Process for the industrial production of acrolein

Abstract

The present application relates to the field of propylene aldehyde preparation, in particular to a method for industrialized preparation of propylene aldehyde, which is carried out in a pry-mounted propylene aldehyde production device, comprising the following steps: S1: mixing glycerol and an ionic liquid catalyst in the mixer (3) to obtain mixed raw materials, S2: introducing the mixed raw materials into a reaction medium in a reaction container (10) through a metering pump (4) to carry out a dehydration reaction, generating a propylene aldehyde product, which is collected and stored by the propylene aldehyde collector (12). The method provided by the present application is carried out in a pry-mounted propylene aldehyde production device, parameters in the preparation process are easy to control, and the propylene aldehyde production efficiency is high, which can produce propylene aldehyde on the oilfield site that needs to treat sewage, that is, it can be used immediately after production, solving the technical problem that propylene aldehyde is difficult to apply to oilfield sewage treatment due to its extremely unstable nature, difficult storage and transportation, and realizing the industrialized application of propylene aldehyde in the field of oilfield sewage treatment.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of acrolein preparation, in particular to a method for industrial preparation of acrolein. BACKGROUND

[0002] Oil wells cause serious scaling and corrosion problems, serious decline in oil production efficiency, water injection problems caused by sulfides and bacteria in the process of water injection and secondary oil recovery in oil fields. Biological fungicides are used on oil fields to prevent bacteria from reproducing at a high speed. Common chemical agents include glutaraldehyde, quaternary ammonium, THPS, etc. The basic goal of biological fungicides is to prevent the approach and penetration of the protective layer of the biofilm by the sessile bacteria. Generally, chemical biological fungicides can achieve this effect. Quaternary amine substances are most effective in penetrating EPS, which surrounds the sessile biofilm. However, the surface active agent characteristics of quaternary amine substances can cause a decrease in production when treating injection wells, and a decrease in product in water injection filters, which limits its use in water flooding. When a high concentration of surface active agent is required to control bacteria, it can cause damage to the formation.

[0003] In water injection systems, acrolein or 2-propenal has been successfully used as a chemical agent to control sessile bacteria, and is a non-corrosive non-surface active agent. Water-soluble biological fungicides exhibit excellent oil solubility, and can penetrate the oil-coated surface and biofilm to effectively treat sessile bacteria. The mechanism of acrolein in treating bacteria is to react with the aldehyde group and amino group in the protein, so that the protein and enzyme in the bacterial cell are denatured. Compared with traditional biological fungicides, acrolein is the best in controlling aerobic bacteria, facultative anaerobic bacteria (GAB), and SRB. In order to improve water quality and solve the water injection problem caused by bacteria and sulfides in secondary oil recovery, adding acrolein to the oil field water is a good treatment method.

[0004] CN103261141A discloses a continuous method for producing acrolein by catalytic dehydration of glycerol or glycerin in the presence of an acid catalyst, which uses a solid acid catalyst and a fluidized bed reactor process. The method needs to be prepared under the condition of fluidized gas, and the parameters are difficult to control during the preparation process. In addition, the fluidized bed reactor is difficult to move, so it is difficult to realize industrial application in oil fields.

[0005] Due to the extremely harsh storage conditions of acrolein and the extremely unstable nature, there are great difficulties in storage and transportation. Oil fields are generally located in remote areas, especially offshore drilling platforms, which are small in space and far from the mainland, affecting the application of acrolein, a high-efficiency oil field sewage treatment agent, in oil fields. SUMMARY

[0006] The present application aims to overcome the technical problem that acrolein is difficult to be applied in industrialization in oilfield sewage treatment in the prior art.

[0007] In order to achieve the above-mentioned purpose, the present application provides a method for industrialized preparation of acrolein, which is carried out in a pry-mounted acrolein production device, the pry-mounted acrolein production device comprising a mixer 3, a metering pump 4, a reaction container 10 and an acrolein collector 12 connected in sequence, wherein the mixer 3 comprises a cavity 301 and flow guides 302 arranged in the cavity 301 and parallel to the ground, the cavity 301 is provided with a glycerol inlet 304, an ionic liquid catalyst inlet 305 and a mixed raw material outlet 306, the setting points of the glycerol inlet 304 and the ionic liquid catalyst inlet 305 are higher than the flow guides 302, the setting point of the mixed raw material outlet 306 is lower than the flow guides 302, a plurality of angular flow guides 303 are arranged on each of the flow guides 302, the angle α between the angular flow guides 303 and the flow guides 302 is 10°-60°, and the setting direction of the angular flow guides 303 is opposite to the flow direction of the material in the mixer 3.

[0008] The method comprises the following steps:

[0009] S1: mixing glycerol and ionic liquid catalyst in the mixer 3 to obtain a mixed raw material, wherein the ionic liquid catalyst comprises pyridine ionic liquid and imidazole ionic liquid, the weight ratio of the pyridine ionic liquid to the imidazole ionic liquid in the ionic liquid catalyst is 1:1-5, and the mixing weight ratio of the glycerol to the ionic liquid catalyst is 1:0.01-0.05;

[0010] S2: introducing the mixed raw material into a reaction medium in the reaction container 10 by the metering pump 4 to carry out a dehydration reaction, to generate an acrolein product, which is collected and stored by the acrolein collector 12, wherein the introduction rate of the mixed raw material is 0.5g / min-50g / min per 1kg of the reaction medium.

[0011] The method provided by the present application is carried out in a pry-mounted acrolein production device, and acrolein can be prepared without the presence of fluidized gas, the parameters in the preparation process are easy to control, the acrolein production efficiency is high, acrolein can be produced on site in an oilfield where sewage needs to be treated, and the acrolein can be used immediately after production, the pry-mounted acrolein production device has a simple structure and is easy to assemble and transport, and can be repeatedly used to prepare acrolein in different oilfields, thereby solving the technical problem that acrolein is difficult to be applied in oilfield sewage treatment due to its extremely unstable nature, difficult storage and transportation, and realizing the industrialization of acrolein in the field of oilfield sewage treatment. BRIEF DESCRIPTION OF DRAWINGS

[0012] Figure 1 is a schematic diagram of the overall connection of the pry-mounted acrolein production equipment according to a preferred embodiment of the present application;

[0013] Figure 2 is a front view of the internal structure of the mixer 3 according to Example 1 of the present application;

[0014] Figure 3 is a top view of the internal structure of the mixer 3 according to Example 1 of the present application;

[0015] Figure 4 is a left view of the internal structure of the mixer 3 according to Example 1 of the present application;

[0016] Figure 5 is a schematic diagram of the structure of the automatic cleaning system according to a preferred embodiment of the present application;

[0017] Figure 6 is a front view of the internal structure of the mixer 3 according to Comparative Example 1 of the present application.

[0018] Explanation of Reference Signs

[0019] 1, glycerol reservoir; 2, ionic liquid catalyst reservoir; 3, mixer; 4, metering pump; 5, preheater; 6, automatic cleaning system; 7, temperature sensor; 8, stirring member; 9, pressure sensor; 10, reaction vessel; 11, condenser; 12, acrolein collector; 13, heating member; 14, circulation pump; 15, filter; 16, heating jacket; 17, control system; 18, vent valve; 19, check valve;

[0020] 301, cavity; 302, flow guide member; 303, corner flow member; 304, glycerol inlet; 305, ionic liquid catalyst inlet; 306, mixed raw material outlet. DETAILED DESCRIPTION

[0021] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are provided as approximations. Any numerical value, however, can inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The ranges and values are approximations that are obtained by the methods used in the art. The endpoints of the ranges and values are provided as approximations and are not to be construed as being limited by the numerical values themselves. Therefore, the ranges and values are approximations that are obtained by the methods used in the art. The endpoints of the ranges and values are provided as approximations and are not to be construed as being limited by the numerical values themselves.

[0022] As described above, the present application provides a method for industrial production of acrolein, which is carried out in pry-mounted acrolein production equipment, as shown in Figure 1 The pry-mounted acrolein production equipment comprises, in sequence, a mixer 3, a metering pump 4, a reaction vessel 10, and an acrolein collector 12, wherein, as shown inFigure 2 As shown, the mixer 3 comprises cavities 301 and flow guides 302 arranged in the cavities 301 and parallel to the ground, the cavities 301 are provided with glycerol inlets 304, ionic liquid catalyst inlets 305 and mixed raw material outlets 306, the setting points of the glycerol inlets 304 and the ionic liquid catalyst inlets 305 are higher than the flow guides 302, the setting points of the mixed raw material outlets 306 are lower than the flow guides 302, each of the flow guides 302 is provided with a plurality of angular flow guides 303, the angle a between the angular flow guides 303 and the flow guides 302 is 10°-60°, and the setting direction of the angular flow guides 303 is opposite to the flow direction of the materials in the mixer 3.

[0023] The method comprises the following steps:

[0024] S1: mixing glycerol and ionic liquid catalyst in the mixer 3 to obtain mixed raw materials, wherein the ionic liquid catalyst comprises pyridine ionic liquid and imidazole ionic liquid, and the weight ratio of the pyridine ionic liquid to the imidazole ionic liquid in the ionic liquid catalyst is 1:1-5, and the mixed weight ratio of the glycerol to the ionic liquid catalyst is 1:0.01-0.05;

[0025] S2: introducing the mixed raw materials into the reaction medium in the reaction container 10 through the metering pump 4 to perform a dehydration reaction to generate a propylene aldehyde product, and the propylene aldehyde product is collected and stored by the propylene aldehyde collector 12, wherein the introduction rate of the mixed raw materials is 0.5g / min-50g / min per 1kg of reaction medium.

[0026] The method provided by the present application is performed in a pry-mounted propylene aldehyde production device, and can prepare propylene aldehyde without the presence of fluidized gas, the parameters in the preparation process are easy to control, the propylene aldehyde production efficiency is high, the propylene aldehyde can be produced on the oilfield site where sewage needs to be treated, and the propylene aldehyde can be used immediately after production, the pry-mounted propylene aldehyde production device has a simple structure and is easy to assemble and transport, and can repeatedly prepare propylene aldehyde in different oilfields, thereby solving the technical problem that propylene aldehyde is extremely unstable in nature, difficult to store and transport, and thus difficult to be applied to oilfield sewage treatment.

[0027] According to some preferred embodiments of the present application, the pyridine ionic liquid is selected from at least one of N-butyl pyridine hydrogen sulfate, N-propyl sulfonic acid pyridine hydrogen sulfate, N-butyl pyridine hydrogen phosphate, propyl sulfonic acid pyridine phosphate; and the imidazole ionic liquid is selected from at least one of methyl imidazole chloride, methyl butyl imidazole sulfate, methyl propyl sulfonic acid imidazole sulfate, methyl propyl sulfonic acid imidazole phosphate. Under this preferred condition, the yield and purity of the propylene aldehyde product are higher.

[0028] Exemplarily, the structure of the N-butylpyridine hydrogen phosphate is shown as Formula I below, the structure of the propylsulfonic acid pyridine phosphate is shown as Formula II below, the structure of the methyl propylsulfonic acid imidazole sulfate is shown as Formula III below, and the structure of the methyl propylsulfonic acid imidazole phosphate is shown as Formula IV below:

[0029]

[0030]

[0031] According to a particularly preferred embodiment of the present application, the ionic liquid catalyst is a mixture of the N-butylpyridine hydrogen sulfate and the methyl imidazole chloride. More preferably, in the ionic liquid catalyst, the weight ratio of the N-butylpyridine hydrogen sulfate to the methyl imidazole chloride is 1:2-4. Under this preferred condition, the yield and purity of the acrolein product are higher.

[0032] According to a particularly preferred embodiment of the present application, the ionic liquid catalyst is a mixture of the N-propylsulfonic acid pyridine hydrogen sulfate and the methyl butyl sulfate imidazole. More preferably, in the ionic liquid catalyst, the weight ratio of the N-propylsulfonic acid pyridine hydrogen sulfate to the methyl butyl sulfate imidazole is 1:1.5-3. Under this preferred condition, the yield and purity of the acrolein product are higher.

[0033] According to some preferred embodiments of the present application, the reaction medium is at least one of the following: heat conducting oil, triphenyl phosphate, t-butyl diphenyl phosphate, triisobutyl phenyl phosphate. This preferred reaction medium is cheap and easy to obtain, and can provide more moderate and stable reaction conditions for the dehydration reaction of glycerol into acrolein.

[0034] According to some preferred embodiments of the present application, the reaction temperature of the dehydration reaction is 280-310°C, and the reaction pressure is 0-0.1 MPa. Under this preferred condition, the generation rate of by-products is lower, and the yield of acrolein is higher.

[0035] According to some preferred embodiments of the present application, as shown in Figure 2 the height of the cavity 301 is h, and the distance between the flow guide 302 and the bottom of the cavity 301 is h / 6-2h / 3. Under this preferred condition, the purity of the acrolein product is higher.

[0036] According to some preferred embodiments of the present application, the cavity 301 is cylindrical, as shown in Figure 3 the cross-sectional radius of the cavity 301 is r, and the distance between the flow guide 302 and the center of the cross section of the cavity 301 is not greater than 2r / 3. Under this preferred condition, the purity of the acrolein product is higher.

[0037] According to some preferred embodiments of the present application, as shown in Figure 2 、 Figure 3 the flow guide 302 is a rotating flow guide, and when the glycerol and ionic liquid catalyst are injected into the mixer 3, the flow guide 302 in the mixer 3 automatically rotates, driving the angular flow guide 303 on the flow guide 302 to rotate, and under this preferred condition, the purity of the acrolein product is higher.

[0038] According to some preferred embodiments of the present application, the rotation rate of the flow guide 302 is 4 r / min-10 r / min, and under this preferred condition, the yield and purity of the acrolein product are higher.

[0039] According to some preferred embodiments of the present application, the angular flow guide 303 is at least one of a butterfly-shaped angular flow guide, a fan-shaped angular flow guide, a triangular angular flow guide, and a square-shaped angular flow guide.

[0040] According to some particularly preferred embodiments of the present application, as shown in Figure 3 、 Figure 4 the angular flow guide 303 is a butterfly-shaped angular flow guide. Under this preferred condition, the purity of the acrolein product is higher.

[0041] According to some preferred embodiments of the present application, as shown in Figure 1 in the skid-mounted acrolein production device, a preheater 5 is further connected between the metering pump 4 and the reaction vessel 10, and a heating source is arranged inside or outside the preheater 5, and the heating source is used to heat the preheater 5; and the method further comprises: introducing the mixed raw materials into the preheater 5 for preheating treatment by the metering pump 4, and then introducing the mixed raw materials into the reaction medium in the reaction vessel 10 for dehydration reaction. Under this preferred condition, the generation of by-products can be effectively reduced, and the yield and purity of acrolein are further improved.

[0042] According to some particularly preferred embodiments of the present application, the preheating treatment temperature is 150°C-200°C, and the preheating treatment pressure is 0-0.1 MPa.

[0043] According to some particularly preferred embodiments of the present application, the outer side of the preheater 5 is provided with a heating jacket 16, and the heating jacket 16 is used to heat the preheater 5 to provide the temperature conditions required for the preheating treatment.

[0044] According to some preferred embodiments of the present application, as shown in Figure 1As shown in the pry-mounted acrolein production device, the reaction container 10 and the acrolein collector 12 are also communicated with a condenser 11; the method further comprises: the acrolein product is subjected to condensation treatment by the condenser 11, and then is collected and stored by the acrolein collector 12. Under the preferred condition, the collection of the acrolein product is more convenient.

[0045] According to some particularly preferred embodiments of the present application, the temperature of the condensation treatment is -4℃ to 5℃.

[0046] According to some particularly preferred embodiments of the present application, the condenser 11 is any one of a straight-tube condenser, a coil condenser, a shell-and-tube condenser, and a plate condenser.

[0047] According to some preferred embodiments of the present application, as shown in the pry-mounted acrolein production device, Figure 5 As shown in the pry-mounted acrolein production device, the pry-mounted acrolein production device is also provided with an automatic cleaning system 6, the automatic cleaning system 6 comprises a circulating pump 14 and a filter 15, one end of the circulating pump 14 is communicated with the filter 15, the other end is communicated with the bottom of the reaction container 10, the other end of the filter 15 communicated with the circulating pump 14 is communicated with the upper part of the reaction container 10. When the automatic cleaning system 6 works, the mixture in the reaction container 10 flows through the filter 15 through the circulating pump 14, and after the solid particle by-products are filtered out by the filter 15, the remaining filtrate is recycled back to the reaction container 10. Under the preferred condition, the by-products in the reaction medium can be effectively removed, and the continuous working time of the pry-mounted acrolein production device can be greatly prolonged.

[0048] According to some preferred embodiments of the present application, as shown in the pry-mounted acrolein production device, Figure 1 As shown in the pry-mounted acrolein production device, the pry-mounted acrolein production device further comprises a glycerol reservoir 1 and an ionic liquid catalyst reservoir 2, the glycerol reservoir 1 is communicated with the glycerol inlet port 304 of the mixer 3, and the ionic liquid catalyst reservoir 2 is communicated with the ionic liquid catalyst inlet port 305 of the mixer 3. The glycerol reservoir 1 is used to store glycerol and provide glycerol for the mixer 3; the ionic liquid catalyst reservoir 2 is used to store ionic liquid catalyst and provide ionic liquid catalyst for the mixer 3.

[0049] According to some preferred embodiments of the present application, the reaction container 10 is further provided with at least one of a heating element 13, a temperature sensor 7, a pressure sensor 9, and a stirring element 8.

[0050] According to some particularly preferred embodiments of the present application, as shown in the pry-mounted acrolein production device, Figure 1As shown, the heating element 13 is located at the bottom of the reaction vessel 10 and is used to heat the mixture inside the reaction vessel 10 to provide the required temperature conditions for the dehydration reaction.

[0051] According to some particularly preferred embodiments of the present invention, such as Figure 1 As shown, the temperature sensor 7 is located at the lower part of the reaction vessel 10. When the skid-mounted acrolein production equipment is working normally, the temperature sensor 7 is located below the surface of the reaction medium liquid in the reaction vessel 10. The temperature sensor 7 is used to monitor the temperature of the reaction medium or mixture in the reaction vessel 10.

[0052] According to some particularly preferred embodiments of the present invention, such as Figure 1 As shown, the pressure sensor 9 is located at the top of the reaction vessel. When the skid-mounted acrolein production equipment is working normally, the pressure measuring element of the pressure sensor 9 is located above the liquid surface of the reaction medium inside the reaction vessel 10. The pressure sensor 9 is used to monitor the gas pressure inside the reaction vessel 10.

[0053] According to some particularly preferred embodiments of the present invention, such as Figure 1 As shown, the reaction vessel 10 is also equipped with a stirring element 8, which is used to stir the mixture in the reaction vessel 10 so that the dehydration reaction can be carried out more fully.

[0054] According to some particularly preferred embodiments of the present invention, the stirring element 8 is any one of a plow-type stirring element, a ribbon-type stirring element, a paddle-type stirring element, or a twin-shaft paddle-type stirring element.

[0055] According to some preferred embodiments of the present invention, the acrolein collector 12 is further provided with a vent valve 18, which is used to vent the impurity gas collected during the collection of the acrolein and balance the gas pressure inside the acrolein collector 12.

[0056] According to some preferred embodiments of the present invention, the feed inlet of the reaction vessel 10 is located at the bottom of the reaction vessel 10, the feed inlet is used to introduce the mixed raw material into the reaction vessel 10, and a check valve 19 is provided at the feed inlet to prevent the mixed raw material delivered to the reaction vessel 10 from flowing back.

[0057] According to some particularly preferred embodiments of the present invention, the check valve 19 is any one of a butterfly check valve, a lift check valve, or a swing check valve.

[0058] According to some preferred embodiments of the present application, the pry-mounted acrolein production device further comprises a control system 17 connected to the glycerol reservoir 1, the ionic liquid catalyst reservoir 2, the mixer 3, the metering pump 4, the preheater 5, the automatic cleaning system 6, the temperature sensor 7, the stirring element 8, the pressure sensor 9, the reaction vessel 10, the condenser 11, the acrolein collector 12, the heating element 13, the circulating pump 14, the filter 15, the heating jacket 16, the vent valve 18, and the check valve 19 through wired or wireless connection, and the control system 17 is used to control the normal operation of the pry-mounted acrolein production device.

[0059] The present application will be described in detail below through examples. In the following examples:

[0060] Ionic liquid catalyst I: mixed by N-butyl pyridine hydrogen sulfate and methyl imidazole chloride with a weight ratio of 1:3, wherein the N-butyl pyridine hydrogen sulfate is purchased from Beijing Huaweiruke Chemical Co., Ltd., with a brand of HWG16703; the methyl imidazole chloride is purchased from Tianjin Xinsisheng Chemical Co., Ltd., with a brand of A-24589;

[0061] Ionic liquid catalyst II: mixed by N-propyl sulfonic acid pyridine hydrogen sulfate and methyl butyl imidazole sulfate with a weight ratio of 1:2, wherein the N-propyl sulfonic acid pyridine hydrogen sulfate is purchased from Beijing Huaweiruke Chemical Co., Ltd., with a brand of HWG1921; the methyl butyl imidazole sulfate is purchased from Zhengzhou Deguan Kai Chemical Co., Ltd., with a purity of 98%;

[0062] Reaction medium: heat-conducting oil L-QD350, Shenyang Xueli Chemical Co., Ltd.

[0063] Glycerol, with a purity of 99wt%.

[0064] Example 1

[0065] The pry-mounted acrolein production device comprises:

[0066] The pry-mounted acrolein production device comprises: Figure 3 Figure 4 ​As shown, the first flow guide, the second flow guide and the third flow guide are respectively arranged in the cavity 301 at a distance of h / 2 from the bottom and at a distance of 0 from the center of the cross section, the second flow guide and the third flow guide are respectively arranged on the two sides of the first flow guide, the second flow guide and the third flow guide are respectively arranged in the cavity 301 at a distance of h / 4 from the bottom and at a distance of r / 3 from the center of the cross section, and the first flow guide, the second flow guide and the third flow guide are parallel to each other, 5 corner flow guides 303 are arranged on each flow guide 302, the angle α between the corner flow guide 303 and the flow guide 302 is 25°, and the setting direction of the corner flow guide 303 is opposite to the flow direction of the material in the mixer 3.

[0067] The pry-mounted acrolein production equipment further comprises a glycerol reservoir 1 and an ionic liquid catalyst reservoir 2, the glycerol reservoir 1 is in communication with the glycerol inlet 304 of the mixer 3, and the ionic liquid catalyst reservoir 2 is in communication with the ionic liquid catalyst inlet 305 of the mixer 3.

[0068] In the pry-mounted acrolein production equipment, the metering pump 4 is further in communication with the preheater 5 outside the reaction container 10.

[0069] The pry-mounted acrolein production equipment further comprises an automatic cleaning system 6, the automatic cleaning system 6 comprises a circulating pump 14 and a filter 15, one end of the circulating pump 14 is in communication with the filter 15, the other end is in communication with the bottom of the reaction container 10, and the other end of the filter 15 in communication with the circulating pump 14 is in communication with the upper part of the reaction container 10.

[0070] In the pry-mounted acrolein production equipment, the reaction container 10 is further in communication with the condenser 11 outside the acrolein collector 12.

[0071] The reaction container 10 further comprises a heating element 13, a temperature sensor 7, a pressure sensor 9 and a stirring element 8.

[0072] The pry-mounted acrolein production equipment further comprises a control system 17, and the control system 17 is used for controlling the operation of the pry-mounted acrolein production equipment.

[0073] A method for preparing acrolein is provided.

[0074] S1: introducing the glycerol in the glycerol reservoir 1 and the ionic liquid catalyst in the ionic liquid catalyst reservoir 2 into the mixer 3 to mix to obtain a mixed raw material, and the rotation rate of the flow guide 302 in the mixer 3 is 5 r / min.

[0075] S2: the mixed raw materials are introduced into the preheater 5 by the metering pump 4 for preheating, and then introduced into the reaction medium in the reaction vessel 10 for dehydration reaction to generate gaseous acrolein products, which are condensed by the condenser 11 and then collected and stored by the acrolein collector 12; wherein the amount of the reaction medium in the reaction vessel 10 is 10 kg, and the stirring rate of the stirring member in the reaction vessel 10 is 8 r / min.

[0076] During the processes in steps S1 and S2, the mixture in the reaction vessel 10 is also cleaned by the automatic cleaning system 6.

[0077] Specifically, the parameters in the preparation process are shown in Table 1.

[0078] Example 2

[0079] The skid-mounted acrolein production equipment is the same as that in Example 1.

[0080] The method for preparing acrolein refers to Example 1, except that the type and amount of the ionic liquid catalyst and the feeding rate of the mixed raw materials are changed. Specifically, the parameters in the preparation process are shown in Table 1.

[0081] Example 3

[0082] The skid-mounted acrolein production equipment refers to Example 1, except that the skid-mounted acrolein production equipment does not include the preheater 5 and the automatic cleaning system 6, and the preparation of acrolein does not include preheating and cleaning of the reaction medium. Specifically, the skid-mounted acrolein production equipment includes:

[0083] The skid-mounted acrolein production equipment includes:

[0084] The skid-mounted acrolein production equipment includes a mixer 3, a metering pump 4, a reaction vessel 10 and an acrolein collector 12 connected in sequence, wherein, as shown in Figure 2 The mixer 3 includes a cavity 301 and a flow guide 302 arranged in the cavity 301 and parallel to the ground, the cavity 301 is provided with a glycerol inlet 304, an ionic liquid catalyst inlet 305 and a mixed raw material outlet 306, the setting points of the glycerol inlet 304 and the ionic liquid catalyst inlet 305 are higher than the flow guide 302, the setting point of the mixed raw material outlet 306 is lower than the flow guide 302, and the number of the flow guide 302 is 3, as shown in Figure 3 , Figure 4As shown, the first flow guide, the second flow guide and the third flow guide are respectively arranged in the cavity 301 at a distance of h / 2 from the bottom, passing through the center of the cross section, and the second flow guide and the third flow guide are respectively arranged on both sides of the first flow guide at a distance of h / 4 from the bottom and a distance of r / 3 from the center of the cross section, and the first flow guide, the second flow guide and the third flow guide are parallel to each other, and five corner flow guides 303 are arranged on each of the flow guides 302, the angle a between the corner flow guide 303 and the flow guide 302 is 25°, and the setting direction of the corner flow guide 303 is opposite to the flow direction of the material in the mixer 3.

[0085] The pry-mounted acrolein production equipment further comprises a glycerol reservoir 1 and an ionic liquid catalyst reservoir 2, the glycerol reservoir 1 is in communication with the glycerol inlet 304 of the mixer 3, and the ionic liquid catalyst reservoir 2 is in communication with the ionic liquid catalyst inlet 305 of the mixer 3.

[0086] In the pry-mounted acrolein production equipment, a condenser 11 is further in communication between the reaction container 10 and the acrolein collector 12.

[0087] The reaction container 10 further comprises a heating element 13, a temperature sensor 7, a pressure sensor 9 and a stirring element 8.

[0088] The pry-mounted acrolein production equipment further comprises a control system 17 for controlling the operation of the pry-mounted acrolein production equipment.

[0089] A method for preparing acrolein:

[0090] S1: introducing the glycerol in the glycerol reservoir 1 and the ionic liquid catalyst in the ionic liquid catalyst reservoir 2 into the mixer 3 to mix to obtain a mixed raw material; the rotation rate of the flow guide 302 in the mixer 3 is 5 r / min;

[0091] S2: introducing the mixed raw material into the reaction medium in the reaction container 10 by the metering pump 4 to perform a dehydration reaction to generate a gaseous acrolein product, and the gaseous acrolein product is condensed by the condenser 11 and then collected and stored by the acrolein collector 12; wherein the amount of the reaction medium in the reaction container 10 is 10 kg, and the stirring rate of the stirring element in the reaction container 10 is 8 r / min.

[0092] Specifically, the parameters in the preparation process are shown in Table 1.

[0093] Comparative Example 1

[0094] The pry-mounted acrolein production device is the reference embodiment 3, different is, the pry-mounted acrolein production device in the mixer 3 is not provided with the flow guide piece 302 and the angle flow piece 303, specifically, the pry-mounted acrolein production device includes:

[0095] Including the mixer 3, the metering pump 4, the reaction container 10 and the acrolein collector 12 connected in sequence, wherein, as shown in the figure, the mixer 3 includes the cavity 301, the cavity 301 is provided with the glycerol inlet 304, the ionic liquid catalyst inlet 305 and the mixed raw material outlet 306 Figure 6

[0096] The pry-mounted acrolein production device further includes the glycerol reservoir 1 and the ionic liquid catalyst reservoir 2, the glycerol reservoir 1 is communicated with the glycerol inlet 304 of the mixer 3, and the ionic liquid catalyst reservoir 2 is communicated with the ionic liquid catalyst inlet 305 of the mixer 3;

[0097] In the pry-mounted acrolein production device, the reaction container 10 is further communicated with the condenser 11 between the acrolein collector 12;

[0098] The reaction container 10 is further provided with a heating element 13, a temperature sensor 7, a pressure sensor 9 and a stirring element 8;

[0099] The pry-mounted acrolein production device further includes a control system 17 for controlling the operation of the pry-mounted acrolein production device.

[0100] The method for preparing acrolein includes the following steps:

[0101] S1: introducing the glycerol in the glycerol reservoir 1 and the ionic liquid catalyst in the ionic liquid catalyst reservoir 2 into the mixer 3 to mix to obtain the mixed raw material;

[0102] S2: introducing the mixed raw material into the reaction container 10 through the metering pump 4 to carry out the dehydration reaction to generate the gaseous acrolein product, and the gaseous acrolein product is collected and stored by the acrolein collector 12 after being condensed by the condenser 11; wherein the stirring rate of the stirring element in the reaction container 10 is 8r / min.

[0103] It should be noted that the reaction container 10 of the present comparative example has no reaction medium, and the specific parameters such as the type of ionic liquid catalyst and the introduction rate of mixed raw material are shown in Table 1.

[0104] Table 1

[0105]

[0106] ​

[0107] Note:

[0108] V1 represents the rate of introducing the mixed raw materials into the reaction container 10;

[0109] V2 represents the rate of collecting the acrolein product into the acrolein collector 12;

[0110] The cleaning treatment represents the filtering and impurity removal treatment of the mixed materials in the reaction container 10 by the automatic cleaning system 6 during the preparation process;

[0111] The acrolein purity represents the purity of acrolein in the acrolein product collected into the acrolein collector 12;

[0112] The continuous operation time limit represents the time during which the skid-mounted acrolein production device can continuously operate under the condition. It should be noted that some by-products are produced during the preparation of acrolein, and the excessive accumulation of by-products will affect the normal progress of the dehydration reaction, and the excessive accumulation of by-products will also cause damage to the skid-mounted acrolein production device.

[0113] As can be seen from the results in Table 1, the method provided by the present application can prepare acrolein without the presence of fluidized gas, the parameters during the preparation process are easy to control, the acrolein production efficiency is high, the purity of the acrolein product is high, the production capacity, production rate and production time limit can be adjusted according to actual needs, acrolein can be produced on site in an oilfield that needs to treat sewage, that is, it can be used immediately after production, which solves the technical problem that acrolein is difficult to apply to oilfield sewage treatment due to its extremely unstable nature, difficult to store and transport, and can realize the industrial application of acrolein in the field of oilfield sewage treatment.

[0114] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A process for the industrial production of acrolein, characterized in that, The method is carried out in a pry-mounted acrolein production device, the pry-mounted acrolein production device comprising a mixer (3), a metering pump (4), a reaction container (10) and an acrolein collector (12) connected in sequence, wherein the mixer (3) comprises a cavity (301) and a flow guide (302) arranged in the cavity (301) and parallel to the ground, the cavity (301) is provided with a glycerol inlet (304), an ionic liquid catalyst inlet (305) and a mixed raw material outlet (306), the setting points of the glycerol inlet (304) and the ionic liquid catalyst inlet (305) are higher than the flow guide (302), the setting point of the mixed raw material outlet (306) is lower than the flow guide (302), a plurality of angle flow guides (303) are arranged on each flow guide (302), the angle between the angle flow guide (303) and the flow guide (302) is 10°-60°, the setting direction of the angle flow guide (303) is opposite to the flow direction of the material in the mixer (3); the flow guide (302) is a rotating flow guide, and the angle flow guide (303) is at least one of a butterfly-shaped angle flow guide, a fan-shaped angle flow guide, a triangular angle flow guide and a square angle flow guide; The method comprises the following steps: S1: mixing glycerol and ionic liquid catalyst in the mixer (3) to obtain mixed raw materials, wherein the ionic liquid catalyst comprises pyridine ionic liquid and imidazole ionic liquid, and the weight ratio of the pyridine ionic liquid to the imidazole ionic liquid in the ionic liquid catalyst is 1:(1-5), and the mixed weight ratio of the glycerol to the ionic liquid catalyst is 1:0.01-0.05; The pyridine ionic liquid is at least one of N-butyl pyridine hydrogen sulfate, N-propyl sulfonic acid pyridine hydrogen sulfate, N-butyl pyridine hydrogen phosphate and propyl sulfonic acid pyridine phosphate; The imidazole ionic liquid is at least one of methyl imidazole chloride, methyl propyl sulfonic acid imidazole sulfate and methyl propyl sulfonic acid imidazole phosphate, The structure of the N-butyl pyridine hydrogen phosphate is shown in the following formula I, the structure of the propyl sulfonic acid pyridine phosphate is shown in the following formula II, the structure of the methyl propyl sulfonic acid imidazole sulfate is shown in the following formula III, and the structure of the methyl propyl sulfonic acid imidazole phosphate is shown in the following formula IV: Formula I; Formula II; Formula III; Formula IV; S2: introducing the mixed raw materials into a reaction medium in the reaction container (10) through the metering pump (4) to carry out a dehydration reaction to generate acrolein products, and the acrolein products are collected and stored by the acrolein collector (12), wherein the introduction rate of the mixed raw materials is 0.5g / min-50g / min per 1kg of reaction medium.

2. The method of claim 1, wherein, The ionic liquid catalyst is a mixture of the N-butyl pyridine hydrogen sulfate and the methyl imidazole chloride.

3. The method of claim 2, wherein, In the ionic liquid catalyst, the weight ratio of the N-butyl pyridine hydrogen sulfate to the methyl imidazole chloride is 1:(2-4).

4. The method of claim 1, wherein, The reaction medium is at least one of heat-conducting oil, triphenyl phosphate, t-butyl diphenyl phosphate and triisobutyl phenyl phosphate.

5. The method of claim 1, wherein, The dehydration reaction temperature is 280-310 DEG C, and the reaction pressure is 0-0.1 MPa.

6. The method of claim 1, wherein, The height of the cavity (301) is h, and the distance between the flow guide (302) and the bottom of the cavity (301) is h / 6-2h / 3.

7. The method of claim 1, wherein, The cavity (301) is cylindrical, the cross-sectional radius of the cavity (301) is r, and the distance between the flow guide (302) and the center of the cross section of the cavity (301) is not greater than 2r / 3.

8. The method according to any one of claims 1 to 7, characterized in that, The pry-mounted acrolein production equipment further comprises a preheater (5) communicated between the metering pump (4) and the reaction vessel (10). The method further comprises: introducing the mixed raw materials into the preheater (5) for preheating treatment, and then introducing the mixed raw materials into the reaction medium in the reaction vessel (10) for dehydration reaction.

9. The method of claim 8, wherein, The preheating treatment temperature is 150-200 DEG C, and the preheating treatment pressure is 0-0.1 MPa.

10. The method according to any one of claims 1-7, characterized in that, The pry-mounted acrolein production equipment further comprises a condenser (11) communicated between the reaction vessel (10) and the acrolein collector (12). The method further comprises: condensing the acrolein product by the condenser (11), and then collecting and storing the acrolein product by the acrolein collector (12).

11. The method of claim 10, wherein, The condensing treatment temperature is -4 DEG C to 5 DEG C.

12. The method according to any one of claims 1-7, characterized in that, The pry-mounted acrolein production equipment further comprises an automatic cleaning system (6), the automatic cleaning system (6) comprises a circulating pump (14) and a filter (15), one end of the circulating pump (14) is communicated with the filter (15), the other end is communicated with the bottom of the reaction vessel (10), and the other end of the filter (15) communicated with the circulating pump (14) is communicated with the upper part of the reaction vessel (10).

13. The method of any of claims 1-7, wherein, The pry-mounted acrolein production equipment further comprises a glycerol reservoir (1) and an ionic liquid catalyst reservoir (2), the glycerol reservoir (1) is communicated with the glycerol inlet port (304) of the mixer (3), and the ionic liquid catalyst reservoir (2) is communicated with the ionic liquid catalyst inlet port (305) of the mixer (3).

14. The method of any of claims 1-7, wherein, The reaction vessel (10) further comprises at least one of a heating element (13), a temperature sensor (7), a pressure sensor (9), and a stirring element (8).

15. The method of any of claims 1-7, wherein, The pry-mounted acrolein production equipment further comprises a control system (17) for controlling the operation of the pry-mounted acrolein production equipment.

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