, and one path of the alkali liquor is input into the subsequent sodium hydroxide product preparation process.
Example 4
The n-butyraldehyde with the temperature of about 90 ℃ and alkali solution with the concentration of 10-11 wt% at normal temperature from an upstream butyraldehyde unit are respectively input into the lower part of a condensation comprehensive tower 1 through pipelines, two streams are respectively input into a first self-condensation reaction stage 11 through the lower part of the condensation comprehensive tower 1, and the n-butyraldehyde undergoes condensation reaction in the first self-condensation reaction stage 11 to obtain a first material. Wherein the feeding mass ratio of raw material n-butyraldehyde to alkali liquor is 9-10; the reaction temperature of the first self-condensation reaction stage 11 is about 90-105℃and the reaction residence time is about 3.5 minutes.
The temperature of the material after the reaction in the first self-condensation reaction stage is 98-101 ℃ after the heat exchange in the primary heat exchange working procedure section 12, and the partial material is input into the second self-condensation reaction stage 13 for continuous reaction. Wherein the reaction temperature of the second self-condensation reaction stage 13 is about 101-112 ℃ and the reaction residence time is about 25min.
The temperature of the material after the reaction in the second self-condensation reaction stage which is output after heat exchange is about 84-88 ℃, the part of the material is input into a chromatography process and separated in a chromatograph 2 to obtain an EPA product of an oil phase, and a sampling detection site is arranged at a proper position of an oil phase outlet of the chromatograph 2 to obtain the raw material conversion rate of 97.7%, the product selectivity of 98.6% and the yield of 96.33%. The water phase separated by the chromatographic apparatus 2 is alkali liquor with the concentration of 4.8-5.1 wt%, one path of the alkali liquor is returned to the alkali liquor preparation process, and the alkali liquor catalyst used in the embodiment is circularly reused with the alkali liquor with the concentration of 30wt%, and one path of the alkali liquor is input into the subsequent sodium hydroxide product preparation process.
It should be noted that the above description of the present application is further detailed in connection with specific embodiments, and it should not be construed that the present application is limited to the specific embodiments; the data listed in the embodiments are not limited to the present technical solution, but only show one specific working condition. It will be apparent to those skilled in the art that several simple modifications and adaptations of the application can be made without departing from the spirit of the application and are intended to be within the scope of the application.
Claims (10)
1. The preparation process of octenal is characterized by comprising a first self-condensation reaction stage and a second self-condensation reaction stage from bottom to top; in the first self-condensation reaction stage, raw material n-butyraldehyde undergoes self-condensation reaction under the catalysis of alkali liquor; after the reaction in the first self-condensation reaction stage, the materials are subjected to heat exchange in a primary heat exchange procedure and then are input into a second self-condensation reaction stage to continue the reaction; the materials after the reaction in the second self-condensation reaction stage are subjected to a secondary heat exchange procedure and then automatically flow into a chromatography procedure to obtain octenal products; wherein the concentration of the alkali liquor is 6-11 wt%.
2. The process for producing octenal according to claim 1, wherein the concentration of the alkali liquid is 7 to 10% by weight.
3. The process for producing octenal according to claim 1, wherein the reaction temperature in the first self-condensation reaction stage is 90 to 120 ℃ and the reaction residence time is 3.5 to 20min; the reaction temperature of the second self-condensation reaction stage is 100-120 ℃, and the reaction residence time is 25-55min.
4. A process for the preparation of octenal according to claim 3, wherein the reaction temperature of the first self-condensation reaction stage is 90-115 ℃.
5. A process for the preparation of octenal according to claim 3, wherein the reaction temperature of the second self-condensation reaction stage is 105-115 ℃.
6. The octenal preparation process according to claim 1, wherein the feed mass ratio of raw material n-butyraldehyde to alkali liquor is (5-12.1): 1.
7. the process for producing octenal according to claim 6, wherein the feed mass ratio of raw material n-butyraldehyde to alkali liquor is (5.8-11): 1.
8. the process for producing octenal according to claim 1, wherein the temperature of the material after the reaction in the second self-condensation reaction stage which is outputted after heat exchange is 80 to 90 ℃.
9. The process for producing octenal according to claim 1, further comprising preheating the raw material n-butyraldehyde at a temperature of 85 to 95 ℃.
10. The octenal preparation process according to claim 1, wherein the aqueous phase output from the chromatography step is input into the upstream alkali liquor preparation step for cyclic use, or the aqueous phase is divided into two paths, one path is input into the upstream alkali liquor preparation step for cyclic use, and the other path is input into the subsequent sodium hydroxide product preparation step.
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