CN116371436A - Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof - Google Patents
Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof Download PDFInfo
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- CN116371436A CN116371436A CN202310077092.2A CN202310077092A CN116371436A CN 116371436 A CN116371436 A CN 116371436A CN 202310077092 A CN202310077092 A CN 202310077092A CN 116371436 A CN116371436 A CN 116371436A
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- phosgene
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- silicon carbide
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- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 title claims abstract description 82
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 24
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 13
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 46
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 18
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 230000007547 defect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, a preparation method thereof and application thereof in catalyzing and hydrolyzing phosgene. The catalyst comprises silicon carbide, cerium oxide and a binder. The preparation method comprises the following steps: a. activating silicon carbide powder by using hydrochloric acid solution, then washing cleanly by using deionized water, and drying to obtain activated silicon carbide powder; b. adding activated silicon carbide powder and a binder into cerium nitrate solution, uniformly mixing and drying to obtain mixed pug; c. and (3) compressing and molding the mixed pug, and drying and sintering to obtain the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning. The catalyst of the invention takes silicon carbide as a carrier and cerium oxide as an active component, has simple manufacturing steps, high phosgene decomposition rate and long service life, is not influenced by organic solvents such as chlorobenzene and the like, and solves the problems of low decomposition efficiency and complex required process devices of the existing SN-7501 and the like.
Description
Technical Field
The invention relates to the technical field of treatment of tail gas containing phosgene in a phosgenation reaction, in particular to a catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and a preparation method and application thereof.
Background
Isocyanate is a generic term for various esters of isocyanic acid, is one of the main raw materials for producing polyurethane materials, and has been widely used in the fields of foam plastics, adhesives, paints, and curing agents.
The isocyanate is mainly produced by the reaction of phosgene and amines, and in the production process of the isocyanate, tail gas containing phosgene is inevitably produced.
Phosgene is also called phosgene, belongs to extremely harmful substances, can generate great harm to human bodies and can be discharged after reaching the standard through treatment.
The method for treating tail gas containing phosgene in isocyanate industry mainly comprises an alkali destruction method, an incineration method, a catalytic hydrolysis method and the like.
The catalytic hydrolysis method is used as a common treatment method for tail gas containing phosgene, and phosgene and water are required to act on the surface of a catalyst. The decomposition efficiency, the service life and the complexity of the process of the catalyst are key factors for restricting the catalytic hydrolysis method.
A common catalyst used for treating tail gas of phosgenation reaction in the prior art is SN-7501 of a silicon-aluminum system, for example, the patent technologies with publication numbers of CN 104096377A and CN 111111432A adopt the catalyst to treat tail gas containing phosgene.
However, the phosgene decomposition catalytic activity of the commercial catalyst of SN-7501 still needs to be improved, and the phosgene decomposition rate is generally less than 90%, thereby leading to the problem that an alkali liquor protection system is generally required in practical use to prevent phosgene leakage due to low phosgene decomposition efficiency.
In addition, the SN-7501 commercial catalyst is easy to be deactivated due to the toxic action of organic solvents such as chlorobenzene and the like. For example, patent specification CN 111111432A discloses that chlorobenzene contained in tail gas affects the activity of catalyst SN-7501, and the solution proposed by the patent technology is to first use a condensation tower to absorb organic solvents such as chlorobenzene, which may complicate the device process.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, which takes silicon carbide as a carrier and cerium oxide as an active component.
The specific technical scheme is as follows:
a catalyst for decomposing phosgene and resisting poisoning by chlorobenzene is prepared from silicon carbide, cerium oxide and adhesive.
The particle size of the silicon carbide is preferably 10-100 mu m, more preferably 20-80 mu m, and the silicon carbide powder with the preferred particle size range is favorable for compression molding.
Based on the mass of the silicon carbide, the mass percentage of cerium oxide in the catalyst which can efficiently decompose phosgene and resist chlorobenzene poisoning is preferably 1% -15%, more preferably 5% -10%, and the cerium oxide with higher content can form more lattice defects, but the content of cerium oxide is too high, so that the improvement of the catalytic performance is not obvious.
The invention also provides a preparation method of the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, which comprises the following steps:
a. activating silicon carbide powder by using hydrochloric acid solution, then washing cleanly by using deionized water, and drying to obtain activated silicon carbide powder;
b. adding activated silicon carbide powder and a binder into cerium nitrate solution, uniformly mixing and drying to obtain mixed pug;
c. and (3) compressing and molding the mixed pug, and drying and sintering to obtain the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning.
In the preparation method of the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, in the step a, the concentration of HCl in the hydrochloric acid solution is preferably 0.8-1mol/L, and more preferably 1mol/L.
In the preparation method of the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, in the step b, the binder is preferably at least one of methylcellulose, carboxymethylcellulose and hydroxyethyl cellulose.
In the preparation method of the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, in the step b, the cerium nitrate solution can be obtained by adding cerium nitrate (such as cerium nitrate hexahydrate) into deionized water for dissolution.
In the preparation method of the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, in the step c, the drying temperature is preferably 80-120 ℃.
In the preparation method of the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, in the step c, the sintering temperature is preferably 400-1000 ℃, more preferably 500-800 ℃, and the preferable temperature range can enable cerium oxide to form lattice defects more easily.
In the preparation method of the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, in the step c, the sintering time is preferably 2-8 hours, and more preferably 3-6 hours.
In the catalyst and the preparation method thereof, the catalyst has low cerium oxide content, low sintering temperature and short sintering time, and the catalytic effect of the catalyst is not obviously improved; too high sintering temperature and too long sintering time can lead to insignificant improvement of the catalytic effect of the catalyst.
In the catalyst and the preparation method thereof, the reason for high efficiency of catalyzing phosgene hydrolysis by the catalyst is probably that a large number of lattice defects are formed in the process of sintering cerium nitrate into cerium dioxide on a silicon carbide carrier, so that phosgene can be adsorbed more easily, and the catalysis efficiency is improved. And chlorobenzene contains benzene ring, has larger molecular structure and is not easy to be adsorbed by the lattice defect of generated cerium dioxide, so the catalyst has excellent anti-chlorobenzene poisoning capability.
The invention also provides an application of the catalyst in catalyzing and hydrolyzing phosgene, and the action principle is as follows:
COCl 2 +H 2 O＝CO 2 +2HCl。
as a general inventive concept, the invention also provides a method for treating tail gas containing phosgene in a phosgenation reaction, and the catalyst is used for catalyzing and hydrolyzing phosgene.
In the method for treating the tail gas containing phosgene in the phosgenation reaction, chlorobenzene can be further contained in the tail gas containing phosgene, and the existence of the chlorobenzene does not influence the activity of the catalyst.
The invention also provides a method for regenerating and activating the catalyst after treating the tail gas containing phosgene for the phosgenation reaction to deactivate, which comprises the following steps: the deactivated catalyst is washed by soaking in ethanol, washed with deionized water, dried, and calcined at 400-1000 deg.c, preferably 500-800 deg.c.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and a preparation method and application thereof, which are suitable for tail gas with phosgene concentration of more than 150000ppm, and the catalyst has high phosgene decomposition efficiency, the decomposition rate can reach 99.9999%, and the phosgene concentration can be reduced to below 0.2ppm after the tail gas is treated.
The catalyst of the invention is used for carrying out phosgene catalytic hydrolysis, the required device and process are simple, an additional alkali washing protection system is not needed, and the catalyst is not influenced by organic solvents (such as chlorobenzene).
The catalyst has long service life, is not easy to deactivate, can recover the catalytic performance of the catalyst to be almost consistent with the original performance through simple recovery and activation operation even after long-time use, and can be recycled.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
The following examples and comparative examples are examples of the treatment of phosgene-containing tail gases produced during the preparation of hexamethylene diisocyanate.
A filler absorption tower using water as an absorbent is adopted, and phosgene-containing tail gas enters from a tower kettle and is decomposed after being contacted with catalyst filler. The reaction temperature in the packing absorption tower is about 45 ℃; the water consumption and the circulation amount of the packing tower are regulated according to the concentration of hydrochloric acid, and the concentration of hydrochloric acid is controlled to be about 3-4wt%.
The method for measuring the phosgene content comprises the following steps: and (3) absorbing the treated tail gas by adopting a NaOH aqueous solution with the mass concentration of 15%, and measuring the chloride ion content in the tail gas by an ion chromatography method to reversely calculate the phosgene concentration.
Example 1
1kg of silicon carbide (particle size of 20-60 micrometers) is immersed in 2-3L of 1mol/L hydrochloric acid solution for 12 hours, then washed to be neutral by deionized water, and dried for 8 hours at 80 ℃ to obtain activated silicon carbide powder.
132.8g of cerium nitrate hexahydrate is taken in 200g of deionized water, heated to 70 ℃ and dissolved uniformly to obtain cerium nitrate solution, activated silicon carbide powder is added into the cerium nitrate solution, 68g of methylcellulose is added, and the temperature is raised to 80 ℃ and stirred for 2 hours to obtain mixed pug.
Drying the mixed pug at 100 ℃ for 1h, then compressing the mixed pug into a cylinder with the diameter of 3mm and the height of 3mm, drying the mixed pug at 110 ℃ for 3h, and sintering the mixed pug at 800 ℃ for 6h to obtain the catalyst. The content of cerium oxide in the catalyst was 5.3wt%.
Filling the catalyst into a packed tower, and introducing tail gas containing 151147ppm of phosgene and 824ppm of chlorobenzene, wherein the gas amount of the tail gas is 1.5Nm 3 And/h, the phosgene decomposition rate is 98.4690 percent, and the phosgene concentration in the treated tail gas is 2314ppm.
Example 2
1kg of silicon carbide (with the particle size of 30-80 microns) is immersed in 2-3L of 1mol/L hydrochloric acid solution for 12 hours, then washed to be neutral by deionized water, and dried for 8 hours at the temperature of 80 ℃ to obtain activated silicon carbide powder.
219.4g of cerium nitrate hexahydrate is taken in 330g of deionized water, heated to 70 ℃ and dissolved uniformly to obtain cerium nitrate solution, activated silicon carbide powder is added into the cerium nitrate solution, 73.2g of hydroxyethyl cellulose is added, and the temperature is raised to 80 ℃ and stirred for 2 hours to obtain mixed pug.
Drying the mixed pug at 110 ℃ for 1h, then compressing the mixed pug into a cylinder with the diameter of 3mm and the height of 3mm, drying the mixed pug at 110 ℃ for 3h, and sintering the mixed pug at 800 ℃ for 6h to obtain the catalyst.
Filling the catalyst into a packed tower, and introducing tail gas containing 149956ppm of phosgene and 810ppm of chlorobenzene, wherein the tail gas amount is 1.5Nm 3 And/h, the phosgene decomposition rate is 99.9999%, and the concentration of phosgene in the treated tail gas is reduced to 0.15ppm.
The catalyst of the invention has low deactivation rate, and in the embodiment, after 2000 hours of continuous operation, the phosgene content in the tail gas after treatment is still lower than 0.5ppm; after 4500 hours of continuous operation, the phosgene content in the treated tail gas is about 1ppm, and the phosgene decomposition rate can still be kept above 99.9993%, which shows that the catalyst has long service life and good catalytic performance.
And (3) when the phosgene content in the treated tail gas exceeds 1ppm, recovering and activating the catalyst.
The catalyst recovery and activation operation of this example comprises the steps of:
s1, firstly soaking and washing the catalyst for 2 hours by using ethanol, then washing the catalyst by using deionized water, and drying the catalyst for 3 hours at 110 ℃.
S2, reactivating the dried catalyst for 1h at 800 ℃.
The catalyst after reactivation is used for treating the tail gas under the same condition, the phosgene content in the treated tail gas is lower than 0.5ppm, and the phosgene decomposition efficiency can reach more than 99.9997 percent, so that the catalyst has the characteristics of easy regeneration and repeated recycling.
Example 3
1kg of silicon carbide (with the particle size of 30-80 microns) is immersed in 2-3L of 1mol/L hydrochloric acid solution for 12 hours, then washed to be neutral by deionized water, and dried for 8 hours at the temperature of 80 ℃ to obtain activated silicon carbide powder.
219.4g of cerium nitrate hexahydrate is taken in 330g of deionized water, heated to 70 ℃ and dissolved uniformly to obtain cerium nitrate solution, activated silicon carbide powder is added into the cerium nitrate solution, 73.2g of hydroxyethyl cellulose is added, and the temperature is raised to 80 ℃ and stirred for 2 hours to obtain mixed pug.
Drying the mixed pug at 110 ℃ for 1h, then compressing the mixed pug into a cylinder with the diameter of 3mm and the height of 3mm, drying the mixed pug at 110 ℃ for 3h, and sintering the mixed pug at 800 ℃ for 6h to obtain the catalyst.
Filling the catalyst into a packed tower, and introducing tail gas containing 150246ppm of phosgene and 1520ppm of chlorobenzene, wherein the gas amount of the tail gas is 1.5Nm 3 And/h, the phosgene decomposition rate is 99.99988 percent, and the concentration of phosgene in the treated tail gas is reduced to 0.18ppm.
From this, it can be seen that the catalyst of the present invention can maintain an extremely high phosgene decomposition rate at a high content of chlorobenzene impurities with little decrease compared to example 2. The catalyst has excellent chlorobenzene poisoning resistance.
Comparative example 1
1kg of commercial catalyst SN-7501 is uniformly loaded into a filler absorption tower, and the tail gas containing 150138ppm of phosgene and 126ppm of chlorobenzene is introduced, and the gas amount of the tail gas is 1.5Nm 3 And/h, the concentration of phosgene in the treated tail gas is 19410.9ppm, and the phosgene decomposition rate is 87.0713%.
Comparative example 2
1kg of commercial catalyst SN-7501 is uniformly loaded into a filler absorption tower, and the tail gas containing 149897ppm of phosgene and 807ppm of chlorobenzene is introduced, and the gas amount of the tail gas is 1.5Nm 3 And/h, the concentration of phosgene in the treated tail gas is 30168.9ppm, and the phosgene decomposition rate is 79.8736%.
Therefore, the commercial catalyst SN-7501 has poor phosgene decomposition catalyzing capability under the condition that chlorobenzene exists in the tail gas, and the SN-7501 catalyst obviously reduces the phosgene decomposition catalyzing capability along with the increase of the chlorobenzene content in the tail gas.
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (10)
1. A catalyst capable of decomposing phosgene with high efficiency and resisting chlorobenzene poisoning is characterized by comprising silicon carbide, cerium oxide and a binder.
2. The catalyst for decomposing phosgene and resisting chlorobenzene poisoning according to claim 1, characterized in that the particle size of the silicon carbide is 10-100 μm, preferably 20-80 μm.
3. The catalyst for decomposing phosgene and resisting chlorobenzene poisoning with high efficiency according to claim 1 or 2, characterized in that the content of cerium oxide in the catalyst is 1-15% by mass, preferably 5-10% by mass, based on the mass of silicon carbide.
4. A method for preparing a catalyst capable of decomposing phosgene with high efficiency and resistant to chlorobenzene poisoning according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
a. activating silicon carbide powder by using hydrochloric acid solution, then washing cleanly by using deionized water, and drying to obtain activated silicon carbide powder;
b. adding activated silicon carbide powder and a binder into cerium nitrate solution, uniformly mixing and drying to obtain mixed pug;
c. and (3) compressing and molding the mixed pug, and drying and sintering to obtain the catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning.
5. The process according to claim 4, wherein in step a, the concentration of HCl in the hydrochloric acid solution is 0.8-1mol/L;
in step c:
the drying temperature is 80-120 ℃;
the sintering temperature is 400-1000 ℃, preferably 500-800 ℃, and the sintering time is 2-8 hours, preferably 3-6 hours.
6. The method according to claim 4, wherein in the step b, the binder is at least one of methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose.
7. Use of a catalyst according to any of claims 1 to 3 for the catalytic hydrolysis of phosgene.
8. A method for treating phosgene-containing tail gases from a phosgenation reaction, characterized in that the catalyst according to any of claims 1 to 3 is used for the catalytic hydrolysis of phosgene.
9. The method of claim 8, wherein the tail gas comprising phosgene further comprises chlorobenzene.
10. A method for the regeneration and activation of a catalyst according to any one of claims 1 to 3 after the deactivation of the tail gas containing phosgene in the treatment of phosgenation reactions, comprising: the deactivated catalyst is washed by soaking in ethanol, washed with deionized water, dried, and calcined at 400-1000 deg.c, preferably 500-800 deg.c.
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