Catalyst for preparing chlorine gas by hydrogen chloride oxidation, and preparation method and application thereof

Abstract

A catalyst for preparing chlorine gas by hydrogen chloride oxidation, comprising the following components calculated according to mass content based on the total weight of the catalyst: 0.5-20 wt % copper; 2-10 wt % manganese; 0.05-2 wt % boron; 0.01-3 wt % chromium; 0.1-10 wt % rare earth metal; 0.1-10 wt % potassium; and 3-15 wt % titanium; also comprising 0.02-1.1 wt % phosphorus; and 0.03-1.9 wt % iron; the carrier content is 55-90 wt %. In the case of a fluidized bed reactor, the present catalyst can achieve a one-way hydrogen chloride conversion rate of 80-85%. Almost all of the 0-1000 mg/kg of chlorinated benzene contained in hydrogen chloride gas can be converted into CO.sub.2 and H.sub.2O without generating polychlorinated benzene.

Claims

1. A catalyst for preparing chlorine gas by hydrogen chloride oxidation, wherein the catalyst comprises a copper element, a manganese element, a boron element, a chromium element, a rare-earth element, a potassium element, a titanium element, a phosphorus element, an iron element and a carrier.

2. The catalyst according to claim 1, wherein based on the total mass of the catalyst, the content of each element in the catalyst is: copper, 0.5-20 wt %, preferably 2-10%; manganese, 2-10 wt %, preferably 2-5 wt %; boron, 0.05-2 wt %, preferably 0.06-1.0 wt %; chromium, 0.01-3.0 wt %, preferably 0.02-2.0 wt %; rare-earth metal, 0.1-10 wt %, preferably 0.5-3.0 wt %; potassium, 0.1-10 wt %, preferably 0.2-2.5 wt %; titanium, 3-15 wt %, preferably 4-14 wt %; phosphorus, 0.02-1.1 wt %, preferably 0.03-0.50 wt %; iron, 0.03-1.9 wt %, preferably 0.04-1.0 wt %; the content of the carrier is 55-90 wt %, preferably 70-90 wt %.

3. The catalyst according to claim 1, wherein the rare-earth metal element is one or both of cerium and lanthanum.

4. The catalyst according to claim 1, wherein the carrier is selected from the group consisting of molecular sieves, kaolin, diatomite, silica, alumina, titania, zirconia, activated carbon, silicon carbide, carbon black, carbon fibers and carbon nanotubes, and combinations thereof.

5. A method of preparing chlorine gas by hydrogen chloride oxidation, using the catalyst according to claim 1, preferably the hydrogen chloride is hydrogen chloride containing chlorobenzene, the hydrogen chloride is hydrogen chloride containing 0-1000 mg/kg of chlorobenzene; the hydrogen chloride is hydrogen chloride containing 100-800 mg/kg of chlorobenzene and/or o-dichlorobenzene.

6. A method of producing a catalyst for preparing chlorine gas by hydrogen chloride oxidation, wherein the method comprises the following steps: (1) a copper-containing compound and a manganese-containing compound are dissolved in a solvent, a carrier is added, the dissolved compounds and the carrier are thoroughly mixed and infiltrated, then are dried, calcined, cooled and ground to obtain Powder A; (2) a boron-containing compound, a potassium-containing compound and a rare-earth metal-containing compound are dissolved in a solvent, Powder A obtained in step (1) is added, the dissolved compounds and Powder A are thoroughly mixed and infiltrated, then are dried, calcined, cooled and ground to obtain Powder B; (3) a copper-containing compound, a chromium-containing compound and a manganese-containing compound are dissolved in a solvent, then titanium dioxide and iron phosphate powder are added, the dissolved compounds, titanium dioxide and iron phosphate powder are thoroughly mixed and infiltrated, then are dried, calcined, cooled and ground to obtain Powder C; and (4) Powder B, Powder C, a carrier, a binder, and a solvent are mixed evenly, then the obtained mixture are dried, calcined, sieved and cooled to obtain the catalyst.

7. The method according to claim 6, wherein the solvent in step (1), the solvent in step (2) and the solvent in step (3) are all water or dilute nitric acid, the solvent in step (4) is water.

8. The method according to claim 6, wherein the content by weight of each component in step (4) is 5-30 parts of Powder B, 10-30 parts of Powder C, 10-40 parts of the carrier and 10-55 parts of the binder, respectively.

9. The method according to claim 6, wherein the rare-earth metal element is one or both of cerium and lanthanum.

10. The method according to claim 6, wherein the carrier in step (1) is a molecular sieve, and the molecular sieve has a specific surface area of 300-600 m.sup.2/g, an average particle size of 0.1-10 μm and a maximum particle size up to 50 μm, preferably the average particle size is 0.5-2 μm and the maximum particle size is up to 10 μm.

11. The method according to claim 6, wherein the carrier in step (1) has a content of 15-100 parts by weight, copper element in the copper-containing compound has a content of 4-8 parts by weight, and manganese element in the manganese-containing compound has a content of 1-10 parts by weight.

12. The method according to claim 6, wherein Powder A in the step (2) has a content of 50-200 parts by weight, boron element in the boron-containing compound has a content of 1-2 parts by weight, potassium element in the potassium-containing compound has a content of 2-10 parts by weight, and rare-earth metal in the rare-earth metal-containing compound has a content of 1-10 parts by weight.

13. The method according to claim 6, wherein the titanium dioxide in step (3) is titanium dioxide having an anatase crystal structure; the titanium dioxide has an average particle size of 0.1-10 μm and a maximum particle size up to 50 μm, preferably the average particle size is 0.2-3 μm and the maximum particle size is up to 15 μm.

14. The method according to claim 6, wherein the iron phosphate in step (3) has an average particle size of 10-100 μm and a maximum particle size up to 500 μm.

15. The method according to claim 6, wherein in step (3), parts by weight of the titanium dioxide, the iron phosphate, copper element in the copper-containing compound, chromium element in the chromium-containing compound and manganese element in the manganese-containing compound are 50-300 parts, 0.1-10 parts, 0.1-2 parts, 0.1-2 parts and 4-30 parts, respectively.

16. The method according to claim 6, wherein the carrier in step (4) is selected from the group consisting of molecular sieves, kaolin, diatomite, silica, alumina, titania, zirconia, activated carbon, silicon carbide, carbon black, carbon fibers and carbon nanotubes, and combinations thereof.

17. The method according to claim 6, wherein the earner in step (4) has an average particle size of 0.1-10 μm and a maximum particle size up to 50 μm, preferably the average particle size is 0.2-3 μm and the maximum particle size is up to 15 μm.

18. The method according to claim 6, wherein the binder in step (4) is selected from the group consisting of aluminum sol, activated aluminum oxide, silica sol, kaolin, clay, pseudoboehmite, silicate ester, titanate ester, potassium water glass (potassium silicate), diatomite, nitric acid and phosphoric acid, and combinations thereof.

19. The method according to claim 6, wherein in step (1), calcination temperature is 300-650° C., preferably 450-650° C., calcination time is 30-120 minutes; in step (2), calcination temperature is 300-650° C., preferably 450-650° C., calcination time is 30-120 minutes; in step (3), calcination temperature is 450-850° C., preferably 550-750° C., calcination time is 60-120 minutes; in step (4), calcination temperature is 300-650° C., preferably 450-650° C., calcination time is 60-180 minutes.

20. The method according to claim 6, wherein Powder A in step (1) has an average particle size of 10-100 μm and a maximum particle size up to 500 μm; Powder B in step (2) has an average particle size of 10-100 μm and a maximum particle size up to 500 μm; Powder C in step (3) has an average particle size of 10-100 μm and a maximum particle size up to 500 μm.

Description

EMBODIMENTS

(1) The embodiments of the present invention will be further illustrated with combination of the examples as follows. It should be noted that the present invention is not limited to the listed examples, but also includes any other well-known changes within the protection scope of the claimed invention.

(2) Test Method of the Conversion Rate of Hydrochloric Acid:

(3) (1) Detection Principle
Cl.sub.2+2KI=2KCl+I.sub.2
I.sub.2+2Na.sub.2S.sub.2O.sub.3=2NaI+Na.sub.2S.sub.4O.sub.6
HCl+NaOH=NaCl+H.sub.2O

(4) (2) Preparation and Calibration of 0.1 mol/L Na.sub.2S.sub.2O.sub.3 Solution

(5) About 6.2 g of Na.sub.2S.sub.2O.sub.3.5H.sub.2O is weighed, dissolved in a suitable amount of freshly boiled and freshly cooled distilled water (O.sub.2 and CO.sub.2 are removed in water), 0.05-0.1 g of Na.sub.2CO.sub.3 (microorganisms are inhibited) is added, and 250 mL of solution is prepared and placed in a brown bottle, saved in the dark; the solution is placed for 1-2 weeks before calibration.

(6) 0.15 g of K.sub.2Cr.sub.2O.sub.7 (dried at 110° C. for 2 h) is accurately weighed in an iodine flask, 10-20 mL of water is added to dissolve the K.sub.2Cr.sub.2O.sub.7, 2 g of KI and 10 mL of H.sub.2SO.sub.4 are added and are shaken well for 5 minutes, then are diluted with 50 mL of water, and are titrated with Na.sub.2S.sub.2O.sub.3 solution until the solution turns light yellow-green, at that time 2 mL of starch indicator is added. The mixture is continuously titrated with Na.sub.2S.sub.2O.sub.3 solution until the solution changes from blue to light green (end point is very light green shown by Cr.sup.3+). Parallel calibration is carried out for 3 times to take the average of the 3 times.

(7) (3) Analysis and Detection Process

(8) a) Sampling: a 250 mL sampling bottle is displaced with the sample gas to be tested for 3 minutes (the gas enters from the bottom and is discharged from the top) to ensure that there are no impurities in the sample bottle. The sample gas in the sample bottle sufficiently reacts with KI. Cl.sub.2 in the sample gas reacts with KI to form I.sub.2 (dissolves in the form of I.sup.3- in the absorption liquid; if I.sub.2 precipitation occurs, the accuracy of the result is likely to be poor and resampling is required), after HCl is absorbed, aqueous hydrochloric acid is formed. Then titration is carried out.

(9) b) Titration of I.sub.2 (I.sup.3-) in the absorption liquid: 25.00 mL of the absorption liquid is taken into a 250 mL conical flask, diluted with 50 mL of distilled water, titrated with the prepared and calibrated Na.sub.2S.sub.2O.sub.3 solution until a light yellow color is shown, 2 mL of starch solution is added, the mixture is titrated continuously until the blue color just disappears, which is the end point. The volume of Na.sub.2S.sub.2O.sub.3 solution consumed by titration is recorded, the content of I.sub.2 (I.sup.3-) in the absorption liquid can be calculated, and then the amount of Cl.sub.2 in the sample gas is calculated.

(10) c) Titration of hydrochloric acid in the absorption liquid: 2-3 drops of phenolphthalein reagent is added to the sample obtained after the completion of the titration in step b), then it is titrated with the prepared and calibrated NaOH standard solution until a red color is shown and the color does not change within half a minute, which is the titration end point. The volume of the NaOH standard solution consumed by titration is reported, the content of H.sup.+ in the absorption liquid can be calculated, and then the amount of HCl in the sample gas is calculated.

(11) (4) Hydrogen chloride conversion rate in the sample is calculated as follows:

(12) $\mathrm{Conv}=\frac{a.Math.b\times {10}^{-3}}{a.Math.b\times {10}^{-3}+c.Math.d\times {10}^{-3}}\times 100\%$

(13) wherein:

(14) a represents the concentration of Na.sub.2S.sub.2O.sub.3 solution, mol/L;

(15) b represents the volume of Na.sub.2S.sub.2O.sub.3 solution consumed by titration, mL;

(16) c represents the concentration of NaOH standard solution, mol/L;

(17) d represents the volume of NaOH standard solution consumed by titration, mL.

(18) Test method for the content and conversion rate of chlorobenzene/o-dichlorobenzene in hydrogen chloride is as follows:

(19) (1) Detection Principle:

(20) Hydrochloric acid containing chlorobenzene/o-dichlorobenzene is adsorbed on an activated carbon packed column, and then the activated carbon is placed in warm ethanol to desorb chlorobenzene/o-dichlorobenzene. The concentration of chlorobenzene/o-dichlorobenzene in ethanol is determined by gas chromatography; the total amount of chlorobenzene/o-dichlorobenzene can then be calculated. The ratio between the total amount of chlorobenzene/o-dichlorobenzene and the total amount of hydrogen chloride entering into the activated carbon packed column is the content of chlorobenzene/o-dichlorobenzene in hydrogen chloride.

(21) The contents of chlorobenzene/o-dichlorobenzene in hydrogen chloride before and after the reaction are compared, the conversion rate of chlorobenzene/o-dichlorobenzene in hydrogen chloride can be calculated.

(22) (2) Analysis and Detection Process

(23) A) A 100 ml empty glass column is taken and filled with at least 60 ml of activated carbon particles. The hydrogen chloride gas containing chlorobenzene/o-dichlorobenzene at a flow rate F is passed through an activated carbon packed column, duration time is t. F is generally controlled at 10-100 ml/min, and t is generally controlled at 20-40 minutes.

(24) B) All the activated carbons after adsorption are transferred into ethanol at 30-50° C. and are soaked for at least 30 minutes, the activated carbons are filtered out; the activated carbons filtered out are transferred into fresh ethanol at 30-50° C. again, and this process is repeated three times; the initial weights of ethanol m.sub.1, m.sub.2, m.sub.3 of the three times are recorded, respectively. The ethanol filtered out is analyzed by gas chromatography for the mass concentration of chlorobenzene/o-dichlorobenzene, the concentrations are denoted as c.sub.1, c.sub.2 and c.sub.3, respectively.

(25) (3) Calculation of the Content of Chlorobenzene/o-Dichlorobenzene in Hydrogen Chloride

(26) $C_1=\frac{.Math.(m_i•c_{i)}}{F.Math.t}$

(27) (1) Calculation of the Conversion Rate of Chlorobenzene/o-Dichlorobenzene in Hydrogen Chloride

(28) $C_{\mathrm{onv}}=\frac{C_0-C_1}{C_0}\times 100\%$

(29) wherein

(30) C.sub.1 represents the content of chlorobenzene/o-dichlorobenzene in hydrogen chloride after the reaction;

(31) C.sub.0 represents the content of chlorobenzene/o-dichlorobenzene in hydrogen chloride before the reaction;

(32) The powder particle size is measured using a HELOS/BF laser particle sizer, Sympatec, Germany.

(33) Preparation of Powder A

(34) 62 kg of copper nitrate (Cu(NO.sub.3).sub.2.6H.sub.2O, 295.56), 49 kg of manganese nitrate (Mn(NO.sub.3).sub.2.4H.sub.2O, 250) aqueous solution with a mass concentration of 50% were weighted and put into 100 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 95 kg of HY molecular sieve (specific surface area: 300 m.sup.2/g, average particle size: 1 μm) (Zibo Jinqi Chemical Technology Co., Ltd.) was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled, ground to obtain 104.6 kg of Powder A. The obtained Powder A was placed in an environment with 28% of relative humidity for later use. The powder was marked as Powder A-1. The average particle size of Powder A-1 was 28 μm (HELOS/BF laser particle sizer, Sympatec, Germany).

(35) 32 kg of copper nitrate (Cu(NO.sub.3).sub.2.6H.sub.2O, 295.56), 35.2 kg of manganese nitrate (Mn(NO.sub.3).sub.2.4H.sub.2O, 250) aqueous solution with a mass concentration of 50% were weighted and put into 130 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 90 kg of HZSM-5 molecular sieve (specific surface area: 600 m.sup.2/g, average particle size: 0.1 μm) (Tianjin Nanhua Catalyst Co., Ltd.) was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower by using a twin-screw pump, at a rate of 15 L/h. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled, ground to obtain 95.4 kg of Powder A. The obtained Powder A was placed under an environment with 28% of relative humidity, and set aside. The powder was marked as Powder A-2. The average particle size of Powder A-2 was 35 μm.

(36) 110 kg of copper nitrate (Cu(NO.sub.3).sub.2.6H.sub.2O, 295.56), 80 kg of manganese nitrate (Mn(NO.sub.3).sub.2.4H.sub.2O, 250) aqueous solution with a mass concentration of 50% were weighted and put into 150 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.1 nitric acid solution. After complete dissolution was determined visually, 72 kg of HY molecular sieve (specific surface area: 400 m.sup.2/g, average particle size: 0.5 μm) (Zibo Jinqi Chemical Technology Co., Ltd.) was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled, suitably ground to obtain 101.3 kg of Powder A. The obtained Powder A was placed under an environment with 28% of relative humidity, and set aside. The powder was marked as Powder A-3. The average particle size of Powder A-3 was 30 μm.

(37) Preparation of Powder B

(38) 1.34 kg of potassium chloride (KCl, 74.55), 1.1 kg of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O, 434.12), 1.1 kg of lanthanum nitrate (La(NO.sub.3).sub.3.6H.sub.2O, 432.905), 1.0 kg of boric acid (H.sub.3BO.sub.3, 61.83) were weighted and put into 30 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 30.3 kg of Powder A-1 was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 24.2 kg of Powder B. The obtained Powder B was placed in an environment with 28% of relative humidity for later use. The powder was marked as Powder B-11. The average particle size of Powder B-11 was 45 μm.

(39) 6.53 kg of potassium chloride (KCl, 74.55), 6.7 kg of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O, 434.12), 6.7 kg of lanthanum nitrate (La(NO.sub.3).sub.3.6H.sub.2O, 432.9055), 4.92 kg of boric acid (H.sub.3BO.sub.3, 61.83) were weighted and put into 60 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 30.1 kg of Powder A-1 was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 29.6 kg of Powder B. The obtained Powder B was placed in an environment with 28% of relative humidity, and set aside. The powder was marked as Powder B-12. The average particle size of Powder B-12 was 48 μm.

(40) 1.34 kg of potassium chloride (KCl, 74.55), 1.1 kg of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O, 434.12), 1.11 kg of lanthanum nitrate (La(NO.sub.3).sub.3.6H.sub.2O, 432.9055), 1.0 kg of boric acid (H.sub.3BO.sub.3, 61.83) were weighted and put into 30 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 30.1 kg of Powder A-2 was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 23.5 kg of Powder B. The obtained Powder B was placed in an environment with 28% of relative humidity for later use. The powder was marked as Powder B-21. The average particle size of Powder B-21 was 42 μm.

(41) 6.55 kg of potassium chloride (KCl, 74.55), 6.7 kg of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O, 434.12), 6.7 kg of lanthanum nitrate (La(NO.sub.3).sub.3.6H.sub.2O, 432.9055), 4.91 kg of boric acid (H.sub.3BO.sub.3, 61.83) were weighted and put into 60 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 30.3 kg of Powder A-2 was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 29.6 kg of Powder B. The obtained Powder B was placed in an environment with 28% of relative humidity, and set aside. The powder was marked as Powder B-22. The average particle size of Powder B-22 was 40 μm.

(42) 1.33 kg of potassium chloride (KCl, 74.55), 1.1 kg of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O, 434.12), 1.09 kg of lanthanum nitrate (La(NO.sub.3).sub.3.6H.sub.2O, 432.9055), 1.03 kg of boric acid (H.sub.3BO.sub.3, 61.83) were weighted and put into 30 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 30.1 kg of Powder A-3 was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 24.2 kg of Powder B. The obtained Powder B was placed in an environment with 28% of relative humidity, and set aside. The powder was marked as Powder B-31. The average particle size of Powder B-31 was 52 μm.

(43) 6.54 kg of potassium chloride (KCl, 74.55), 6.76 kg of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O, 434.12), 6.71 kg of lanthanum nitrate (La(NO.sub.3).sub.3.6H.sub.2O, 432.9055), 4.94 kg of boric acid (H.sub.3BO.sub.3, 61.83) were weighted and put into 60 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 30.3 kg of Powder A-3 was continuously added. The mixture was continuously stirred, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 500° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 29.6 kg of Powder B. The obtained Powder B was placed in an environment with 28% of relative humidity, and set aside. The powder was marked as Powder B-32. The average particle size of Powder B-32 was 47 μm.

(44) Preparation of Powder C

(45) 2.17 kg of iron nitrate (Fe(NO.sub.3).sub.3.9H.sub.2O, 404.02) was put into 3.5 kg of water and the mixture was stirred until iron nitrate was completely dissolved; 1.11 kg of ammonium dihydrogen phosphate (NH.sub.4H.sub.2PO.sub.4, 132.97) was put into 2.0 kg of water and the mixture was stirred until ammonium dihydrogen phosphate was completely dissolved, then the solution was slowly added to the iron nitrate aqueous solution, the mixture was continuously stirred for 30 minutes, then the precipitate was removed and placed in an oven at 90° C. for 1 hour. Then the precipitate was calcined using a muffle furnace. The heating rate of the muffle furnace was 2° C./min and the calcination temperature was 600° C. The calcination time was about 1 hour, then the calcined materials were cooled to obtain 2.0 kg of iron phosphate powder, the power was placed in an environment with 28% of relative humidity for later use.

(46) 0.93 kg of copper nitrate (Cu(NO.sub.3).sub.2.6H.sub.2O, 295.56), 16 kg of manganese nitrate aqueous solution with the mass concentration of 50% and 1.54 kg of chromium nitrate (Cr(NO.sub.3).sub.3.9H.sub.2O, 399.99) were weighed and put into 15 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 12 kg of titanium dioxide (TiO.sub.2, 79.88, average particle size: 0.1 μm) and 500 g of iron phosphate (FePO.sub.4, 150.82, average particle size: 20 μm) were continuously added. The mixture was stirred continuously, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 600° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 10.5 kg of Powder C. The Powder C was placed in an environment with 28% of relative humidity for later use. The powder was marked as Powder C-1. The average particle size of Powder C-1 was 25 μm.

(47) 155 g of copper nitrate (Cu(NO.sub.3).sub.2.6H.sub.2O, 295.56), 13 kg of manganese nitrate aqueous solution with a mass concentration of 50% and 256 kg of chromium nitrate (Cr(NO.sub.3).sub.3.9H.sub.2O, 399.99) were weighed and put into 15 kg of deionized water, then the pH was adjusted to 0.3 with 1 mol.Math.L.sup.−1 nitric acid solution. After complete dissolution was determined visually, 16 kg of titanium dioxide (TiO.sub.2, 79.88, average particle size: 1.0 μm) and 500 g of iron phosphate (FePO.sub.4, 150.82, average particle size: 20 μm) were continuously added. The mixture was stirred continuously, and a small spoon was used to sample several times to observe the slurry. If the slurry was not evenly distributed, stir was continued. If the slurry was uniform, the slurry was then fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a muffle furnace. The heating rate of the muffle furnace was 2° C./min, the calcination temperature was 600° C., and the calcination time was about 1 hour, then the calcined materials were cooled to obtain 14.2 kg of Powder C. The Powder C was placed in an environment with 28% of relative humidity for later use. The powder was marked as Powder C-2. The average particle size of Powder C-2 was 18 μm.

Example 1

(48) Preparation of Catalyst:

(49) At room temperature (about 25° C.), 3.0 kg of Powder B-11, 2.5 kg of Powder C-1 and 4.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) were taken and mixed well then were added to 26 kg of deionized water being stirred. Then, 1.0 kg of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd., particle size: 0.1-2.0 μm, solid content: 65 wt %, the same hereinafter), 1.0 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 1.0 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 2362 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 8.3 kg of catalyst product was obtained.

(50) Catalyst Performance Test:

(51) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C., and 4 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 2 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 2:1; the mass space velocity of hydrogen chloride was 0.39 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 81.5%, the average conversion rate of chlorobenzene was 98.6%, 212 mg of hexachlorobenzene and 23 mg of pentachlorobenzene were collected.

Example 2

(52) Preparation of Catalyst:

(53) At room temperature (about 25° C.), 4.0 kg of Powder B-11, 3.5 kg of Powder C-2, 3.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) and 800 g of carbon black (Changzhou Fengshuo Chemical Co., Ltd.) were taken and mixed well then were added to 26 kg of deionized water being stirred. Then, 400 g of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 6.0 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 2.0 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 5823 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 9.1 kg of catalyst product was obtained.

(54) Catalyst Performance Test:

(55) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 3 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 1.5 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 2:1; the mass space velocity of hydrogen chloride was 0.29 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 83.7%, the average conversion rate of chlorobenzene was 99.1%, 101 mg of hexachlorobenzene and 14 mg of pentachlorobenzene were collected.

Example 3

(56) Preparation of Catalyst:

(57) At room temperature (about 25° C.), 2.0 kg of Powder B-12, 3.5 kg of Powder C-1, 4.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) and 3.0 kg of kaolin (Jinan Bofa Chemical Raw Materials Co., Ltd.) were taken and mixed well then were added to 20 kg of deionized water being stirred. Then, 400 g of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 7.5 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 2.5 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 5341 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 12.2 kg of catalyst product was obtained.

(58) Catalyst Performance Test:

(59) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 2 L/min of hydrogen chloride gas (containing o-dichlorobenzene of 974 mg/Nm.sup.3) and 2 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 1:1; the mass space velocity of hydrogen chloride was 0.20 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 84.7%, the average conversion rate of o-dichlorobenzene was 98.3%, 119 mg of hexachlorobenzene and 8 mg of pentachlorobenzene were collected.

Example 4

(60) Preparation of Catalyst:

(61) At room temperature (about 25° C.), 3.0 kg of Powder B-12, 2.0 kg of Powder C-2, 2.5 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) and 1.0 kg of kaolin (Jinan Bofa Chemical Raw Materials Co., Ltd.) were taken and mixed well then were added to 23 kg of deionized water being stirred. Then, 500 g of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 3.0 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 2.5 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 4093 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 7.3 kg of catalyst product was obtained.

(62) Catalyst Performance Test:

(63) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 3 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 1.5 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 2:1; the mass space velocity of hydrogen chloride was 0.29 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 82.9%, the average conversion rate of chlorobenzene was 96.9%, 162 mg of hexachlorobenzene and 42 mg of pentachlorobenzene were collected.

Example 5

(64) Preparation of Catalyst:

(65) At room temperature (about 25° C.), 2.0 kg of Powder B-21, 4.0 kg of Powder C-1 and 4.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) were taken and mixed well then were added to 36 kg of deionized water being stirred. Then, 2.0 kg of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 3.0 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 3.5 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were carefully added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 1825 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 10.2 kg of catalyst product was obtained.

(66) Catalyst Performance Test:

(67) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 10 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 10 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 1:1; the mass space velocity of hydrogen chloride was 0.98 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 82.3%, the average conversion rate of chlorobenzene was 97.0%, 802 mg of hexachlorobenzene and 93 mg of pentachlorobenzene were collected.

Example 6

(68) Preparation of Catalyst:

(69) At room temperature (about 25° C.), 2.5 kg of Powder B-22, 3.0 kg of Powder C-2, 5.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) and 300 g of Y molecular sieve (Zibo Jinqi Chemical Technology Co., Ltd.) were taken and mixed well then were added to 25 kg of deionized water being stirred. Then, 1.4 kg of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 3.0 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 1.5 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 3864 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 10.1 kg of catalyst product was obtained.

(70) Catalyst Performance Test:

(71) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 2 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 1 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 2:1; the mass space velocity of hydrogen chloride was 0.20 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 80.2%, the average conversion rate of chlorobenzene was 99.5%, 69 mg of hexachlorobenzene and 4 mg of pentachlorobenzene were collected.

Example 7

(72) Preparation of Catalyst:

(73) At room temperature (about 25° C.), 3.0 kg of Powder B-31, 4.0 kg of Powder C-2, 3.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) and 3.0 kg of Y molecular sieve (Zibo Jinqi Chemical Technology Co., Ltd.) were taken and mixed well then were added to 35 kg of deionized water being stirred. Then, 2.0 kg of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 4.0 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 1.5 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 4028 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 12.5 kg of catalyst product was obtained.

(74) Catalyst Performance Test:

(75) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 6 L/min of hydrogen chloride gas (containing o-dichlorobenzene 974 mg/Nm.sup.3) and 3 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 2:1; the mass space velocity of hydrogen chloride was 0.59 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 82.6%, the average conversion rate of o-dichlorobenzene was 98.1%, 360 mg of hexachlorobenzene and 48 mg of pentachlorobenzene were collected.

Example 8

(76) Preparation of Catalyst:

(77) At room temperature (about 25° C.), 5.0 kg of Powder B-31, 4.0 kg of Powder C-2 and 4.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) were taken and mixed well then were added to 22 kg of deionized water being stirred. Then, 680 g of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 10.0 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 3.4 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and dilute nitric acid was slowly added finally, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 8531 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 11.6 kg of catalyst product was obtained.

(78) Catalyst Performance Test:

(79) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 4 L/min of hydrogen chloride gas (containing o-dichlorobenzene 974 mg/Nm.sup.3) and 1.33 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 3:1; the mass space velocity of hydrogen chloride was 0.39 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 80.2%, the average conversion rate of o-dichlorobenzene was 99.4%, 95 mg of hexachlorobenzene and 11 mg of pentachlorobenzene were collected.

Example 9

(80) Preparation of Catalyst:

(81) At room temperature (about 25° C.), 2.5 kg of Powder B-32, 4.0 kg of Powder C-1 and 4.0 kg of α-alumina powder (Zibo Shuoren Alumina Science and Technology Co., Ltd.) were taken and mixed well then were added to 30 kg of deionized water being stirred. Then, 1.2 kg of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 2.5 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 1.5 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added, and then dilute nitric acid was slowly added, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 1597 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 8.6 kg of catalyst product was obtained.

(82) Catalyst Performance Test:

(83) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 5 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 2 L/min of oxygen were introduced, the molar ratio of hydrogen chloride to oxygen was 2.5:1; the mass space velocity of hydrogen chloride was 0.49 gHCl/(gcat×h), the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 100 h. The average conversion rate of HCl was measured to be 83.6%, the average conversion rate of chlorobenzene was 98.8%, 274 mg of hexachlorobenzene and 36 mg of pentachlorobenzene were collected.

(84) TABLE-US-00001 Compositions of the catalysts/wt % Rare Examples Cu Mn B Cr earth K Ti P Fe Carrier Example 1 3.09 3.64 0.15 0.29 0.59 0.59 10.26 0.15 0.26 80.99 Example 2 3.04 3.17 0.16 0.05 0.63 0.63 13.15 0.14 0.25 78.78 Example 3 1.19 2.87 0.23 0.29 1.17 0.93 10.27 0.15 0.26 82.64 Example 4 2.05 2.30 0.52 0.03 2.61 2.07 9.96 0.11 0.19 80.14 Example 5 1.31 3.88 0.08 0.38 0.33 0.33 13.74 0.20 0.35 79.39 Example 6 0.83 2.19 0.34 0.04 1.71 1.36 11.76 0.13 0.23 81.42 Example 7 3.58 3.23 0.10 0.04 0.41 0.40 12.84 0.14 0.25 79.00 Example 8 5.68 3.93 0.16 0.04 0.65 0.64 12.27 0.13 0.24 76.27 Example 9 2.95 4.45 0.36 0.40 1.79 1.41 14.34 0.20 0.37 73.72

Comparative Example 1

(85) Please refer to Example 4 in CN201010567038.9.

(86) 2.63 kg of copper chloride (CuCl.sub.2.2H.sub.2O) was taken and dissolved in 4 L of deionized water, then 6 kg of HY molecular sieve was added, the mixture was well stirred then was stewed for 12 hours. After being dried at 90° C., a solid was obtained, which was smashed and ground to obtain Powder A-4.

(87) 92 g of boric acid (H.sub.3BO.sub.3, 61.83), 305 g of potassium chloride (KCl, 74.55), 135 g of manganese nitrate, 815 g of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O, 372.116) and 4.05 g of lanthanum nitrate (La(NO.sub.3).sub.3.6H.sub.2O), 432.9055) were taken and dissolved in 25 L of deionized water, then all Powder A-4 was added, 300 g of pseudoboehmite (Zibo Jinqi Chemical Technology Co., Ltd.), 4 kg of aluminum sol with a concentration of 20 wt % (Zibo Jinqi Chemical Technology Co., Ltd.) and 2.5 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were slowly added during stirring, and then dilute nitric acid was slowly added, the pH of the materials was controlled to be 0.3. The temperature of the materials during the entire mixing process was controlled at 35-40° C. 30 minutes later, the viscosity of the slurry was determined to be 1362 mPa.Math.s. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 7.3 kg of catalyst product was obtained.

(88) Catalyst Performance Test:

(89) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 5 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 2 L/min of oxygen were introduced, the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 10 h. The average conversion rate of HCl was measured to be 79.2%, the average conversion rate of chlorobenzene was 96.4%, 5.72 g of hexachlorobenzene, 809 mg of pentachlorobenzene and 140 mg of other chlorobenzenes were collected.

Comparative Example 2

(90) Please refer to Example 1 in CN200910027312.0.

(91) 1.74 kg of cerium nitrate (Ce(NO.sub.3).sub.3.6H.sub.2O), 550 g of potassium chloride (KCl) and 1.35 kg of copper chloride (CuCl.sub.2.2H.sub.2O) were taken and dissolved in 20 L of deionized water, then 2.58 kg of manganese nitrate (Mn(NO.sub.3).sub.2) aqueous solution with a concentration of 50% was added. 5.4 kg of ReY molecular sieve (Zibo Jinqi Chemical Technology Co., Ltd.) and 3 kg of silica sol with a concentration of 20 wt % (Shandong Baite New Material Co., Ltd.) were added during stirring. The mixed slurry was fed into a centrifugal spray drying tower at a rate of 15 L/h using a twin-screw pump. Following the spray drying tower, the materials were collected using a cyclone separator and a bag-type dust collector. All the collected materials were calcined in a small-scale rotary kiln. The heating rate of the materials was 3° C./min, the maximum calcination temperature was 500° C., and the residence time of the materials in the high temperature section was approximately 3 hours. Finally, 4.5 kg of catalyst product was obtained.

(92) Catalyst Performance Test:

(93) 1 kg of the catalyst was placed in a fluidized bed reactor having an inner diameter of 30 mm and a height of 700 mm, the catalyst bed was preheated to 280° C. with air preheated to about 300° C. and 5 L/min of hydrogen chloride gas (containing chlorobenzene of 990 mg/Nm.sup.3) and 2.5 L/min of oxygen were introduced, the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400-420° C., the reaction was conducted continuously for 10 h. The average conversion rate of HCl was measured to be 78.8%, the average conversion rate of chlorobenzene was 93.2%, 3.25 g of hexachlorobenzene, 461 mg of pentachlorobenzene and 54 mg of other chlorobenzenes were collected.