CN115301172A - System and method for continuously preparing carbamide peroxide by using microreactor - Google Patents

System and method for continuously preparing carbamide peroxide by using microreactor Download PDF

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CN115301172A
CN115301172A CN202210786443.2A CN202210786443A CN115301172A CN 115301172 A CN115301172 A CN 115301172A CN 202210786443 A CN202210786443 A CN 202210786443A CN 115301172 A CN115301172 A CN 115301172A
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CN115301172B (en
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陈光文
廉应江
韩梅
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Dalian Institute of Chemical Physics of CAS
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    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
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    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/007—Feed or outlet devices as such, e.g. feeding tubes provided with moving parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J4/008—Feed or outlet control devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/007—Aspects relating to the heat-exchange of the feed or outlet devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/00864—Channel sizes in the nanometer range, e.g. nanoreactors
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    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00867—Microreactors placed in series, on the same or on different supports
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention belongs to the technical field of chemical industry, and particularly relates to a system and a method for continuously preparing carbamide peroxide by a microreactor. The system is formed by connecting a first-stage microreactor, a second-stage extension filler reaction tube and a cooling kettle in series. Firstly, raw materials of urea aqueous solution and hydrogen peroxide are mixed in a microreactor to react, the generated reaction liquid enters an extension filler reaction tube to complete the reaction, and finally the material enters a cooling kettle, and carbamide peroxide is crystallized and separated out in the cooling kettle. The invention adopts the microreactor to realize the continuous preparation of the carbamide peroxide, simplifies the process flow, has short reaction period, improves the safety and controllability of the preparation process, and has the yield of the carbamide peroxide of more than 85 percent and the oxygen content of the product of more than 15.58 percent.

Description

System and method for continuously preparing carbamide peroxide by using microreactor
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a device for preparing carbamide peroxide and a using method thereof.
Background
Urea Peroxide (also called carbamide Peroxide) is an adduct of hydrogen Peroxide and Urea and has the formula CO (NH) 2 ) 2 ·H 2 O 2 The appearance is white crystal powder, flake or granule, and can be dissolved in organic solvent. The industrial production of urea peroxide starts in japan. At present, the main production countries are the United states, japan and the like, and in recent years, foreign development and application have been greatly developed, and the production process is mature.
The carbamide peroxide has wide application in the fields of pharmacy, daily chemicals, agricultural breeding, textile, food, feed, printing and dyeing, metallurgy, building and the like. Compared with peroxides such as sodium percarbonate, calcium peroxide and the like, the carbamide peroxide has the advantages of high active oxygen content, neutral aqueous solution, weak skin irritation, small damage to textiles and the like, is expected to replace other oxidants such as calcium peroxide, sodium perborate and sodium percarbonate in production and life, and has wide application prospect.
At present, two synthesis processes of urea peroxide are available, namely a dry method and a wet method. The dry process has the advantages of short flow, simple process, high yield and the like, but the process requires high hydrogen peroxide concentration, complex equipment, harsh technical conditions, high energy consumption and poor product stability, and hydrogen peroxide and urea belong to liquid-solid reaction in the production process, so that the hydrogen peroxide and urea are easy to mix unevenly to cause incomplete reaction and influence the product quality. Because of the high price of high-concentration hydrogen peroxide, the process is difficult to realize large-scale industrial production.
The wet process adopts low-concentration hydrogen peroxide as a raw material, and the hydrogen peroxide reacts with urea in a liquid phase, so that the product quality is relatively stable. Although the wet production equipment is simple, the technical conditions are easy to achieve, and the product stability is good, the process flow is long, and the concentration of hydrogen peroxide can be diluted by using the urea aqueous solution, so that the defects of slow reaction, high energy consumption, reduced yield and the like are caused. At present, most production enterprises adopt an intermittent kettle wet preparation process.
Compared with a conventional batch kettle, the microreactor has the advantages of high heat and mass transfer coefficients, good mixing performance, easy temperature control, safe and controllable process and the like. The micro-reactor has excellent heat transfer and mass transfer capacity, and can realize uniform mixing of materials and high-efficiency transfer of reaction heat. The efficient mass transfer and heat transfer characteristics of the microreactor are utilized to realize the heat transfer and mass transfer in the urea peroxide preparation process, the mixing efficiency of urea and hydrogen peroxide is improved, the urea and hydrogen peroxide are fully reacted, and the process safety is improved. A microreactor is adopted to prepare carbamide peroxide, and a new method and means are provided for solving the problems in the batch kettle preparation process. Therefore, novel efficient and safe continuous preparation equipment and method are problems to be solved urgently.
Disclosure of Invention
Aiming at the characteristics of the process of preparing the urea peroxide by the batch still wet method, the invention provides a system and a method for continuously preparing the urea peroxide by using a microreactor, which can enhance the mass transfer and reaction heat transfer capacity in the reaction process, remarkably reduce the volume and reaction time of the batch reactor, and improve the conversion rate of raw materials, the utilization rate of hydrogen peroxide and the process safety by using the efficient mixing and excellent mass transfer and heat transfer characteristics of the microreactor. Meanwhile, the combination of the micro-reactor and the cooling kettle improves the production efficiency. Compared with the traditional intermittent preparation method, the method can realize the continuous production of urea peroxide, has high raw material conversion rate, high hydrogen peroxide utilization rate, environmental friendliness, high process safety, product yield of more than 90 percent and oxygen content of more than 16.80 percent, and has important commercial value.
The technical scheme adopted by the invention is as follows:
on one hand, the invention provides a micro-reaction system for preparing urea peroxide, which comprises two micro-reactors and a cooling kettle, wherein the micro-reactors are a first-stage micro-reactor and a second-stage extension filler reaction tube, and the first-stage micro-reactor, the second-stage extension filler reaction tube and the cooling kettle are sequentially connected in series; the first-stage microreactor is internally provided with micro heat exchange equipment, the second-stage extension filler reaction tube is connected with heat exchange equipment, and the temperature of the reaction system is controlled through the micro heat exchange equipment and the heat exchange equipment.
Based on the technical scheme, preferably, the first-stage microreactor is connected with the second-stage extension filler reaction tube through a pipeline, and the second-stage extension tube reactor is connected with the cooling kettle through a pipeline.
Based on the technical scheme, preferably, the first-stage microreactor comprises a microchannel reactor, a microjet reactor or a microporous mixing reactor, a microheat exchanger is arranged in the first-stage microreactor, the microheat exchanger is a fin type heat exchanger, the second-stage prolonged reaction tube is a sleeve type heat exchanger, the inner part of the sleeve type heat exchanger is a second-stage prolonged reaction tube, and the diameter of an external sleeve of the second-stage prolonged reaction tube is 19mm multiplied by the thickness of 1.5mm.
Based on the technical scheme, preferably, the hydraulic diameter of the microchannel reactor is 0.1-5 mm; the hydraulic diameter of the micro jet reactor is 0.5-10 mm; the diameter of the micropore type mixing reactor is 0.1-5 mm.
Based on the technical scheme, preferably, the second-stage extension filler reaction tube has an inner diameter of 4-8mm, preferably 4-6mm, a length of 100-800 cm and a thickness of 1mm, is made of stainless steel, and is filled with 1.5 x 1.5mm of triangular spiral filler or other reinforced mixed filler. 4-68-4
Based on the technical scheme, preferably, the cooling kettle is a common glass kettle or a metal kettle, and the temperature of the cooling kettle is controlled by an external coolant so that the carbamide peroxide is crystallized and separated out in the cooling kettle.
On the other hand, the invention provides a method for continuously preparing urea peroxide by using a micro-reactor, wherein the micro-reaction system is used, a urea aqueous solution and a hydrogen peroxide solution are mixed and react in a first-stage micro-reactor, a reaction solution is formed after the reaction solution passes through the first-stage micro-reactor, then the reaction solution is continuously mixed and continuously reacted in a second-stage extension filler reaction tube until the raw materials are completely converted, the raw materials flow out and enter a cooling kettle, the temperature of the cooling kettle is controlled, the generated product urea peroxide is crystallized and separated out, and the product urea peroxide is obtained by suction filtration.
Based on the technical scheme, preferably, the urea aqueous solution is prepared firstly, so that the mass concentration of the urea is 10wt% -50 wt%, and the used solvent is water.
Based on the technical scheme, the concentration of the hydrogen peroxide solution is preferably 25-50%.
Based on the technical scheme, preferably, a urea solution and a hydrogen peroxide solution are mixed and reacted in the microreactor, and the molar ratio of urea to hydrogen peroxide is 1.0-1.3.
Based on the technical scheme, the reaction temperature of the materials in the microreactor is preferably 20-60 ℃.
Based on the technical scheme, the temperature in the cooling kettle is preferably controlled to be 0-5 ℃.
Based on the technical scheme, the total residence time of the materials in the microreactor is preferably 0.5-3 minutes.
The method for continuously preparing urea peroxide by using the microreactor specifically comprises the following steps:
(1) Preparing a urea solution: adding urea into water at room temperature, stirring to completely dissolve the urea to form a transparent urea aqueous solution, wherein the mass concentration of the urea is 50wt% or other concentrations;
(2) The concentration of hydrogen peroxide is 25-50%;
(3) The urea solution and the hydrogen peroxide solution are input into the first-stage microreactor through two continuous conveying devices for mixing and reacting, the formed reaction liquid enters the second-stage extension filler reaction tube for continuous reaction, the reaction temperature of the first-stage microreactor and the tubular reactor is controlled through the micro heat exchange device and the heat exchange device, and the reaction liquid flows into the cooling kettle after the raw materials are completely converted.
(4) Controlling the temperature of the cooling kettle at 0-5 ℃, and cooling and crystallizing the material after the material enters the cooling kettle to separate out the product.
The invention has the beneficial effects that: (1) The continuous preparation of carbamide peroxide in the microreactor is realized; (2) Compared with an intermittent kettle wet method for preparing carbamide peroxide, the method has the advantages that the micro jet flow reactor is adopted for continuous preparation, and the flow rate of reaction liquid is controlled, so that the mixing efficiency is high, the mass transfer and heat transfer are high, the temperature in the reaction process is controllable, the product yield and the oxygen content are high, and the like; (3) The micro-reactor has small volume, simplifies the process flow and is easy to amplify; (4) The materials in the reactor can be quickly and fully mixed and reacted and then flow out of the reactor, so that the retention time of reaction liquid in the reactor is shortened, and hydrolysis and other side reactions of products are avoided; (5) The controllability of the preparation process is improved, the safety of the production process is high, and the safety risk caused by heat release in the reaction process is avoided, so that the yield and the product quality of the reaction product are improved, the yield of carbamide peroxide reaches over 85 percent, and the oxygen content of the product is over 15.58 percent. (6) The process of the invention uses water as solvent, has no organic solvent, can recycle filtrate, has environment-friendly production process and has high commercial value.
The characteristic advantages of the invention are apparent from the description of the examples which follow.
Drawings
FIG. 1 is a flow chart of the present invention for continuous preparation of carbamide peroxide.
In the figure, 1 is a constant flow pump, 2 is a micro jet reactor, 3 is an extended packed tubular reactor, and 4 is a cooling kettle.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following examples are provided to further illustrate the present invention, but the scope of the present invention is not limited by these examples. The reagents used in the examples are commercially available reagents, and the technical means used in the examples are conventional means known to those skilled in the art.
Example 1 microreactor continuous preparation of carbamide peroxide
As shown in fig. 1, a micro-reaction system for preparing urea peroxide comprises a micro-jet reactor 2, an extended filler tubular reactor 3 and a cooling kettle 4, wherein the micro-jet reactor 2, the extended filler tubular reactor 3 and the cooling kettle 4 are connected in series in sequence; the micro jet reactor 2 is connected with two constant flow pumps 1, and the extension filler tubular reactor 3 is connected with the cooling kettle 4 through a pipeline. The micro heat exchanger is arranged in the first-stage micro reactor, the micro heat exchanger is a fin type heat exchanger, the extension filler tubular reactor 3 is provided with heat exchange equipment and is a sleeve type heat exchanger, and the diameter of an external sleeve of the extension filler tubular reactor 3 is 19mm multiplied by the thickness of 1.5mm. The temperature of the reaction system is controlled by a micro heat exchanger and a double-pipe heat exchanger. The hydraulic diameter of the micro jet reactor 2 is 0.25mm, and the length is 700cm; the extended packing tubular reactor 3 is a stainless steel tube having an inner diameter of 4mm × a thickness of 1mm and a length of 500cm, and is filled with a triangular spiral packing having a diameter of 1.5 × 1.5mm and a hydraulic diameter of 1.0mm.
(1) Urea (1.67mol, 100g) was added to a 500ml single-neck flask, 100g of water was added thereto, and the mixture was dissolved by stirring to form a transparent urea aqueous solution having a urea mass concentration of 50.0wt% as a raw material phase A.30wt% of hydrogen peroxide solution is used as B.
(2) The flow rate of the two raw material phases A is 3.0ml/min, the flow rate of the raw material phase B is 3.1ml/min, the two raw material phases A and B are input into a micro-jet reactor 2 through two advection pumps 1, and the two raw material phases are fully mixed and reacted in the first-stage micro-jet reactor 2; the reaction materials are further continuously mixed and reacted in the second-stage extension filler tubular reactor 3, and the reaction materials flow out of the reactor and enter the cooling kettle 4 after being completely converted. Meanwhile, the reaction temperature of the micro jet reactor and the extended packing tubular reactor is controlled to be 30 ℃, and the reaction liquid flows out of the reactors after the total retention time of the reaction liquid in the two reactors is 1.6 min. And (3) feeding the reaction liquid into a cooling kettle, controlling the temperature of the cooling kettle to be 0-5 ℃, stirring and cooling to obtain a large amount of white solid product urea peroxide, and performing suction filtration to obtain the product urea peroxide, wherein the product yield is 86.8%, and the oxygen content is 16.57%.
Examples 2-5 microreactor continuous preparation of carbamide peroxide
The same system for the continuous preparation of carbamide peroxide as in example 1 was used. In the reaction process, the reaction temperatures were different, and in examples 2 to 5, the reaction temperatures were controlled to 35 ℃, 40 ℃, 45 ℃ and 50 ℃, respectively, and the specific results are shown in table 1.
TABLE 1 Effect of different temperatures on Urea peroxide yield and active oxygen content
Figure BDA0003728696240000051
Examples 6-8 continuous preparation of carbamide peroxide in microreactor
The same system for the continuous preparation of carbamide peroxide as in example 1 was used. Controlling the reaction temperature of the micro jet reactor 2 and the extended tubular reactor 3 to be 35 ℃, enabling reaction materials to enter the microreactor according to different flow rates, mixing and reacting and then flowing out of the reactors, wherein the flow rates of the materials A and B in the embodiment 6 are 3.0ml/min and 3.1ml/min respectively, and the total residence time of the reaction materials in the two reactors is 1.6 minutes; example 7 the flow rates of materials A and B were 6.0ml/min and 6.1ml/min, respectively, with a total residence time of the reaction mass in both reactors of 0.8 minutes; example 8 the flow rates of feed A and B were 9.0ml/min and 9.3ml/min, respectively, and the total residence time of the reaction mass in both reactors was 0.5 minutes. And (3) allowing the reaction solution to enter a cooling kettle with the temperature controlled at 0-5 ℃, stirring to obtain a large amount of white solid product carbamide peroxide, and performing suction filtration to obtain the product carbamide peroxide. The specific results are shown in Table 2.
TABLE 2 Effect of different residence times on Urea peroxide yield and active oxygen content
Figure BDA0003728696240000061
Examples 9-10 continuous preparation of carbamide peroxide by microreactor
The same system for the continuous preparation of carbamide peroxide as in example 1 was used. Controlling the reaction temperature of the micro jet reactor 2 and the extension tubular reactor 3 to be 35 ℃, wherein the phase A is urea aqueous solution with the mass concentration of 50.0wt%, and the phase B is hydrogen peroxide with the mass concentration of 30wt% and 50wt%, respectively. Two reaction materials enter the microreactor to mix and react according to different flow rates, the flow rates of the materials A and B are respectively 9.0ml/min and 9.3ml/min, and the reaction materials flow out of the reactors after the total residence time of the reaction materials in the two reactors is 30 seconds. And (3) allowing the reaction solution to enter a cooling kettle with the temperature controlled at 0-5 ℃, stirring to obtain a large amount of white solid product carbamide peroxide, and performing suction filtration to obtain the product carbamide peroxide. Specific results are shown in Table 3.
TABLE 3 Effect of different concentrations of hydrogen peroxide on carbamide peroxide yield and active oxygen content
Figure BDA0003728696240000062
By the system for continuously preparing the carbamide peroxide by the micro-jet reactor 2, the high-efficiency mass and heat transfer characteristics of the micro-jet reactor 2 are utilized, so that the problems of low raw material conversion rate and active oxygen content and production safety caused by reaction heat release in the production process in the prior art are effectively solved, and the raw material conversion rate, the active oxygen content of the product and the production safety are improved.
It will be understood by those skilled in the art that various modifications and changes may be made to the present invention. Such modifications and adaptations are intended to be within the scope of the present invention as defined by the claims.

Claims (9)

1. A micro-reaction system for continuously preparing carbamide peroxide in a micro-reactor is characterized by comprising a first-stage micro-reactor, a second-stage extension filler reaction tube and a cooling kettle, wherein the first-stage micro-reactor, the second-stage extension filler reaction tube and the cooling kettle are sequentially connected in series; the first-stage microreactor is provided with a micro heat exchange device, and the second-stage extension filler reaction tube is provided with a heat exchange device.
2. The system of claim 1, wherein the first stage microreactor comprises a micro-porous mixing reactor, a microchannel mixing reactor, a jet mixing reactor, or a impinging stream mixing reactor; and the second-stage extension filler reaction tube is internally provided with filler.
3. The system of claim 1, wherein the micro heat exchange device is a finned heat exchanger; the hydraulic diameter of the microchannel reactor is 0.1-5 mm; the hydraulic diameter of the micro jet reactor is 0.5-10 mm; the diameter of the micropore type mixing reactor is 0.1-5 mm.
4. The system of claim 1, wherein the second stage extended packing reaction tube has an inner diameter of 4 to 8mm, and the packing contained therein is a triangular spiral packing.
5. The system of claim 1, wherein the first stage microreactor houses a micro heat exchanger, wherein the micro heat exchanger is a finned heat exchanger; the second-stage extension reaction tube is a sleeve-type heat exchanger; the cooling kettle is a glass kettle or a metal kettle.
6. A method for continuously preparing carbamide peroxide in a microreactor uses the micro-reaction system as claimed in any one of claims 1-5, and is characterized in that a urea solution and a hydrogen peroxide solution are mixed and react in a first-stage microreactor, the formed reaction solution enters a second-stage extension filler reaction tube to continue mixing and reacting until the reaction is completed, the reaction solution enters a cooling kettle, and after cooling crystallization, the carbamide peroxide is obtained by suction filtration.
7. The method for preparing urea peroxide according to claim 6, wherein the reaction temperature is controlled to be 20-60 ℃ and the temperature of the cooling kettle is 0-5 ℃.
8. The method for preparing carbamide peroxide according to claim 6, wherein the molar ratio of urea to hydrogen peroxide is 1.0-1.3.
9. Process for urea peroxide according to claim 6, characterized in that the aqueous hydrogen peroxide solution used has a concentration comprised between 25 and 50%.
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