CN103977744B - A kind of method of catalytic degradation hexachloro-benzene - Google Patents
A kind of method of catalytic degradation hexachloro-benzene Download PDFInfo
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- CN103977744B CN103977744B CN201410244652.XA CN201410244652A CN103977744B CN 103977744 B CN103977744 B CN 103977744B CN 201410244652 A CN201410244652 A CN 201410244652A CN 103977744 B CN103977744 B CN 103977744B
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Abstract
The invention discloses a kind of method of catalytic degradation hexachloro-benzene, the method is: one, by Catalyst packing in fixed bed reactors, reduction treatment is carried out to catalyst; Two, the hydrogen of hexachloro-benzene steam and preheating is mixed obtain gaseous mixture, process to be restored terminates to pass into gaseous mixture in backward fixed bed reactors, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; Three, the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen is sent into condensation in condenser, benzene is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower and use ammonia absorption hydrogen chloride, unreacted hydrogen is returned after compressor compression and recycles.Adopt during method catalytic hydrogenation of the present invention degraded hexachloro-benzene and do not need to add solvent, and by-product benzene and ammonium chloride, can reach the zero-emission of pollutant, be a kind of friendly process of efficient degradation hexachloro-benzene.
Description
Technical field
The invention belongs to technical field of catalytic hydrogenation, be specifically related to a kind of method of catalytic degradation hexachloro-benzene.
Background technology
Aromatic chlorides industrially has a very wide range of applications, but be the noxious material of harm humans health, because its structural stability is high, be difficult to degraded at occurring in nature, therefore the researcher of countries in the world is making great efforts the high-efficiency detoxicating method exploring Halogen organic pollution.
Hexachloro-benzene is one of 12 kinds of persistence organic pollutants (POPs).Hexachloro-benzene has the structure of full symmetric, and chlorine replacement number is many, and toxicity is large, degrades very difficult.According to investigations, domesticly in chemical process, at least produce 600 tons of hexachloro-benzenes every year, existed by the hexachloro-benzene refuse sealed up for safekeeping and leak and the risk of diffusion, huge hidden danger is existed to periphery ecological environment security.Hexachloro-benzene normally adopts simple burning method process, may produce bioxin in burning process, causes larger harm to environment.The hexachloro-benzene processing method of therefore actively seeking high-efficiency environment friendly has very important significance.
The people such as Dong Yuhuan are standby a kind of novel couple of supported bimetal catalyst: PVP-PdCl2-MnXm/MontK10-PEG400, hydrogen migration method is adopted to carry out catalysis dechlorination to the hexachloro-benzene in aqueous phase, reaction condition is gentle, hexachloro-benzene conversion ratio can be made to reach 100%, but catalyst preparing is too complicated, be difficult to a large amount of production, separation difficulty after reaction, noble metal reclaims difficulty, reaction time is relatively long, because the solubility of hexachloro-benzene in aqueous phase is low, so the treating capacity of hexachloro-benzene is also few in the unit interval.
The people such as Xiao Yong discuss the progress of hexachloro-benzene degraded in recent years and minimizing technology, Chinese scholars expand the research to hexachloro-benzene degraded mainly through following methods, as: photochemical catalytic oxidation, microbial degradation, irradiation method, electrochemical process and catalytic hydrogenation method, the degraded of these methods to hexachloro-benzene all has certain effect, but most method still rests on laboratory and theoretical research stage, due to each side reason and difficulty, also there is no the method that can be applicable to practical application at present.
The Chinese patent 201010281630.2 invention method of a kind of catalyst of phosphatizing nickel for chlorobenzene compound hydrogenation-dechlorination, fixed bed reactors are adopted to achieve the continuous dechlorination reaction of the chlorobenzene compound of below 3 chlorine, conversion ratio is improve after catalyst modification, obtain good result, but Ni catalyst exists certain insecurity, the stability of catalyst need to investigate.In addition, the stability of hexachloro-benzene is higher, and this catalyst is not necessarily applicable to the catalytic hydrogenation and dechlorination reaction of hexachloro-benzene.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of method of catalytic degradation hexachloro-benzene.Adopt the method catalytic degradation hexachloro-benzene, treating capacity is large, and hexachloro-benzene transforms completely, the molar yield of hexachloro-benzene is 100%, product benzene and the selective of hydrogen chloride are 100%, and product separation purification process is simple and energy consumption is low, and the murder by poisoning ion that undopes in product; Do not need to add solvent during catalytic hydrogenation degraded hexachloro-benzene, and by-product benzene and ammonium chloride, can reach the zero-emission of pollutant, be a kind of friendly process of efficient degradation hexachloro-benzene.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of catalytic degradation hexachloro-benzene, and it is characterized in that, the method comprises the following steps:
Step one, by Catalyst packing in fixed bed reactors, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas of nitrogen dilution, with the heating rate of 0.1 DEG C/min ~ 2 DEG C/min, the temperature of fixed bed reactors is risen to 280 DEG C ~ 450 DEG C, insulation 2h ~ 10h carries out reduction treatment to catalyst; Described catalyst comprises Al
2o
3carrier, is carried on Al
2o
3active component on carrier and auxiliary agent, in catalyst, the mass percentage of active component is 0.05% ~ 3%, the mass percentage of auxiliary agent is 0.01% ~ 2.5%, and described active component is Pt, Pd, Ag, Ru or Rh, and described auxiliary agent is Na, K, Mg, Ba, Sn or Fe; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 3% ~ 10%; The flow of the reducibility gas of nitrogen dilution and the mass ratio of catalyst are (3 ~ 20): 1, and wherein the unit of flow is mL/min, and the unit of quality is g;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 150 DEG C ~ 260 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 280 DEG C ~ 450 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, in catalyst described in step one, the mass percentage of active component is 0.1% ~ 1.5%, and the mass percentage of auxiliary agent is 0.05% ~ 1.5%.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, in described catalyst, the mass percentage of active component is 0.2% ~ 0.4%, and the mass percentage of auxiliary agent is 0.2% ~ 1.0%.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, Al described in step one
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 0.5mm ~ 3mm, and specific area is 150m
2/ g ~ 280m
2/ g.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, reducibility gas described in step one is hydrogen.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, the mol ratio of the steam of hexachloro-benzene described in step 2 and hydrogen is 1:(5 ~ 100), the mass space velocity of described hexachloro-benzene steam is 0.05g/gcat/hr ~ 0.6g/gcat/hr.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, the time of staying of the steam of hexachloro-benzene described in step 2 in fixed bed reactors is 1min ~ 10min.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, reaction temperature described in step 2 is 320 DEG C ~ 400 DEG C.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, the condensation temperature of condenser described in step 3 is-30 DEG C ~ 0 DEG C.
The method of above-mentioned a kind of catalytic degradation hexachloro-benzene, the volume of ammoniacal liquor described in step 3 is 6.5 ~ 13 times of hexachloro-benzene vapour volume.
The preparation method of the catalyst that the present invention adopts is:
Step one, the presoma of active component and the presoma of auxiliary agent being dissolved in inorganic acid and mixing, obtain solution A, the pH value regulating solution A is 0.1 ~ 4.0; The presoma of described active component is the hydrochloride of active component or the nitrate of active component, and the presoma of auxiliary agent is the carbonate of the hydrochloride of auxiliary agent, the nitrate of auxiliary agent or auxiliary agent; Described inorganic acid to be mass concentration be 5% ~ 10% hydrochloric acid, mass concentration be 5% ~ 10% nitric acid or mass concentration be the sulfuric acid of 5% ~ 10%;
Step 2, by Al
2o
3carrier is placed in treatment fluid, at 50 DEG C ~ 98 DEG C, soak 0.5h ~ 4h; Described treatment fluid is aqueous citric acid solution, sodium citrate aqueous solution, ammoniacal liquor, sodium hydrate aqueous solution or potassium hydroxide aqueous solution, and the mass concentration for the treatment of fluid is 0.01% ~ 10%;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 40 DEG C ~ 80 DEG C, stirs 8h ~ 15h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 2h ~ 12h under the condition of 400 DEG C ~ 600 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
The present invention compared with prior art has the following advantages:
1, method of the present invention can be degraded hexachloro-benzene efficiently, hexachloro-benzene is made to be converted into benzene and hydrogen chloride completely by catalytic hydrogenation and dechlorination, use ammonia absorption byproduct hydrogen chloride again, thus side product sodium chloride, the catalyst single life-span adopted reaches more than 400h, catalyst is renewable, still has higher catalytic activity after regenerating 30 times.
2, the present invention adopts fixed bed reactors, can continuous catalytic hydrogenation degraded hexachloro-benzene, and reaction condition is gentle and be easy to control.
3, adopt the inventive method catalytic degradation hexachloro-benzene, treating capacity is large, and hexachloro-benzene transforms completely, the molar yield of hexachloro-benzene is 100%, product benzene and the selective of hydrogen chloride are 100%, and product separation purification process is simple and energy consumption is low, and the murder by poisoning ion that undopes in product.
4, adopt during method catalytic hydrogenation of the present invention degraded hexachloro-benzene and do not need to add solvent, and by-product benzene and ammonium chloride, can reach the zero-emission of pollutant, be a kind of friendly process of efficient degradation hexachloro-benzene.
Below by embodiment, technical solution of the present invention is described in further detail.
Detailed description of the invention
Catalysts and its preparation method of the present invention is described by following examples 1 to embodiment 13:
Embodiment 1
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pt on carrier and auxiliary agent Na; In described catalyst, the mass percentage of active component Pt is 0.1%, and the mass percentage of auxiliary agent Na is 2.5%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 3mm, and specific area is 150m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the platinum chloride of platiniferous 0.1g with to be dissolved in mass concentration be in the hydrochloric acid of 5% and mix containing the sodium chloride of sodium 2.5g, obtain solution A, the pH value regulating solution A is 0.1;
Step 2, by 97.4gAl
2o
3carrier is placed in the aqueous citric acid solution that mass concentration is 0.01%, at 50 DEG C, soak 4h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 80 DEG C, stirs 8h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 12h under the condition of 400 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 2
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Ru on carrier and auxiliary agent Fe; In described catalyst, the mass percentage of active component is 3%, and the mass percentage of auxiliary agent is 0.01%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 0.5mm, and specific area is 280m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, be in the hydrochloric acid of 10% and mix being dissolved in mass concentration containing the ruthenium trichloride of ruthenium 3g and the ferric nitrate of iron content 0.01g, obtain solution A, the pH value regulating solution A is 2.0;
Step 2, by 96.99gAl
2o
3carrier is placed in the sodium citrate aqueous solution that mass concentration is 10%, at 98 DEG C, soak 0.5h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 40 DEG C, stirs 15h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 2h under the condition of 600 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 3
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component A g on carrier and auxiliary agent Mg; In described catalyst, the mass percentage of active component is 0.3%, and the mass percentage of auxiliary agent is 0.05%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 1mm, and specific area is 200m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the silver chlorate of argentiferous 0.3g with to be dissolved in mass concentration be in the sulfuric acid of 10% and mix containing the magnesium carbonate of magnesium 0.05g, obtain solution A, the pH value regulating solution A is 3.0;
Step 2, by 99.65gAl
2o
3carrier is placed in the sodium hydrate aqueous solution that mass concentration is 5%, at 90 DEG C, soak 1h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 50 DEG C, stirs 12h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 6h under the condition of 500 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 4
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pd on carrier and auxiliary agent K; In described catalyst, the mass percentage of active component is 0.3%, and the mass percentage of auxiliary agent is 0.9%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 1mm, and specific area is 240m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the palladium chloride containing palladium 0.3g with to be dissolved in mass concentration be in the nitric acid of 5% and mix containing the potassium chloride of potassium 0.9g, obtain solution A, the pH value regulating solution A is 0.2;
Step 2, by 98.8gAl
2o
3carrier is placed in the potassium hydroxide aqueous solution that mass concentration is 0.02%, at 65 DEG C, soak 3h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 65 DEG C, stirs 12h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 4h under the condition of 550 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 5
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pd on carrier and auxiliary agent Fe; In described catalyst, the mass percentage of active component is 0.5%, and the mass percentage of auxiliary agent is 0.1%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 200m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, be in the hydrochloric acid of 7% and mix being dissolved in mass concentration containing the palladium chloride of palladium 0.5g and the frerrous chloride of iron content 0.1g, obtain solution A, the pH value regulating solution A is 0.3;
Step 2, by 99.4gAl
2o
3carrier is placed in the ammoniacal liquor that mass concentration is 0.1%, at 80 DEG C, soak 1h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 75 DEG C, stirs 10h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 5h under the condition of 500 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 6
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pt on carrier and auxiliary agent Na; In described catalyst, the mass percentage of active component is 0.8%, and the mass percentage of auxiliary agent is 0.05%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 0.8mm, and specific area is 280m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the platinum chloride of platiniferous 0.8g with to be dissolved in mass concentration be in the sulfuric acid of 5% and mix containing the sodium carbonate of sodium 0.05g, obtain solution A, the pH value regulating solution A is 0.5;
Step 2, by 99.15gAl
2o
3carrier is placed in the sodium citrate aqueous solution that mass concentration is 0.15%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 6h under the condition of 450 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 7
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pt on carrier and auxiliary agent Sn; In described catalyst, the mass percentage of active component is 1.0%, and the mass percentage of auxiliary agent is 0.1%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 215m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, the stannic chloride of the platinous chloride of platiniferous 1.0g and stanniferous 0.1g is dissolved in mass concentration is in the sulfuric acid of 8% and mix, and obtain solution A, the pH value regulating solution A is 1.0;
Step 2, by 98.9gAl
2o
3carrier is placed in the sodium hydrate aqueous solution that mass concentration is 0.02%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 7h under the condition of 600 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 8
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pd on carrier and auxiliary agent B a; In described catalyst, the mass percentage of active component is 0.3%, and the mass percentage of auxiliary agent is 0.2%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 190m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, be in the nitric acid of 10% and mix being dissolved in mass concentration containing the palladium chloride of palladium 0.3g and the brium carbonate of baric 0.2g, obtain solution A, the pH value regulating solution A is 0.8;
Step 2, by 99.5gAl
2o
3carrier is placed in the aqueous citric acid solution that mass concentration is 0.05%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 8h under the condition of 530 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 9
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Rh on carrier and auxiliary agent K; In described catalyst, the mass percentage of active component is 1.5%, and the mass percentage of auxiliary agent is 1.5%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 220m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the rhodium chloride of rhodium-containing 1.5g with to be dissolved in mass concentration be in the nitric acid of 8% and mix containing the potassium nitrate of potassium 1.5g, obtain solution A, the pH value regulating solution A is 0.7;
Step 2, by 97gAl
2o
3carrier is placed in the aqueous citric acid solution that mass concentration is 0.03%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 6h under the condition of 540 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 10
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pd on carrier and auxiliary agent Na; In described catalyst, the mass percentage of active component is 0.2%, and the mass percentage of auxiliary agent is 0.6%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 220m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the palladium chloride containing palladium 0.2g with to be dissolved in mass concentration be in the hydrochloric acid of 8% and mix containing the sodium nitrate of sodium 0.6g, obtain solution A, the pH value regulating solution A is 0.7;
Step 2, by 99.2gAl
2o
3carrier is placed in the sodium citrate aqueous solution that mass concentration is 0.03%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 6h under the condition of 540 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 11
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pt on carrier and auxiliary agent K; In described catalyst, the mass percentage of active component is 0.4%, and the mass percentage of auxiliary agent is 1.0%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 220m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the platinous chloride of platiniferous 0.4g with to be dissolved in mass concentration be in the nitric acid of 8% and mix containing the potassium nitrate of potassium 1.0g, obtain solution A, the pH value regulating solution A is 0.7;
Step 2, by 98.6gAl
2o
3carrier is placed in the aqueous citric acid solution that mass concentration is 0.03%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 6h under the condition of 540 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 12
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pd on carrier and auxiliary agent K; In described catalyst, the mass percentage of active component is 0.05%, and the mass percentage of auxiliary agent is 0.1%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 220m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, by the palladium chloride containing palladium 0.05g with to be dissolved in mass concentration be in the nitric acid of 5% and mix containing the potassium nitrate of potassium 0.1g, obtain solution A, the pH value regulating solution A is 4.0;
Step 2, by 99.85gAl
2o
3carrier is placed in the sodium citrate aqueous solution that mass concentration is 10%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 6h under the condition of 540 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
Embodiment 13
The catalyst of the present embodiment comprises Al
2o
3carrier, is carried on Al
2o
3active component Pt on carrier and auxiliary agent Sn; In described catalyst, the mass percentage of active component is 0.1%, and the mass percentage of auxiliary agent is 0.2%; Described Al
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 2mm, and specific area is 215m
2/ g.
The preparation method of catalyst comprises the following steps:
Step one, the stannic chloride of the platinous chloride of platiniferous 0.1g and stanniferous 0.2g is dissolved in mass concentration is in the sulfuric acid of 8% and mix, and obtain solution A, the pH value regulating solution A is 1.0;
Step 2, by 99.7gAl
2o
3carrier is placed in the sodium hydrate aqueous solution that mass concentration is 10%, at 70 DEG C, soak 2h;
Step 3, by step 2 through soak after Al
2o
3carrier takes out and solution A after being placed in step one adjust ph, then under the heating condition of 70 DEG C, stirs 11h post-drying, obtains sample;
Step 4, sample described in step 3 being placed in Muffle furnace, is roasting 7h under the condition of 600 DEG C in temperature, the catalyst of the hexachloro-benzene that obtains degrading.
The method of catalytic degradation hexachloro-benzene of the present invention is described by following examples 14 to embodiment 20:
Embodiment 14
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 1,2 or 3, and catalytic degradation method is as follows:
Step one, by 6g Catalyst packing in ratio of height to diameter be 4:1 fixed bed reactors in, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas (hydrogen) of nitrogen dilution, with the heating rate of 1 DEG C/min, the temperature of fixed bed reactors is risen to 360 DEG C, insulation 5h carries out reduction treatment to catalyst; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 5%; The flow of the reducibility gas of described nitrogen dilution is 50mL/min;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 200 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 360 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; The mol ratio of described hexachloro-benzene steam and hydrogen is 1:10; The mass space velocity of described hexachloro-benzene steam is 0.3g/gcat/hr; The time of staying of described hexachloro-benzene steam in fixed bed reactors is 5min;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle; The condensation temperature of described condenser is-20 DEG C; The volume of described ammoniacal liquor is 10 times of hexachloro-benzene vapour volume.
Table 1 embodiment 14 catalytic degradation result
Reusability after the catalyst regeneration adopt the present embodiment, after regenerating 30 times, catalytic degradation the results are shown in Table 2.The renovation process of catalyst is: after catalytic hydrogenation and dechlorination reaction terminates, fixed bed reactors are down to room temperature, then pass into nitrogen in fixed bed reactors, being full of nitrogen in bed bioreactor to be fixed passes into the air of nitrogen dilution or the oxygen with nitrogen dilution, diluted concentration (percent by volume namely shared by air or oxygen) is 1% ~ 10%, the flow (mL/min) of the air with nitrogen dilution or the oxygen with nitrogen dilution and the ratio of loaded catalyst (g) are 2 ~ 10:1, simultaneously with the heating rate of 0.5 DEG C/min ~ 5 DEG C/min, fixed bed reactors are warming up to 400 DEG C ~ 550 DEG C, cool after insulation 3h ~ 8h, complete the regeneration of catalyst.
Catalytic degradation result after table 2 catalyst regeneration 30 times
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Hexachloro-benzene conversion ratio | 100％ | 100％ | 100％ |
| Benzene and hydrogen chloride selective | 100％ | 100％ | 100％ |
Embodiment 15
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 4,5 or 6, and catalytic degradation method is as follows:
Step one, by 7g Catalyst packing in ratio of height to diameter be 5:1 fixed bed reactors in, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas (hydrogen) of nitrogen dilution, with the heating rate of 0.5 DEG C/min, the temperature of fixed bed reactors is risen to 320 DEG C, insulation 8h carries out reduction treatment to catalyst; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 5%; The flow of the reducibility gas of described nitrogen dilution is 70mL/min;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 210 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 320 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; The mol ratio of described hexachloro-benzene steam and hydrogen is 1:50; The mass space velocity of described hexachloro-benzene steam is 0.2g/gcat/hr; The time of staying of described hexachloro-benzene steam in fixed bed reactors is 7min;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle; The condensation temperature of described condenser is-30 DEG C; The volume of described ammoniacal liquor is 13 times of hexachloro-benzene vapour volume.
Table 3 embodiment 15 catalytic degradation result
Reusability after the catalyst regeneration adopt the present embodiment, after regenerating 30 times, catalytic degradation the results are shown in Table 4.Catalyst regenerates according to renovation process described in embodiment 14.
Catalytic degradation result after table 4 catalyst regeneration 30 times
| Catalyst | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Hexachloro-benzene conversion ratio | 100％ | 100％ | 100％ |
| Benzene and hydrogen chloride selective | 100％ | 100％ | 100％ |
Embodiment 16
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 7,8 or 9, and catalytic degradation method is as follows:
Step one, by 8g Catalyst packing in ratio of height to diameter be 5:1 fixed bed reactors in, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas (hydrogen) of nitrogen dilution, with the heating rate of 0.5 DEG C/min, the temperature of fixed bed reactors is risen to 380 DEG C, insulation 2h carries out reduction treatment to catalyst; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 10%; The flow of the reducibility gas of described nitrogen dilution is 160mL/min;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 220 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 380 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; The mol ratio of described hexachloro-benzene steam and hydrogen is 1:20; The mass space velocity of described hexachloro-benzene steam is 0.4g/gcat/hr; The time of staying of described hexachloro-benzene steam in fixed bed reactors is 2min;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle; The condensation temperature of described condenser is 0 DEG C; The volume of described ammoniacal liquor is 6.5 times of hexachloro-benzene vapour volume.
Table 5 embodiment 16 catalytic degradation result
Reusability after the catalyst regeneration adopt the present embodiment, after regenerating 30 times, catalytic degradation the results are shown in Table 6.Catalyst regenerates according to renovation process described in embodiment 14.
Catalytic degradation result after table 6 catalyst regeneration 30 times
| Catalyst | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Hexachloro-benzene conversion ratio | 100％ | 100％ | 100％ |
| Benzene and hydrogen chloride selective | 100％ | 100％ | 100％ |
Embodiment 17
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 10,11 or 12, and catalytic degradation method is as follows:
Step one, by 6g Catalyst packing in ratio of height to diameter be 3:1 fixed bed reactors in, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas (hydrogen) of nitrogen dilution, with the heating rate of 2 DEG C/min, the temperature of fixed bed reactors is risen to 400 DEG C, insulation 2h carries out reduction treatment to catalyst; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 8%; The flow of the reducibility gas of described nitrogen dilution is 60mL/min;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 200 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 400 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; The mol ratio of described hexachloro-benzene steam and hydrogen is 1:100; The mass space velocity of described hexachloro-benzene steam is 0.4g/gcat/hr; The time of staying of described hexachloro-benzene steam in fixed bed reactors is 1min;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle; The condensation temperature of described condenser is 0 DEG C; The volume of described ammoniacal liquor is 7 times of hexachloro-benzene vapour volume.
Table 7 embodiment 17 catalytic degradation result
Reusability after the catalyst regeneration adopt the present embodiment, after regenerating 30 times, catalytic degradation the results are shown in Table 8.Catalyst regenerates according to renovation process described in embodiment 14.
Catalytic degradation result after table 8 catalyst regeneration 30 times
| Catalyst | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| Hexachloro-benzene conversion ratio | 100％ | 100％ | 100％ |
| Benzene and hydrogen chloride selective | 100％ | 100％ | 100％ |
Embodiment 18
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 2,5 or 9, and catalytic degradation method is as follows:
Step one, by 7g Catalyst packing in ratio of height to diameter be 4:1 fixed bed reactors in, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas (hydrogen) of nitrogen dilution, with the heating rate of 2 DEG C/min, the temperature of fixed bed reactors is risen to 330 DEG C, insulation 10h carries out reduction treatment to catalyst; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 3%; The flow of the reducibility gas of described nitrogen dilution is 21mL/min;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 180 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 330 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; The mol ratio of described hexachloro-benzene steam and hydrogen is 1:80; The mass space velocity of described hexachloro-benzene steam is 0.3g/gcat/hr; The time of staying of described hexachloro-benzene steam in fixed bed reactors is 3min;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle; The condensation temperature of described condenser is-10 DEG C; The volume of described ammoniacal liquor is 13 times of hexachloro-benzene vapour volume.
Table 9 embodiment 18 catalytic degradation result
Reusability after the catalyst regeneration adopt the present embodiment, after regenerating 30 times, catalytic degradation the results are shown in Table 10.Catalyst regenerates according to renovation process described in embodiment 14.
Catalytic degradation result after table 10 catalyst regeneration 30 times
| Catalyst | Embodiment 2 | Embodiment 5 | Embodiment 9 |
| Hexachloro-benzene conversion ratio | 100％ | 100％ | 100％ |
| Benzene and hydrogen chloride selective | 100％ | 100％ | 100％ |
Embodiment 19
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 1,7 or 13, and catalytic degradation method is as follows:
Step one, by 9g Catalyst packing in ratio of height to diameter be 3.5:1 fixed bed reactors in, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas (hydrogen) of nitrogen dilution, with the heating rate of 2 DEG C/min, the temperature of fixed bed reactors is risen to 450 DEG C, insulation 4h carries out reduction treatment to catalyst; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 8%; The flow of the reducibility gas of described nitrogen dilution is 100mL/min;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 260 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 450 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; The mol ratio of described hexachloro-benzene steam and hydrogen is 1:25; The mass space velocity of described hexachloro-benzene steam is 0.6g/gcat/hr; The time of staying of described hexachloro-benzene steam in fixed bed reactors is 5min;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle; The condensation temperature of described condenser is-10 DEG C; The volume of described ammoniacal liquor is 10 times of hexachloro-benzene vapour volume.
Table 11 embodiment 19 catalytic degradation result
Reusability after the catalyst regeneration adopt the present embodiment, after regenerating 30 times, catalytic degradation the results are shown in Table 12.Catalyst regenerates according to renovation process described in embodiment 14.
Catalytic degradation result after table 12 catalyst regeneration 30 times
| Catalyst | Embodiment 1 | Embodiment 7 | Embodiment 13 |
| Hexachloro-benzene conversion ratio | 100％ | 100％ | 100％ |
| Benzene and hydrogen chloride selective | 100％ | 100％ | 100％ |
Embodiment 20
The catalyst that the present embodiment adopts is catalyst prepared by embodiment 3,6 or 10, and catalytic degradation method is as follows:
Step one, by 5g Catalyst packing in ratio of height to diameter be 5:1 fixed bed reactors in, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas (hydrogen) of nitrogen dilution, with the heating rate of 0.1 DEG C/min, the temperature of fixed bed reactors is risen to 280 DEG C, insulation 5h carries out reduction treatment to catalyst; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 10%; The flow of the reducibility gas of described nitrogen dilution is 50mL/min;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 150 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 280 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen; The mol ratio of described hexachloro-benzene steam and hydrogen is 1:5; The mass space velocity of described hexachloro-benzene steam is 0.05g/gcat/hr; The time of staying of described hexachloro-benzene steam in fixed bed reactors is 10min;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle; The condensation temperature of described condenser is-20 DEG C; The volume of described ammoniacal liquor is 8 times of hexachloro-benzene vapour volume.
Table 13 embodiment 20 catalytic degradation result
Reusability after the catalyst regeneration adopt the present embodiment, after regenerating 30 times, catalytic degradation the results are shown in Table 14.Catalyst regenerates according to renovation process described in embodiment 14.
Catalytic degradation result after table 14 catalyst regeneration 30 times
| Catalyst | Embodiment 3 | Embodiment 6 | Embodiment 10 |
| Hexachloro-benzene conversion ratio | 100％ | 100％ | 100％ |
| Benzene and hydrogen chloride selective | 100％ | 100％ | 100％ |
The above; it is only preferred embodiment of the present invention; not any restriction is done to the present invention, every above embodiment is done according to invention technical spirit any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (9)
1. a method for catalytic degradation hexachloro-benzene, is characterized in that, the method comprises the following steps:
Step one, by Catalyst packing in fixed bed reactors, at room temperature in the fixed bed reactors being filled with catalyst, pass into nitrogen to the air emptying in fixed bed reactors, then in fixed bed reactors, pass into the reducibility gas of nitrogen dilution, with the heating rate of 0.1 DEG C/min ~ 2 DEG C/min, the temperature of fixed bed reactors is risen to 280 DEG C ~ 450 DEG C, insulation 2h ~ 10h carries out reduction treatment to catalyst; Described catalyst comprises Al
2o
3carrier, is carried on Al
2o
3active component on carrier and auxiliary agent, in catalyst, the mass percentage of active component is 0.05% ~ 3%, the mass percentage of auxiliary agent is 0.01% ~ 2.5%, and described active component is Pt, Pd, Ag, Ru or Rh, and described auxiliary agent is Na, K, Mg, Ba, Sn or Fe; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 3% ~ 10%; The flow of the reducibility gas of nitrogen dilution and the mass ratio of catalyst are (3 ~ 20): 1, and wherein the unit of flow is mL/min, and the unit of quality is g;
Step 2, hexachloro-benzene steam and the hydrogen that is preheated to 150 DEG C ~ 260 DEG C mixed obtain gaseous mixture, the reducibility gas passing into nitrogen dilution is stopped after reduction treatment described in step one terminates, in fixed bed reactors, pass into described gaseous mixture simultaneously, be under the condition of 280 DEG C ~ 450 DEG C in reaction temperature, carry out catalytic hydrogenation and dechlorination reaction on a catalyst, obtain the mist of benzene vapour, hydrogen chloride gas and unreacted hydrogen;
Step 3, the mist of benzene vapour described in step 2, hydrogen chloride gas and unreacted hydrogen sent in condenser and carries out condensation, the benzene vapour in mist is made to be converted into liquid state, then the hydrogen chloride gas in mist and unreacted hydrogen are sent in absorption tower, use ammonia absorption hydrogen chloride gas, finally unreacted hydrogen is returned in step 2 after compressor compression and recycle;
Reducibility gas described in step one is hydrogen.
2. the method for a kind of catalytic degradation hexachloro-benzene according to claim 1, is characterized in that, in catalyst described in step one, the mass percentage of active component is 0.1% ~ 1.5%, and the mass percentage of auxiliary agent is 0.05% ~ 1.5%.
3. the method for a kind of catalytic degradation hexachloro-benzene according to claim 2, is characterized in that, in described catalyst, the mass percentage of active component is 0.2% ~ 0.4%, and the mass percentage of auxiliary agent is 0.2% ~ 1.0%.
4. the method for a kind of catalytic degradation hexachloro-benzene according to claim 1,2 or 3, is characterized in that, Al described in step one
2o
3carrier is γ-Al
2o
3, Al
2o
3the particle diameter of carrier is 0.5mm ~ 3mm, and specific area is 150m
2/ g ~ 280m
2/ g.
5. the method for a kind of catalytic degradation hexachloro-benzene according to claim 1,2 or 3, it is characterized in that, the mol ratio of the steam of hexachloro-benzene described in step 2 and hydrogen is 1:(5 ~ 100), the mass space velocity of described hexachloro-benzene steam is 0.05g/gcat/hr ~ 0.6g/gcat/hr.
6. the method for a kind of catalytic degradation hexachloro-benzene according to claim 1,2 or 3, is characterized in that, the time of staying of the steam of hexachloro-benzene described in step 2 in fixed bed reactors is 1min ~ 10min.
7. the method for a kind of catalytic degradation hexachloro-benzene according to claim 1,2 or 3, is characterized in that, reaction temperature described in step 2 is 320 DEG C ~ 400 DEG C.
8. the method for a kind of catalytic degradation hexachloro-benzene according to claim 1,2 or 3, is characterized in that, the condensation temperature of condenser described in step 3 is-30 DEG C ~ 0 DEG C.
9. the method for a kind of catalytic degradation hexachloro-benzene according to claim 1,2 or 3, is characterized in that, the volume of ammoniacal liquor described in step 3 is 6.5 ~ 13 times of hexachloro-benzene vapour volume.
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| CN104741117B (en) * | 2015-03-16 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | Method and catalyst for preparing benzene and cyclohexane by catalytically hydrogenating liquid phase of aryl chloride |
| CN105503706A (en) * | 2015-12-28 | 2016-04-20 | 衢州学院 | Dehalogenation degradation method for halogenated pyridine compound |
| CN105709735B (en) * | 2016-01-21 | 2019-01-29 | 巨化集团技术中心 | A kind of chlorobenzene catalytic converting catalyst and its preparation method and application |
| CN110813314B (en) * | 2019-11-20 | 2022-08-30 | 西安凯立新材料股份有限公司 | Catalyst for producing benzene by continuous hydrogenation and dechlorination of chlorobenzene and preparation method and application thereof |
| CN111939968B (en) * | 2020-05-31 | 2024-02-09 | 南京克米斯璀新能源科技有限公司 | Catalyst for dechlorination of hexachlorobenzene |
| CN112608215A (en) * | 2020-12-10 | 2021-04-06 | 广东石油化工学院 | Selective hydrogenation dechlorination method for hexachlorobenzene |
| CN112608214A (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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