CN109485540A - A kind of method that catalytic distillation degradation hexachloro-benzene generates chlorobenzene and dichloro-benzenes - Google Patents
A kind of method that catalytic distillation degradation hexachloro-benzene generates chlorobenzene and dichloro-benzenes Download PDFInfo
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Abstract
The invention discloses the methods that a kind of catalytic distillation degradation hexachloro-benzene generates chlorobenzene and dichloro-benzenes, this method uses fixed-bed catalytic destilling tower, the chlorine on hexachloro-benzene is gradually removed in a manner of being segmented catalytic hydrogenation, hexachloro-benzene and hydrogen enter from fixed-bed catalytic distillation tower bottom, dechlorination reaction occurs by catalyst bed, since the product boiling point of generation gradually decreases, so product moves up, go out from tower top, control catalyst and catalytic reaction condition can control the composition of overhead product, make the purity of the dichloro-benzenes obtained and chlorobenzene up to 99% or more.
Description
Technical field
The invention belongs to selective catalytic hydrogenation technical fields, and in particular to a kind of selective catalytic hydrogenation dealuminated USY cataluyst six
Method of the chlorobenzene to chlorobenzene and dichloro-benzenes.
Background technique
Hexachloro-benzene (HCB) is classified as in 2B class carcinogenic substance inventory by international cancer research institution, the World Health Organization in 2017,
Hexachloro-benzene is to the pollution of environment mainly from agricultural production and chemical pollution.Agriculturally, hexachloro-benzene is used as fungicide,
Protect onion, wheat, the seed of sorghum and soil disinfection.In terms of chemical industry, hexachloro-benzene is used also as a kind of solvent, and production
As manufacture intermediate or addition in synthetic rubber, polyvinyl chloride (PVC) plastics, pyrotechnics, munitions, timber preservative and dyestuff
Agent.Also hexachloro-benzene can be generated in the combustion process of municipal refuse.
The biodegrading process of hexachloro-benzene has microbial method, photocatalytic oxidation, radiation method, electrochemical process and catalytic hydrogenation method.
Microbial method is degraded hexachloro-benzene, this method efficiency is lower, the time mainly to screen based on bacterium with bacteriogenic degrading enzyme
Long and degradation difficulty is big, and the application of the practical scale of distance is farther out.Li Fanxiu et al. is using optically catalytic TiO 2 to degradation
Hexachloro-benzene waste water is studied, the results showed that has feasibility using light-catalysed method, but experiment is only limitted to hexachloro-benzene
Waste water, chlordene benzene concentration is lower, also requires further study to the degradation of processing high concentration hexachloro-benzene waste.Catalytic hydrogenation
Hexachloro-benzene efficiency of degrading is higher, has very strong practicability, Chinese patent 201410246756.4 and 201410244652.X are provided
The Catalyst And Method of catalytic hydrogenation degradation hexachloro-benzene, the key of this method is the activity and stability of catalyst, by adding
Hexachloro-benzene is degraded to benzene and hydrogen chloride by the mode of hydrogen dechlorination, and the catalyst activity is higher, directly that the chlorine on hexachloro-benzene is complete
It is stripped of, in fact, controlling the rate sum number of dechlorination reaction if catalyst and catalysis reaction process are improved and optimized
Amount, it is possible to obtain the intermediate of high added value, such as chlorobenzene, dichloro-benzenes or polystream compound.
Summary of the invention
It is high added value in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of continuous catalysis degradation hexachloro-benzene
The method of product chlorobenzene and dichloro-benzenes.
To achieve the above object, technical solution of the present invention is made of following step:
1, catalyst preparation
Cobalt chloride and lithium chloride are dissolved into the ethanol water that volume fraction is 40%~60%, θ-oxidation is added
Aluminium dipping 12 hours or more, is placed in 120~150 DEG C drying 2~6 hours in baking oven, places into 550~650 DEG C of roastings in Muffle furnace
It burns 2~3 hours, obtains catalyst precursor；Palladium chloride and iridium chloride are dissolved into the methanol that volume fraction is 40%~60%
In aqueous solution, above-mentioned catalyst precursor is added, dipping 12 hours or more, it is small to be placed in 120~150 DEG C of dryings 2~6 in baking oven
When, it places into Muffle furnace and roasts 2~3 hours for 550~650 DEG C, obtain catalyst.
2, Catalyst packing
It is divided into six sections of diluted catalyst of filling coconut husk granulated carbon from top to bottom in fixed-bed catalytic destilling tower, and from upper
The mass percentage of the catalyst loaded to lower each section is followed successively by 8%~12%, 0%, 18%~22%, 38%~42%,
58%~62%, 78%~82%；The second to five section of the fixed-bed catalytic destilling tower is provided with gas supplementing opening.
3, catalyst pre-treatment
It is passed through in nitrogen displacement tower air 3 hours or more from fixed-bed catalytic distillation tower bottom, is then switched to nitrogen
Pure hydrogen, while heating up to fixed-bed catalytic destilling tower, make its from top to bottom temperature of each section be followed successively by 180~220 DEG C,
190~230 DEG C, 240~260 DEG C, 290~300 DEG C, 290~310 DEG C, 300~320 DEG C, heating rate is 1~2 DEG C/minute
Clock, constant temperature is kept for 2~6 hours after rising to target temperature, is activated to catalyst；After activation of catalyst is complete, fixed bed is urged
Change destilling tower from top to bottom temperature of each section be successively reduced to 130~140 DEG C, 175~185 DEG C, 215~225 DEG C, 250~260 DEG C,
275~285 DEG C, 230~240 DEG C, and keep in this temperature；Then hydrogen chloride gas is added in the hydrogen being passed through, makes hydrogen
Volumetric concentration be 20%~40%.
4, catalysis reaction
It is passed through after hexachloro-benzene is heated to 230~240 DEG C from fixed-bed catalytic destilling tower bottom, while logical from each section of gas supplementing opening
Enter the gaseous mixture of hydrogen chloride and hydrogen, the volumetric concentration of hydrogen is 20%~40% in the gaseous mixture, is urged to control fixed bed
Changing the molar ratio of hexachloro-benzene and hydrogen in destilling tower is 1:1.1~3.0, and reaction product dichloro-benzenes is from fixed-bed catalytic destilling tower
Second segment goes out, and chlorobenzene goes out from first segment；Hydrogen chloride goes out from top of tower, reuses after circulation.
It is in terms of 100% by the quality of catalyst, the total load amount of palladium and iridium is in preferred catalyst in above-mentioned steps 1
0.5%~0.8%, the total load amount of cobalt and lithium is 0.4%~1.0%.
In above-mentioned steps 2, preferably fixed-bed catalytic destilling tower from top to bottom every section filling catalyst quality percentage composition
It is followed successively by 10%, 0%, 20%, 40%, 60%, 80%.
It in above-mentioned steps 3, heats up to fixed-bed catalytic destilling tower, preferably making it, temperature of each section is followed successively by from top to bottom
200 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 300 DEG C, 300 DEG C, each section of the fixed-bed catalytic destilling tower all use cycle of higher pressure water
Heat temperature raising.
In above-mentioned steps 3, hydrogen chloride gas further preferably is added in the hydrogen being passed through, makes the volumetric concentration of hydrogen
30%.
In above-mentioned steps 4, preferably control fixed-bed catalytic destilling tower in the molar ratio of hexachloro-benzene and hydrogen be 1:1.2~
1.9。
In above-mentioned steps 4, the dichloro-benzenes is the mixture of o-dichlorohenzene, m-dichlorobenzene, paracide.
9, the degradation of catalytic distillation described in any one hexachloro-benzene generates chlorobenzene and dichloro-benzenes according to claim 1~8
Method, it is characterised in that: the reaction tube inner member and connecting pipe of the catalytic rectifying tower are all made of carbon steel liner enamel or glass
Glass material.
Beneficial effects of the present invention are as follows:
1, serious carcinogenic substance hexachloro-benzene being changed into high value added product, selectivity is good, and it is high-efficient, it is practical.
2, by control catalyst, catalytic reaction condition and hydrogen proportion etc. factors, the degree of adjustable dechlorination reaction,
Selectivity prepares chlorobenzene and dichloro-benzenes.
3, from monochloro-benzene to hexachloro-benzene, boiling point is gradually increased, and the separation that polystream is carried out using boiling point is existed simultaneously
Catalytic hydrogenation and dechlorination is carried out during separation, controls catalyst and reaction condition can get purity and the higher chlorobenzene of added value
And dichloro-benzenes.
4, catalysis and rectifying separation are combined, controls reaction condition, realize that serialization degradation hexachloro-benzene is additional to height
It is worth the process of product.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of fixed-bed catalytic destilling tower of the present invention.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and examples, but protection scope of the present invention not only limits
In these embodiments.
Embodiment 1
1, catalyst preparation
0.44g cobalt chloride and 4.28g lithium chloride are dissolved into the ethanol water that 100mL volume fraction is 50%, are added
Enter 98.3g θ-aluminium oxide, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven, places into 600 DEG C of roastings in Muffle furnace
It burns 2 hours, obtains catalyst precursor.It is 50% that 0.67g palladium chloride and 0.66g iridium chloride, which are dissolved into 110mL volume fraction,
Methanol aqueous solution in, be added above-mentioned catalyst precursor, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven,
It places into Muffle furnace and roasts 2 hours for 600 DEG C, obtain catalyst.Palladium in the catalyst, iridium, cobalt and lithium load capacity be respectively
0.4wt%, 0.4wt%, 0.2wt% and 0.7wt%.
2, Catalyst packing
Fixed-bed catalytic destilling tower is divided into six sections from top to bottom, in each section of diluted catalysis of filling coconut husk granulated carbon
Agent, and from top to bottom (i.e. from first segment to the 6th section) mass percentage of the catalyst of each section of filling be followed successively by 10%,
0%, 20%, 40%, 60%, 80%.The second to five section of fixed-bed catalytic destilling tower is provided with gas supplementing opening, catalytic rectifying tower
Reaction tube inner member and connecting pipe be all made of carbon steel liner enamel.
3, catalyst pre-treatment
Air 3 hours in nitrogen displacement tower are passed through from fixed-bed catalytic distillation tower bottom, nitrogen is then switched to pure hydrogen
Gas, while heat temperature raising is carried out to fixed-bed catalytic destilling tower using cycle of higher pressure water, making it, temperature of each section is successively from top to bottom
It is 200 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 300 DEG C and 300 DEG C, heating rate is 1 DEG C/min, rises to constant temperature after target temperature
It is kept for 4 hours, catalyst is activated.After activation of catalyst is complete, by fixed-bed catalytic destilling tower temperature of each section from top to bottom
140 DEG C, 180 DEG C, 225 DEG C, 255 DEG C, 285 DEG C and 240 DEG C are successively reduced to, and is kept in this temperature；Then in the hydrogen being passed through
Middle addition hydrogen chloride gas makes the volumetric concentration 30% of hydrogen.
4, catalysis reaction
It is passed through after hexachloro-benzene is heated to 240 DEG C from fixed-bed catalytic destilling tower bottom, while being passed through chlorine from each section of gas supplementing opening
Change the gaseous mixture of hydrogen and hydrogen, the volumetric concentration of hydrogen is 30% in the gaseous mixture, to control in fixed-bed catalytic destilling tower
The molar ratio of hexachloro-benzene and hydrogen is 1:1.8.Reaction product dichloro-benzenes goes out from the second segment of fixed-bed catalytic destilling tower, chlorobenzene from
First segment goes out, dichloro-benzenes (o-dichlorohenzene, m-dichlorobenzene, paracide mixture) purity be 99.1%, chlorobenzene purity is
99.0%.Hydrogen chloride goes out from top of tower, can rejoin in hydrogen and reuse by circulation.
Embodiment 2
1, catalyst preparation
1.10g cobalt chloride and 3.05g lithium chloride are dissolved into the ethanol water that 100mL volume fraction is 50%, are added
Enter 98.3g θ-aluminium oxide, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven, places into 600 DEG C of roastings in Muffle furnace
It burns 2 hours, obtains catalyst precursor.It is 50% that 0.67g palladium chloride and 0.49g iridium chloride, which are dissolved into 110mL volume fraction,
Methanol aqueous solution in, be added above-mentioned catalyst precursor, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven,
It places into Muffle furnace and roasts 2 hours for 600 DEG C, obtain catalyst.Palladium in the catalyst, iridium, cobalt and lithium load capacity be respectively
0.4wt%, 0.3wt%, 0.5wt% and 0.5wt%.
2, Catalyst packing
Fixed-bed catalytic destilling tower is divided into six sections from top to bottom, in each section of diluted catalysis of filling coconut husk granulated carbon
Agent, and from top to bottom (i.e. from first segment to the 6th section) mass percentage of the catalyst of each section of filling be followed successively by 10%,
0%, 20%, 40%, 60%, 80%.The second to five section of fixed-bed catalytic destilling tower is provided with gas supplementing opening, catalytic rectifying tower
Reaction tube inner member and connecting pipe be all made of carbon steel liner enamel.
3, catalyst pre-treatment
Air 3 hours in nitrogen displacement tower are passed through from fixed-bed catalytic distillation tower bottom, nitrogen is then switched to pure hydrogen
Gas, while heat temperature raising is carried out to fixed-bed catalytic destilling tower using cycle of higher pressure water, making it, temperature of each section is successively from top to bottom
It is 200 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 300 DEG C and 300 DEG C, heating rate is 1 DEG C/min, rises to constant temperature after target temperature
It is kept for 4 hours, catalyst is activated.After activation of catalyst is complete, by fixed-bed catalytic destilling tower temperature of each section from top to bottom
135 DEG C, 185 DEG C, 220 DEG C, 255 DEG C, 275 DEG C and 230 DEG C are successively reduced to, and is kept in this temperature；Then in the hydrogen being passed through
Middle addition hydrogen chloride gas makes the volumetric concentration 30% of hydrogen.
4, catalysis reaction
It is passed through after hexachloro-benzene is heated to 230 DEG C from fixed-bed catalytic destilling tower bottom, while being passed through chlorine from each section of gas supplementing opening
Change the gaseous mixture of hydrogen and hydrogen, the volumetric concentration of hydrogen is 30% in the gaseous mixture, to control in fixed-bed catalytic destilling tower
The molar ratio of hexachloro-benzene and hydrogen is 1:1.7.Reaction product dichloro-benzenes goes out from the second segment of fixed-bed catalytic destilling tower, chlorobenzene from
First segment goes out, dichloro-benzenes (o-dichlorohenzene, m-dichlorobenzene, paracide mixture) purity be 98.5%, chlorobenzene purity is
98.1%.Hydrogen chloride goes out from top of tower, can rejoin in hydrogen and reuse by circulation.
Embodiment 3
1, catalyst preparation
0.44g cobalt chloride and 2.44g lithium chloride are dissolved into the ethanol water that 100mL volume fraction is 50%, are added
Enter 98.8g θ-aluminium oxide, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven, places into 600 DEG C of roastings in Muffle furnace
It burns 2 hours, obtains catalyst precursor.It is 50% that 0.67g palladium chloride and 0.33g iridium chloride, which are dissolved into 110mL volume fraction,
Methanol aqueous solution in, be added above-mentioned catalyst precursor, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven,
It places into Muffle furnace and roasts 2 hours for 600 DEG C, obtain catalyst.Palladium in the catalyst, iridium, cobalt and lithium load capacity be respectively
0.4wt%, 0.2wt%, 0.2wt% and 0.4wt%.
2, Catalyst packing
Fixed-bed catalytic destilling tower is divided into six sections from top to bottom, in each section of diluted catalysis of filling coconut husk granulated carbon
Agent, and from top to bottom (i.e. from first segment to the 6th section) mass percentage of the catalyst of each section of filling be followed successively by 10%,
0%, 20%, 40%, 60%, 80%.The second to five section of fixed-bed catalytic destilling tower is provided with gas supplementing opening, catalytic rectifying tower
Reaction tube inner member and connecting pipe be all made of carbon steel liner enamel.
3, catalyst pre-treatment
Air 3 hours in nitrogen displacement tower are passed through from fixed-bed catalytic distillation tower bottom, nitrogen is then switched to pure hydrogen
Gas, while heat temperature raising is carried out to fixed-bed catalytic destilling tower using cycle of higher pressure water, making it, temperature of each section is successively from top to bottom
It is 200 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 300 DEG C and 300 DEG C, heating rate is 1 DEG C/min, rises to constant temperature after target temperature
It is kept for 4 hours, catalyst is activated.After activation of catalyst is complete, by fixed-bed catalytic destilling tower temperature of each section from top to bottom
135 DEG C, 175 DEG C, 220 DEG C, 255 DEG C, 280 DEG C and 235 DEG C are successively reduced to, and is kept in this temperature；Then in the hydrogen being passed through
Middle addition hydrogen chloride gas makes the volumetric concentration 30% of hydrogen.
4, catalysis reaction
It is passed through after hexachloro-benzene is heated to 235 DEG C from fixed-bed catalytic destilling tower bottom, while being passed through chlorine from each section of gas supplementing opening
Change the gaseous mixture of hydrogen and hydrogen, the volumetric concentration of hydrogen is 30% in the gaseous mixture, to control in fixed-bed catalytic destilling tower
The molar ratio of hexachloro-benzene and hydrogen is 1:1.5.Reaction product dichloro-benzenes goes out from the second segment of fixed-bed catalytic destilling tower, chlorobenzene from
First segment goes out, dichloro-benzenes (o-dichlorohenzene, m-dichlorobenzene, paracide mixture) purity be 97.9%, chlorobenzene purity is
97.4%.Hydrogen chloride goes out from top of tower, can rejoin in hydrogen and reuse by circulation.
Embodiment 4
1, catalyst preparation
0.88g cobalt chloride and 0.61g lithium chloride are dissolved into the ethanol water that 110mL volume fraction is 50%, are added
Enter 99.0g θ-aluminium oxide, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven, places into 600 DEG C of roastings in Muffle furnace
It burns 2 hours, obtains catalyst precursor.It is 50% that 0.50g palladium chloride and 0.33g iridium chloride, which are dissolved into 100mL volume fraction,
Methanol aqueous solution in, be added above-mentioned catalyst precursor, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven,
It places into Muffle furnace and roasts 2 hours for 600 DEG C, obtain catalyst.Palladium in the catalyst, iridium, cobalt and lithium load capacity be respectively
0.3wt%, 0.2wt%, 0.4wt% and 0.1wt%.
2, Catalyst packing
Fixed-bed catalytic destilling tower is divided into six sections from top to bottom, in each section of diluted catalysis of filling coconut husk granulated carbon
Agent, and from top to bottom (i.e. from first segment to the 6th section) mass percentage of the catalyst of each section of filling be followed successively by 10%,
0%, 20%, 40%, 60%, 80%.The second to five section of fixed-bed catalytic destilling tower is provided with gas supplementing opening, catalytic rectifying tower
Reaction tube inner member and connecting pipe be all made of carbon steel liner enamel.
3, catalyst pre-treatment
Air 3 hours in nitrogen displacement tower are passed through from fixed-bed catalytic distillation tower bottom, nitrogen is then switched to pure hydrogen
Gas, while heat temperature raising is carried out to fixed-bed catalytic destilling tower using cycle of higher pressure water, making it, temperature of each section is successively from top to bottom
It is 200 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 300 DEG C and 300 DEG C, heating rate is 1 DEG C/min, rises to constant temperature after target temperature
It is kept for 4 hours, catalyst is activated.After activation of catalyst is complete, by fixed-bed catalytic destilling tower temperature of each section from top to bottom
130 DEG C, 177 DEG C, 218 DEG C, 250 DEG C, 280 DEG C and 235 DEG C are successively reduced to, and is kept in this temperature；Then in the hydrogen being passed through
Middle addition hydrogen chloride gas makes the volumetric concentration 30% of hydrogen.
4, catalysis reaction
It is passed through after hexachloro-benzene is heated to 235 DEG C from fixed-bed catalytic destilling tower bottom, while being passed through chlorine from each section of gas supplementing opening
Change the gaseous mixture of hydrogen and hydrogen, the volumetric concentration of hydrogen is 30% in the gaseous mixture, to control in fixed-bed catalytic destilling tower
The molar ratio of hexachloro-benzene and hydrogen is 1:1.2.Reaction product dichloro-benzenes goes out from the second segment of fixed-bed catalytic destilling tower, chlorobenzene from
First segment goes out, dichloro-benzenes (o-dichlorohenzene, m-dichlorobenzene, paracide mixture) purity be 97.4%, chlorobenzene purity is
96.1%.Hydrogen chloride goes out from top of tower, can rejoin in hydrogen and reuse by circulation.
Embodiment 5
1, catalyst preparation
0.44g cobalt chloride and 1.22g lithium chloride are dissolved into the ethanol water that 110mL volume fraction is 50%, are added
Enter 99.0g θ-aluminium oxide, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven, places into 600 DEG C of roastings in Muffle furnace
It burns 2 hours, obtains catalyst precursor.It is 50% that 0.33g palladium chloride and 0.66g iridium chloride, which are dissolved into 100mL volume fraction,
Methanol aqueous solution in, be added above-mentioned catalyst precursor, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven,
It places into Muffle furnace and roasts 2 hours for 600 DEG C, obtain catalyst.Palladium in the catalyst, iridium, cobalt and lithium load capacity be respectively
0.2wt%, 0.4wt%, 0.2wt% and 0.2wt%.
2, Catalyst packing
Fixed-bed catalytic destilling tower is divided into six sections from top to bottom, in each section of diluted catalysis of filling coconut husk granulated carbon
Agent, and from top to bottom (i.e. from first segment to the 6th section) mass percentage of the catalyst of each section of filling be followed successively by 10%,
0%, 20%, 40%, 60%, 80%.The second to five section of fixed-bed catalytic destilling tower is provided with gas supplementing opening, catalytic rectifying tower
Reaction tube inner member and connecting pipe be all made of carbon steel liner enamel.
3, catalyst pre-treatment
Air 3 hours in nitrogen displacement tower are passed through from fixed-bed catalytic distillation tower bottom, nitrogen is then switched to pure hydrogen
Gas, while heat temperature raising is carried out to fixed-bed catalytic destilling tower using cycle of higher pressure water, making it, temperature of each section is successively from top to bottom
It is 200 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 300 DEG C and 300 DEG C, heating rate is 1 DEG C/min, rises to constant temperature after target temperature
It is kept for 4 hours, catalyst is activated.After activation of catalyst is complete, by fixed-bed catalytic destilling tower temperature of each section from top to bottom
138 DEG C, 180 DEG C, 215 DEG C, 258 DEG C, 285 DEG C and 235 DEG C are successively reduced to, and is kept in this temperature；Then in the hydrogen being passed through
Middle addition hydrogen chloride gas makes the volumetric concentration 30% of hydrogen.
4, catalysis reaction
It is passed through after hexachloro-benzene is heated to 235 DEG C from fixed-bed catalytic destilling tower bottom, while being passed through chlorine from each section of gas supplementing opening
Change the gaseous mixture of hydrogen and hydrogen, the volumetric concentration of hydrogen is 30% in the gaseous mixture, to control in fixed-bed catalytic destilling tower
The molar ratio of hexachloro-benzene and hydrogen is 1:1.9.Reaction product dichloro-benzenes goes out from the second segment of fixed-bed catalytic destilling tower, chlorobenzene from
First segment goes out, dichloro-benzenes (o-dichlorohenzene, m-dichlorobenzene, paracide mixture) purity be 98.2%, chlorobenzene purity is
97.8%.Hydrogen chloride goes out from top of tower, can rejoin in hydrogen and reuse by circulation.
Embodiment 6
1, catalyst preparation
0.66g cobalt chloride and 3.66g lithium chloride are dissolved into the ethanol water that 110mL volume fraction is 50%, are added
Enter 98.3g θ-aluminium oxide, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven, places into 600 DEG C of roastings in Muffle furnace
It burns 2 hours, obtains catalyst precursor.It is 50% that 0.50g palladium chloride and 0.82g iridium chloride, which are dissolved into 100mL volume fraction,
Methanol aqueous solution in, be added above-mentioned catalyst precursor, impregnate 12 hours, be subsequently placed in 150 DEG C drying 4 hours in baking oven,
It places into Muffle furnace and roasts 2 hours for 600 DEG C, obtain catalyst.Palladium in the catalyst, iridium, cobalt and lithium load capacity be respectively
0.3wt%, 0.5wt%, 0.3wt% and 0.6wt%.
2, Catalyst packing
Fixed-bed catalytic destilling tower is divided into six sections from top to bottom, in each section of diluted catalysis of filling coconut husk granulated carbon
Agent, and from top to bottom (i.e. from first segment to the 6th section) mass percentage of the catalyst of each section of filling be followed successively by 10%,
0%, 20%, 40%, 60%, 80%.The second to five section of fixed-bed catalytic destilling tower is provided with gas supplementing opening, catalytic rectifying tower
Reaction tube inner member and connecting pipe be all made of carbon steel liner enamel.
3, catalyst pre-treatment
Air 3 hours in nitrogen displacement tower are passed through from fixed-bed catalytic distillation tower bottom, nitrogen is then switched to pure hydrogen
Gas, while heat temperature raising is carried out to fixed-bed catalytic destilling tower using cycle of higher pressure water, making it, temperature of each section is successively from top to bottom
It is 200 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 300 DEG C and 300 DEG C, heating rate is 1 DEG C/min, rises to constant temperature after target temperature
It is kept for 4 hours, catalyst is activated.After activation of catalyst is complete, by fixed-bed catalytic destilling tower temperature of each section from top to bottom
140 DEG C, 185 DEG C, 220 DEG C, 260 DEG C, 285 DEG C and 240 DEG C are successively reduced to, and is kept in this temperature；Then in the hydrogen being passed through
Middle addition hydrogen chloride gas makes the volumetric concentration 30% of hydrogen.
4, catalysis reaction
It is passed through after hexachloro-benzene is heated to 240 DEG C from fixed-bed catalytic destilling tower bottom, while being passed through chlorine from each section of gas supplementing opening
Change the gaseous mixture of hydrogen and hydrogen, the volumetric concentration of hydrogen is 30% in the gaseous mixture, to control in fixed-bed catalytic destilling tower
The molar ratio of hexachloro-benzene and hydrogen is 1:1.8.Reaction product dichloro-benzenes goes out from the second segment of fixed-bed catalytic destilling tower, chlorobenzene from
First segment goes out, dichloro-benzenes (o-dichlorohenzene, m-dichlorobenzene, paracide mixture) purity be 99.0%, chlorobenzene purity is
99.2%.Hydrogen chloride goes out from top of tower, can rejoin in hydrogen and reuse by circulation.
Claims (9)
1. a kind of method that catalytic distillation degradation hexachloro-benzene generates chlorobenzene and dichloro-benzenes, it is characterised in that this method is by following step
It is rapid:
(1) catalyst preparation
Cobalt chloride and lithium chloride are dissolved into the ethanol water that volume fraction is 40%~60%, θ-aluminium oxide, leaching is added
Stain 12 hours or more, be placed in 120~150 DEG C drying 2~6 hours in baking oven, place into Muffle furnace 550~650 DEG C of roastings 2~
3 hours, obtain catalyst precursor；Palladium chloride and iridium chloride are dissolved into the methanol aqueous solution that volume fraction is 40%~60%
In, above-mentioned catalyst precursor is added, dipping 12 hours or more, is placed in 120~150 DEG C drying 2~6 hours in baking oven, then put
Enter in Muffle furnace and roast 2~3 hours for 550~650 DEG C, obtains catalyst；
(2) Catalyst packing
It is divided into six sections of diluted catalyst of filling coconut husk granulated carbon from top to bottom in fixed-bed catalytic destilling tower, and from top to bottom
The mass percentage of the catalyst of each section of filling is followed successively by 8%~12%, 0%, 18%~22%, 38%~42%, 58%
~62%, 78%~82%；The second to five section of the fixed-bed catalytic destilling tower is provided with gas supplementing opening；
(3) catalyst pre-treatment
It is passed through in nitrogen displacement tower air 3 hours or more from fixed-bed catalytic distillation tower bottom, nitrogen is then switched to pure hydrogen
Gas, while heating up to fixed-bed catalytic destilling tower, make its from top to bottom temperature of each section be followed successively by 180~220 DEG C, 190~
230 DEG C, 240~260 DEG C, 290~300 DEG C, 290~310 DEG C, 300~320 DEG C, heating rate is 1~2 DEG C/min, is risen
Constant temperature is kept for 2~6 hours after to target temperature, is activated to catalyst；After activation of catalyst is complete, fixed-bed catalytic is distilled
Tower from top to bottom temperature of each section be successively reduced to 130~140 DEG C, 175~185 DEG C, 215~225 DEG C, 250~260 DEG C, 275~
285 DEG C, 230~240 DEG C, and keep in this temperature；Then hydrogen chloride gas is added in the hydrogen being passed through, makes the volume of hydrogen
Concentration is 20%~40%；
(4) catalysis reaction
It is passed through after hexachloro-benzene is heated to 230~240 DEG C from fixed-bed catalytic destilling tower bottom, while being passed through chlorine from each section of gas supplementing opening
Change the gaseous mixture of hydrogen and hydrogen, the volumetric concentration of hydrogen is 20%~40% in the gaseous mixture, to control fixed-bed catalytic steaming
Evaporating in tower the molar ratio of hexachloro-benzene and hydrogen is 1:1.1~3.0, reaction product dichloro-benzenes from fixed-bed catalytic destilling tower second
Section goes out, and chlorobenzene goes out from first segment；Hydrogen chloride goes out from top of tower, reuses after circulation.
2. the method that catalytic distillation degradation hexachloro-benzene according to claim 1 generates chlorobenzene and dichloro-benzenes, it is characterised in that:
In step (1), by the quality of catalyst be 100% in terms of, in catalyst the total load amount of palladium and iridium be 0.5%~0.8%, cobalt and
The total load amount of lithium is 0.4%~1.0%.
3. the method that catalytic distillation degradation hexachloro-benzene according to claim 1 generates chlorobenzene and dichloro-benzenes, it is characterised in that:
In step (2), the catalyst quality percentage composition of fixed-bed catalytic destilling tower every section of filling from top to bottom is followed successively by 10%, 0%,
20%, 40%, 60%, 80%.
4. the method that catalytic distillation degradation hexachloro-benzene according to claim 1 generates chlorobenzene and dichloro-benzenes, it is characterised in that:
In step (3), heat up to fixed-bed catalytic destilling tower, make its from top to bottom temperature of each section be followed successively by 200 DEG C, 200 DEG C,
250℃、300℃、300℃、300℃。
5. the method that catalytic distillation degradation hexachloro-benzene according to claim 4 generates chlorobenzene and dichloro-benzenes, it is characterised in that:
In step (3), each section of the fixed-bed catalytic destilling tower all uses cycle of higher pressure water heat temperature raising.
6. the method that catalytic distillation degradation hexachloro-benzene according to claim 1 generates chlorobenzene and dichloro-benzenes, it is characterised in that:
In step (3), hydrogen chloride gas is added in the hydrogen being passed through, makes the volumetric concentration 30% of hydrogen.
7. the method that catalytic distillation degradation hexachloro-benzene according to claim 1 generates chlorobenzene and dichloro-benzenes, it is characterised in that:
In step (4), the gaseous mixture of hydrogen chloride and hydrogen is passed through from each section of gas supplementing opening, the volumetric concentration of hydrogen is in the gaseous mixture
20%~40%, to control in fixed-bed catalytic destilling tower the molar ratio of hexachloro-benzene and hydrogen as 1:1.2~1.9.
8. the method that catalytic distillation degradation hexachloro-benzene according to claim 1 generates chlorobenzene and dichloro-benzenes, it is characterised in that:
In step (4), the dichloro-benzenes is the mixture of o-dichlorohenzene, m-dichlorobenzene, paracide.
9. the method that the degradation of catalytic distillation described in any one hexachloro-benzene generates chlorobenzene and dichloro-benzenes according to claim 1~8,
It is characterized by: the reaction tube inner member and connecting pipe of the catalytic rectifying tower are all made of carbon steel liner enamel or glass material
Matter.
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| CN112058081A (en) * | 2020-09-11 | 2020-12-11 | 庞洁 | Method for removing hexachlorobenzene generated in spice extraction process |
| CN112608215A (en) * | 2020-12-10 | 2021-04-06 | 广东石油化工学院 | Selective hydrogenation dechlorination method for hexachlorobenzene |
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