CN100363471C - A kind of residue hydrodemetallization catalyst and preparation method thereof - Google Patents

Abstract

The present invention relates to a hydrogenation demetalization catalyst for residual oil, which contains one kind of macroporous alumina supporters, and molybdenum and/or tungsten and nickel and/or cobalt metal components supported on the alumina supporters, wherein the median pore diameter of each of the alumina supporters is from 25 to 35 nanometers, the pore volume is larger than 1.2 to 2.0 milliliters, and the specific surface area is 200 to 350 meter<2>/gram. The alumina supporter is prepared by that aluminum carbonate ammonium and one kind of nitrogen containing compounds except for acid are mixed, molded and calcined. Compared with the existing hydrogenation demetalization catalyst for redidue oil, the hydrogenation demetalization property of the catalyst of the present invention is improved, and simultaneously, the method for preparing the catalyst has the advantages of simple operation and easy implementation.

Description

A kind of residue hydrodemetallization catalyst and preparation method thereof

technical field

The invention relates to a hydrorefining catalyst and a preparation method thereof, more specifically to a residual oil hydrodemetallization catalyst and a preparation method thereof.

Background technique

Hydrodemetallization catalysts used for heavy oil, especially for vacuum residues with high metal content, are prone to rapid decline in activity and deactivation due to the deposition of metal impurities such as nickel and vanadium during use. Catalysts with larger pore volume and larger pore diameter have strong metal and carbon storage capacity, which can slow down the deactivation of the catalyst and prolong the operation period of the catalyst.

The pore structure of the catalyst is determined by the carrier that constitutes the catalyst. Therefore, the preparation of a carrier with a larger pore volume and larger pore diameter is an important step in the preparation of residual oil, especially for the preparation of vacuum residue hydrodemetallization catalysts with high metal content. key.

CN 1054393C discloses a residual oil hydrogenation demetallization catalyst and its preparation method. The catalyst uses Group VIII and/or Group VIB metal elements as active components and supports them on a large-pore alumina carrier. The carrier has a pore volume of 0.80-1.20ml/g (mercury intrusion method), a specific surface area of 110-200m ² /g, a programmable pore diameter of 15-20nm and a bulk density of 0.50-0.60g/m1. Its preparation method is to add physical pore-enlarging agent and chemical pore-enlarging agent at the same time during the kneading process of pseudo-boehmite, knead it into a plastic body, extrude it, dry and roast it to obtain a carrier, and then spray the active component Partially added to the carrier, dried and calcined to obtain the catalyst.

CN1297786A discloses a large pore volume pseudo-boehmite preparation process and its forming method. The method uses an acidified aluminum salt solution and a mixed ammonium solution to synthesize a composite salt of aluminum (ammonium aluminum carbonate) [NH ₄ Al(OH) _a (CO ₃ ) _b ·nH ₂ O] (a, b, n are positive numbers, 2a+b=4, 0.5≤a≤1.5, 1≤b≤3, 0≤n≤6), and then between 180 Calcination at 350°C for 5-16 hours to transform the crystal, to obtain a pseudo-boehmite powder with a pore volume of 0.6-1.5 ml/g and a bulk specific gravity of less than 0.25 g/ml. The powder is kneaded or rolled, dilute acid is used as a peptizer, and activated by roasting to obtain a molding carrier with a pore volume of 0.6-1.2 ml/g and a bulk density of 0.40-0.80 g/ml.

In the existing methods for preparing hydrodemetallization catalysts, whether the composition of pseudo-boehmite, physical pore-enlarging agent and chemical pore-enlarging agent is used to prepare macroporous alumina carrier, or the compound salt [NH ₄ Al(OH ) _a (CO ₃ ) _b ·nH ₂ O] After peptization and molding according to conventional methods, it is difficult to prepare a macroporous alumina support with larger pore diameter and pore volume, and the catalyst thus prepared has poor hydrodemetallization performance.

Contents of the invention

The object of the present invention is to provide a new method for preparing a hydrodemetallization catalyst and the catalyst prepared by the method for the shortcomings in the existing method for preparing a hydrodemetallization catalyst.

The method provided by the present invention includes introducing molybdenum and/or tungsten and nickel and/or cobalt metal components into a macroporous alumina carrier, wherein the macroporous alumina carrier is composed of a kind of ammonium aluminum carbonate and a The nitrogen-containing compound other than acid is prepared by mixing, molding and roasting, and the nitrogen-containing compound is used in an amount of 2-20% by weight based on ammonium aluminum carbonate.

The catalyst provided by the present invention contains a macroporous alumina carrier and molybdenum and/or tungsten and cobalt and/or nickel metal components loaded on the carrier, and the catalyst is prepared by the above-mentioned method provided by the present invention.

Compared with the existing method, the present invention prepares a macroporous alumina carrier with larger pore diameter and pore volume, and the hydrogenation demetallization performance of the catalyst obtained by loading the hydrogenation active metal component on the carrier is obviously improved. In addition, the method is simple to operate and easier to implement.

For example, the method provided by the invention is used to mix aluminum ammonium carbonate with urea (the consumption of urea is 10% by weight), and the mixture is extruded and calcined to obtain a pore volume of 1.68 ml/g and a median pore diameter of 33.2 A nano-alumina carrier is impregnated with an aqueous solution containing nickel and molybdenum metal components to obtain a catalyst with a molybdenum oxide content of 9.6% by weight and a nickel oxide content of 2.1% by weight. ^-1 , the vacuum residue with a vanadium content of 58.6 μg·g ^-1 , other metals (iron, calcium, sodium) of 18.1 μg·g ^-1 , and a carbon residue of 15.7% by weight was used as a raw material for evaluation. After 200 hours of reaction Sampling analysis shows that its nickel removal and vanadium rates are 68.2% and 76.9% respectively; and the catalyst containing 9.6% by weight of molybdenum oxide and 2.1% by weight of nickel oxide prepared according to the existing method has a carrier pore volume of 0.74 milliliters/gram, medium The value pore diameter is 19.0 nanometers, and the same raw material oil and reaction conditions are used for evaluation. After 200 hours of reaction, sampling and analysis show that the nickel removal rate and vanadium rate are only 50.2% and 61.3% respectively.

Detailed ways

According to the method provided by the present invention, wherein said nitrogen-containing compounds except acids refer to nitrogen-containing compounds other than nitrogen-containing inorganic acids and organic acids, preferably water-soluble nitrogen-containing compounds, such as ammonium citrate , ammonium bicarbonate, ammonium acetate, ammonium oxalate, and urea, based on ammonium aluminum carbonate, the amount of the ammonium salt is 2-20% by weight, preferably 4-15% by weight.

The preferred composition of the ammonium aluminum carbonate is (NH ₄ )mAlO(OH)(HCO ₃ )m·nH ₂ O, wherein 0<m<1, 0<n≤5, more preferably 0.2≤m≤0.5, 0.5 ≤n≤4.

The aluminum ammonium carbonate can be commercially available, or can be prepared by any existing method, and the preferred preparation method includes reacting an aqueous solution of an aluminum-containing compound with an aqueous solution of ammonium bicarbonate, sinking, washing and drying , the reaction conditions include a pH value of 6.0-9.0, preferably 6.5-8.5, and a temperature of 5-45°C, preferably 10-40°C; the precipitation conditions include a temperature of 5-65°C, preferably 10-55°C , The precipitation time is 0.5-12 hours, preferably 1-6 hours.

The aluminum-containing compound is selected from one or more of aluminum sulfate, aluminum ammonium sulfate, aluminum nitrate and aluminum chloride.

The washing is a conventional method, for example, when the aluminum-containing compound is aluminum sulfate or aluminum chloride, the washing should finally make (NH ₄ )mAlO(OH)(HCO ₃ )m·nH ₂ O The content of sulfate or chloride ions is less than 1% by weight.

The mixing of ammonium aluminum carbonate and the nitrogen-containing compound may be directly mixing the ammonium aluminum carbonate and the nitrogen-containing compound, or the nitrogen-containing compound may be formulated into an aqueous solution, and then mixed with the nitrogen-containing compound Mix the ammonium aluminum carbonate. The molding is carried out by conventional methods, such as tablet pressing, ball rolling, extrusion and other methods. When forming by the usual method, it is permissible to introduce auxiliary agents into the mixture to ensure the smooth progress of the forming. For example, when extruding, an appropriate amount of extrusion aids and water can be introduced into the mixture, and then extruded. The type and amount of the extrusion aid can be conventional in the art, for example, it can be selected from one or more of kale powder, methyl cellulose, starch, polyvinyl alcohol, and polyethanol.

The calcination can be carried out by conventional methods, wherein the calcination temperature is preferably 350-650°C, more preferably 500-600°C, and the calcination time is preferably 1-8 hours, more preferably 2-4 hours.

According to the method provided by the present invention, the median pore diameter of the carrier is 25-35 nanometers, the pore volume is greater than 1.2 to 2.0 ml/g, and the specific surface area is 200-350 ^m2 /g.

The content of cobalt and/or nickel, molybdenum and/or tungsten in the catalyst is the conventional content of hydrodemetallization catalysts. Generally speaking, based on the catalyst, the content of cobalt and/or nickel is 0.3-8% by weight, preferably 0.5-5% by weight, the content of molybdenum and/or tungsten is 0.5-15% by weight, preferably 3-15% by weight.

The method for introducing molybdenum and/or tungsten and nickel and/or cobalt metal components is well known to those skilled in the art, generally speaking, it is sufficient to deposit molybdenum and/or tungsten and nickel and/or cobalt metal components on the The macroporous alumina support is impregnated with a solution containing molybdenum and/or tungsten and nickel and/or cobalt metal compounds under conditions on the macroporous alumina support. Wherein, in terms of oxides, the amount of each component is such that the final catalyst contains 0.5-15% by weight of molybdenum and/or tungsten, and 0.3-8% by weight of cobalt and/or nickel.

The molybdenum-containing compound is selected from one or more of molybdenum-containing soluble compounds, such as one or more of molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide and ammonium molybdate , Ammonium paramolybdate.

The tungsten-containing compound is selected from one or more of tungsten-containing soluble compounds, such as one or more of tungstate, metatungstate, ethyl metatungstate, preferably among them, metatungstate ammonium ammonium tungstate, ethyl tungstate ammonium.

The cobalt-containing compound is selected from one or more of cobalt-containing soluble compounds, such as one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt soluble complexes , preferably cobalt nitrate and basic cobalt carbonate.

The nickel-containing compound is selected from one or more of nickel-containing soluble compounds, such as one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes , preferably nickel nitrate and basic nickel carbonate.

The catalyst provided by the invention is suitable for hydrodemetallization of heavy hydrocarbon raw materials to produce raw material oil with low metal content and high added value. The heavy hydrocarbon feedstock includes crude oil, atmospheric or vacuum residue, and atmospheric or vacuum distillate oil.

The following examples will further illustrate the present invention.

The reagents used in the examples are chemically pure reagents unless otherwise specified.

In the example, sulfate radical and carbonate radical are determined by infrared absorption method, chloride ion is determined by ion selective electrode method, nitrogen is determined by chemiluminescence method, and aluminum and water are determined by ignition gravimetric method.

Examples 1-6 illustrate ammonium aluminum carbonate and its preparation.

Example 1

Take by weighing aluminum sulfate (Beijing Chemical Plant product) 666 grams, add deionized water and dissolve into molar concentration and be the solution a1 of 0.5, take by weighing 800 grams of ammonium bicarbonate (Beijing Chemical Plant product), add deionized water and dissolve into molar concentration of 2.5 solution b1. Add solution a1 and solution b1 to a 10-liter gelation tank in parallel flow and react at the same time. During the reaction process, the pH value is controlled at 6.5 and the temperature is 15°C. The resulting white precipitate is precipitated at 55°C for 1.5 hours and filtered. , the filter cake was washed three times with 10 times (weight) deionized water at 55°C, and dried in a drying oven at 120°C for 4 hours to obtain ammonium aluminum carbonate A, whose chemical formula was (NH ₄ ) _0.3 AlO(OH)(HCO ₃ ) _0.3 ·3H ₂ O, the sulfate ion content is 0.3% by weight.

Example 2

Take by weighing 483 grams of aluminum chloride (product of Beijing Chemical Plant), add deionized water to dissolve into a solution a2 with a molar concentration of 1, take by weighing 800 grams of ammonium bicarbonate (product of Beijing Chemical Plant), add deionized water to dissolve into a molar concentration is solution b2 of 2. Add solution a2 and solution b2 into a 10-liter gelation tank simultaneously in parallel flow for reaction. During the reaction, the pH value is controlled to be 8.0 and the temperature is 30°C. The resulting white precipitate is precipitated at 30°C for 1.5 hours and filtered. , the filter cake was washed twice with 20 times (weight) of deionized water at 30°C, and dried at 120°C in a drying oven for 4 hours to obtain ammonium aluminum carbonate B, whose chemical formula was (NH ₄ ) _0.4 AlO(OH)(HCO ₃ ) _0.4 ·2H ₂ O, the chloride ion content is 0.4% by weight.

Example 3

Take by weighing aluminum nitrate (Beijing chemical plant product) 750 grams, add deionized water and dissolve into molar concentration and be 1 solution a3, take by weighing 800 grams of ammonium bicarbonate (Beijing chemical plant product), add deionized water and dissolve into molar concentration of 2.5 solution b3. Add solution a3 and solution b3 to a 10-liter gelation tank in parallel and react simultaneously. During the reaction process, the pH value is controlled at 7.0 and the temperature is 25°C. The resulting white precipitate is precipitated at 25°C for 1.5 hours. Filter and dry in a drying oven at 120°C for 4 hours to obtain aluminum ammonium carbonate C, whose chemical formula is (NH ₄ ) _0.5 AlO(OH)(HCO ₃ ) _0.5 ·3H ₂ O.

Example 4

Take by weighing aluminum sulfate (Beijing chemical plant product) 666 grams, add deionized water and dissolve into molar concentration and be the solution a4 of 0.3, take by weighing ammonium bicarbonate (Beijing chemical plant product) 1000 grams, add deionized water and dissolve into molar concentration of 2.5 solution b4. Add solution a4 and solution b4 to a 10-liter gelation tank simultaneously in a co-current manner for reaction. During the reaction, control the pH value to 7.5 and the temperature at 40°C. The resulting white precipitate will settle at 40°C for 1.5 hours. Filter, wash the filter cake three times with 10 times (weight) deionized water at 40°C, and dry at 120°C for 4 hours in a drying oven to obtain ammonium aluminum carbonate D, whose chemical formula is (NH ₄ ) _0.2 AlO(OH)(HCO ₃ ) _0.2 ·4H ₂ O, the sulfate ion content is 0.3% by weight.

Example 5

Take by weighing 483 grams of aluminum chloride (product of Beijing Chemical Plant), add deionized water to dissolve into molar concentration and be solution a5 of 0.5, take by weighing 800 grams of ammonium bicarbonate (product of Beijing Chemical Plant), add deionized water to dissolve into molar concentration is solution b5 of 2. Add solution a5 and solution b5 to a 10-liter gelation tank simultaneously in a co-current manner for reaction. During the reaction, control the pH value to 7.0 and the temperature at 15°C. The resulting white precipitate is precipitated at 55°C for 1.5 hours. Filter, wash the filter cake three times with 10 times (weight) deionized water at 55°C, and dry at 120°C for 4 hours in a drying oven to obtain ammonium aluminum carbonate E, whose chemical formula is (NH ₄ ) _0.3 AlO(OH)(HCO ₃ ) _0.3 ·2H ₂ O, the chloride ion content is 0.2% by weight.

Example 6

Prepare aluminum ammonium carbonate according to CN 1297786A method.

Take by weighing aluminum sulfate (Beijing chemical plant product) 700 grams, add deionized water and dissolve into molar concentration and be 0.5 solution f1, take by weighing ammonium carbonate (Beijing chemical plant product) 188 grams, ammonium bicarbonate (Beijing chemical plant product) 395 gram, measuring concentration is 200 milliliters of 25% by weight ammoniacal liquor (Beijing chemical plant product), and ammonium carbonate, ammonium bicarbonate, ammoniacal liquor are mixed and add deionized water to be dissolved into containing _NH Concentration is 10% by weight solution f2. Add solution f1 and solution f2 to a 10-liter gelation tank simultaneously in a co-current manner for reaction. During the reaction, control the pH value to 8.15 and the temperature to 80°C. Filter and wash the formed white precipitate, and recycle the filter cake Slurry was matured for 6 hours, filtered, washed three times with 10 times (weight) of deionized water at 40°C, and dried at 105°C in a drying oven for 4 hours, and the filter cake obtained aluminum ammonium carbonate F, whose chemical formula was NH ₄ Al(OH)( CO ₃ ) ₂ ·3H ₂ O, the sulfate ion content is 0.3% by weight.

Examples 7-12 illustrate the macroporous alumina carrier and its preparation method in the method provided by the present invention.

Example 7

Mix 100 grams of ammonium aluminum carbonate A with 4 grams of safflower powder, add 105 milliliters of a solution containing 10 grams of urea, extrude it into a trefoil strip with an equivalent diameter of 1.2 mm on a screw extruder, and dry it at 120 ° C for 2 hours, 600 ℃ for 2 hours to obtain carrier G, whose pore volume, specific surface area, and median pore diameter are listed in Table 1.

Example 8

Mix 100 grams of aluminum ammonium carbonate B with 4 grams of squat powder, add 98 milliliters of a solution containing 4 grams of ammonium oxalate, extrude it into a trefoil-shaped strip with an equivalent diameter of 1.2 mm on a screw extruder, and dry it at 120 ° C for 2 hours. Calcined at 550°C for 2 hours to obtain carrier H, whose pore volume, specific surface area, and median pore diameter are listed in Table 1.

Example 9

Mix 100 grams of ammonium aluminum carbonate C with 4 grams of squat powder, add 100 milliliters of a solution containing 4 grams of ammonium acetate, extrude it into a trefoil strip with an equivalent diameter of 1.2 mm on a screw extruder, and dry it at 120 ° C for 2 hours. Calcined at 580°C for 2 hours to obtain carrier I, whose pore volume, specific surface area, and median pore diameter are listed in Table 1.

Example 10

Mix 100 grams of ammonium aluminum carbonate D with 4 grams of safflower powder, add 96 ml of a solution containing 7 grams of ammonium citrate, extrude into a trefoil strip with an equivalent diameter of 1.2 mm on a screw extruder, and dry at 120 ° C for 2 hours , and calcined at 540°C for 2 hours to obtain carrier J, whose pore volume, specific surface area, and median pore diameter are listed in Table 1.

Example 11

Mix 100 grams of ammonium aluminum carbonate E with 4 grams of squat powder, add 105 milliliters of a solution containing 14 grams of urea, extrude it into a trefoil strip with an equivalent diameter of 1.2 mm on a screw extruder, and dry it at 120 ° C for 2 hours, 500 ℃ for 2 hours to obtain carrier K, whose pore volume, specific surface area, and median pore diameter are listed in Table 1.

Example 12

Mix 100 grams of ammonium aluminum carbonate F with 4 grams of squat powder, add 105 milliliters of a solution containing 10 grams of urea, extrude it into a trefoil strip with an equivalent diameter of 1.2 mm on a screw extruder, and dry it at 120 ° C for 2 hours. Calcined at 500°C for 2 hours to obtain carrier L, whose pore volume, specific surface area, and median pore diameter are listed in Table 1.

Comparative example 1

The ammonium aluminum carbonate F was roasted at 300°C for 8 hours to crystallize, and then pulverized to obtain pseudo-boehmite powder FN. Get 100 grams of the pseudo-boehmite powder FN and mix it with 4 grams of fenugreek powder, add 50 milliliters of a solution containing 3 milliliters of 65% by weight of nitric acid, and extrude it into a trefoil strip with an equivalent diameter of 2.5 mm on the extruder. After drying at 120°C for 2 hours and calcining at 550°C for 4 hours, the carrier DL was obtained, and its pore volume, specific surface area, and median pore diameter are listed in Table 1.

Table 1

example 7 8 9 10 11 12 Comparative example 1 carrier G h I J K L DL Specific surface/m² g^-1pore volume/ml g^-1median pore diameter/nm intensity/N mm< sup>-1</sup> 270.11.6833.28.8 290.31.5429.010.4 285.61.5630.010.2 296.41.4828.211.1 275.91.6533.09.6 300.21.2628.112.8 308.10.7419.014.0

Examples 13-15 illustrate the methods provided by the present invention and the catalysts prepared by the methods.

Example 13

Get 200 grams of the carrier G prepared in Example 7, impregnate it with 500 milliliters of ammonium molybdate and nickel nitrate mixed solution containing 86 grams/liter of MoO ₃ and 18 grams/liter of NiO for 1 hour, dry at 120° C. for 2 hours after filtering, and bake at 500° C. After 4 hours, catalyst C1 was obtained. The contents of molybdenum oxide and nickel oxide in catalyst C1 are listed in Table 2.

Comparative example 2

Get 200 grams of carrier DL prepared in Comparative Example 1, impregnate with 500 milliliters of MoO ₈₆ g/L, NiO18 g/L ammonium molybdate and nickel nitrate mixed solution for 1 hour, filter and dry at 120°C for 2 hours, 500 ℃ calcined for 4 hours to obtain catalyst DC1. The contents of molybdenum oxide and nickel oxide in catalyst DC1 are listed in Table 2.

Example 14

Get 200 grams of the carrier I prepared in Example 9, impregnate with 320 milliliters of ammonium molybdate and nickel nitrate mixed solution containing MoO 64.8 g/L, NiO13.1 g/L for 2 hours, dry at 120° C. for 2 hours, and bake at ₅₅₀ ° C. After 2 hours, catalyst C2 was obtained. The contents of molybdenum oxide and nickel oxide in catalyst C2 are listed in Table 2.

Example 15

Take 200 grams of the carrier K prepared in Example 11, impregnate it with 500 milliliters of a mixed solution of ammonium molybdate and nickel nitrate containing 120 grams/liter of MoO ₃ and 5 grams/liter of NiO for 1 hour, dry it at 120°C for 2 hours after filtering, and bake at 480°C After 4 hours, catalyst C3 was obtained. The contents of molybdenum oxide and nickel oxide in catalyst C3 are listed in Table 2.

Table 2

example 13 Comparative example 2 14 15 catalyst C1 DC1 C2 C3 Metal content MoO₃/wt%NiO/wt% 9.632.11 9.652.10 9.221.87 13.662.97

Examples 16-18 illustrate the hydrodemetallization performance of catalysts provided by the present invention.

Examples 16-18

The vacuum residue with nickel content of 18.9μg·g ^-1 , vanadium content of 58.6μg·g ^-1 , other metals (iron, calcium, sodium) of 18.1μg·g ^-1 and carbon residue of 15.7% by weight is Feedstock, catalysts were evaluated on a 100 ml small fixed bed reactor.

Catalysts C1, C2, and C3 are broken into particles with a diameter of 2-3 mm, and the catalyst loading is 100 milliliters. The reaction conditions are: reaction temperature 385°C, hydrogen partial pressure 14 MPa, liquid hourly space velocity 0.45 h-1, hydrogen-oil volume ratio 350, and sampling after 200 hours of reaction.

The plasma emission spectrometry (AES/ICP) method was used to measure the content of nickel, vanadium and other metals (iron, calcium, sodium) in the produced oil, and the metal removal rate was calculated. The results are listed in Table 3.

The RIPP 149-90 method was used to measure the residual carbon content in the produced oil, and the carbon removal rate was calculated. The results are listed in Table 3.

Comparative example 3

The hydrodemetallization and carbon residue removal performance of the catalyst DC1 was evaluated according to the method of Example 16, and the results are shown in Table 3.

table 3

example 16 Comparative example 3 17 18 catalyst C1 DC1 C2 C3 Demetallized nickel/wt% Demetallized vanadium/wt% Other metals removed/wt% Carbon residue removed/wt% 68.276.958.040.2 50.261.344.223.6 64.173.556.237.8 71.879.460.243.1

As can be seen from the results in Table 3, the present invention provides catalyst C1 with a nickel removal rate higher than DC1 by 18.0 percentage points, a vanadium removal rate higher than DC1 by 15.6 percentage points, and other metal (iron, calcium, sodium) removal rates higher than DC1 13.8 percentage points higher, and the carbon residue removal rate is 16.6 percentage points higher than DC1, indicating that the catalyst provided by the invention is obviously better than the catalyst prepared by the prior art in terms of metal removal and carbon residue performance.

Claims (8)

1. the preparation method of a residuum hydrogenating and metal-eliminating catalyst, be included in and introduce molybdenum and/or tungsten and nickel and/or cobalt metal component in the macropore alumina supporter, wherein, described macropore alumina supporter by comprise with a kind of aluminium carbonate ammonium mix with nitrogenous compound beyond a kind of deacidification, the method preparation of moulding and roasting, with the aluminium carbonate ammonium is benchmark, and the consumption of described nitrogenous compound is 2-20 weight %.

2. method according to claim 1, it is characterized in that, described nitrogenous compound is selected from one or more in ammonium citrate, bicarbonate of ammonia, ammonium acetate, ammonium oxalate, the urea, is benchmark with the aluminium carbonate ammonium, and the consumption of described nitrogenous compound is 4-15 weight %.

3. method according to claim 1 is characterized in that, described aluminium carbonate ammonium consist of (NH ₁) mAlO (OH) (HCO ₃) mnH ₂O, 0＜m wherein＜1,0＜n≤5.

4. method according to claim 3 is characterized in that, described 0.2≤m≤0.5,0.5≤n≤4.

5. method according to claim 1 is characterized in that, described maturing temperature is 350-650 ℃, and roasting time is 1-8 hour.

6. method according to claim 5 is characterized in that, described maturing temperature is 450-600 ℃, and roasting time is 2-4 hour.

7. method according to claim 1 is characterized in that, the pore volume of described macropore alumina supporter is greater than 1.2 to 2 milliliters/gram, and specific surface is a 200-350 rice ²/ gram, mean pore sizes is the 25-35 nanometer.

8. residuum hydrogenating and metal-eliminating catalyst, this catalyzer contain a kind of macropore alumina supporter and load on molybdenum and/or tungsten and cobalt and/or nickel metal component on this carrier, and this catalyzer is according to any described method preparation among the claim 1-7.