CN115779882A - Preparation method and application of activated carbon catalyst for phosgene synthesis - Google Patents
Preparation method and application of activated carbon catalyst for phosgene synthesis Download PDFInfo
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- CN115779882A CN115779882A CN202211573048.2A CN202211573048A CN115779882A CN 115779882 A CN115779882 A CN 115779882A CN 202211573048 A CN202211573048 A CN 202211573048A CN 115779882 A CN115779882 A CN 115779882A
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Abstract
The invention provides a preparation method and application of an activated carbon catalyst for phosgene synthesis, wherein the preparation method comprises the following steps: stirring and soaking the activated carbon in an acid solution, and then carrying out ultrasonic washing in water to obtain modified activated carbon; mixing a complexing agent, a solvent and the modified activated carbon, and performing complexing treatment to obtain the complex modified activated carbon; and sequentially drying and roasting the complex modified activated carbon to obtain the activated carbon catalyst. The acid solution and the specific complexing agent are utilized to modify the activated carbon, so that the content of metal ions such as Al, fe and the like influencing heat resistance in the activated carbon is controlled within a certain range, the heat resistance of the activated carbon is effectively improved, and the service cycle of the activated carbon is prolonged.
Description
Technical Field
The invention belongs to the field of phosgene synthesis, and particularly relates to a preparation method and application of an activated carbon catalyst for phosgene synthesis.
Background
Phosgene, also known as phosgene, has the flavor of rotten licorice, rotten apple. As an important organic synthesis intermediate, the compound is mainly applied to the fields of pesticides, coatings, dyes, initiators, medicines, fine chemicals, isocyanate and the like. Industrial production of phosgene predominantly based on CO and Cl 2 Phosgene is prepared as a starting material in a shell and tube reactor packed with a catalyst.
The phosgene synthesis principle is CO + Cl 2 →COCl 2 The reaction is strongly exothermic, the unit chlorine exotherm is 116kJ/mol, and the reaction heat needs to be removed in time because the exotherm is large. The existing phosgene synthesis reactor is mainly a vertical tubular fixed bed reactor with a tube side filled with an active carbon catalyst and a shell side provided with a cooling medium pair.
CN109289714A discloses a filling method of phosgene synthesis reaction catalyst, which reduces the loss of active carbon by filling 100-300mm large-particle ceramic balls at the upper and lower parts of an active carbon bed layer and covering 1-2 layers of screens. However, the reaction rate and the heat release rate cannot be reduced by the traditional filling mode, the temperature runaway is avoided, and the situation of activated carbon powder ablation is still serious.
CN110449147A discloses a catalyst for phosgene synthesis, a preparation method and an application thereof, the active components of the catalyst include activated carbon and carbon nanotubes, wherein the mass ratio of the carbon nanotubes to the activated carbon is 0.01-0.1: 1, preferably 0.02 to 0.08:1. the preparation method comprises the following steps: treating the activated carbon and the carbon nano tube in a nitric acid solution, taking out, washing and drying to obtain mixed powder of the activated carbon and the carbon nano tube; the mixed powder is evenly mixed with hydrochloric acid solution of polyvinyl alcohol and glutaraldehyde and kneaded into a plastic blank, extruded into strips for molding, and then cured, dried and roasted to obtain the catalyst for phosgene synthesis. The catalyst has high activity, high heat conductivity and high structural stability.
The existing mature technology and the technology with higher energy utilization rate have the contradiction: water is used as a cooling medium, so that high-grade steam cannot be generated, energy waste is caused, and corrosion risk is caused; and the high boiling point oil is used as a cooling medium, the operating temperature of the reaction tube is increased, the activated carbon has poor high temperature resistance and oxidation resistance, the activated carbon is easy to ablate and pulverize, the service cycle of the reactor is shortened, and the running stability of the device is poor.
Therefore, in order to improve the phosgene synthesis energy utilization rate and produce high-grade steam, the performance of the activated carbon needs to be improved, and the heat resistance of the activated carbon needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method and application of an activated carbon catalyst for phosgene synthesis, wherein the preparation method improves the heat resistance of the activated carbon catalyst for phosgene synthesis by accurately controlling the content of metal ions directly related to the heat resistance in the activated carbon for phosgene synthesis, so that the activated carbon catalyst can be suitable for a phosgene synthesis steam generation system, the safe and stable operation level of the device is improved, and the utilization efficiency of phosgene synthesis energy is also improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an activated carbon catalyst for phosgene synthesis, the method comprising the steps of:
(1) Stirring and soaking the activated carbon in an acid solution, and then carrying out ultrasonic washing in water to obtain modified activated carbon;
(2) Mixing a complexing agent, a solvent and the modified activated carbon obtained in the step (1), and performing complexing treatment to obtain the complexed modified activated carbon;
(3) And (3) drying and roasting the complex modified activated carbon obtained in the step (2) in sequence to obtain the activated carbon catalyst.
Firstly, reducing the content of metal ions in the activated carbon to a certain range by using an acid solution, then adding a specific complexing agent into the acid-washed activated carbon, and complexing the complexing agent with the residual metal ions to generate a complex which is attached to the surfaces of active carbon pore channels; on one hand, the content of metal ions such as Al, fe and the like which influence the heat resistance in the activated carbon can be controlled within a certain range, the heat resistance of the activated carbon is effectively improved, and the metal ions and the activated carbon in the phosgene synthesis process and the Cl in the phosgene synthesis reaction process are avoided 2 Halide is formed to further destroy the framework of the activated carbon, and on the other hand, the formed complex can also play a role in strengthening the framework, so that the aim of prolonging the service cycle of the activated carbon is fulfilled; the prepared activated carbon catalyst has the characteristics of difficult pulverization and high temperature resistance.
As a preferable technical scheme of the invention, the activated carbon in the step (1) comprises coconut shell activated carbon and/or coal-based activated carbon.
Preferably, the particle size of the activated carbon in step (1) is 2-7mm, for example, 2mm, 3mm, 4mm, 5mm, 6mm or 7mm, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 3-5mm.
Preferably, the mass ratio of the activated carbon and the acid solution in the step (1) is 1 (2.5-5), and may be, for example, 1.
Preferably, the mass concentration of the acid solution in the step (1) is 1% to 30%, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, etc., preferably 4% to 10%.
Preferably, the acid in the acid solution of step (1) comprises any one of hydrochloric acid, phosphoric acid or silicic acid or a combination of at least two of them, typical but non-limiting examples being: a combination of hydrochloric acid and phosphoric acid, a combination of phosphoric acid and silicic acid or a combination of silicic acid and hydrochloric acid, and the like.
As a preferred embodiment of the present invention, the temperature of the agitation soaking in the step (1) is 25 to 150 ℃, and may be, for example, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 70 ℃, 90 ℃, 120 ℃ or 150 ℃, but is not limited to the above-mentioned values, and other values not listed in the numerical range are also applicable, and preferably 40 to 70 ℃.
Preferably, the stirring soaking time in the step (1) is 3-5h, such as 3h, 3.4h, 3.8h, 4h, 4.4h, 4.8h or 5h, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the ultrasonic washing temperature in step (1) is 25-100 deg.C, such as 25 deg.C, 30 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C or 100 deg.C, but not limited to the enumerated values, and other values in the range of values are equally applicable, preferably 30-50 deg.C.
Preferably, the pulse frequency of the ultrasonic washing in the step (1) is 10-30kHz, such as 10kHz, 12kHz, 15kHz, 20kHz, 22kHz, 25kHz, 27kHz or 30kHz, etc., but not limited to the values listed, and other values not listed in the range of values are equally applicable, preferably 12-25kHz.
Preferably, the pulse width of the ultrasonic washing in step (1) is 50-500ms, such as 50ms, 100ms, 150ms, 200ms, 250ms, 300ms, 400ms or 500ms, but not limited to the enumerated values, and other unrecited values in the range of values are also applicable, preferably 100-450ms.
Preferably, the ultrasonic washing in step (1) is carried out for 1-20h, such as 1h, 3h, 5h, 7h, 10h, 12h, 15h, 17h or 20h, but not limited to the recited values, and other values not recited in the range of values are also applicable, preferably 5-10h.
Preferably, the agitation soaking and ultrasonic washing in the step (1) are alternately performed 1 to 5 times, for example, 1 time, 2 times, 3 times, 4 times or 5 times, etc., but not limited to the recited values, and other values not recited in the range of values are also applicable, preferably 2 to 3 times.
As a preferred embodiment of the present invention, the total content of the metal elements in the modified activated carbon in the step (1) is 5000 to 30000ppm, for example, 500ppm, 1000ppm, 5000ppm, 10000ppm, 15000ppm, 20000ppm, 25000ppm or 30000ppm, but not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 5000 to 15000ppm.
Preferably, the Al element content in the modified activated carbon in the step (1) is 1000-8000ppm, such as 1000ppm, 2000ppm, 3000ppm, 4000ppm, 5000ppm, 6000ppm, 7000ppm or 8000ppm, etc., but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 2000-5000ppm.
Preferably, the modified activated carbon in step (1) has an Fe element content of 1000-5000ppm, such as 1000ppm, 2000ppm, 3000ppm, 4000ppm or 5000ppm, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 1500-3000ppm.
As a preferred technical solution of the present invention, the complexing agent in step (2) includes any one of or a combination of at least two of rhodotricarboxylic acid ammonium salt, alizarin red S, alizarin violet, and ethylenediaminetetraacetic acid, and the combinations are exemplified by, typically but not limited to: a combination of ammonium rhodotricarboxylate and alizarin red S, a combination of alizarin red S and ethylenediaminetetraacetic acid or a combination of alizarin violet and ethylenediaminetetraacetic acid, and the like.
Preferably, in step (2), the mass ratio of the complexing agent to the modified activated carbon is (0.01-0.1): 1, and may be, for example, 0.01.
In the invention, the mass ratio of the complexing agent to the solvent in the step (2) is (0.01-0.1): 1, preferably (0.05-0.08): 1.
In the invention, the solvent in the step (2) comprises water.
Preferably, the step (2) of the complex treatment temperature is 20-100 degrees C, for example can be 20 degrees C, 30 degrees C, 40 degrees C, 50 degrees C, 60 degrees C, 70 degrees C, 80 degrees C, 90 degrees C or 100 degrees C, but not limited to the enumerated values, the range of other values are also applicable, preferably 40-50 degrees C.
Preferably, the complexing treatment in step (2) is carried out for 1-10h, such as 1h, 3h, 5h, 7h or 10h, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 4-7h.
Preferably, the complexing treatment in the step (2) further comprises ultrasonic washing.
In the present invention, the ultrasonic washing is performed at least three times.
Preferably, the ultrasonically washed lotion comprises water.
Preferably, the ultrasonic washing temperature is 25-80 ℃, for example, can be 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, but not limited to the enumerated values, the numerical range of other not enumerated values are also applicable, preferably 30-50 ℃.
Preferably, the pulse frequency of the ultrasonic washing is 10 to 30kHz, such as 10kHz, 12kHz, 15kHz, 20kHz, 22kHz, 25kHz, 27kHz or 30kHz, etc., but not limited to the cited values, and other values not listed in the range of values are equally applicable, preferably 12 to 25kHz.
Preferably, the pulse width of the ultrasonic washing is 50 to 500ms, for example, 50ms, 100ms, 150ms, 200ms, 250ms, 300ms, 400ms, or 500ms, etc., but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 100 to 450ms.
Preferably, the ultrasonic washing time is 1 to 20 hours, such as 1 hour, 3 hours, 5 hours, 7 hours, 10 hours, 12 hours, 15 hours, 17 hours or 20 hours, but not limited to the enumerated values, and other unrecited values within the numerical range are also applicable, preferably 5 to 10 hours.
As a preferred embodiment of the present invention, the total content of the metal elements in the complex modified activated carbon in the step (2) is 700 to 20000ppm, for example 700ppm, 1000ppm, 5000ppm, 10000ppm, 12000ppm, 15000ppm, 17000ppm or 20000ppm, etc., but not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 1100 to 8000ppm.
Preferably, the Al element content in the complex modified activated carbon in the step (2) is 500-5000ppm, such as 500ppm, 1000ppm, 2000ppm, 3000ppm, 4000ppm or 5000ppm, but not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 800-2500ppm.
Preferably, the content of Fe element in the complex modified activated carbon in the step (2) is 200 to 3000ppm, such as 200ppm, 500ppm, 700ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm or 3000ppm, but not limited to the values listed, and other values not listed in the value range are also applicable, preferably 300 to 1500ppm.
As a preferred embodiment of the present invention, the temperature for the drying in step (3) is 150 to 200 ℃, for example, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the drying time in step (3) is 4-8h, such as 4h, 5h, 6h, 7h or 8h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the roasting in step (3) is performed under the protection of inert gas.
Preferably, the inert gas comprises nitrogen and/or argon.
Preferably, the calcination temperature in step (3) is 500 to 800 ℃, for example 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, etc., but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 600 to 700 ℃.
Preferably, the calcination time in step (3) is 5-15h, such as 5h, 7h, 9h, 10h, 12h, 14h or 15h, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 8-12h.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) According to the mass ratio of 1 (2.5-5), soaking activated carbon with the particle size of 2-7mm in an acid solution with the mass concentration of 1% -30%, stirring at 25-150 ℃ for 3-5h, then carrying out ultrasonic washing in water for 1-20h, and alternately carrying out stirring soaking and ultrasonic washing for 1-5 times to obtain the modified activated carbon with the total content of metal elements of 5000-30000ppm, the content of Al elements of 1000-8000ppm and the content of Fe elements of 1000-5000ppm;
the temperature of the ultrasonic washing is 25-100 ℃, the pulse frequency is 10-30kHz and the pulse width is 50-500ms;
(2) Mixing a complexing agent, a solvent and the modified activated carbon in the step (1) according to a mass ratio (0.01-0.1) of 1;
(3) And (3) drying the complex modified activated carbon obtained in the step (2) at 150-200 ℃ for 4-8h, and roasting at 500-800 ℃ for 5-15h under the protection of inert gas to obtain the activated carbon catalyst.
In a second aspect, the present invention provides an activated carbon catalyst for phosgene synthesis, wherein the activated carbon catalyst is prepared by the preparation method of the first aspect.
Preferably, the total content of metal elements in the activated carbon catalyst is 700-20000ppm, preferably 1100-8000ppm.
Preferably, the content of Al element in the activated carbon catalyst is 500-5000ppm, preferably 800-2500ppm.
Preferably, the content of Fe element in the activated carbon catalyst is 200-3000ppm, preferably 300-1500ppm.
In a third aspect, the present invention provides a method for producing phosgene, the method comprising: mixing chlorine and carbon monoxide, filling the mixture into a phosgene synthesis reaction device containing the activated carbon catalyst of the second aspect, and reacting under the action of the activated carbon catalyst to synthesize phosgene.
In the present invention, the phosgene synthesis reaction apparatus includes any one of a tubular reaction tube, a spiral tubular reactor, a fixed bed tubular reactor, or a double-tube plate-type fixed bed reactor, and preferably a fixed bed tubular reactor widely used in the art.
In the present invention, the pressure in the phosgene synthesis reaction apparatus is 0.1 to 0.5Mpag, and may be, for example, 0.1Mpag, 0.2Mpag, 0.3Mpag, 0.4Mpag or 0.5Mpag, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In the present invention, the inlet temperature of the phosgene synthesis reaction apparatus is 10 to 60 ℃ and may be, for example, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ or 60 ℃ or the like, but is not limited to the exemplified values, and other values not exemplified in the numerical range are also applicable, and preferably 20 to 40 ℃.
In the invention, the phosgene synthesis reaction device is provided with a coolant circulation space, and coolant flows through the coolant circulation space and is used for absorbing reaction heat generated by synthesizing phosgene; after absorbing the reaction heat, the coolant in the coolant flowing space is led into the steam generator and exchanges heat with water for converting into steam, so that high-grade steam is generated. Wherein, the shell side of the phosgene synthesis reaction device is provided with a coolant flow space, in particular to a space surrounding the tubes in the phosgene synthesis reaction device.
In the present invention, the coolant comprises any one of chlorobenzene, o-dichlorobenzene, carbon tetrachloride, decahydronaphthalene or alkylbenzene type heat transfer oil or a combination of at least two of them, preferably o-dichlorobenzene and/or decahydronaphthalene, more preferably decahydronaphthalene.
In the present invention, the pressure of the steam generated in the steam generator is 0.2 to 3.0Mpag, and may be, for example, 0.3Mpag, 0.5Mpag, 1.0Mpag, 1.5Mpag, 2.0Mpag, 2.5Mpag, or 3.0Mpag, but is not limited to the above-mentioned values, and other values not listed in the numerical range are also applicable, and preferably 1.0 to 2.5Mpag.
Preferably, the molar ratio of chlorine to carbon monoxide is (0.8-1.0): 1, which can be, for example, 0.8.
In the invention, the carbon monoxide and the chlorine are fully mixed in the mixed gas in advance and then enter from the bottom of the phosgene synthesis reaction device. The mixing method of carbon monoxide and chlorine gas includes line mixing, nozzle mixing, stirring mixing, static mixer mixing, and the like, and preferably a combination of stirring mixing and static mixer mixing, and more preferably static mixer mixing.
In the invention, the phosgene synthesized in the phosgene synthesis reaction device is sent into a phosgene synthesis protection device, so that the unreacted chlorine and carbon monoxide can further react. Wherein the activated carbon catalyst of the second aspect is filled in bulk in the phosgene synthesis protection device.
In the invention, the reaction pressure of the phosgene synthesis protection device is 0.1-0.5MPag, preferably 0.2-0.4Mpag.
In the invention, the outlet temperature of the phosgene synthesis protection device is controlled below 100 ℃, preferably 50-80 ℃, and more preferably 60-70 ℃.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method provided by the invention, the acid solution and the specific complexing agent are utilized to modify the activated carbon, so that the content of metal ions such as Al and Fe which affect the heat resistance in the activated carbon is controlled within a certain range, the heat resistance of the activated carbon is effectively improved, and the service cycle of the activated carbon is prolonged;
(2) The active carbon catalyst provided by the invention can be suitable for high-temperature operation conditions, so that a cooling medium for phosgene synthesis can select high-boiling-point substances without considering the tolerance capacity of the active carbon, thereby achieving the purposes of producing high-grade steam, ensuring the safe high-load stable operation of a device and greatly improving the utilization rate of phosgene synthesis energy.
Drawings
FIG. 1 is a schematic flow diagram of a phosgene preparation process provided by the present invention;
wherein, 1-chlorine gas feed line; 2-a carbon monoxide feed line; 3-a mixing device; 4-phosgene synthesis reaction device; 5-a steam generating device; 6-air bag; 7-phosgene synthesis protection device; 8-coolant input line; 9-boiler water conveying pipe; 10-a phosgene outlet line; 11-15 are all pipelines.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of an activated carbon catalyst for phosgene synthesis, which comprises the following steps:
(1) Soaking 1t of coconut shell activated carbon with the particle size of 4mm in 3t of dilute hydrochloric acid with the mass concentration of 5%, stirring and soaking for 5h at 40 ℃, then performing ultrasonic washing for 5h in water, wherein the ultrasonic washing temperature is 30 ℃, the pulse frequency is 15kHz and the pulse width is 150ms, and the stirring and soaking and the ultrasonic washing are alternately performed for 2 times to obtain the modified activated carbon with the total content of metal elements of 7342ppm, the content of Al elements of 2740ppm and the content of Fe elements of 1830ppm;
(2) Mixing 60kg of ammonium rhodotricarboxylate, 1t of water and the modified activated carbon obtained in the step (1), performing complexing treatment for 5 hours at 40 ℃, and then performing ultrasonic washing for 3 times in water, wherein the ultrasonic washing temperature is 30 ℃, the ultrasonic washing time is 5 hours, the pulse frequency is 15kHz, and the pulse width is 150ms; the total content of metal elements in the obtained complex modified activated carbon is 4892ppm, the content of Al elements is 1435ppm, and the content of Fe elements is 1256ppm;
(3) And (3) drying the complex modified activated carbon obtained in the step (2) at 150 ℃ for 4h, and roasting at 600 ℃ for 8h under the protection of nitrogen to obtain the activated carbon catalyst.
Example 2
The embodiment provides a preparation method of an activated carbon catalyst for phosgene synthesis, which comprises the following steps:
(1) Soaking 1t of coal-based activated carbon with the particle size of 4mm in 3t of dilute hydrochloric acid with the mass concentration of 5%, stirring and soaking for 5 hours at 40 ℃, then performing ultrasonic washing for 2 hours in water, wherein the stirring and soaking and the ultrasonic washing are alternately performed for 2 times, the ultrasonic washing temperature is 30 ℃, the pulse frequency is 15kHz, and the pulse width is 150ms; the total content of metal elements in the obtained modified activated carbon is 8121ppm, the content of Al elements is 3042ppm and the content of Fe elements is 2284ppm;
(2) Mixing 60kg of alizarin violet, 1 ton of water and the modified activated carbon obtained in the step (1), performing complexing treatment for 5 hours at 40 ℃, and then performing ultrasonic washing for 3 times in water, wherein the ultrasonic washing temperature is 30 ℃, the ultrasonic washing time is 5 hours, the pulse frequency is 15kHz, and the pulse width is 150ms; the obtained complex modified activated carbon has the total content of 5034ppm of metal elements, the content of Al elements of 1678ppm and the content of Fe elements of 1332ppm;
(3) And (3) drying the complex modified activated carbon obtained in the step (2) at 150 ℃ for 4h, and roasting at 600 ℃ for 8h under the protection of nitrogen to obtain the activated carbon catalyst.
Example 3
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as that of example 1 except that the diluted hydrochloric acid used in step (1) has a mass concentration of 1%.
Example 4
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as that of example 1 except that the diluted hydrochloric acid used in step (1) has a mass concentration of 30%.
Example 5
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as that of example 1, except that the mass ratio of the coconut shell activated carbon to the dilute hydrochloric acid in the step (1) is 1.
Example 6
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as that of example 1, except that the mass ratio of the coconut shell activated carbon to the dilute hydrochloric acid in the step (1) is 1.
Example 7
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the stirring and soaking temperature in step (1) is 25 ℃.
Example 8
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the stirring and soaking temperature in step (1) is 150 ℃.
Example 9
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the amount of ammonium rhodotricarboxylate added in step (2) is 10 kg.
Example 10
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as that of example 1 except that the amount of ammonium rhodotricarboxylate added in step (2) is 100 kg.
Comparative example 1
This comparative example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the operation of step (1) is not performed.
Comparative example 2
This comparative example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the operation of step (2) is not performed.
Comparative example 3
The comparative example uses unmodified coconut shell activated carbon as a catalyst, and coconut shell activated carbon (industrial product) is produced by Nippon Hejian Co Ltd.
Comparative example 4
The comparative example uses unmodified coal-based activated carbon as a catalyst, and the coal-based activated carbon (industrial product) is produced by Ningxia Guanghuaqisi activated carbon Co.
After microwave digestion is performed on the modified activated carbon in the step (1) and the prepared activated carbon catalyst in the above examples and comparative examples, metal ion content measurement is performed by using ICP, and the total content of metal elements, the content of Al element, and the content of Fe element are shown in tables 1 and 2, respectively.
TABLE 1
Note: in tables 1 and 2, the total content of the metal elements means metal elements of Al, fe, cr, ni, mg, cu, cr, na and K.
The activated carbon catalysts prepared in the above examples and comparative examples were used for synthesizing phosgene, carbon monoxide (industrial product) which is a raw material for synthesizing phosgene was produced by a gas-making device in the tobacco-station-Wanhua industrial park, and chlorine (industrial product) was produced by a chlorine-hydrogen workshop of the tobacco-station-Wanhua chlor-alkali company.
The flow diagram of the phosgene preparation process is shown in figure 1, and the phosgene preparation method comprises the following steps: mixing chlorine and carbon monoxide in a mixing device 3 according to a molar ratio of 0.93, then feeding the mixture into a phosgene synthesis reaction device 4 filled with 4.8t of activated carbon catalyst for reaction to synthesize phosgene, wherein the pressure of the phosgene synthesis reaction device 4 is 0.4Mpag, the inlet temperature in the phosgene synthesis reaction device 4 is 30 ℃, the phosgene outlet temperature of the phosgene synthesis reaction device 4 is controlled at 230 ℃, the diameter of a tube array of the phosgene synthesis reaction device 4 is 40mm, the length of the tube array is 5000mm, and a thermocouple is arranged in the tube array of the phosgene synthesis reaction device 4 to monitor the hot spot temperature; phosgene at the outlet of the phosgene synthesis reaction device 4 enters a phosgene synthesis protection device 7, unreacted chlorine and carbon monoxide further react completely, the pressure of the phosgene synthesis protection device 7 is controlled to be 0.4MPag, and the outlet temperature of the phosgene synthesis protection device 7 is controlled to be 65 ℃. The coolant on the shell side of the phosgene synthesis reaction device 4 is decalin, the decalin enters the steam generating device 5 after being gasified on the shell side to exchange heat with boiler water (and part of condensed water from the air bag 6), and the pressure of a byproduct steam is 2.5Mpag.
The results of the annual mass loss and the operating cycle of the activated carbon catalysts prepared in the above examples and comparative examples in the synthesis of phosgene are shown in table 3.
TABLE 3
The following points can be derived from tables 1-3:
(1) In the activated carbon catalyst prepared by the preparation method provided by the embodiment 1-2 of the invention, the acid solution and the complexing agent are utilized to control the content of metal ions such as Al and Fe which affect the heat resistance of the activated carbon within a certain range, so that the heat resistance of the activated carbon is effectively improved, and the activated carbon is prevented from reacting with Cl in the phosgene synthesis reaction process 2 Halide is formed, so that the loss of the active carbon catalyst is reduced, and the service cycle of the active carbon is prolonged;
(2) It is understood from the combination of examples 1 and 3-4 that when the concentration of the acid solution is too low, the content of metal ions such as Al and Fe affecting the heat resistance of the activated carbon cannot be reduced to a certain range, and the metal ions such as Al and Fe react with Cl during the phosgene synthesis process 2 Halide is formed to destroy the activated carbon skeleton, and further the loss of the activated carbon catalyst is increased; when the concentration of the acid solution is too high, the scale of the activated carbon skeleton is easily damaged although the acid solution has stronger removal capacity on metal ions, so that the strength of the activated carbon is reduced, and the service life is shortened;
(3) It can be seen from the combination of examples 1 and 5-6 that when the mass ratio of the activated carbon to the acid solution is too low, the effect of removing metal ions cannot be achieved, so that the content of metal ions in the activated carbon is too high, and the service life of the activated carbon in the phosgene synthesis process is reduced; when the mass ratio of the activated carbon to the acid solution is too high, the scale of the activated carbon skeleton is easily damaged although the activated carbon has stronger removal capacity on metal ions, so that the strength of the activated carbon is reduced, and the service life is shortened;
(4) When the amount of the complexing agent added is too small, it is not possible to reduce the color tone, as is clear from the combination of example 1 and examples 9 to 10The content of metal ions such as Al, fe and the like which have influence on the heat resistance of the activated carbon is reduced to a certain range, so that the metal ions such as Al, fe and the like are mixed with Cl in the phosgene synthesis process 2 Halide is formed to destroy the activated carbon skeleton, and further the loss of the activated carbon catalyst is increased; when the addition amount of the complexing agent is excessive, although metal ions can be effectively complexed to reduce the content of the complexing agent, excessive complex is easily formed to block a pore channel, so that the catalytic performance of the activated carbon is reduced, the temperature distribution in the pore channel is not uniform, and the service life is shortened;
(5) It is understood from the combination of example 1 and comparative examples 1-2 that the content of metal ions such as Al and Fe affecting the heat resistance of the activated carbon could not be reduced to a certain range without complexing with an acid solution or a complexing agent, resulting in the metal ions such as Al and Fe being complexed with Cl during the phosgene synthesis process 2 The formation of halides in turn destroys the activated carbon skeleton, further leading to increased loss of activated carbon catalyst.
The applicant states that the present invention is described by the above embodiments to explain the detailed structural features of the present invention, but the present invention is not limited to the above detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of an activated carbon catalyst for phosgene synthesis is characterized by comprising the following steps:
(1) Stirring and soaking the activated carbon in an acid solution, and then carrying out ultrasonic washing in water to obtain modified activated carbon;
(2) Mixing a complexing agent, a solvent and the modified activated carbon obtained in the step (1), and performing complexing treatment to obtain the complexed modified activated carbon;
(3) And (3) drying and roasting the complex modified activated carbon obtained in the step (2) in sequence to obtain the activated carbon catalyst.
2. The method according to claim 1, wherein the activated carbon of step (1) comprises coconut shell activated carbon and/or coal-based activated carbon;
preferably, the particle size of the activated carbon in the step (1) is 2-7mm, preferably 3-5mm;
preferably, the mass ratio of the activated carbon and the acid solution in the step (1) is 1 (2.5-5), preferably 1 (2.5-4);
preferably, the mass concentration of the acid solution in the step (1) is 1-30%, and preferably 4-10%;
preferably, the acid in the acid solution of step (1) comprises any one of hydrochloric acid, phosphoric acid or silicic acid or a combination of at least two of the two.
3. The method for preparing according to claim 1 or 2, wherein the temperature of the stirring soaking in the step (1) is 25-150 ℃, preferably 40-70 ℃;
preferably, the stirring and soaking time of the step (1) is 3-5h;
preferably, the temperature of the ultrasonic washing in the step (1) is 25-100 ℃, preferably 30-50 ℃;
preferably, the pulse frequency of the ultrasonic washing in the step (1) is 10-30kHz, preferably 12-25kHz;
preferably, the pulse width of the ultrasonic washing in the step (1) is 50-500ms, preferably 100-450ms;
preferably, the ultrasonic washing time of the step (1) is 1-20h, preferably 5-10h;
preferably, the stirring soaking and the ultrasonic washing in the step (1) are alternately performed for 1 to 5 times, preferably for 2 to 3 times.
4. The production method according to any one of claims 1 to 3, wherein the total content of the metal elements in the modified activated carbon of step (1) is 5000 to 30000ppm, preferably 5000 to 15000ppm;
preferably, the content of Al element in the modified activated carbon in the step (1) is 1000-8000ppm, preferably 2000-5000ppm;
preferably, the content of Fe element in the modified activated carbon in the step (1) is 1000-5000ppm, and preferably 1500-3000ppm.
5. The preparation method according to any one of claims 1 to 4, wherein the complexing agent in step (2) comprises any one of or a combination of at least two of ammonium rhodantricarboxylate, alizarin red S, alizarin violet, or ethylenediaminetetraacetic acid;
preferably, the mass ratio of the complexing agent to the modified activated carbon in the step (2) is (0.01-0.1): 1, preferably (0.05-0.08): 1;
preferably, the temperature of the complexing treatment in the step (2) is 20-100 ℃, preferably 40-50 ℃;
preferably, the complexing treatment time of the step (2) is 1-10h, preferably 4-7h;
preferably, the complexing treatment in the step (2) further comprises ultrasonic washing;
preferably, the ultrasonically washed lotion comprises water;
preferably, the temperature of the ultrasonic washing is 25-80 ℃, preferably 30-50 ℃;
preferably, the pulse frequency of the ultrasonic washing is 10-30kHz, preferably 12-25kHz;
preferably, the pulse width of the ultrasonic washing is 50 to 500ms, preferably 100 to 450ms;
preferably, the time of the ultrasonic washing is 1 to 20 hours, preferably 5 to 10 hours.
6. The production method according to any one of claims 1 to 5, wherein the total content of metal elements in the complex modified activated carbon of the step (2) is 700 to 20000ppm, preferably 1100 to 8000ppm;
preferably, the Al element content in the complex modified activated carbon in the step (2) is 500-5000ppm, preferably 800-2500ppm;
preferably, the Fe element content in the complexation modified activated carbon in the step (2) is 200-3000ppm, preferably 300-1500ppm.
7. The method according to any one of claims 1 to 6, wherein the temperature for the drying in step (3) is 150 to 200 ℃;
preferably, the drying time in the step (3) is 4-8h;
preferably, the roasting in the step (3) is carried out under the protection of inert gas;
preferably, the inert gas comprises nitrogen and/or argon;
preferably, the roasting temperature in the step (3) is 500-800 ℃, preferably 600-700 ℃;
preferably, the roasting time in the step (3) is 5 to 15 hours, and is preferably 8 to 12 hours.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) According to the mass ratio of 1 (2.5-5), soaking activated carbon with the particle size of 2-7mm in an acid solution with the mass concentration of 1-30%, stirring at 25-150 ℃ for 3-5h, then carrying out ultrasonic washing in water for 1-20h, and alternately carrying out stirring soaking and ultrasonic washing for 1-5 times to obtain the modified activated carbon with the total content of metal elements of 5000-30000ppm, the content of Al elements of 1000-8000ppm and the content of Fe elements of 1000-5000ppm;
the temperature of the ultrasonic washing is 25-100 ℃, the pulse frequency is 10-30kHz and the pulse width is 50-500ms;
(2) Mixing a complexing agent, a solvent and the modified activated carbon in the step (1) according to a mass ratio (0.01-0.1) of 1:1, complexing at 20-100 ℃ for 1-10h, and then carrying out ultrasonic washing in water to obtain the complex modified activated carbon with the total content of metal elements of 500-20000ppm, the content of Al elements of 500-5000ppm and the content of Fe elements of 200-3000ppm;
(3) And (3) drying the complex modified activated carbon obtained in the step (2) at 150-200 ℃ for 4-8h, and roasting at 500-800 ℃ for 5-15h under the protection of inert gas to obtain the activated carbon catalyst.
9. An activated carbon catalyst for phosgene synthesis, characterized in that the activated carbon catalyst is prepared by the preparation method of any one of claims 1-8;
preferably, the total content of the metal elements in the activated carbon catalyst is 700-20000ppm, preferably 1100-8000ppm;
preferably, the content of Al element in the activated carbon catalyst is 500-5000ppm, preferably 800-2500ppm;
preferably, the content of Fe element in the activated carbon catalyst is 200-3000ppm, and preferably 300-1500ppm.
10. A method for producing phosgene, the method comprising: mixing chlorine and carbon monoxide, filling the mixture into a phosgene synthesis reaction device containing the activated carbon catalyst of claim 9, and reacting under the action of the activated carbon catalyst to synthesize phosgene.
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