CN103041820B - Preparation method of spherical hydrogenation catalyst - Google Patents
Preparation method of spherical hydrogenation catalyst Download PDFInfo
- Publication number
- CN103041820B CN103041820B CN201110313784.XA CN201110313784A CN103041820B CN 103041820 B CN103041820 B CN 103041820B CN 201110313784 A CN201110313784 A CN 201110313784A CN 103041820 B CN103041820 B CN 103041820B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- acid
- spherical
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a spherical hydrogenation catalyst. According to the method, the spherical hydrogenation catalyst is prepared by adopting a spherical carrier prepared by a spherical size stabilization method and then loading an active metal component through an impregnation method, wherein the carrier adopts a way of adding a gemini surfactant 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. In addition, the gemini surfactant is adopted, so that Na<+>, Ca<2+>, K<+>, Cl<->, Br<->, F<->, I<-> and other negative and positive hetero ions can not be introduced; and furthermore, the gemini surfactant is larger in molecular weight and good in reaming effect. The catalyst has the advantages of larger pore volume, larger specific surface area, uniform spherical particles, easiness for loading and unloading, and easiness for meeting the requirements of dense phase loading.
Description
Technical field
The present invention relates to a kind of preparation method of spheric catalyst, especially spherical hydrogenation catalyst.The method can be used for oil Wax hydrofining catalyst, also can be used for the hydrotreating 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, shortage and the in poor quality of paraffin resource is caused; Meanwhile, the growth of domestic paraffin output and increasing of market demand kind, cause the increase in demand of processing paraffin inferior and high melting-point wax; And the requirement increasingly stringent of environmental regulation, then require the production of catalyst and use pollution-free as far as possible and realization to clean operation.Therefore the catalyst for hydrogen refining of paraffin wax research carrying out Gao Huo ﹑ low cost and environment-friendly type is necessary.
The petroleum waxes hydrofining catalytic catalyst of current commercial Application is the bar shaped of cylinder Huo tri-﹑ bunge bedstraw herb substantially, and it is high that this kind of catalyst has shaping efficiency, the advantage that output is large.But the feature due to 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 dense-phase loader cannot be installed in the reactor of so little diameter, so cannot dense phase loading be realized.Therefore, petroleum waxes hydrofining catalytic catalyst should be prepared into spherical, the filling of spheric catalyst and drawing off easily, and easily reaches the requirement of dense phase loading.
At present, industrial hydrotreating catalyst normally with aluminium oxide or containing the aluminium oxide of a small amount of auxiliary agent for carrier, the preparation method of spheric granules catalyst mainly contains: shaping, spherical whole grain method etc. in spray drying forming, shaping, the oil of rolling.
Spray drying forming utilizes spraying dry principle, produces a kind of method of powdery, microsphered products.Namely 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 namely atomized) of slurry solids; require that atomized drop is thinner; therefore, spray shaping is suitable for preparing microballoon (several microns or tens microns) catalyst, prepared by fluidized catalytic cracking catalyst many employings spray drying process.
Rotational forming sends in the container slowly run by powder, suitable quantity of water (or other binding agent), together with powder particles is reunited under liquid bridge with capillary force action, form micronucleus, under rotating at container the frictional force and rolling impact effect produced, constantly turn round in powder layer, 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, intensity difference, is difficult to prepare more short grained ball, and during operation, dust is larger.Due to the above-mentioned deficiency of the method, its application reduces gradually.
Shaping in oil is the characteristic utilizing colloidal sol gelation under suitable pH value and concentration, colloidal sol with droplet form, in the media such as instillation kerosene, due to capillary effect, shrink balling-up, then gelation forms granule.This kind of method also exists problem of environmental pollution, and its application also reduces gradually.
Spherical whole grain method will add water, peptizing agent and shaping assistant in material, and kneading becomes magma shape plastic, then joins in banded extruder, extrudes cylindrical bars by cylindrical orifice plate, through pelletizing, and spin, dry, roasting, obtained spherical carrier of catalyst.And then impregnated activated metal, obtain spheric catalyst.This kind of method is not polluted environment, and the preparation of spheric catalyst is just to this future development.
CN1085594A discloses a kind of Wax hydrofining catalyst; with Mo, Ni for active component; the preparation process of this catalyst: with the sial mixed sols of ammonia neutralization after low temperature aging; after filtration, washing, with phosphoric acid and nitric acid peptization, then shaping by oil ammonia column; carrier is shaping by oil ammonia column; this globulation is complicated, and has ammonia and nitrogen pollution problem, does not meet environmental protection requirement.Dripping employing manual operations in ball and oil ammonia column forming process, workers with long time is exposed to and is full of in the environment of ammonia, causes larger injury to its healthy meeting.
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 pore volume integration rate within the scope of 0 ~ 100nm is between 95% ~ 99% for pore volume integration rate within the scope of 4 ~ 15nm.This catalyst has higher activity and selectivity when being used for Wax hydrofining.But the method is also taked by the oil ammonia column balling-up under room temperature, process is complicated, has ammonia and nitrogen pollution in production process, and balling-up granularity heterogeneity, and 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, adds deionized water and nitric acid, mixes, obtained magma shape plastic; Described peptizing agent is nitric acid, citric acid, acetic acid or tartaric acid or aforementioned mixture two or more arbitrarily.Will certainly be there is stronger interaction in such strong acid and aluminium oxide, can cause pore volume and specific surface loss seriously, 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 for active metal with tungsten, molybdenum and nickel (or cobalt), with the aluminium oxide of siliceous and phosphorus two kinds of auxiliary agents for carrier, its preparation method is flooded tungstenic-nickel or the cobalt aqueous solution respectively by siliceous and alumina support that is phosphorus, obtained containing molybdenum-boron aqueous solution.Wherein siliceous and alumina support that is 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 synergic adjustment effect of two kinds of composite assistants, makes catalyst have rational pore structure, suitable surface acid property.This catalyst can process the oil wax material comprising high-melting-point wax material, can the petroleum paraffin product of production food-grade.CN03133997.2 discloses a kind of pertroleum wax hydrogenation catalyst and preparation method thereof.The method adopts CO
2siliceous and the phosphorus aluminium hydroxide prepared of neutralisation is as the carrier material of catalyst, wherein siliceous is that substep adds with the silicon in phosphorus aluminium hydroxide and phosphorus two kinds of auxiliary agents, plastic is carried out after the siliceous and phosphorous compound of part mixes with sodium aluminate solution, the silicon-containing compound of part adds after plastic or in ageing process, major part phosphorus-containing compound generates at aluminium hydroxide and adds in peptization or slurrying process after washing, most silicon and phosphorus is made to be distributed in the surface of aluminium hydroxide like this, the effect of effective performance silicon and phosphorus synergic adjustment catalyst surface physicochemical property and pore structure.This catalyst, at processing oil wax material, has good activity and selectivity when comprising high-smelting point petroleum wax.Petroleum waxes hydrofining catalytic catalyst in above-mentioned two patents, adopt extrusion molding, shaping efficiency is high, the catalyst that particle equivalent diameter is smaller can be prepared, solve the diffusion mass transfer problem of heavy constituent, but this kind of preparation method wants to make spheric catalyst, shaping efficiency can not be too high, need to improve.
Prior art adopts extrusion pelletizing legal system for the method for spheric catalyst, is all generally will add peptizing agent and shaping assistant in material.Peptizing agent generally is nitric acid, citric acid, acetic acid or tartaric acid etc.Shaping assistant is generally sesbania powder or polyethylene glycol etc.Adhesive, the rheological characteristic of the cylindrical bars extruded by cylinder orifice plate 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 with large pore volume, bigger serface and weakly acidic spherical hydrogenation catalyst.The spherical hydrogenation catalyst spheric granules degree of the method gained is homogeneous, and intensity is high, and yield is high, loses little.When this catalyst is used for oil wax material hydrogenation, there is good hydrofinishing and aromatic saturation ability.
The preparation method of spherical hydrogenation catalyst of the present invention, comprising:
(1) aluminium oxide precursor, Gemini surface active agent, adhesive are mixed, wherein the addition of adhesive is 2.0% ~ 10.0% of alumina weight, and the addition of Gemini surface active agent is 0.5% ~ 8.0% of alumina weight;
(2) step (1) gained mixture through kneading, extrusion and predrying after, with Spheroidgranulatemachine pelletizing and balling-up, then dry and roasting, obtains spherical carrier of catalyst;
(3) spherical carrier of catalyst of step (2) gained adopts infusion process supported active metals component, then carries out drying and roasting, obtains spherical hydrogenation catalyst.
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 introduces the method for silicon and phosphorus, introduce the method for boron, phosphorus, silicon, zirconium and titanium in CN 200410050777.5 in such as CN01114183.2, CN03133997.2, CN03134003.2.
In step (1), the addition sequence of aluminium oxide precursor, Gemini surface active agent and adhesive is unrestricted.Described adhesive adopt in little porous aluminum oxide, aluminum nitrate and aluminum sulfate one or more mix obtained with inorganic acid and/or organic acid, wherein inorganic acid and/or organic acid addition account for 30% ~ 60% of adhesive weight.Wherein the character of 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 select one or more in nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, and be preferably nitric acid, described organic acid can select one or more in acetic acid, citric acid, oxalic acid.
Described Shuangzi (Gemini) surfactant can select Bis-quaternary Ammonium Surfactants series and acetylenic glycols Gemini surface active agent 400 series in one or more.Bis-quaternary Ammonium Surfactants series is conventional dibrominated-N, N '-two (dimethyl dodecyl base) propane-diammonium, N, N '-dimethyl carboxybetaine, 1, two dodecyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol, 1, one or more in two myristyl-N, the N-dimethyl amine bromide-2-propyl alcohol of 3-etc., acetylenic glycols Gemini surface active agent 400 series is conventional have in Cido-420, Cido-440, Cido-465, Cido-485 surfactant one or more.In mixing, in kneading process, in order to further facilitate extruded moulding, also extrusion aid can be added, one or more in such as sesbania powder, polyethylene glycol etc.For ensureing catalyst carrier tool macropore ratio in need, can add expanding agent in preparation process, the addition of expanding agent is 0.1% ~ 5.0% of aluminium oxide precursor weight.Described expanding agent can select 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.
Predrying temperature described in step (2) is 20 ~ 70 DEG C, and the time is 0.2 ~ 1.0 hour, and described drying is 90 ~ 130 DEG C of dryings 2 ~ 4 hours in temperature, and roasting is 600 ~ 900 DEG C of roastings 3 ~ 6 hours in temperature.
Spheroidgranulatemachine described in step (2) adopts existing Spheroidgranulatemachine.
In step (3), before the drying, preferably material after dipping is deposited 0.5 ~ 2.0 hour in air or inert gas, prevent spheric catalyst from occurring bursting phenomenon in roasting process.Baking temperature described in step (3) is 100 ~ 120 DEG C, and drying time is 2.0 ~ 5.0 hours, and roasting is 350 ~ 550 DEG C in temperature, and roasting time is 3.0 ~ 6.0 hours.Described infusion process can adopt conventional method to carry out, active metal wherein can be group VIII and group vib metal, wherein group VIII metal is Ni or Co, group vib metal is W or Mo, with the weight of catalyst for benchmark, the content of group VIII metal (with oxide basis) is 0.5wt% ~ 9.0wt%, and the content of group vib metal (with metal oxide) is 5.0wt% ~ 30.0 wt%.
The present invention's spherical carrier of catalyst used adopts spherical whole grain legal system standby, by adding the mode of Gemini surface active agent in aluminium oxide precursor, improve the physical property of alumina carrier surface, have adjusted the adhesive of material in carrier forming process, rheological characteristic, reduce carrier shaping after plastic degeneration, increase substantially the yield of ball type carrier, improve the intensity of ball type carrier, improve the ratio of ball type carrier whole grain, both embody the advantage of cationic and anionic surfactant, do not introduce Na simultaneously
+, Ca
2+, K
+, Cl
-, Br
-, F
-, I
-etc. negative and positive heteroion, Gemini surface active agent molecular weight is comparatively large in addition, and reaming is effective.This catalyst pore volume, specific area are comparatively large, and the spheric granules of catalyst is even, make the filling of catalyst and draw off easily, easily reaching the requirement of dense phase loading.
Spheric catalyst prepared by the present invention can be used in the unifining process of the more paraffin raw material of tenor.Wherein in paraffin raw material, tenor can at 5 more than μ g/g, or 10 more than μ g/g, or 20 more than μ g/g.Hydrofinishing conditions can adopt this area usual terms, as reaction pressure (hydrogen dividing potential drop) 3 ~ 16MPa, and reaction temperature 230 ~ 310 DEG C, liquid volume air speed 0.5 ~ 2.0h
-1, hydrogen/wax volume ratio is 200 ~ 800.
Detailed description of the invention
Spherical hydrogenation catalyst prepared by the inventive method, in hydrorefining paraffin wax process, preferably adopts silicon and boron additive.This catalyst take aluminium oxide as main component, containing boron oxide and silica, boron oxide weight content is in the carrier generally 0.5% ~ 10.0%, is preferably 2.0% ~ 8.0%, silica weight content is in the carrier generally 0.5% ~ 20.0%, is preferably 2.0% ~ 15.0%.In the preparation process of described spherical carrier of catalyst, silicon source and boron source add 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, silicon source can add in arbitrary step of aluminium oxide precursor, anion surfactant, cationic surfactant, adhesive mixing, and boron source adds after above-mentioned mixing of materials is even again.
The character of above-mentioned spherical hydrogenation catalyst is as follows: with the weight of catalyst for benchmark, MoO
3or WO
3content be 5.0wt% ~ 30.0wt%, being preferably the content of 12.0wt% ~ 23.0wt%, NiO or CoO is 0.5wt% ~ 9.0wt%, and be preferably 1.0wt% ~ 8.0wt%, specific area is 150 ~ 300m
2/ g, is preferably 180 ~ 250m
2/ g, pore volume is 0.30 ~ 0.70cm
3/ g, is preferably 0.35 ~ 0.45 cm
3/ g, meleic acid amount is 0.20 ~ 0.80mmol/g, is preferably 0.30 ~ 0.70mmol/g, mechanical strength>=35.0 N/ grain.
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 20.0 grams of waterglass, 8.0 grams of Sodium Polyacrylates and 15.0 grams of polyethylene glycol, mixing, then (wherein little porous aluminum oxide is 35.0wt% to add 14 grams of adhesive
,red fuming nitric acid (RFNA) is 34.4wt%, water is 30.6wt%) and the mixture (N of Gemini surface active agent, N '-dimethyl carboxybetaine is 4 grams), then add with 100ml 50 DEG C water-soluble boric acid 6.5 grams, fully mix, be kneaded into plastic shape after 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 hydrogenation catalyst carrier.
Take ball type carrier 100 grams, 100ml dipping solution floods.(wherein MoO
3content be the content of 25.2 g/100ml, NiO be 6.6g/100ml, the content of phosphorus is 2.1 g/100ml), wet bulb catalyst places 1.0 hours in atmosphere, and then 110 DEG C of dryings 2 hours, 450 DEG C of roastings obtain catalyst A in 4 hours.
Embodiment 2
Get boehmite powder prepared by 200g carbonizatin method (containing Al (OH)
3< 3wt %), 25.0 gram Ludox, 10.0 grams of methylcellulose and 3.0 grams of sesbania powder mixing, after mixing, add the mixture 1 of 18 grams of adhesive (wherein little porous aluminum oxide is 30.0wt%, and SPA is 39.1wt%, and water is 30.9wt%) and surfactant, two dodecyl-N, the N-dimethyl amine bromide-2-propyl alcohol of 3-is 6 grams
), then add with 100ml 70 DEG C water-soluble boric acid 6.5 grams, fully mix, be kneaded into plastic shape after 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 dry 4 hours, at 600 DEG C, constant temperature calcining 4.0 hours, made spherical hydrogenation catalyst carrier.
Take ball type carrier 100 grams, 100ml dipping solution floods.(wherein MoO
3the content of content to be the content of 27.3 g/100ml, NiO be 3.8g/100ml, CoO be 0.8g/100ml, the content of phosphorus is 1.6g/100ml), wet bulb catalyst places 1.5 hours in atmosphere, and then 120 DEG C of dryings 2 hours, 500 DEG C of roastings obtain catalyst B in 4 hours.
Embodiment 3
Get the standby boehmite powder of 200g aluminum nitrate legal system (containing Al (OH)
3< 3 wt %), 20.0 grams of Ludox, 6.0 grams of carbon blacks and 3.0 grams of sesbania powder mixing, then add 20 grams of adhesive
(wherein little porous aluminum oxide is 40.0 wt %
,citric acid is 38.6 wt %, water is 21.4wt%) and after the mixture (acetylenic glycols Gemini surface active agent Cido-420 is 4 grams) of surfactant mixes, add again with 100ml 60 DEG C water-soluble boric acid 6.0, fully mix, be kneaded into plastic shape after be extruded into bar shaped (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 dry 3 hours, at 600 DEG C, constant temperature calcining 4.0 hours, made spherical carrier of catalyst.
Take ball type carrier 100 grams, 100ml dipping solution carries out flooding (MoO
3content be 19.1g/100ml, WO
3the content of content to be the content of 7.9 g/100ml, NiO be 3.8g/100ml, CoO be 1.3g/100ml, the content of phosphorus is 3.5 g/100ml), wet bulb catalyst places 2.5 hours in atmosphere, and then 130 DEG C of dryings 2 hours, 550 DEG C of roastings obtain catalyst C in 3 hours.
Embodiment 4
Get the standby boehmite powder of 200g aluminum nitrate legal system (containing Al (OH)
3< 3 wt %), 22.0 grams of Ludox, 6.1 grams of carbon blacks and 2.8 grams of sesbania powder mixing, then add 22 grams of adhesive
(wherein little porous aluminum oxide is 40.0 wt %
,citric acid is 38.6 wt %, water is 21.4 wt %) and the mixture (1 of Gemini surface active agent, two myristyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol is 4 grams) mix after, add again with 100ml 60 DEG C water-soluble boric acid 6.0, fully mix, be kneaded into plastic shape after be extruded into bar shaped (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 dry 3 hours, at 600 DEG C, constant temperature calcining 4.0 hours, made spherical carrier of catalyst.
Take ball type carrier 100 grams, 100ml dipping solution carries out flooding (MoO
3content be 19.1g/100ml, WO
3the content of content to be the content of 7.9 g/100ml, NiO be 3.8g/100ml, CoO be 1.3g/100ml, the content of phosphorus is 3.5 g/100ml), wet bulb catalyst places 2.5 hours in atmosphere, and then 130 DEG C of dryings 2 hours, 550 DEG C of roastings obtain catalyst D in 3 hours.
Comparative example 1
Take boehmite powder prepared by 200g carbonizatin method (containing Al (OH)
3< 3wt %), add 20.0 grams of waterglass, 8.0 grams of Sodium Polyacrylates and 15.0 grams of polyethylene glycol, mixing, then add 14 grams of adhesive (wherein little porous aluminum oxide 35.0wt%
,red fuming nitric acid (RFNA) is 34.4 wt%, and water is 30.6 wt%), then add with 100ml 50 DEG C water-soluble boric acid 6.5 grams, fully mix, be kneaded into plastic shape after be extruded into bar shaped.(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 dry 3 hours, at 600 DEG C, constant temperature calcining 3.0 hours, obtained spherical hydrogenation catalyst carrier.
Take ball type carrier 100 grams, 100ml dipping solution carries out flooding (MoO
3content be 18.7g/100ml, WO
3content be the content of 8.0 g/100ml, NiO be 4.0g/100ml, the content of phosphorus is 3.5 g/100ml), wet bulb catalyst places 2.5 hours in atmosphere, and then 130 DEG C of dryings 2 hours, 550 DEG C of roastings obtain catalyst E in 3 hours.
Comparative example 2
Get boehmite powder prepared by 200g carbonizatin method (containing Al (OH)
3< 3wt %), 25.0 gram Ludox, 10.0 grams of methylcellulose and 3.0 grams of sesbania powder mixing, add 4.2 grams of hexadecyltrimethylammonium chlorides again, after mixing, add 12 grams of adhesive (wherein little porous aluminum oxide 30.0wt%, SPA is 39.1wt%, water is 30.9wt%), then add with 100ml 70 DEG C water-soluble boric acid 6.5 grams, fully mix, be kneaded into plastic shape after be extruded into bar shaped (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 dry 4 hours, at 600 DEG C, constant temperature calcining 4.0 hours, made spherical hydrogenation catalyst carrier.
Take ball type carrier 100 grams, 100ml dipping solution floods.(wherein MoO
3content be the content of 25.2g/100ml, NiO be 6.6g/100ml, the content of phosphorus is 2.1 g/100ml), wet bulb catalyst places 1.5 hours in atmosphere, and then 120 DEG C of dryings 2 hours, 500 DEG C of roastings obtain catalyst F in 4 hours.
Comparative example 3
Get the standby boehmite powder of 200g aluminum nitrate legal system (containing Al (OH)
3< 3 wt %) 20.0 grams of Ludox, 6.0 grams of carbon blacks and 3.5 grams of sesbania powder mixing, then (wherein little porous aluminum oxide is 40.0 wt % to add 20 grams of adhesive
,citric acid is 38.6wt%, water is 21.4 wt %) and the mixture (octadecyl benzenesulfonic acid sodium content is 4 grams) of surfactant, add again after mixing with 100ml 60 DEG C water-soluble boric acid 6.0 grams, fully mix, be kneaded into plastic shape after be extruded into bar shaped (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 dry 3 hours, at 600 DEG C, constant temperature calcining 4.0 hours, made spherical carrier of catalyst.
Take ball type carrier 100 grams, 100ml dipping solution carries out flooding (wherein MoO
3the content of content to be the content of 27.3g/100ml, NiO be 3.8g/100ml, CoO be 0.8g/100ml, the content of phosphorus is 1.6g/100ml), wet bulb catalyst places 1.5 hours in atmosphere, and then 120 DEG C of dryings 2 hours, 500 DEG C of roastings obtain catalyst G in 4 hours.
The physicochemical property of above-mentioned each routine catalyst carrier is in table 1, and the character of catalyst is in table 2.The raw materials used oil properties of above-mentioned each routine evaluating catalyst is shown in 3, and process conditions are in table 4, and evaluation result is in table 5.
The physicochemical property of 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 | 290 | 284 | 278 | 275 | 243 | 280 | 300 |
| Pore volume, cm 3/g | 0.775 | 0.752 | 0.764 | 0.758 | 0.490 | 0.660 | 0.685 |
| Average pore diameter, nm | 10.7 | 10.6 | 11.0 | 11.0 | 8.1 | 9.4 | 9.1 |
| Intensity, N/ grain | 55 | 60 | 65 | 53 | 30 | 32 | 35 |
| Particle diameter, mm | 1.84 | 2.02 | 2.23 | 2.22 | 1.84 | 2.01 | 2.24 |
| Qualified products, wt% | 90 | 95 | 98 | 95 | 75 | 80 | 78 |
| Plastic degeneration, wt% | 2.6 | 2.4 | 2.1 | 2.0 | 4.5 | 3.5 | 4.0 |
| Acid distribution | |||||||
| Weak acid center, mmol/g | 0.30 | 0.31 | 0.31 | 0.30 | 0.35 | 0.34 | 0.38 |
| Middle strong acid center, mmol/g | 0.25 | 0.27 | 0.30 | 0.29 | 0.30 | 0.32 | 0.35 |
| Strong acid center, mmol/g | 0.03 | 0.05 | 0.03 | 0.02 | 0.08 | 0.10 | 0.07 |
[note]: adopt ammonia absorption-TPD method to measure, wherein 150 ~ 250 DEG C, 250 ~ 400 DEG C, 400 ~ 500 DEG C correspond respectively to ammonia at weak acid center, the desorption temperature of middle strong acid center and strong acid center.
The physico-chemical property of each routine catalyst of table 2 compares
| A | B | C | D | E | F | G | |
| Chemical composition | |||||||
| WO 3，wt% | - | - | 5.8 | 5.7 | 5.7 | - | - |
| MoO 3，wt % | 19.2 | 21.2 | 14.0 | 14.1 | 14.2 | 19.2 | 21.2 |
| NiO，wt % | 5.0 | 2.9 | 2.8 | 2.9 | 3.0 | 5.1 | 2.9 |
| CoO，wt % | - | 0.6 | 1.0 | 0.9 | 0.9 | - | 0.6 |
| Specific surface, m 2/ g | 242 | 245 | 238 | 235 | 230 | 249 | 248 |
| Pore volume, cm 3/g | 0.60 | 0.54 | 0.53 | 0.55 | 0.46 | 0.52 | 0.50 |
| Average pore diameter, nm | 9.9 | 8.8 | 8.9 | 9.4 | 8.0 | 7.9 | 8.1 |
Table 3 raw material oil properties
| Fusing point, DEG C | 60.3 |
| Oil content, wt % | 0.48 |
| Sai Shi color, number | +1 |
| Light stability, number | 7 |
| Simple and easy FDA (aromatic hydrocarbon ultraviolet absorption value) | |
| 280 ~ 289 | 0.387 |
| 290 ~ 299 | 0.250 |
Table 4 process conditions
| Reaction temperature/DEG C | 270 |
| Volume space velocity/h during liquid -1 | 1.5 |
| Reaction pressure/MPa | 6 |
| Hydrogen wax volume ratio | 300 |
The Activity evaluation of each routine catalyst of table 5
| A | B | C | D | E | F | G | |
| Fusing point, DEG C | 60.3 | 60.3 | 60.3 | 60.3 | 60.4 | 60.5 | 60.5 |
| Oil content, wt % | 0.48 | 0.48 | 0.48 | 0.48 | 0.51 | 0.50 | 0.50 |
| Sai Shi color, number | +30 | +30 | +30 | +30 | +30 | +30 | +30 |
| Light stability, number | 3 | 3 | 3 | 3 | 4 | 3~4 | 3~4 |
| Readily carbonizable substance | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Simple and easy FDA (aromatic hydrocarbon ultraviolet absorption value) | |||||||
| 280 ~ 289 | 0.032 | 0.041 | 0.042 | 0.040 | 0.065 | 0.055 | 0.057 |
| 290 ~ 299 | 0.010 | 0.011 | 0.013 | 0.012 | 0.024 | 0.027 | 0.031 |
Claims (13)
1. a preparation method for spherical hydrogenation catalyst, comprising:
(1) aluminium oxide precursor, Gemini surface active agent, adhesive are mixed, wherein the addition of adhesive is 2.0% ~ 10.0% of alumina weight, and the addition of Gemini surface active agent is 0.5% ~ 8.0% of alumina weight; Described Gemini surface active agent be Bis-quaternary Ammonium Surfactants series and acetylenic glycols Gemini surface active agent 400 series in one or more; Described adhesive adopt in little porous aluminum oxide, aluminum nitrate and aluminum sulfate one or more mix obtained with inorganic acid and/or organic acid, wherein inorganic acid and/or organic acid addition account for the 30wt% ~ 70wt% of adhesive weight; Wherein said inorganic acid selects one or more in nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, and one or more in acetic acid, citric acid, oxalic acid selected by described organic acid;
(2) step (1) gained mixture through kneading, extrusion and predrying after, with Spheroidgranulatemachine pelletizing and balling-up, then dry and roasting, obtains spherical carrier of catalyst; Described predrying temperature is 20 ~ 70 DEG C, and the time is 0.2 ~ 1.0 hour;
(3) spherical carrier of catalyst of step (2) gained adopts infusion process supported active metals component, then carries out drying and roasting, obtains spherical hydrogenation catalyst.
2. in accordance with the method for claim 1, it is characterized in that described Bis-quaternary Ammonium Surfactants series is dibrominated-N, N '-two (dimethyl dodecyl base) propane-diammonium, N, N '-dimethyl carboxybetaine, 1, two dodecyl-the N of 3-, N-dimethyl amine bromide-2-propyl alcohol, 1, two myristyl-the N of 3-, one or more in N-dimethyl amine bromide-2-propyl alcohol, acetylenic glycols Gemini surface active agent 400 series is one or more in Cido-420, Cido-440, Cido-465, Cido-485 surfactant.
3. 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.
4. in accordance with the method for claim 1, it is characterized in that, in mixing, kneading process, adding extrusion aid and/or expanding agent.
5. in accordance with the method for claim 1, it is characterized in that the predrying temperature described in step (2) is 20 ~ 70 DEG C, the time is 0.2 ~ 1.0 hour; Described drying is be 90 ~ 130 DEG C of drying times in temperature is 2 ~ 4 hours, and roasting is be 600 ~ 900 DEG C of roastings in temperature is 3 ~ 6 hours.
6. in accordance with the method for claim 1, it is characterized in that described spherical carrier of catalyst take aluminium oxide as main component, containing boron oxide and silica, boron oxide weight content is in the carrier 0.5% ~ 10.0%, and silica weight content is in the carrier 0.5% ~ 20.0%.
7. in accordance with the method for claim 6, it is characterized in that in described spherical carrier of catalyst, the weight content of boron oxide is 2.0% ~ 8.0%, and the weight content of silica is 2.0% ~ 15.0%.
8. according to the method described in claim 6 or 7, it is characterized in that in the preparation process of described spherical carrier of catalyst, silicon source and boron source add in step (1), and wherein silicon source is waterglass or Ludox, and boron source adopts boric acid.
9. in accordance with the method for claim 8, 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.
10. in accordance with the method for claim 8, it is characterized in that in the preparation process of described spherical carrier of catalyst, silicon source adds in arbitrary step of aluminium oxide precursor, Gemini surface active agent, adhesive mixing, and boron source adds after above-mentioned mixing of materials is even again.
11. in accordance with the method for claim 1, it is characterized in that in step (3), before the drying, is that material after dipping is deposited 0.5 ~ 2.0 hour in air or inert gas.
12. in accordance with the method for claim 1, and it is characterized in that the baking temperature described in step (3) is 100 ~ 120 DEG C, drying time is 2.0 ~ 5.0 hours, and roasting is 350 ~ 550 DEG C in temperature, and roasting time is 3.0 ~ 6.0 hours.
13. in accordance with the method for claim 1, it is characterized in that described active metal is group VIII and group vib metal, wherein group VIII metal is Ni or Co, group vib metal is W or Mo, with the weight of catalyst for benchmark, group VIII metal with the content of oxide basis for 0.5wt% ~ 9.0wt%, group vib metal with the content of oxide basis for 5.0wt% ~ 30.0 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110313784.XA CN103041820B (en) | 2011-10-17 | 2011-10-17 | Preparation method of spherical hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110313784.XA CN103041820B (en) | 2011-10-17 | 2011-10-17 | Preparation method of spherical hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103041820A CN103041820A (en) | 2013-04-17 |
| CN103041820B true CN103041820B (en) | 2015-05-13 |
Family
ID=48054817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110313784.XA Active CN103041820B (en) | 2011-10-17 | 2011-10-17 | Preparation method of spherical hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103041820B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593074B (en) * | 2013-11-04 | 2016-07-27 | 中国石油化工股份有限公司 | A kind of high melting-point wax hydrogenation method |
| CN107176617B (en) * | 2017-06-08 | 2019-07-05 | 南京工业大学 | A kind of preparation method of ball-aluminium oxide |
| CN114149072B (en) * | 2021-12-28 | 2023-10-13 | 华夏碧水环保科技股份有限公司 | Preparation method of microorganism-loadable water treatment filler and filler system |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6528034B1 (en) * | 1999-11-09 | 2003-03-04 | Board Of Trustees Of Michigan State University | Ultra-stable lamellar mesoporous silica compositions and process for the prepration thereof |
| CN1511785A (en) * | 2002-12-30 | 2004-07-14 | 新加坡纳米材料科技有限公司 | Silicon dioxide mesoporous material and its preparing method |
| CN101239330A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing micro-spherical catalyst carrier |
| CN101240190A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Boiling bed hydrogenation treatment catalyst and its preparing process |
| CN101327933A (en) * | 2007-06-21 | 2008-12-24 | 中国石油天然气集团公司 | Silicon based mesoporous composite material loaded with transient metal and preparation thereof |
| CN101342491A (en) * | 2008-08-18 | 2009-01-14 | 湖北双雄催化剂有限公司 | Preparation of spherical high-pressure sulphur resistant translation catalyst |
-
2011
- 2011-10-17 CN CN201110313784.XA patent/CN103041820B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6528034B1 (en) * | 1999-11-09 | 2003-03-04 | Board Of Trustees Of Michigan State University | Ultra-stable lamellar mesoporous silica compositions and process for the prepration thereof |
| CN1511785A (en) * | 2002-12-30 | 2004-07-14 | 新加坡纳米材料科技有限公司 | Silicon dioxide mesoporous material and its preparing method |
| CN101239330A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing micro-spherical catalyst carrier |
| CN101240190A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Boiling bed hydrogenation treatment catalyst and its preparing process |
| CN101327933A (en) * | 2007-06-21 | 2008-12-24 | 中国石油天然气集团公司 | Silicon based mesoporous composite material loaded with transient metal and preparation thereof |
| CN101342491A (en) * | 2008-08-18 | 2009-01-14 | 湖北双雄催化剂有限公司 | Preparation of spherical high-pressure sulphur resistant translation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 《以拟薄水铝石为铝源合成中孔氧化铝》;卞龙春等;《工业催化》;20100331;第18卷(第3期);第37页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103041820A (en) | 2013-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2404667B1 (en) | A hydrocracking catalyst, process for preparing the same and use thereof | |
| CN102441368B (en) | Method for preparing hydro-demetalization catalyst for heavy oil | |
| US6207611B1 (en) | Catalyst for hydrodemetalization of heavy oil | |
| CN103100397B (en) | Preparation method of hydrotreating catalyst | |
| CN101433865B (en) | Residual oil hydrocatalyst carrier and preparation method thereof | |
| CN103785401B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
| CN108147417B (en) | Preparation method of micron spherical silicon oxide | |
| CN105983443B (en) | A kind of alumina supporter and preparation method thereof | |
| CN107252688A (en) | A kind of DCPD hydrogenation of petroleum resin catalyst and its preparation method and application | |
| CN103041820B (en) | Preparation method of spherical hydrogenation catalyst | |
| JP2011508667A (en) | Catalyst comprising at least one specific zeolite and at least one silica-alumina, and method for hydrocracking hydrocarbon feedstock using said catalyst | |
| CN105709789B (en) | A kind of hydrocracking heavy oil catalyst and its preparation method and application | |
| CN108144602B (en) | Preparation method of high-wear-resistance micron noble metal loaded silicon oxide carrier catalyst | |
| CN102728335A (en) | Preparation method of boron-modified alumina carrier | |
| CN103041837B (en) | A kind of preparation method of spherical hydrogenation catalyst | |
| CN103041869B (en) | Preparation method of spherical catalyst carrier | |
| CN103041868B (en) | Preparation method of spherical catalyst carrier | |
| CN101940954A (en) | Method for preparing alumina supporters | |
| CN102861588B (en) | Residual oil hydrogenation demetalization catalyst and preparation method thereof | |
| CN103285935B (en) | Hydrogenation protection catalyst and preparation method thereof | |
| CN109722280B (en) | Carrier and catalyst for hydrotreatment and preparation method and application thereof | |
| CN102861614B (en) | Method for preparing alumina supporter with large pore volume | |
| CN111375438A (en) | Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof | |
| CN109833896A (en) | A kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst | |
| CN104646072B (en) | A kind of preparation method of carrier of hydrogenating catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |