CN103041868B - Preparation method of spherical catalyst carrier - Google Patents
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Abstract
The invention discloses a preparation method of a spherical catalyst carrier. According to the method, a spherical size stabilization method is adopted for preparation, and an anion surfactant and a cation surfactant are added into an aluminum oxide precursor, so that the physical properties of the surface of an aluminum oxide carrier are improved, the adhesion and rheology of materials during the carrier forming process are regulated, the plastic deformation of the carrier after forming is reduced, the yield of the spherical carrier is greatly improved, the strength of the spherical carrier is improved, and the proportion of complete particles in the spherical carrier is improved.
Description
Technical field
The present invention relates to a kind of preparation method of spherical carrier of catalyst, especially spherical catalyst carrier for hydrgenating.The method can be used for oil wax material hydrofining catalyst carrier, also can be used for the carrier of hydrogenating catalyst of heavy distillate, is particularly suitable for the reactor that ratio of height to diameter is large, reactor diameter is less.
Background technology
In recent years, along with minimizing day by day and the in poor quality of high wax content oil resource, caused shortage and the in poor quality of paraffin resource; Meanwhile, increasing of the growth of domestic paraffin output and market demand kind, causes the increase in demand of processing paraffin inferior and high melting-point wax; And environmental regulation require increasingly stringent, require the production of catalyst and use pollution-free as far as possible and realization to clean operation.Therefore be necessary to carry out the catalyst for hydrogen refining of paraffin wax research of Gao Huo ﹑ low cost and environment-friendly type.
The petroleum waxes hydrofining catalytic catalyst of commercial Application is the bar shaped of cylinder Huo tri-﹑ bunge bedstraw herb substantially at present, and it is high that this class catalyst has shaping efficiency, the advantage that output is large.But because the feature of pertroleum wax class hydrogenation reactor is that ratio of height to diameter is large, reactor diameter less (0.80～1.40m), be unfavorable for the filling of catalyst and draw off, if adopt cylinder and the uniform dense phase loading of the more difficult realization of clover bar shaped catalyst at this type of reactor, because in the reactor of so little diameter, dense-phase loader cannot be installed, so cannot realize dense phase loading.Therefore, petroleum waxes hydrofining catalytic catalyst should be prepared into spherical, the filling of spheric catalyst and drawing off easily, and easily reach the requirement of dense phase loading.
At present, industrial hydrotreating catalyst is normally taking aluminium oxide or the aluminium oxide that contains a small amount of auxiliary agent as carrier, and the preparation method of spheric granules catalyst mainly contains: moulding in spray drying forming, rolling moulding, oil, spherical whole grain method etc.
Spray drying forming is to utilize spraying drying principles, a kind of method of producing powdery, microspheroidal product.Adopt atomizer that raw slurry is dispersed into droplet, and use heated-air drying droplet.The key problem in technology of spray shaping is the micronize (being atomization) of slurry solids; require atomized drop thinner; therefore, spray shaping is suitable for preparing microballoon (several microns or tens microns) catalyst, and fluidized catalytic cracking catalyst adopts spray drying process preparation more.
Rotational forming is that powder, suitable quantity of water (or other binding agent) are sent in the container slowly running, powder particulate liquid bridge with under capillary force action reunite together with, form micronucleus, rotate at container under the frictional force and rolling impact effect producing, constantly in powder layer revolution, grow up, finally become a certain size spheric granules and leave container.Rotational forming treating capacity is large, and equipment investment is few, and running rate is high, but grain density is not high, and intensity difference is difficult to the more short grained ball of preparation, and when operation, dust is larger.Due to the above-mentioned deficiency of the method, its application reduces gradually.
In oil, moulding is the characteristic of utilizing colloidal sol gelation under suitable pH value and concentration, and colloidal sol, with droplet form, is splashed in the media such as kerosene, due to capillary effect, shrink balling-up, then gelation forms granule.This kind of method exists problem of environmental pollution, and its application also reduces gradually.
Spherical whole grain method is in material, to add water, peptizing agent and shaping assistant, and kneading becomes magma shape plastic, then joins in banded extruder, extrudes cylindrical bars by cylindrical orifice plate, through pelletizing, and spin, dry, roasting, makes spherical carrier of catalyst.This kind of method do not polluted environment, and the preparation of ball type carrier is just to this future development.
CN1085594A discloses a kind of Wax hydrofining catalyst; taking Mo, Ni as active component; the preparation process of this catalyst: the sial mixed sols with ammonia neutralization after low temperature aging; after filtering, washing, with phosphoric acid and nitric acid peptization, then by oil ammonia column moulding; carrier is by oil ammonia column moulding; this balling-up process complexity, and have ammonia and nitrogen pollution problem, do not meet environmental protection requirement.In a ball and oil ammonia column forming process, adopt manual operations, workers with long time is exposed in the environment that is full of ammonia, and its healthy meeting is caused to larger injury.
CN01114183.2 discloses a kind of Wax hydrofining catalyst and preparation method thereof.The method adopts a kind of large pore volume, bigger serface, pore size distribution high concentration and weakly acidic SiO
2-P
2o
5-Al
2o
3as carrier, using W and Ni as active metal component, Ni/W (mole) ratio is 0.30～0.80.Catalyst pore volume is 0.40～0.55cm
3/ g, bore dia is that to account for bore dia be that pore volume integration rate within the scope of 0～100nm is between 95%～99% to the pore volume integration rate within the scope of 4～15nm.This catalyst has higher activity and selectivity while being used for Wax hydrofining.But the method is also taked by the oil ammonia column balling-up under room temperature, and process complexity, has ammonia and nitrogen pollution in production process, and balling-up granularity heterogeneity, intensity is lower, and yield is low, and shaping efficiency is low.
CN200910079772.8 discloses a kind of teeth spherical heavy oil hydrotreating catalyst and preparation method thereof.The preparation of alumina support precursor: add peptizing agent, expanding agent and shaping assistant in aluminium hydroxide, after mixing, add deionized water and nitric acid, mix, make magma shape plastic; Described peptizing agent is nitric acid, citric acid, acetic acid or tartaric acid or aforementioned two or more mixture arbitrarily.Will certainly there is stronger interaction in strong acid and aluminium oxide like this, can cause pore volume and specific surface loss serious, and the pore volume of final catalyst and specific area are reduced.
CN03134003.2 discloses a kind of oil wax material Hydrobon Catalyst And Its Preparation Method, this catalyst is taking tungsten, molybdenum and nickel (or cobalt) as active metal, taking the aluminium oxide of siliceous and two kinds of auxiliary agents of phosphorus as carrier, its preparation method is to be flooded respectively tungstenic-nickel or the cobalt aqueous solution, made containing molybdenum-boron aqueous solution by siliceous and alumina support phosphorus.Wherein siliceous and alumina support phosphorus is with CO
2siliceous aluminium hydroxide prepared by neutralisation, as raw material, adds phosphorous compound to prepare in carrier forming process.The method can regulate the physicochemical property of catalyst effectively by the collaborative regulating action of two kinds of composite assistants, make catalyst have rational pore structure, suitable surface acid property.This catalyst can be processed the oil wax material including high-melting-point wax material, petroleum paraffin product that can production food stage.CN03133997.2 discloses a kind of pertroleum wax hydrogenation catalyst and preparation method thereof.The method is to adopt CO
2siliceous and phosphorus aluminium hydroxide prepared by neutralisation is as the carrier material of catalyst, wherein the silicon in siliceous and phosphorus aluminium hydroxide and two kinds of auxiliary agents of phosphorus are that substep adds, after mixing with sodium aluminate solution, the siliceous and phosphorous compound of part carries out plastic, the silicon-containing compound of part adds after plastic or in ageing process, most of phosphorus-containing compound generates after washing and adds in peptization or pulp process at aluminium hydroxide, make so most silicon and phosphorus be distributed in the surface of aluminium hydroxide, the effectively collaborative effect that regulates catalyst surface physicochemical property and pore structure of performance silicon and phosphorus.This catalyst, at processing oil wax material, has good activity and selectivity while comprising high-smelting point petroleum wax.Petroleum waxes hydrofining catalytic catalyst in above-mentioned two patents, to adopt extrusion molding, shaping efficiency is high, can prepare the smaller catalyst of particle equivalent diameter, solve the diffusion mass transfer problem of heavy constituent, but this kind of preparation method wants to make spheric catalyst, shaping efficiency can be too not high, need to improve.
The spherical whole grain legal system of available technology adopting, for the method for spheric catalyst, is all generally in material, to add peptizing agent and shaping assistant.Peptizing agent generally is nitric acid, citric acid, acetic acid or tartaric acid etc.Shaping assistant is generally sesbania powder or polyethylene glycol etc.The cylindrical bars that above-mentioned material is extruded by cylinder orifice plate, adhesive and rheological characteristic are bad, cause shaping efficiency not high.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of spherical carrier of catalyst.The method balling-up granularity homogeneous, intensity is high, and yield is high, loses little.
The preparation method of spherical carrier of catalyst of the present invention, comprising:
(1) aluminium oxide precursor is mixed with anion surfactant, cationic surfactant, adhesive, wherein the addition of adhesive is alumina weight 2.0%～10.0%, the addition of anion surfactant is 0.5% ~ 8.0% of alumina weight, and the addition of cationic surfactant is alumina weight 0.1% ~ 2.0%;
(2) mixture of step (1) gained through kneading, extrusion and predrying after, with Spheroidgranulatemachine pelletizing and balling-up, then dry and roasting, obtains spherical carrier of catalyst;
Wherein the addition sequence of aluminium oxide precursor and anion surfactant and cationic surfactant, adhesive adds one of as follows in step (1): I, to after first adding anion surfactant to mix in adhesive, add again cationic surfactant, then said mixture is joined in aluminium oxide precursor; II, aluminium oxide precursor is mixed with cationic surfactant after, then add the mixture of adhesive and anion surfactant; III, to after adding anion surfactant to mix in adhesive, then join in aluminium oxide precursor, finally add cationic surfactant; IV, in aluminium oxide precursor, add the mixture of adhesive and anion surfactant, then add cationic surfactant.
Spherical carrier of catalyst of the present invention can also contain adjuvant component, and described auxiliary agent is one or more in silicon, zirconium, titanium, iron, phosphorus, boron etc.The mode of auxiliary agent introducing carrier can be any mode in prior art and introduces, and such as introducing the method for silicon and phosphorus in CN01114183.2, CN03133997.2, CN03134003.2, introduces the method for boron, phosphorus, silicon, zirconium and titanium in CN 200410050777.5.
Adhesive described in step (1) adopts one or more in little porous aluminum oxide, aluminum nitrate and aluminum sulfate to mix and make with inorganic acid and/or organic acid, and wherein inorganic acid and/or organic acid addition account for the 30wt% ~ 70wt% of adhesive weight.The character of wherein little porous aluminum oxide is generally as follows: specific area is for being 200m
2/ g ~ 400m
2/ g, pore volume is 0.3ml/g ~ 0.6ml/g.Described inorganic acid can be selected one or more in nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, is preferably nitric acid, and described organic acid can be selected one or more in acetic acid, citric acid, oxalic acid.Said anion surfactant is how one or more in sulfonic acid series, organic aliphatic acid series, alkylbenzenesulfonate series, alkyl naphthalene sulfonate series, organic sulfate series, organic phosphate series of alkyl benzene sulphonate series, alkyl.Described cationic surfactant comprises one or more in organic quaternary ammonium salt series, organic quaternary alkylphosphonium salt series.
Mixing, in kneading process, in order to further facilitate extruded moulding, also can add extrusion aid, such as one or more in sesbania powder, polyethylene glycol etc.For ensureing that catalyst carrier has the macropore ratio needing, in preparation process, can add expanding agent, the addition of expanding agent is 0.1% ~ 5.0% of aluminium oxide precursor weight.Described expanding agent can be selected conventional kind, as one or more of the conventional Flammable Solid Class 4.1 powder such as methylcellulose, starch derivatives, Sodium Polyacrylate, carbon black, and optimization polypropylene acid sodium.
The described predrying temperature of step (2) is 20 ~ 70 DEG C, and the time is 0.2 ~ 1.0 hour, described dry be to be 90～130 DEG C in temperature to be dried be 2～4 hours, roasting is to be 600～900 DEG C of roastings 3～6 hours in temperature.
The described Spheroidgranulatemachine of step (2) adopts existing Spheroidgranulatemachine.
Spherical carrier of catalyst of the present invention is to adopt spherical whole grain legal system standby, by add respectively the mode of specific anion surfactant and cationic surfactant in aluminium oxide precursor, improve the physical property of alumina carrier surface, adhesive, the rheological characteristic of material in carrier forming process are regulated, reduce the plastic degeneration after carrier moulding, increase substantially the yield of ball type carrier, improved the intensity of ball type carrier, improved the ratio of the complete particle of ball type carrier.
Detailed description of the invention
The inventive method is prepared spherical carrier of catalyst, for hydrorefining paraffin wax process, preferably adopts silicon and boron additive.This catalyst carrier is taking aluminium oxide as main component, contain boron oxide and silica, the weight content of boron oxide in carrier is generally 0.5%～10.0%, is preferably 2.0%～8.0%, the weight content of silica in carrier is generally 0.5%～20.0%, is preferably 2.0%～15.0%.In the preparation process of described spherical carrier of catalyst, He Peng source, silicon source adds in step (1), and wherein silicon source is waterglass or Ludox, and boron source adopts boric acid.Described boric acid preferably adopts the mode of boric acid aqueous solution or boric acid acid solution to add, and wherein the temperature of solution is 30～100 DEG C, is preferably 40～80 DEG C.
In the preparation process of described spherical carrier of catalyst, in arbitrary step that silicon source can be mixed at aluminium oxide precursor, anion surfactant, cationic surfactant, adhesive, add, boron source adds after above-mentioned mixing of materials is even again.
The character of above-mentioned spherical carrier of catalyst is as follows: specific area is 200～350m
2/ g, is preferably 250～300m
2/ g, pore volume is 0.5～1.0cm
3/ g, is preferably 0.60～0.90 cm
3/ g, average pore diameter 6～20nm, is preferably 7～10nm, and meleic acid amount is 0.20～0.80mmol/g, is preferably 0.30～0.70mmol/g, mechanical strength>=35.0 N/mm.
For further illustrating the inventive method, enumerate following examples.Wt% is mass fraction.
Embodiment 1
Take boehmite powder prepared by 200g carbonizatin method (containing Al (OH)
3<3wt%), add 16.0 grams of waterglass, 9.5 grams of Sodium Polyacrylates and 15.0 grams of polyethylene glycol, obtain the mixture of salic precursor, to 16 grams of adhesive, (wherein little porous aluminum oxide is 30.5wt%, red fuming nitric acid (RFNA) is 37.5wt%, water: 32.0wt%) in add 2.0 grams of sodium p-octadecyl toluene sulfonates, after mixing, add again 3.5 grams of softex kws, must be containing the adhesive mixture of surfactant, then the adhesive mixture containing surfactant is joined in the mixture of salic precursor, add again with 6.5 grams of 50 DEG C of water-soluble boric acid of 100ml.After fully mixing, be kneaded into plastic shape, be extruded into bar shaped.(diameter of bar shaped orifice plate is 1.9mm).Then in the drying box of 30 DEG C predrying 0.35 hour, through Spheroidgranulatemachine cutting, balling-up, at 110 DEG C dry 3 hours, at 600 DEG C, constant temperature calcining 3.0 hours, obtained spherical catalyst carrier for hydrgenating.
Embodiment 2
Get boehmite powder prepared by 200g carbonizatin method (containing Al (OH)
3< 3wt %), 20.0 gram Ludox, 10.0 grams of methylcellulose and 3.0 grams of sesbania powder mix, add again 5.0g neopelex, after mixing, (wherein little porous aluminum oxide is 25.5wt%, and SPA is 40.0wt% to add 20 grams of adhesive, water: 34.5wt%) and 3.8 grams of hexadecyltrimethylammonium chlorides, then add with 6.5 grams of 70 DEG C of water-soluble boric acid of 100ml.After fully mixing, be kneaded into plastic shape, be extruded into bar shaped.(diameter of bar shaped orifice plate is 2.1mm).Then in the drying box of 40 DEG C predrying 0.3 hour.Through cutting, the balling-up of Spheroidgranulatemachine, then at 110 DEG C, be dried 4 hours, at 600 DEG C, constant temperature calcining 4.0 hours, makes spherical catalyst carrier for hydrgenating.
Embodiment 3
Get the standby boehmite powder of 200g aluminum nitrate legal system (containing Al (OH)
3< 3 wt %), 10.0 gram Ludox, 6.0 grams of carbon blacks and 3.0 grams of sesbania powder mix, add again 23 grams of adhesive (wherein little porous aluminum oxide is 45.5wt%, and concentrated hydrochloric acid is 34.0wt%, water: 20.5wt%) and 4.0 grams of lauryl sodium sulfate, after mixing, add again 3.5 grams of hexadecyltrimethylammonium chlorides, then add with 6.0 grams of 100ml 60 DEG C of water-soluble boric acid, be extruded into bar shaped after fully mixing, be kneaded into plastic shape.(the diameter 2.3mm of bar shaped orifice plate) then in the drying box of 20 DEG C predrying 0.7 hour.Through cutting, the balling-up of Spheroidgranulatemachine, then at 110 DEG C, be dried 3 hours, at 600 DEG C, constant temperature calcining 4.0 hours, makes spherical carrier of catalyst.
Embodiment 4
Get the standby boehmite powder of 200g aluminum nitrate legal system (containing Al (OH)
3< 3 wt %), 6.0 grams of carbon blacks and 3.0 grams of sesbania powder mix, (wherein little porous aluminum oxide is 25.3wt% to add 20 grams of adhesive again, citric acid is 45.0wt%, water: 29.7wt%) and 5.0 grams of lauryl sodium sulfate, after mixing, then add 3.5 grams of hexadecyltrimethylammonium chlorides and appropriate deionized water, be extruded into bar shaped after fully mixing, be kneaded into plastic shape.(the diameter 2.0mm of bar shaped orifice plate) then in the drying box of 20 DEG C predrying 0.7 hour.Through cutting, the balling-up of Spheroidgranulatemachine, then at 110 DEG C, be dried 3 hours, at 600 DEG C, constant temperature calcining 4.0 hours, makes spherical carrier of catalyst.
Comparative example 1
Take boehmite powder prepared by 200g carbonizatin method (containing Al (OH)
3< 3wt %), add 16.0 grams of waterglass, 20.0 grams of Sodium Polyacrylates and 15.0 grams of polyethylene glycol, mix, add again 16 grams of adhesive (wherein little porous aluminum oxide is 30.5wt%, and red fuming nitric acid (RFNA) is 37.5wt%, water: 32.0wt%), add again with 6.5 grams of 100ml 50 DEG C of water-soluble boric acid, be extruded into bar shaped after fully mixing, be kneaded into plastic shape.(diameter of bar shaped orifice plate is 1.9mm).Then in the drying box of 40 DEG C predrying 0.3 hour.Through Spheroidgranulatemachine cutting, balling-up, then at 110 DEG C, be dried 3 hours, at 600 DEG C, constant temperature calcining 3.0 hours, obtains spherical catalyst carrier for hydrgenating.
Comparative example 2
Get boehmite powder prepared by 200g carbonizatin method (containing Al (OH)
3< 3wt %), 20 grams of Ludox, 10.0 grams of methylcellulose and 3.0 grams of sesbania powder mix, add 4.0 grams of hexadecyltrimethylammonium chlorides, after mixing, (wherein little porous aluminum oxide is 25.5wt% to add 20 grams of adhesive again, SPA is 40.0wt%, water: 34.5wt%), then add with 6.5 grams of 100ml 70 DEG C of water-soluble boric acid, be extruded into bar shaped after fully mixing, be kneaded into plastic shape.(diameter of bar shaped orifice plate is 2.1mm).Then in the drying box of 30 DEG C predrying 0.35 hour.Through cutting, the balling-up of Spheroidgranulatemachine, then at 110 DEG C, be dried 4 hours, at 600 DEG C, constant temperature calcining 4.0 hours, makes spherical catalyst carrier for hydrgenating.
Comparative example 3
Get the standby boehmite powder of 200g aluminum nitrate legal system (containing Al (OH)
3< 3 wt %) 20 grams of Ludox, 5.0 grams of carbon blacks and 3.5 grams of sesbania powder mix, (wherein little porous aluminum oxide is 25.3wt% to add 22 grams of adhesive again, citric acid is 45.0wt%, water: 29.7wt%) and 8 grams of octadecyl benzene sulfonic acid sodium salts, after mixing, add again with 6.0 grams of 100ml 60 DEG C of water-soluble boric acid, be extruded into bar shaped after fully mixing, be kneaded into plastic shape.(the diameter 2.3mm of bar shaped orifice plate).Then in the drying box of 50 DEG C predrying 0.2 hour.Through cutting, the balling-up of Spheroidgranulatemachine, then at 110 DEG C, be dried 3 hours, at 600 DEG C, constant temperature calcining 4.0 hours, makes spherical carrier of catalyst.
The physicochemical property of the each embodiment carrier of table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Specific area, m 2/ g | 304 | 300 | 305 | 298 | 243 | 280 | 300 |
| Pore volume, cm 3/g | 0.735 | 0.706 | 0.721 | 0.665 | 0.490 | 0.660 | 0.685 |
| Average pore diameter, nm | 9.7 | 9.4 | 9.5 | 8.9 | 8.1 | 9.4 | 9.1 |
| Intensity, N/ grain | 60 | 55 | 65 | 38 | 30 | 32 | 35 |
| Particle diameter, mm | 1.85 | 2.05 | 2.26 | 1.94 | 1.80 | 2.01 | 2.21 |
| Qualified products, wt% | 88 | 95 | 98 | 92 | 75 | 78 | 80 |
| Plastic degeneration, wt% | 2.7 | 2.5 | 2.0 | 3.0 | 4.5 | 3.5 | 4.0 |
| Acid distributes | ? | ? | ? | ? | ? | ? | ? |
| Weak acid center, mmol/g | 0.31 | 0.32 | 0.30 | 0.21 | 0.48 | 0.40 | 0.38 |
| Middle strong acid center, mmol/g | 0.26 | 0.28 | 0.29 | 0.20 | 0.30 | 0.32 | 0.35 |
| Strong acid center, mmol/g | 0.04 | 0.06 | 0.02 | 0 | 0.10 | 0.11 | 0.14 |
[note]: adopt ammonia absorption-TPD method to measure, wherein 150 ~ 250 DEG C, 250 ~ 400 DEG C, 400 ~ 500 DEG C correspond respectively to the desorption temperature of ammonia at weak acid center, middle strong acid center and strong acid center.
Claims (11)
1. a preparation method for spherical carrier of catalyst, the character of described spherical carrier of catalyst is as follows: specific area is 200～350m
2/ g, pore volume is 0.5～1.0cm
3/ g, average pore diameter 6～20nm, meleic acid amount is 0.20～0.80mmol/g, mechanical strength>=35.0N/mm; Its preparation process comprises:
(1) aluminium oxide precursor is mixed with anion surfactant, cationic surfactant, adhesive, wherein the addition of adhesive is alumina weight 2.0%～10.0%, the addition of anion surfactant is 0.5%～8.0% of alumina weight, and the addition of cationic surfactant is alumina weight 0.1%～2.0%;
(2) mixture of step (1) gained through kneading, extrusion and predrying after, with Spheroidgranulatemachine pelletizing and balling-up, then dry and roasting, obtains spherical carrier of catalyst;
Wherein the addition sequence of aluminium oxide precursor and anion surfactant and cationic surfactant, adhesive adds one of as follows in step (1): I, to after first adding anion surfactant to mix in adhesive, add again cationic surfactant, then said mixture is joined in aluminium oxide precursor; II, aluminium oxide precursor is mixed with cationic surfactant after, then add the mixture of adhesive and anion surfactant; III, to after adding anion surfactant to mix in adhesive, then join in aluminium oxide precursor, finally add cationic surfactant; IV, in aluminium oxide precursor, add the mixture of adhesive and anion surfactant, then add cationic surfactant;
Said anion surfactant is how one or more in sulfonic acid series, organic aliphatic acid series, alkylbenzenesulfonate series, alkyl naphthalene sulfonate series, organic sulfate series, organic phosphate series of alkyl benzene sulphonate series, alkyl; Described cationic surfactant is one or more in organic quaternary ammonium salt series, organic quaternary alkylphosphonium salt series.
2. in accordance with the method for claim 1, it is characterized in that described spherical carrier of catalyst contains adjuvant component, described auxiliary agent is one or more in silicon, zirconium, titanium, iron, phosphorus, boron.
3. in accordance with the method for claim 1, it is characterized in that the adhesive described in step (1) adopts one or more in little porous aluminum oxide, aluminum nitrate and aluminum sulfate to mix and make with inorganic acid and/or organic acid, wherein inorganic acid and/or organic acid addition account for the 30wt%～70wt% of adhesive weight.
4. in accordance with the method for claim 3, it is characterized in that described inorganic acid selects one or more in nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid; Described organic acid is selected one or more in acetic acid, citric acid, oxalic acid.
5. in accordance with the method for claim 1, it is characterized in that, in ball type carrier preparation process, add extrusion aid and/or expanding agent.
6. in accordance with the method for claim 1, it is characterized in that the described predrying temperature of step (2) is 20～70 DEG C, time is 0.2～1.0 hour, described dry be to be that be 2～4 hours 90～130 DEG C of drying times in temperature, roasting is to be that 600～900 DEG C of roastings are 3～6 hours in temperature.
7. in accordance with the method for claim 1, it is characterized in that described spherical carrier of catalyst is taking aluminium oxide as main component, contain boron oxide and silica, the weight content of boron oxide in carrier is 0.5%～10.0%, and the weight content of silica in carrier is 0.5%～20.0%.
8. in accordance with the method for claim 7, it is characterized in that in described spherical carrier of catalyst, the weight content of boron oxide is 2.0%～8.0%, the weight content of silica is 2.0%～15.0%.
9. according to the method described in claim 7 or 8, it is characterized in that in the preparation process of described spherical carrier of catalyst, He Peng source, silicon source adds in step (1), wherein silicon source is waterglass or Ludox, and boron source adopts boric acid.
10. in accordance with the method for claim 9, it is characterized in that described boric acid adopts the mode of boric acid aqueous solution or boric acid acid solution to add, the temperature of solution is 30～100 DEG C.
11. according to the method described in claim 9 or 10, it is characterized in that in the preparation process of described spherical carrier of catalyst, in arbitrary step that mix at aluminium oxide precursor, anion surfactant, cationic surfactant, adhesive in silicon source, add, boron source adds after above-mentioned mixing of materials is even again.
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