METHOD FOR PREPARING CATALYST USED FOR PREPARING CHLORINE, CATALYST AND METHOD FOR PREPARING CHLORINE

Abstract

The present invention relates to a method for preparing catalyst used for preparing chlorine by oxidizing hydrogen chloride. The method is mixing a slurry mainly containing boron and chromium with a slurry mainly containing copper, boron, alkali-metal elements, rare-earth elements, aluminum sol, silica sol, carrier and optionally other metal elements, the mixing temperature being not more than 100 C., and the residence time being not more than 120 minutes, the mixed slurry is successively treated with spray drying, high temperature calcination, so that the catalyst is obtained. The present invention also relates to the catalyst prepared through the method, use of the catalyst used in the process of preparing chlorine by oxidizing hydrogen chloride and a method for preparing chlorine by using the catalyst. The catalyst is used for preparing chlorine by oxidizing hydrogen chloride with oxygen or air in fluidized bed reactor.

Claims

1. A method for preparing catalysts used for preparing chlorine by oxidizing hydrogen chloride, comprising the steps of: mixing a slurry A with a slurry B under the condition of a mixing temperature being >X C. and 100 C., and a residence time being 120 minutes to obtain a mixed slurry; treating the mixed slurry with spray drying to obtain catalyst precursor particles; and calcining the catalyst precursor particles to obtain the catalysts, wherein, X C. is the highest value among the solidifying points of slurry A, slurry B and the mixed slurry; slurry A is acidic and contains boron and chromium; slurry B contains copper, boron, alkali-metal elements, rare-earth elements, aluminum sol, silica sol, carrier and optionally at least one of other metal elements selected from the group consisting of magnesium, calcium, barium, manganese, ruthenium and titanium.

2. The method according to claim 1, wherein slurry A is formed by mixing boron-containing compound, chromium-containing compound and water; based on the weight of slurry A, the slurry A contains: 0.12 wt %, preferably 0.31 wt % boron by weight of boron element; and 0.15 wt %, preferably 0.34 wt % chromium by weight of chromium element.

3. The method according to claim 1, wherein the pH value of slurry A is 0.16.0, preferably 0.33.0.

4. The method according to claim 1, wherein, based on the weight of slurry A, the content of insoluble substances is 0.3 wt %, preferably 0.1 wt %.

5. The method according to claim 1, wherein, based on the weight of slurry B, the slurry B contains: by weight of copper element, 27.5 wt % of copper; by weight of boron element, 0.052.5 wt % of boron; by weight of alkali-metal elements, 13.5 wt % of alkali-metal elements; by weight of rare-earth elements, 1.55.5 wt % of rare-earth elements; by weight of aluminum oxide, 0.115 wt %, preferably 0.15 wt % of aluminum sol; by weight of silica, 0.125 wt %, preferably 0.110 wt % of silica sol; 575 wt %, preferably 1550 wt % of carrier; 05 wt % of other metal elements; and the balance is water.

6. The method according to claim 5, wherein the alkali-metal elements are potassium and/or sodium; the rare-earth element is at least one of the elements selected from the group consisting of cerium, lanthanum, praseodymium and neodymium; the carrier is at least one of the carriers selected from the group consisting of molecular sieve, kaolin, kieselguhr, silica, alumina, titanium dioxide and zirconium dioxide.

7. The method according to claim 1, wherein, when the mixing temperature is between 50100 C., the residence time is 10 minutes, preferably 310 minutes; when the mixing temperature is between 3050 C., the residence time is 30 minutes, preferably 1025 minutes; when the mixing temperature is >X C. and 30 C., the residence time is 120 minutes, preferably 20100 minutes, more preferably 4070 minutes, wherein X is the highest value among the solidifying points of slurry A, slurry B and the mixed slurry.

8. The method according to claim 1, wherein the volume ratio between slurry B and slurry A is 520.

9. The method according to claim 2, wherein the boron-containing compound is at least one of the compounds selected from the group consisting of boron trichloride, boron oxide, boric acid, chromium diboride, boron nitride, boron nitrite, potassium borate and sodium borate; the chromium-containing compound is at least one of the compounds selected from the group consisting of chromium chloride, chromium nitrate, chromium trioxide, chromium diboride, dichromic acid, potassium dichromate, sodium dichromate, chromic acid, potassium chromate and sodium chromate.

10. The method according to claim 1, wherein the calcination is carried out at the temperature of 450750 C. for 30 mins20 hrs.

11. A catalyst prepared according to the method of claim 1.

12. (canceled)

13. A method for preparing chlorine by oxidizing hydrogen chloride, wherein the catalyst according to claim 11 is used as the reaction catalyst of the hydrogen chloride oxidizing reaction in a fluidized bed reactor.

14. The method according to claim 13, wherein the highest temperature in the reactor is controlled between 320500 C., preferable 350450 C.

15. The method according to claim 13, wherein the space velocity of hydrogen chloride is 0.051.5 h-1, the molar ratio between hydrogen chloride and oxygen is 14, and the absolute pressure of the reaction is from ordinary pressure to 5 atmospheric pressure.

16. The method according to claim 2, wherein the pH value of slurry A is 0.16.0, preferably 0.33.0.

17. The method according to claim 2, wherein, based on the weight of slurry A, the content of insoluble substances is 0.3wt %, preferably 0.1 wt %.

18. A catalyst prepared according to the method of claim 2.

19. A catalyst prepared according to the method of claim 3.

20. A catalyst prepared according to the method of claim 4.

21. The method according to claim 14, wherein the space velocity of hydrogen chloride is 0.051.5 h-1, the molar ratio between hydrogen chloride and oxygen is 14, and the absolute pressure of the reaction is from ordinary pressure to 5 atmospheric pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention will be further illustrated below with the combination of the examples. But the present invention is not limited to the listed examples; it should also include any other common changes within the extent of the claims.

[0031] The test method for the conversion of hydrogen chloride :

[0032] In each example, during the test of the catalyst performance, it is sampled 23 times for each 24 h to analyze, and the average conversion in the whole operation process is treated as the conversion of the catalyst.

[0033] The test method for the conversion of hydrogen chloride each time is as follows:

(1) Testing Principles

[0034]
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

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

[0035] About 6.2 g of Na.sub.2S.sub.2O.sub.3.Math.5H.sub.2O is weighed and dissolved in a suitable amount of newly boiled and just cooled distilled water (to remove O.sub.2 and CO.sub.2 in the water), 0.05-0.1 g of Na.sub.2CO.sub.3 is added (to inhibit microorganism), and 250 mL of the solution is prepared and placed in a brown bottle and stored in dark; A calibration is performed after 1-2 weeks of storing.

[0036] 0.15 g of K.sub.2Cr.sub.2O.sub.7 (dried at 110 C. for 2 h) is weighed accurately in iodine flask, 1020mL of water is added to dissolve, and 2 g of KI and 10 mL of H.sub.2SO.sub.4 with weight concentration of 1 wt % are added and the iodine flask is well shaken and placed for 5 minutes, then 50 mL water is added for dilution; the Na.sub.2S.sub.2O.sub.3 solution is used for titration until the solution turn into light yellow-green, then 2 mL of starch indicator is added, and Na.sub.2S.sub.2O.sub.3 solution is again used for titration until the solution turns into light green from blue (the end point is the very light green of Cr.sup.3+). 3 times of parallel calibration are performed and the average value is taken.

(3) Process of Sampling and Analyzing

[0037] a) sampling: 250 mL sampling bottle is replaced with sample gas to be measured for 3 min (the gas entered from the bottom and come out from the top), making sure the sampling bottle is free of impurities. The sample gas in the sampling bottle is reacted sufficiently with the KI water solution with the weight concentration of 15 wt %, the Cl.sub.2 in the sample gas is reacted with KI to produce I.sub.2 (it is dissolved in the absorption liquid in the form of I.sub.3.sup., if I.sub.2 precipitation appears, the result will not be accurate, then resampling is required), and hydrochloric acid water solution is formed after HCl is absorbed. Then titration is performed.

[0038] b) the titration of the I.sub.2 (I.sub.3.sup.) in the absorption liquid: 25.00 mL of absorption liquid is taken into 250 mL conical flask, 50 mL of distilled water is added for dilution, the prepared and calibrated Na.sub.2S.sub.2O.sub.3 solution is used to titrate the absorption liquid until it turns into light yellow, then 2 mL of starch solution is added, titration is continued until the blue just disappear, and it is the end point. The volume of the Na.sub.2S.sub.2O.sub.3 solution consumed in titration is recorded, the amount of I.sub.2 (I.sub.3.sup.) in the absorption liquid is calculated, and then the amount of Cl.sub.2 in the sample gas to be measured is calculated.

[0039] c) the titration of the hydrochloric acid in the absorption liquid: 23 drops of phenolphthalein is added to the sample where the titration in step b) ended, the colorless liquid turns to red, and the red color does not change in half a minute (if the colorless liquid did not turns to red, then if it is sure that the experiment process is right, then it indicates that there's no hydrochloric acid in the absorption liquid). Then the prepared and calibrated NaOH standard solution is used for titration until it turns into colorless, and it is the end of the titration. The volume of the NaOH standard solution consumed in the titration is recorded, and the amount of H.sup.+ in the absorption liquid can be calculated, then the amount of HCl in the sample gas to be measured is calculated.

[0040] (4) the conversion Cony of the hydrogen chloride in the sample is calculated:

[00001]$\mathrm{Conv}=\frac{a.Math.b{10}^{-3}}{a.Math.b{10}^{-3}+c.Math.d{10}^{-3}}100.Math.\%$

[0041] wherein:

[0042] a represents the concentration of Na.sub.2S.sub.2O.sub.3 solution, mol/L;

[0043] b represents the volume of the Na.sub.2S.sub.2O.sub.3 solution consumed during titration, mL;

[0044] c represents the concentration of NaOH standard solution, mol/L;

[0045] d represents the volume of the NaOH standard solution consumed during titration, mL.

The method for the Measurement of the Abrasion Index of the Catalyst (Straight Tube Method):

[0046] The measurement of the abrasion index is carried out according to the method in Q/TSH3490909-2006 of the standard The measurement of the abrasion index of the catalytic cracking catalyst, straight tube method.

The Measurement of the Particle Size Distribution of the Catalysts:

[0047] The measurement is carried out with Sympatec laser particle size analyzer, with 95% industrial alcohol as the dispersant.

[0048] VMD: volume mean diameter; unless otherwise indicated, the average particle size of the catalysts in the present invention all denotes volume mean diameter.

[0049] SMD: surface area mean diameter.

The Preparation of Slurry A:

[0050] 2 kg of boric acid, 5 kg of potassium dichromate were weighed and added to 100 kg of deionized water, then the pH was adjusted to 0.3 by 2 mol.Math.L.sup.1 of hydrochloric acid, the solution was stirred sufficiently under ambient temperature for 3 hours, and slurry A-1 was obtained with 2.25 g of contents that were insoluble.

[0051] 2 kg of boric acid, 10 kg of chromium trioxide were weighed and added to 100 kg of deionized water, then the pH was adjusted to 3.0 by 0.1 mol.Math.L.sup.1 of KOH, the solution was stirred sufficiently under ambient temperature for 3 hours, and slurry A-2 was obtained with 4.93 g of contents that were insoluble.

[0052] 5 kg of boric acid, 2 kg of chromic chloride hexahydrate were weighed and added to 100 kg of deionized water, then the pH was adjusted to 1.0 by 1 mol.Math.L.sup.1 of nitric acid, the solution was stirred sufficiently under ambient temperature for 3 hours, and slurry A-3 was obtained with 1.71 g of contents that were insoluble.

The Preparation of Slurry B:

[0053] 35 kg of copper chloride dihydrate, 10 kg of potassium chloride, 18 kg of cerium nitrate hexahydrate, 3 kg of boric acid, 18 kg of lanthanum nitrate hexahydrate were added to 200 kg of deionized water and were stirred until completely dissolved, then 2 kg of aluminum sol with the concentration of 20 wt % (Zi Bo Jin Qi Chemical Technology Co. Ltd, A20, the same below), 4 kg of silica sol with the concentration of 20 wt % (Shan Dong Bal Si Te material Co. Ltd, N20, the same below), 100 kg of inert alumina powder were added then sufficiently stirred for 2 hours under ambient temperature to obtain slurry B-1.

[0054] 25 kg of copper chloride dihydrate, 10 kg of potassium chloride, 22 kg of cerium nitrate hexahydrate, 2 kg of boric acid, 16 kg of lanthanum nitrate hexahydrate, 1 kg of manganous nitrate solution with the concentration of 50 wt %, 0.5 kg of ruthenium trichloride were added to 200 kg of deionized water and were stirred until completely dissolved, then 2 kg of aluminum sol, 4 kg of silica sol, 100 kg of inert alumina powder were added then sufficiently stirred for 2 hours under ambient temperature to obtain slurry B-2.

[0055] 30 kg of copper chloride dihydrate, 8 kg of potassium chloride, 15 kg of cerium nitrate hexahydrate, 2 kg of boric acid, 10 kg of lanthanum nitrate hexahydrate, 0.5 kg of manganous nitrate solution with the concentration of 50 wt %, 0.5 kg of anhydrous calcium chloride were added to 200 kg of deionized water and were stirred until completely dissolved, then 2 kg of aluminum sol, 4 kg of silica sol, 100 kg of inertalumina powder were added then sufficiently stirred for 2 hours under ambient temperature to obtain slurry B-3.

EXAMPLE 1

Preparation of the Catalyst:

[0056] Under ambient temperature (about 25 C.), 3 L of slurry A-1 was added slowly and continuously into 18 L of vigorously stirred slurry B-1, the mixing temperature was 33 C., the residence time was about 15 mins, the mixed slurry was fed into a centrifugal spray drying tower by a two-screw pump at the rate of 15 L/h, and a cyclone separator and a bag-type dust collector were used to collect the materials from the spray drying tower. The materials collected by the cyclone separator were calcined with muffle furnace, the heating rate of the muffle furnace was 2 C./min, the temperature for calcination was 500 C., and the calcination time was about 1 h, then 8.6 kg of finished catalyst were obtained after cooling.

[0057] After analyzing, the mean particle size of the catalyst was 56.1 m, VMD/SMD=1.3, and the abrasion index was 1.1%.

The Test of the Catalyst Performance:

[0058] 1 kg of the catalyst was placed into a fluidized bed reactor with an internal diameter of 30 mm, a height of 700 mm, the catalyst bed was preheated to 280 C. by the air that had been preheated to 300 C., then 4 L/min of hydrogen chloride gas and 2 L/min of oxygen were inlet, the reaction pressure was adjusted to 0.3 MPa (absolute pressure), the hot-spot temperature was adjusted to 400420 C., and the reaction continued for 1000 hrs. The detailed information was recorded in table 1.

EXAMPLE 2

Preparation of the Catalyst:

[0059] Under ambient temperature (about 25 C.), 1 L of slurry A-2 was added slowly and continuously into 20 L of vigorously stirred slurry B-2, the mixing temperature was 32 C., the residence time was about 15 mins, then the spray drying, cyclone separating, bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 8.1 kg of finished catalyst was obtained after cooling.

[0060] After analyzing, the mean particle size of the catalyst was 53.4 m, VMD/SMD=1.2, and the abrasion index was 1.6%.

The Test of the Catalyst Performance:

[0061] The test of the catalyst performance was carried out as in example 1, and the detailed information was recorded in table 1.

EXAMPLE 3

Preparation of the Catalyst:

[0062] Under ambient temperature (about 25 C.), 2 L of slurry A-3 was added slowly and continuously into 20 L of vigorously stirred slurry B-3, the mixing temperature was 33 C., the residence time was about 15 mins, then the spray drying, cyclone separating , bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 9.0 kg of finished catalyst was obtained after cooling.

[0063] After analyzing, the mean particle size of the catalyst was 55.3 m, VMD/SMD=1.2, and the abrasion index was 1.7%.

The Test of the Catalyst Performance:

[0064] The test of the catalyst performance was carried out as in example 1, and the detailed information was recorded in table 1.

EXAMPLE 4

Preparation of the Catalyst:

[0065] Under ambient temperature (about 25 C.), 3 L of slurry A-1 was added slowly and continuously into 18 L of vigorously stirred slurry B-1, the mixing temperature was 25 C., the residence time was about 45 mins, then the spray drying, cyclone separating , bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 8.9 kg of finished catalyst was obtained after cooling.

[0066] After analyzing, the mean particle size of the catalyst was 53.7 m, VMD/SMD=1.3, and the abrasion index was 2.1%.

The Test of the Catalyst Performance:

[0067] The test of the catalyst performance was carried out as in example 1, and the detailed information was recorded in table 1.

EXAMPLE 5

Preparation of the Catalyst

[0068] Under ambient temperature (about 25 C.), 3 L of slurry A-1 was added slowly and continuously into 18 L of vigorously stirred slurry B-1, the mixing temperature was 67 C., the residence time was about 8 mins, then the spray drying, cyclone separating, bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 8.8 kg of finished catalyst was obtained after cooling.

[0069] After analyzing, the mean particle size of the catalyst was 57.3 m, VMD/SMD=1.4, and the abrasion index was 1.7%.

The test of the Catalyst Performance:

[0070] The test of the catalyst performance was carried out as in example 1, and the detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 1

Preparation of the Catalyst:

[0071] Under ambient temperature (about 25 C.), 20 L of slurry B-1 at the temperature of 32 C. was subjected to spray drying, cyclone separating, bag-type dust collecting, and calcination that were carried out under the same process conditions as that in example 1, and 8.7 kg of finished catalyst was obtained after cooling.

[0072] After analyzing, the mean particle size of the catalyst was 41.7 m, VMD/SMD=1.2, and the abrasion index was 9.5%.

The Test of the Catalyst Performance:

[0073] The test of the catalyst performance was carried out as in example 1, when the reaction lasted for 560 hrs, the pressure of the reactor bed increased, the temperatures of each reaction zone were not as consistent as before, the reaction was ended, the reactor was detached, and it is found that there was serious agglomeration of the catalysts. The detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 2

Preparation of the Catalyst:

[0074] Under ambient temperature (about 25 C.), 20 L of slurry B-2 at the temperature of 26 C. was subjected to spray drying, cyclone separating bag-type dust collecting, and calcination that were carried out under the same process conditions as that in example 1, and 8.4 kg of finished catalyst was obtained after cooling.

[0075] After analyzing, the mean particle size of the catalyst was 42.2 m, VMD/SMD=1.3, and the abrasion index was 7.9%.

The Test of the Catalyst Performance:

[0076] The test of the catalyst performance was carried out as in example 1, when the reaction lasted for 420 hrs, the pressure of the reactor bed increased, the temperatures of each reaction zone were not as consistent as before, the reaction was ended, the reactor was detached, and it is found that there was serious agglomeration of the catalysts. The detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 3

Preparation of the Catalyst:

[0077] Under ambient temperature (about 25 C.), 20 L of slurry B-3 at the temperature of 73 C. was subjected to spray drying, cyclone separating, bag-type dust collecting, and calcination that were carried out under the same process conditions as that in example 1, and 8.4 kg of finished catalyst was obtained after cooling.

[0078] After analyzing, the mean particle size of the catalyst was 45.4 m, VMD/SMD=1.3, and the abrasion index was 13.2%.

The Test of the Catalyst Performance:

[0079] The test of the catalyst performance was carried out as in example 1, when the reaction lasted for 620 hrs, the pressure of the reactor bed increased, the temperatures of each reaction zone were not as consistent as before, the reaction was ended, the reactor was detached, and it is found that there was serious agglomeration of the catalysts. The detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 4

Preparation of the Catalyst:

[0080] Under ambient temperature (about 25 C.), 2 L of slurry A-1 was added slowly and continuously into 20 L of vigorously stirred slurry B-1, the mixing temperature was 85 C., the residence time was about 15 mins, then the spray drying, cyclone separating,bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 4.8 kg of finished catalyst was obtained after cooling. Wherein on the surface of the spray drying tower, a large amount of catalyst precursors were attached.

[0081] After analyzing, the mean particle size of the catalyst was 80.7 m, VMD/SMD=3.3, and the abrasion index was 3.5%.

The Test of the Catalyst Performance:

[0082] The test of the catalyst performance was carried out as in example 1, the reaction lasted for 5 hrs, and the detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 5

Preparation of the Catalyst:

[0083] Under ambient temperature (about 25 C.), 2 L of slurry A-1 was added slowly and continuously into 20 L of vigorously stirred slurry B-1, the mixing temperature was 34 C., the residence time was about 45 mins, then the spray drying, cyclone separating, bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 5.2 kg of finished catalyst was obtained after cooling. Wherein on the surface of the spray drying tower, a large amount of catalyst precursors were attached.

[0084] After analyzing, the mean particle size of the catalyst was 72.1 m, VMD/SMD=2.6, and the abrasion index was 4.2%.

The Test of the Catalyst Performance:

[0085] The test of the catalyst performance was carried out as in example 1, the reaction lasted for 5 hrs, and the detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 6

Preparation of the Catalyst:

[0086] Under ambient temperature (about 25 C.), 2 L of slurry A-1 was added slowly and continuously into 20 L of vigorously stirred slurry B-1, the mixing temperature was 23 C., the residence time was about 165 min, then the spray drying, cyclone separating, bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 3.9 kg of finished catalyst was obtained after cooling. Wherein on the surface of the spray drying tower, a large amount of catalyst precursors were attached.

[0087] After analyzing, the mean particle size of the catalyst was 92.3 m, VMD/SMD=3.2, and the abrasion index was 3.9%.

The Test of the Catalyst Performance:

[0088] The test of the catalyst performance was carried out as in example 1, the reaction lasted for 5 hrs, and the detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 7

Preparation of the Catalyst:

[0089] Under ambient temperature (about 25 C.), 2 kg of iron nitrate nonahydrate was added into slurry B-1 and was completely dissolved by stirring to obtain slurry B-1-1; 3L of slurry A-1 was added slowly and continuously into 18 L of vigorously stirred slurry B-1-1, the mixing temperature was 25 C., the residence time was about 45 mins, then the spray drying, cyclone separating, bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 8.7 kg of finished catalyst was obtained after cooling.

[0090] After analyzing, the mean particle size of the catalyst was 53.4 m, VMD/SMD=1.3, and the abrasion index was 2.2%.

The Test of the Catalyst Performance:

[0091] The test of the catalyst performance was carried out as in example 1, and the detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 8

Preparation of the Catalyst:

[0092] Under ambient temperature (about 25 C.), 1.5 kg of nickel nitrate hexahydrate was added into slurry B-1 and was completely dissolved by stirring to obtain slurry B-1-2; 3L of slurry A-1 was added slowly and continuously into 18 L of vigorously stirred slurry B-1-2, the mixing temperature was 25 C., the residence time was about 45 mins, then the spray drying, cyclone separating, bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 8.9 kg of finished catalyst was obtained after cooling.

[0093] After analyzing, the mean particle size of the catalyst was 53.6 m, VMD/SMD=1.3, and the abrasion index was 2.1%.

The Test of the Catalyst Performance:

[0094] The test of the catalyst performance was carried out as in example 1, and the detailed information was recorded in table 1.

COMPARATIVE EXAMPLE 9

Preparation of the Catalyst:

[0095] Under ambient temperature (about 25 C.), 1.5 kg of potassium sulphate was added into slurry B-1 and was completely dissolved by stirring to obtain slurry B-1-3; 3L of slurry A-1 was added slowly and continuously into 18 L of vigorously stirred slurry B-1-3, the mixing temperature was 25 C., the residence time was about 45 mins, then the spray drying, cyclone separating, bag-type dust collecting, and calcination were carried out under the same process conditions as that in example 1, and 8.7 kg of finished catalyst was obtained after cooling.

[0096] After analyzing, the mean particle size of the catalyst was 53.9 m, VMD/SMD=1.3, and the abrasion index was 1.9%.

The Test of the Catalyst Performance:

[0097] The test of the catalyst performance was carried out as in example 1, and the detailed information was recorded in table 1.

TABLE-US-00001 TABLE 1 Information of the Information catalysts of slurry Information of mixing Average Catalyst performance B/A Residence Abrasion particle Volume Mixing time index size VMD/ Mean A B ratio temperature Mins wt % m SMD conversion % agglomeration Example 1 A-1 B-1 6 33 15 1.1 56.1 1.3 83.4 None within 1000 hrs Example 2 A-2 B-2 20 32 15 1.6 53.4 1.2 82.3 None within 1000 hrs Example 3 A-3 B-3 10 33 15 1.7 55.3 1.2 82.7 None within 1000 hrs Example 4 A-1 B-1 6 25 45 2.1 53.7 1.3 82.2 None within 1000 hrs Example 5 A-1 B-1 6 67 8 1.7 57.3 1.4 80.8 None within 1000 hrs Comparative B-1 32 9.5 41.7 1.2 82.7 Agglomeration example 1 appeared at 560 hrs Comparative B-2 26 7.9 42.2 1.3 81.1 Agglomeration example 2 appeared at 420 hrs Comparative B-3 73 13.2 45.4 1.3 81.1 Agglomeration example 3 appeared at 620 hrs Comparative A-1 B-1 10 85 15 3.5 80.7 3.3 82.1 * example 4 Comparative A-1 B-1 10 34 45 4.2 72.1 2.6 83.2 example 5 Comparative A-1 B-1 10 23 165 3.9 92.3 3.2 82.6 example 6 Comparative A-1 B-1-1 6 25 45 2.2 53.4 1.3 81.6 ** example 7 Comparative A-1 B-1-2 6 25 45 2.1 53.6 1.3 82.4 example 8 Comparative A-1 B-1-3 6 25 45 1.9 53.9 1.3 68.5 * example 9

[0098] In the above table, B-1-1 contains about 0.06 wt % of Fe; B-1-2 contains about 0.06 wt % of Ni; B-1-3 contains about 0.06 wt % of S;

[0099] *: long-term evaluation was not made;

[0100] **: open placement, agglomeration appeared within 100 hrs; the catalysts that were not agglomerate weren't agglomerate within the 1000 hrs reaction process but agglomerated right after the reaction ended.