CN115779882B - Preparation method and application of active carbon catalyst for phosgene synthesis - Google Patents
Preparation method and application of active carbon catalyst for phosgene synthesis Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 70
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 27
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- 238000010668 complexation reaction Methods 0.000 claims description 13
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
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- 239000003245 coal Substances 0.000 claims description 5
- JKYKXTRKURYNGW-UHFFFAOYSA-N 3,4-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(O)C(S(O)(=O)=O)=C2 JKYKXTRKURYNGW-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
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- PHLYOKFVXIVOJC-UHFFFAOYSA-N gallein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C(O)=C1OC1=C(O)C(O)=CC=C21 PHLYOKFVXIVOJC-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention provides a preparation method and application of an active 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 performing ultrasonic washing in water to obtain modified activated carbon; mixing a complexing agent, a solvent and the modified activated carbon, and carrying out complexing treatment to obtain complexing modified activated carbon; and (3) sequentially drying and roasting the complexing 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 affecting 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 active carbon catalyst for phosgene synthesis.
Background
Phosgene, also known as phosgene, has the flavor of rotting licorice and rotting apples. It is used as an important organic synthesis intermediate and is mainly applied to the fields of pesticides, paint, dye, initiator, medicine, fine chemicals, isocyanate and the like. The industrial production of phosgene is carried out mainly from CO and Cl 2 as raw materials in a tube reactor filled with a catalyst.
The phosgene synthesis principle is CO+Cl 2→COCl2, the reaction is a strong exothermic reaction, the unit chlorine exothermic amount is 116kJ/mol, and the reaction heat needs to be removed in time due to the large exothermic amount of the reaction. The existing phosgene synthesis reactor is mainly a vertical tubular fixed bed reactor with an activated carbon catalyst on the tube side and a cooling medium pair on the shell side.
CN109289714a discloses a method for filling catalyst for phosgene synthesis reaction, which is characterized by that the upper and lower positions of active carbon bed layer are filled with 100-300mm large granular ceramic balls, and covered with 1-2 layers of screen meshes so as to reduce loss of active carbon. However, the traditional filling method can not reduce the reaction rate and the heat release rate, avoids the generation of flying temperature, and still has serious active carbon powdering ablation.
CN110449147a discloses a catalyst for phosgene synthesis, and a preparation method and application thereof, the active components of the catalyst comprise active carbon and carbon nanotubes, wherein the mass ratio of the carbon nanotubes to the active 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 nitric acid solution, taking out, washing and drying to obtain mixed powder of the activated carbon and the carbon nano tube; mixing the mixed powder with hydrochloric acid solution of polyvinyl alcohol and glutaraldehyde, kneading to obtain plastic blank, extruding to form strip, curing, drying and roasting. The catalyst has high activity, high heat conduction and high structural stability.
The existing mature technology and the technology with higher energy utilization rate have contradiction points: high-grade steam cannot be generated by using water as a cooling medium, so that energy waste is caused, and corrosion risks exist; and the high boiling point oil is used as a cooling medium, the operation temperature of the reaction tube is increased, the high temperature resistance and the oxidation resistance of the activated carbon are poor, the activated carbon is easy to burn and pulverize, the service cycle of the reactor is shortened, and the operation stability of the device is poor.
Therefore, in order to improve the energy utilization rate of phosgene synthesis and produce high-grade steam, the performance of the activated carbon needs to be improved, and the heat resistance of the activated carbon is improved.
Disclosure of Invention
The invention aims to provide a preparation method and application of an active carbon catalyst for phosgene synthesis, wherein the preparation method improves the heat resistance of the active carbon catalyst for phosgene synthesis by precisely controlling the content of metal ions directly related to the heat resistance in the active carbon for phosgene synthesis, so that the active carbon catalyst can be suitable for a steam generating system for phosgene synthesis, and not only improves the safe and stable operation level of a device, but also improves the energy utilization efficiency of phosgene synthesis.
In order to achieve the aim of the invention, 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 performing 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 carrying out complexing treatment to obtain a complexing modified activated carbon;
(3) And (3) sequentially drying and roasting the complexation modified activated carbon in the step (2) to obtain the activated carbon catalyst.
Firstly, reducing the content of metal ions in activated carbon to a certain range by utilizing an acid solution, then adding a specific complexing agent into the activated carbon after pickling, and complexing the complexing agent and the residual metal ions to generate a complex attached to the surface of an activated carbon pore channel; on one hand, the content of metal ions such as Al, fe and the like which affect heat resistance in the activated carbon can be controlled within a certain range, so that the heat resistance of the activated carbon is effectively improved, the metal ions and the activated carbon are prevented from forming halides with Cl 2 in the phosgene synthesis reaction process in the phosgene synthesis process, so that the skeleton of the activated carbon is damaged, and on the other hand, the formed complex can also play a role of strengthening the skeleton, so that the purpose of prolonging the service cycle of the activated carbon is achieved; the prepared active 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, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 3-5mm.
Preferably, the mass ratio of the activated carbon to the acid solution in the step (1) is 1 (2.5-5), for example, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, but not limited to the recited values, other non-recited values in the range of values are equally applicable, and preferably 1 (2.5-4).
Preferably, the mass concentration of the acid solution in step (1) is 1% -30%, for example, 1%, 5%, 10%, 15%, 20%, 25% or 30%, etc., preferably 4% -10%.
Preferably, the acid in the acid solution of step (1) comprises any one or a combination of at least two of hydrochloric acid, phosphoric acid or silicic acid, typical but non-limiting examples of which are: 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, etc.
As a preferred embodiment of the present invention, the temperature of the stirring and soaking in the step (1) is 25 to 150℃and may be, for example, 25℃30℃40℃50℃70℃90℃120℃150℃or the like, but not limited to the values listed, and other values not listed in the range of values are equally applicable, preferably 40 to 70 ℃.
Preferably, the stirring and soaking time in the step (1) is 3-5h, for example, 3h, 3.4h, 3.8h, 4h, 4.4h, 4.8h or 5h, etc., but the stirring and soaking time is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the temperature of the ultrasonic washing in the step (1) is 25 to 100 ℃, for example, 25 ℃, 30 ℃, 50 ℃, 60 ℃, 70 ℃,80 ℃,90 ℃, or 100 ℃, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 30 to 50 ℃.
Preferably, the pulse frequency of the ultrasonic washing in the step (1) is 10-30kHz, and may be, for example, 10kHz, 12kHz, 15kHz, 20kHz, 22kHz, 25kHz, 27kHz or 30kHz, etc., but is not limited to the values recited, and other non-recited values within the range of values are equally applicable, preferably 12-25kHz.
Preferably, the pulse width of the ultrasonic washing in step (1) is 50-500ms, for example, 50ms, 100ms, 150ms, 200ms, 250ms, 300ms, 400ms or 500ms, but not limited to the recited values, other non-recited values in the range of values are equally applicable, and preferably 100-450ms.
Preferably, the time of ultrasonic washing in step (1) is 1-20h, for example, 1h, 3h, 5h, 7h, 10h, 12h, 15h, 17h or 20h, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 5-10h.
Preferably, the stirring 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 are not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 2 to 3 times.
In a preferred embodiment of the present invention, the total content of metal elements in the modified activated carbon in the step (1) is 5000 to 30000ppm, and for example, 500ppm, 1000ppm, 5000ppm, 10000ppm, 15000ppm, 20000ppm, 25000ppm or 30000ppm may be used, but the present invention is not limited to the values recited therein, and other values not recited therein are equally applicable, and preferably 5000 to 15000ppm.
Preferably, the content of Al element in the modified activated carbon in the step (1) is 1000-8000ppm, for example, 1000ppm, 2000ppm, 3000ppm, 4000ppm, 5000ppm, 6000ppm, 7000ppm or 8000ppm, etc., but not limited to the values listed, other non-listed values in the numerical range are equally applicable, preferably 2000-5000ppm.
Preferably, the content of Fe element in the modified activated carbon in the step (1) is 1000-5000ppm, for example, 1000ppm, 2000ppm, 3000ppm, 4000ppm or 5000ppm, etc., but not limited to the values listed, and other values not listed in the value range are equally applicable, preferably 1500-3000ppm.
As a preferred embodiment of the present invention, the complexing agent of step (2) comprises any one or a combination of at least two of ammonium rhodotricarboxylic acid, alizarin red S, alizarin violet or ethylenediamine tetraacetic acid, typical but non-limiting examples of which are: a combination of ammonium rhodinate and alizarin red S, a combination of alizarin red S and ethylenediamine tetraacetic acid or a combination of alizarin violet and ethylenediamine tetraacetic acid, and the like.
Preferably, the mass ratio of the complexing agent and the modified activated carbon in the step (2) is (0.01-0.1): 1, for example, 0.01:1, 0.03:1, 0.05:1, 0.07:1, 0.09:1 or 0.1:1, etc., but not limited to the recited values, other non-recited values in the numerical range are equally applicable, and preferably (0.05-0.08): 1.
In the present 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 present invention, the solvent of step (2) includes water.
Preferably, the temperature of the complexation treatment in the step (2) is 20 to 100 ℃, for example, 20 ℃, 30 ℃,40 ℃, 50 ℃, 60 ℃, 70 ℃,80 ℃,90 ℃, or 100 ℃, etc., but the temperature is not limited to the values listed, and other values not listed in the numerical range are applicable as well, preferably 40 to 50 ℃.
Preferably, the time of the complexing treatment in step (2) is 1-10h, for example, 1h, 3h, 5h, 7h or 10h, etc., but not limited to the recited values, other non-recited values in the range of values are equally applicable, preferably 4-7h.
Preferably, the complexing treatment of 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 temperature of the ultrasonic washing is 25 to 80 ℃, for example, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or the like, but not limited to the recited values, other non-recited values within the range of values are equally applicable, and preferably 30 to 50 ℃.
Preferably, the pulse frequency of the ultrasonic washing is 10-30kHz, and can be, for example, 10kHz, 12kHz, 15kHz, 20kHz, 22kHz, 25kHz, 27kHz or 30kHz, etc., but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable, and preferably 12-25kHz.
Preferably, the pulse width of the ultrasonic washing is 50-500ms, for example, 50ms, 100ms, 150ms, 200ms, 250ms, 300ms, 400ms or 500ms, etc., but not limited to the recited values, other non-recited values in the range of values are equally applicable, and preferably 100-450ms.
Preferably, the ultrasonic washing time is 1-20h, for example, 1h, 3h, 5h, 7h, 10h, 12h, 15h, 17h or 20h, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 5-10h.
In 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, and for example, 700ppm, 1000ppm, 5000ppm, 10000ppm, 12000ppm, 15000ppm, 17000ppm, 20000ppm, etc. may be used, but the present invention is not limited to the values listed, and other values not listed in the numerical range are equally applicable, and preferably 1100 to 8000ppm.
Preferably, the content of Al element in the complexation-modified activated carbon in the step (2) is 500-5000ppm, for example, 500ppm, 1000ppm, 2000ppm, 3000ppm, 4000ppm or 5000ppm, etc., but not limited to the values listed, other values not listed in the numerical range are equally applicable, and preferably 800-2500ppm.
Preferably, the Fe element content in the complex modified activated carbon in the step (2) is 200 to 3000ppm, for example, 200ppm, 500ppm, 700ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm or 3000ppm, etc., but not limited to the values listed, other values not listed in the numerical range are equally applicable, and preferably 300 to 1500ppm.
In a preferred embodiment of the present invention, the temperature of the drying in the step (3) is 150 to 200 ℃, for example, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
Preferably, the drying time in the step (3) is 4-8h, for example, 4h, 5h, 6h, 7h or 8h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the roasting in the step (3) is performed under the protection of inert gas.
Preferably, the inert gas comprises nitrogen and/or argon.
Preferably, the temperature of the calcination in the step (3) is 500 to 800 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or the like, but not limited to the values listed, other non-listed values within the range of values are equally applicable, and preferably 600 to 700 ℃.
Preferably, the roasting time in the step (3) is 5-15h, for example, 5h, 7h, 9h, 10h, 12h, 14h or 15h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 8-12h.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) According to the mass ratio of 1, (2.5-5), soaking active carbon with the particle size of 2-7mm in an acid solution with the mass concentration of 1% -30%, stirring for 3-5h at 25-150 ℃, then performing ultrasonic washing in water for 1-20h, and alternately performing stirring soaking and ultrasonic washing for 1-5 times to obtain the modified active carbon with the total content of metal elements of 5000-30000ppm, the content of Al element of 1000-8000ppm and the content of Fe element of 1000-5000ppm;
the ultrasonic washing temperature is 25-100 ℃, the pulse frequency is 10-30kHz, and the pulse width is 50-500ms;
(2) Mixing complexing agent, solvent and the modified active carbon in the step (1) according to the mass ratio of (0.01-0.1) of 1:1, carrying out complexing treatment for 1-10 hours at 20-100 ℃, and then carrying out ultrasonic washing in water to obtain the complexing modified active carbon, wherein the total content of metal elements in the complexing modified active carbon is 500-20000ppm, the content of Al element is 500-5000ppm and the content of Fe element is 200-3000ppm;
(3) And (3) drying the complexation modified activated carbon in the step (2) at 150-200 ℃ for 4-8 hours, and roasting the activated carbon for 5-15 hours at 500-800 ℃ 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, the activated carbon catalyst being 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 preparing phosgene, the method comprising: mixing chlorine and carbon monoxide, filling the mixture into a phosgene synthesis reaction device containing the active carbon catalyst in the second aspect, and reacting to synthesize phosgene under the action of the active carbon catalyst.
In the present invention, the phosgene synthesis reaction device comprises any one of a tubular reactor, a spiral tubular reactor, a fixed bed tubular reactor or a double-tube-type fixed bed reactor, and is preferably a fixed bed tubular reactor widely used in the art.
In the present invention, the pressure of the phosgene synthesis reaction device is 0.1 to 0.5Mpa, for example, 0.1Mpa, 0.2Mpa, 0.3Mpa, 0.4Mpa, or 0.5Mpa, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
In the present invention, the inlet temperature of the phosgene synthesis reaction device may be 10 to 60℃and may be, for example, 10℃20℃30℃40℃50℃60℃or the like, but not limited to the values recited, and other values not recited in the numerical range are applicable as well, and preferably 20 to 40 ℃.
In the invention, the phosgene synthesis reaction device is provided with a coolant circulation space, wherein coolant circulates in the coolant circulation space and is used for absorbing reaction heat generated by synthesizing phosgene; and after the coolant in the coolant circulation space absorbs the reaction heat, introducing the coolant into the steam generator, and performing heat exchange with water for converting the coolant into steam, thereby generating high-grade steam. Wherein, the shell side of the phosgene synthesis reaction device is provided with a coolant circulation space, in particular to a space surrounding a tube array in the phosgene synthesis reaction device.
In the present invention, the coolant includes any one or a combination of at least two of chlorobenzene, o-dichlorobenzene, carbon tetrachloride, decalin or alkylbenzene type heat transfer oil, preferably o-dichlorobenzene and/or decalin, more preferably decalin.
In the present invention, the pressure of the steam generated in the steam generator is 0.2 to 3.0Mpa, for example, 0.3Mpa, 0.5Mpa, 1.0Mpa, 1.5Mpa, 2.0Mpa, 2.5Mpa, or 3.0Mpa, etc., but not limited to the values listed, other non-listed values within the range of values are equally applicable, preferably 1.0 to 2.5 Mpa.
Preferably, the molar ratio of chlorine to carbon monoxide is (0.8-1.0): 1, which may be, for example, 0.8:1, 0.84:1, 0.88:1, 0.9:1, 0.94:1, 0.98:1 or 1:1, etc., but is not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 1.0:1.
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 means of carbon monoxide and chlorine include pipe mixing, nozzle mixing, stirring mixing, static mixer mixing, etc., preferably a combination of stirring mixing and static mixer mixing, 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 unreacted chlorine and carbon monoxide are further reacted. Wherein the active carbon catalyst of the second aspect is filled in bulk piles in the phosgene synthesis protection device.
In the present invention, the reaction pressure of the phosgene synthesis protector is 0.1-0.5MPag, preferably 0.2-0.4Mpag.
In the present invention, the outlet temperature of the phosgene synthesis protector is controlled to be 100℃or less, preferably 50 to 80℃and more preferably 60 to 70 ℃.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
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, fe and the like affecting 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 high-boiling point substance can be selected as a cooling medium for phosgene synthesis without considering the tolerance capability of active carbon, thereby achieving the purposes of producing high-grade steam, ensuring the safe and high-load stable operation of the device, and greatly improving the utilization rate of the phosgene synthesis energy.
Drawings
FIG. 1 is a schematic flow chart of a phosgene preparation process provided by the invention;
Wherein, 1-chlorine gas feed line; a 2-carbon monoxide feed line; 3-a mixing device; a 4-phosgene synthesis reaction device; 5-a steam generating device; 6, air bag; 7-phosgene synthesis protection device; 8-a coolant input line; 9-boiler water delivery pipe; 10-phosgene output line; 11-15 are all pipelines.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of an active 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 in water for 5h, wherein the ultrasonic washing temperature is 30 ℃, the pulse frequency is 15kHz, and the pulse width is 150ms, and the stirring and soaking and 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 element of 2740ppm and the content of Fe element of 1830ppm;
(2) Mixing 60kg of ammonium rhodiola tricarboxylic acid, 1t of water and the modified activated carbon in the step (1), carrying out complexation treatment for 5 hours at 40 ℃, and then carrying out ultrasonic washing for 3 times in water, wherein the temperature of ultrasonic washing is 30 ℃, the time is 5 hours, the pulse frequency is 15kHz and the pulse width is 150ms; the obtained complexation modified activated carbon has the total content of metal elements of 4892ppm, the content of Al element of 1435ppm and the content of Fe element of 1256ppm;
(3) And (3) drying the complexation modified activated carbon in the step (2) for 4 hours at 150 ℃ and roasting the activated carbon for 8 hours at 600 ℃ under the protection of nitrogen to obtain the activated carbon catalyst.
Example 2
The embodiment provides a preparation method of an active carbon catalyst for phosgene synthesis, which comprises the following steps:
(1) 1t of coal-based activated carbon with the particle size of 4mm is soaked in 3t of dilute hydrochloric acid with the mass concentration of 5%, stirred and soaked for 5 hours at 40 ℃, then ultrasonic washing is carried out in water for 2 hours, the stirring and soaking and the ultrasonic washing are alternately carried out for 2 times, the temperature of the ultrasonic washing 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, 1t of water and the modified activated carbon in the step (1), carrying out complexation treatment for 5 hours at 40 ℃, and then carrying out ultrasonic washing for 3 times in water, wherein the temperature of ultrasonic washing is 30 ℃, the 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 metal elements of 5034ppm, the content of Al element of 1678ppm and the content of Fe element of 1332ppm;
(3) And (3) drying the complexation modified activated carbon in the step (2) for 4 hours at 150 ℃ and roasting the activated carbon for 8 hours at 600 ℃ 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 example 1 except that the mass concentration of the dilute hydrochloric acid in step (1) is 1%.
Example 4
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the mass concentration of the dilute hydrochloric acid in step (1) is 30%.
Example 5
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the mass ratio of coconut shell activated carbon to dilute hydrochloric acid in step (1) is 1:1.
Example 6
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as example 1 except that the mass ratio of the coconut shell activated carbon to the dilute hydrochloric acid in step (1) is 1:6.
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 temperature of the agitation and soaking 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 temperature of the agitation and soaking 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 in example 1 except that the ammonium rhodiola tricarboxylic acid in step (2) is added in an amount of 10 kg.
Example 10
This example provides a method for preparing an activated carbon catalyst for phosgene synthesis, which is the same as in example 1 except that the ammonium rhodiola tricarboxylic acid in step (2) is added in an amount of 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 in 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 in example 1 except that the operation of step (2) is not performed.
Comparative example 3
The comparative example uses unmodified coconut activated carbon as a catalyst, and the coconut activated carbon (industrial product) is produced by the company of Geranium japonicum.
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 guang Hua Jisai activated carbon limited company.
After the modified activated carbon and the prepared activated carbon catalyst in step (1) in the above examples and comparative examples were subjected to microwave digestion, metal ion content measurement was performed using ICP, and the total content of metal elements, al element content and Fe element content thereof were shown in tables 1 and 2, respectively.
TABLE 1
Note that: in tables 1 and 2, the total content of the metal elements means Al, fe, cr, ni, mg, cu, cr, na and K metal elements.
The active carbon catalysts prepared in the examples and the comparative examples are used for synthesizing phosgene, and the raw material carbon monoxide (industrial product) for synthesizing phosgene is produced by a gas making device in a Wanhua industrial garden, and chlorine (industrial product) is produced by a chlor-hydro workshop of Wanhua chlor alkali company.
A schematic flow chart of a phosgene preparation process is shown in FIG. 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 0.93:1, then entering a phosgene synthesis reaction device 4 filled with 4.8t of active 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 temperature of a phosgene outlet of the phosgene synthesis reaction device 4 is controlled at 230 ℃, the diameter of a tube row of the phosgene synthesis reaction device 4 is 40mm, the length of the tube row of the phosgene synthesis reaction device 4 is 5000mm, and a thermocouple is arranged in the tube row of the phosgene synthesis reaction device 4 to monitor the temperature of hot spots; the phosgene at the outlet of the phosgene synthesis reaction device 4 enters a phosgene synthesis protection device 7, unreacted chlorine and carbon monoxide are further reacted 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 shell side coolant of the phosgene synthesis reaction device 4 is decalin, the decalin is gasified at the shell side and then enters the steam generation device 5 to exchange heat with boiler water (and part of condensed water from the gas bag 6), and the pressure of byproduct steam is 2.5Mpag.
The results of the annual mass loss and the run time of the activated carbon catalysts prepared in the above examples and comparative examples during the synthesis of phosgene are shown in Table 3.
TABLE 3 Table 3
From tables 1-3, the following points can be found:
(1) The active carbon catalyst prepared by the preparation method provided by the embodiment 1-2 of the invention utilizes the acid solution and the complexing agent to control the content of metal ions such as Al, fe and the like which influence the heat resistance of the active carbon within a certain range, thereby effectively improving the heat resistance of the active carbon, avoiding the active carbon from forming halide with Cl 2 in the phosgene synthesis reaction process, reducing the loss of the active carbon catalyst and prolonging the service cycle of the active carbon;
(2) It is known 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, fe, etc. which affect the heat resistance of the activated carbon cannot be reduced to a certain range, so that the metal ions such as Al, fe, etc. form halide with Cl 2 in the phosgene synthesis process to further damage the skeleton of the activated carbon, and further the loss of the activated carbon catalyst is increased; when the concentration of the acid solution is too high, although the acid solution has stronger removing capability on metal ions, the scale of the active carbon framework is easily damaged, so that the strength of the active carbon is reduced, and the service life is shortened;
(3) It is known from the comprehensive 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 the metal ions cannot be achieved, so that the content of the 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, although the metal ions are removed strongly, the scale of the activated carbon framework is easily damaged, so that the intensity of the activated carbon is reduced, and the service life is shortened;
(4) It is known from the combination of examples 1 and 9-10 that when the amount of the complexing agent is too small, the content of metal ions such as Al, fe, etc., which affect the heat resistance of the activated carbon, cannot be reduced to a certain range, so that the metal ions such as Al, fe, etc., form halides with Cl 2 during the phosgene synthesis process to damage the skeleton of the activated carbon, and further the loss of the activated carbon catalyst is increased; when the adding amount of the complexing agent is too much, although the metal ions can be effectively complexed to reduce the content of the complexing agent, too much complex is easy to form to block the pore canal, so that the catalytic performance of the activated carbon is reduced, the temperature distribution in the pore canal is uneven, and the service life is shortened;
(5) It is apparent from the combination of example 1 and comparative examples 1 to 2 that when the acid solution or complexing agent is not used, the content of metal ions such as Al, fe, etc., which affect the heat resistance of the activated carbon, cannot be reduced to a certain range, so that the metal ions such as Al, fe, etc., form halides with Cl 2 during the phosgene synthesis process to damage the skeleton of the activated carbon, and further, the loss of the activated carbon catalyst is increased.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (63)
1. A method for preparing an activated carbon catalyst for phosgene synthesis, which is characterized by comprising the following steps:
(1) Stirring and soaking the activated carbon in an acid solution, and then performing 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 carrying out complexing treatment to obtain a complexing modified activated carbon;
(3) Drying and roasting the complexation modified activated carbon in the step (2) in sequence to obtain the activated carbon catalyst;
wherein the mass ratio of the activated carbon to the acid solution in the step (1) is 1 (2.5-5);
the mass concentration of the acid solution in the step (1) is 1% -30%;
the mass ratio of the complexing agent to the modified activated carbon in the step (2) is (0.01-0.1): 1;
The roasting in the step (3) is carried out under the protection of inert atmosphere;
the roasting temperature in the step (3) is 500-800 ℃.
2. The method of claim 1, wherein the activated carbon of step (1) comprises coconut activated carbon and/or coal-based activated carbon.
3. The method according to claim 1, wherein the activated carbon in step (1) has a particle size of 2 to 7mm.
4. A method according to claim 3, wherein the activated carbon in step (1) has a particle size of 3-5mm.
5. The preparation method according to claim 1, wherein the mass ratio of the activated carbon to the acid solution in the step (1) is 1 (2.5-4).
6. The preparation method according to claim 1, wherein the mass concentration of the acid solution in the step (1) is 4% -10%.
7. The method of claim 1, wherein the acid in the acid solution of step (1) comprises hydrochloric acid or phosphoric acid.
8. The method according to claim 1, wherein the temperature of the stirring and soaking in the step (1) is 25-150 ℃.
9. The method according to claim 8, wherein the temperature of the stirring and soaking in the step (1) is 40-70 ℃.
10. The method according to claim 1, wherein the stirring and soaking time in the step (1) is 3-5 hours.
11. The method of claim 1, wherein the ultrasonic washing in step (1) is performed at a temperature of 25-100 ℃.
12. The method of claim 11, wherein the ultrasonic washing in step (1) is performed at a temperature of 30-50 ℃.
13. The method of claim 1, wherein the ultrasonic washing in step (1) is performed at a pulse frequency of 10-30kHz.
14. The method of claim 13, wherein the ultrasonic wash of step (1) is pulsed at a frequency of 12-25kHz.
15. The method of claim 1, wherein the ultrasonic wash of step (1) has a pulse width of 50-500ms.
16. The method of claim 15, wherein the ultrasonic wash of step (1) has a pulse width of 100-450ms.
17. The method of claim 1, wherein the ultrasonic washing in step (1) is performed for a period of 1 to 20 hours.
18. The method of claim 17, wherein the ultrasonic washing of step (1) is for a period of time ranging from 5 to 10 hours.
19. The method of claim 1, wherein the stirring soaking and ultrasonic washing in step (1) are alternately performed 1 to 5 times.
20. The method of claim 19, wherein the agitation soaking and ultrasonic washing in step (1) are alternately performed 2 to 3 times.
21. The method according to claim 1, wherein the total content of metal elements in the modified activated carbon in the step (1) is 5000 to 30000ppm.
22. The method of claim 21, wherein the modified activated carbon in step (1) has a total content of metal elements of 5000 to 15000ppm.
23. The method according to claim 1, wherein the content of Al element in the modified activated carbon in the step (1) is 1000 to 8000ppm.
24. The method according to claim 23, wherein the content of Al element in the modified activated carbon in the step (1) is 2000 to 5000ppm.
25. The method according to claim 1, wherein the content of Fe element in the modified activated carbon in the step (1) is 1000 to 5000ppm.
26. The method according to claim 25, wherein the content of Fe element in the modified activated carbon in the step (1) is 1500 to 3000ppm.
27. The method of claim 1, wherein the complexing agent of step (2) comprises any one or a combination of at least two of ammonium rhodotricarboxylic acid, alizarin red S, alizarin violet, or ethylenediamine tetraacetic acid.
28. The method according to claim 1, wherein the mass ratio of the complexing agent to the modified activated carbon in the step (2) is (0.05-0.08): 1.
29. The method according to claim 1, wherein the temperature of the complexation treatment in the step (2) is 20 to 100 ℃.
30. The method of claim 29, wherein the temperature of the complexation treatment in step (2) is 40-50 ℃.
31. The method according to claim 1, wherein the time of the complexation treatment in the step (2) is 1 to 10 hours.
32. The method of claim 31, wherein the complexing in step (2) is for a period of time ranging from 4 to 7 hours.
33. The method of claim 1, wherein the complexing treatment of step (2) is followed by ultrasonic washing.
34. The method of preparation of claim 33, wherein the ultrasonically washed lotion comprises water.
35. The method of claim 33, wherein the ultrasonic washing is performed at a temperature of 25-80 ℃.
36. The method of claim 35, wherein the ultrasonic washing is performed at a temperature of 30-50 ℃.
37. The method of claim 33, wherein the ultrasonic wash pulses have a frequency of 10-30kHz.
38. The method of claim 37, wherein the ultrasonic wash pulses have a frequency of 12-25kHz.
39. The method of claim 33, wherein the ultrasonic wash has a pulse width of 50-500ms.
40. The method of claim 39, wherein the ultrasonic wash has a pulse width of 100-450ms.
41. The method of claim 33, wherein the ultrasonic washing is performed for a period of 1 to 20 hours.
42. The method of claim 41, wherein the ultrasonic washing is performed for a period of 5 to 10 hours.
43. The method according to claim 1, wherein the total content of metal elements in the complex modified activated carbon in the step (2) is 700 to 20000ppm.
44. The process according to claim 43, wherein the total content of metal elements in the complex modified activated carbon in step (2) is 1100 to 8000ppm.
45. The method according to claim 1, wherein the content of Al element in the complex modified activated carbon in the step (2) is 500 to 5000ppm.
46. The process according to claim 45, wherein the content of Al element in the complex modified activated carbon in step (2) is 800 to 2500ppm.
47. The method according to claim 1, wherein the content of Fe element in the complex modified activated carbon in the step (2) is 200 to 3000ppm.
48. The process of claim 47, wherein the Fe element content of the complex modified activated carbon in step (2) is 300-1500ppm.
49. The method according to claim 1, wherein the temperature of the drying in step (3) is 150 to 200 ℃.
50. The method according to claim 1, wherein the drying time in step (3) is 4 to 8 hours.
51. The method of claim 1, wherein the inert atmosphere comprises nitrogen and/or argon.
52. The method of claim 1, wherein the firing in step (3) is at a temperature of 600-700 ℃.
53. The method of claim 1, wherein the calcination in step (3) is performed for a period of 5 to 15 hours.
54. The method of claim 53, wherein the calcination in step (3) is performed for a period of 8 to 12 hours.
55. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) According to the mass ratio of 1, (2.5-5), soaking active carbon with the particle size of 2-7mm in an acid solution with the mass concentration of 1% -30%, stirring for 3-5h at 25-150 ℃, then performing ultrasonic washing in water for 1-20h, and alternately performing stirring soaking and ultrasonic washing for 1-5 times to obtain the modified active carbon with the total content of metal elements of 5000-30000ppm, the content of Al element of 1000-8000ppm and the content of Fe element of 1000-5000ppm;
the ultrasonic washing temperature is 25-100 ℃, the pulse frequency is 10-30kHz, and the pulse width is 50-500ms;
(2) Mixing complexing agent, solvent and the modified active carbon in the step (1) according to the mass ratio of (0.01-0.1) of 1:1, carrying out complexing treatment for 1-10 hours at 20-100 ℃, and then carrying out ultrasonic washing in water to obtain the complexing modified active carbon, wherein the total content of metal elements in the complexing modified active carbon is 500-20000ppm, the content of Al element is 500-5000ppm and the content of Fe element is 200-3000ppm;
(3) And (3) drying the complexation modified activated carbon in the step (2) at 150-200 ℃ for 4-8 hours, and roasting the activated carbon at 500-800 ℃ for 5-15 hours under the protection of inert atmosphere to obtain the activated carbon catalyst.
56. An activated carbon catalyst for phosgene synthesis, characterized in that it is produced by the production method according to any one of claims 1 to 55.
57. The activated carbon catalyst of claim 56, wherein the total content of metal elements in the activated carbon catalyst is 700-20000ppm.
58. The activated carbon catalyst of claim 57, wherein the total content of metallic elements in the activated carbon catalyst is 1100-8000ppm.
59. The activated carbon catalyst of claim 56, wherein the content of elemental Al in the activated carbon catalyst is 500-5000ppm.
60. The activated carbon catalyst of claim 59, wherein the content of elemental Al in the activated carbon catalyst is 800-2500ppm.
61. The activated carbon catalyst of claim 56, wherein the content of Fe element in the activated carbon catalyst is 200-3000ppm.
62. The activated carbon catalyst of claim 61, wherein the content of Fe element in the activated carbon catalyst is 300-1500ppm.
63. A method for preparing phosgene, comprising: mixing chlorine and carbon monoxide, filling the mixture into a phosgene synthesis reaction device containing the active carbon catalyst of any one of claims 56-62, and reacting to synthesize phosgene under the action of the active carbon catalyst.
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| CN104415770B (en) * | 2013-08-26 | 2016-08-31 | 万华化学集团股份有限公司 | A kind of catalyst preparing phosgene and the method preparing phosgene |
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| EP3294450A4 (en) * | 2015-05-11 | 2019-02-27 | W.R. Grace & Co.-Conn. | Process to produce modified clay, modified clay produced and use thereof |
| CN107321353B (en) * | 2017-06-29 | 2020-04-10 | 万华化学集团股份有限公司 | Preparation method of medium-low temperature selective catalytic reduction denitration catalyst |
| CN111760581B (en) * | 2019-08-30 | 2021-07-23 | 万华化学（宁波）有限公司 | Catalyst for preparing phosgene, preparation method thereof and method for preparing phosgene and comprehensively utilizing energy |
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