CN101376832A - Preparation of bubbling bed hydrotreating catalyst - Google Patents
Preparation of bubbling bed hydrotreating catalyst Download PDFInfo
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- CN101376832A CN101376832A CNA2007100126673A CN200710012667A CN101376832A CN 101376832 A CN101376832 A CN 101376832A CN A2007100126673 A CNA2007100126673 A CN A2007100126673A CN 200710012667 A CN200710012667 A CN 200710012667A CN 101376832 A CN101376832 A CN 101376832A
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Abstract
The invention discloses a preparation method of a boiling bed hydrotreatment catalyst. During the preparation method of the catalyst, alumina fibers and aluminum dihydrogen phosphate are added, thus improving the mechanical intensity of the catalyst, improving the service life of the catalyst and reducing the product cost. In the method, the aluminum dihydrogen phosphate with better acidity is preferably added into a bond, thus being capable of easing the strong mutual effects between an acid and a refractory porous inorganic oxide as well as the alumina fibers and reducing the loss of pore volumes and specific surface area. Besides, as the aluminum dihydrogen phosphate contains 6 hydroxide radicals, the aluminum dihydrogen phosphate is easy to form a complex compound with metals and is beneficial to improving the mutual effect between a carrier and active metals, thereby improving the activity of the catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of boiling bed hydrogenation treatment catalyst, particularly a kind of preparation method who is used for the boiling bed hydrogenation treatment catalyst of heavy oil product stable hydrogenation.
Background technology
The catalytic hydrogenation process that is generally used for heavy oil product mainly is a fixed bed hydrogenation technology.Fixed-bed reactor are particularly suitable for handling lighter and cleaner charging, as petroleum naphtha, intermediate oil, gas oil and common residual oil etc.The characteristics of fixed-bed reactor be operate more steady, control also be easier to.Use fixed-bed process hydrotreatment heavy oil product to have following several respects problem: because heavy oil product is heavier and contain more mechanical impurity, catalytic reaction condition can compare harshness; High-nitrogen stock meeting accelerator activator inactivation, the catalyzer life cycle is very short, and product property can't guarantee; Beds pressure drop height; For satisfying product index, complicated design increases cost of investment thereby fixed bed reactor system just needs employing.And boiling bed hydrogenation technique is to make catalyzer be swelling state, and adds and eject the every day by live catalyst and keep catalyst activity.These characteristics make it can handle heavier and contain the raw material of more mechanical impurity and do not stop up bed, but at entire operation quality of production isostatic product all in the cycle, and the device production cycle is long.Simultaneously, it is more easy to control that boiling bed hydrogenation technique also has temperature of reaction, and raw material can be adjusted, and system is than advantage such as the investment of fixed bed system is low.Therefore, boiling bed hydrogenation technique is a kind of good inferior heavy, residual hydrocracking technology.
Because boiling bed hydrogenation reaction self, boiling bed hydrogenation catalyst remains boiling state in reactor, and therefore intensity and the wear resisting property to hydrogenation catalyst has higher requirement than fixed bed hydrogenation catalyzer.At present, boiling bed hydrogenation catalyst generally is to adopt the fixed bed hydrogenation catalyzer, is carrier with the refractory inorganic oxides, be active ingredient with group vib and/or group VIII metal, and each component all is to exist with fine powder sintering shape form.The intensity of this catalyzer and wear resisting property await further to improve.
USP 5,308, and 472 disclose a kind of employed dealuminzation Y molecular sieve catalyzer that contains of ebullated bed mild hydrocracking reaction that can be used for.This catalyzer can be used for hydrodemetallation (HDM) (HDM), hydrogenating desulfurization (HDS) and the hydrocracking (HC) of heavy feed stock (as residual oil), improves the transformation efficiency of boiling point at 1000 ℉ heavy hydrocarbons, increases the intermediate oil yield simultaneously.Described catalyzer contains the VIII family metal oxide of 1.0～6.0wt%, the molybdenum oxide of 12.0～25.0wt% and the phosphorous oxides of 0.1～5.0wt%, is supported on porous alumina or siliceous aluminum oxide and the hydrogen shape acidifying dealuminzation Y molecular sieve.The specific surface area of described catalyzer is at 200～300m
2/ g, total pore volume 0.55～0.75ml/g, with following pore size distribution: promptly wherein be lower than 40% total pore volume and be present in the hole that diameter is lower than 10nm, at least 25%～50% total pore volume is present in the hole of diameter 10～16nm, be present in the hole of diameter greater than 16nm with 25%～50% total pore volume, 15%～40% total pore volume is present in the hole of diameter greater than 25nm, and the total pore volume less than 10% is present in the hole of big bore dia greater than 150nm.This catalyzer is owing to contain the dealuminzation Y molecular sieve, one side lytic activity height, be difficult to guarantee hydrogenation oil property and product yield, on the other hand, the ratio that accounts for total pore volume owing to macropore in the catalyzer is very high, but do not propose to increase the method for catalyst strength, so catalyst strength and wear resistance still await further raising.
Chinese patent CN99113299.8 discloses a kind of preparation method of residual oil hydrocatalyst, and this catalyzer is with γ-Al
2O
3Or/and the low silica-alumina ratio molecular sieve is a carrier matrix, be active ingredient with VIII family and group vib metallic element, particularly Mo-Ni, interpolation Ti is a coagent.The Preparation of catalysts method is to adopt complete kneading method, promptly aluminum hydroxide solid elastomer powder and molecular sieve are mixed by a certain percentage, add a kind of basic solution that contains VI B metal then earlier, fully mix and pinch, wetting by alkali solution fully to material, add the acidic solution of a kind of VIII of containing family and VI B family metallic element again, mix to pinch to material and become plastic, extruded moulding, drying, roasting promptly get catalyzer.The catalyzer pore volume that obtains in this patent, specific surface area are all very big, but the basic solution that contains VI B metal that adds in preparation process contains ammonia, can produce ammonia, polluted by nitrogen to the operation operating mode.
Summary of the invention
The object of the present invention is to provide the preparation method of the boiling bed hydrogenation treatment catalyst of good, low-cost, the no ammonia of a kind of physical strength and wear resisting property, polluted by nitrogen.
The preparation method of boiling bed hydrogenation treatment catalyst of the present invention, this catalyzer comprises refractory inorganic oxides, active metal component, sapphire whisker and auxiliary agent phosphorus, preparation process is as follows:
(1), refractory inorganic oxides mixes with the solution that contains the hydrogenation activity component and is wetting;
(2), aperture refractory inorganic oxides and peptization acid peptization are made tackiness agent;
(3), the tackiness agent of making in the step (2) is joined in the moistening material of step (1) gained the mixed paste, extruded moulding pinched into;
(4), with the forming composition of step (3) 100～150 ℃ of dryings 0.5～24 hour, at 350～700 ℃ of roasting 1-12 hours, obtain catalyzer;
Wherein auxiliary agent phosphorus partly or entirely comes from aluminium dihydrogen phosphate, described aluminium dihydrogen phosphate adding method adopts following a kind of at least: a, aluminium dihydrogen phosphate add in the solution that contains the hydrogenation activity component of step (1), mix with refractory inorganic oxides then, b, aluminium dihydrogen phosphate and aperture refractory inorganic oxides and peptization acid are mixed and made into tackiness agent;
Wherein sapphire whisker can adopt following at least a method:
A, in step (1), in the refractory inorganic oxides preparation process, introduce the sapphire whisker powder;
B, in step (1), sapphire whisker and refractory inorganic oxides powder mix wetting with the solution that contains the hydrogenation activity component;
C, in step (2), sapphire whisker is mixed and made into tackiness agent with aperture refractory inorganic oxides and peptization acid.
Described sapphire whisker preferably adopts method b, can make the sapphire whisker homodisperse, and keeps the sapphire whisker structure, thereby improves the physical strength of catalyzer.Described aluminium dihydrogen phosphate preferably adopts method b to add.
The length of sapphire whisker of the present invention is 4～500 microns, preferred 4～200 microns, be preferably 10～80 microns, and diameter is 3～100 microns, preferred 3～50 microns, the content in catalyzer is 3wt%～10wt%, is preferably 3wt%～8wt%.Described sapphire whisker is preferably selected the active oxidation aluminum fiber for use, its specific surface 120～280m
2/ g, pore volume are 0.01～0.20ml/g.
In the inventive method, the add-on of aluminium dihydrogen phosphate (in phosphorus) accounts for the 1wt%～4wt% of total catalyst weight.
In the inventive method, the phosphorus in the hydrogenation catalyst can also conventional form be introduced phosphorus except introduce in the catalyzer with aluminium dihydrogen phosphate, such as the phosphoric acid class, but needs the total amount of phosphorus in the control catalyst will be below 4wt%.
In the described boiling bed hydrogenation treatment catalyst, hydrogenation activity component and refractory porous inorganic oxide all can be the composition and the content of conventional hydrotreating catalyst, and each component all is present in the catalyzer with fine powder sintering shape, described hydrogenation activity component can be selected from one or more in group vib metal and the group VIII metal, that described group vib metal is the most frequently used is Mo and/or W, and the group VIII metal is the most frequently used is among Fe, Ni and the Co one or more; In the optional self-alumina of described refractory porous inorganic oxide, silicon oxide, magnesium oxide, aluminum oxide one magnesium oxide, silicon oxide-aluminum oxide, silicon oxide-magnesium oxide, titanium oxide-magnesium oxide, zirconium white, silicon oxide-aluminum oxide-magnesium oxide and the clay one or more can also contain in auxiliary agent such as phosphorus, the boron one or more.
Used tackiness agent can adopt conventional preparing as the aperture refractory inorganic oxides of binder ingredients and the method for peptization acid peptization in the hydrogenation catalyst preparation process of the present invention, described aperture refractory inorganic oxides, as in clay, silicon oxide, aluminum oxide, sial, zirconium white and the titanium oxide-magnesium oxide one or more, be preferably little porous aluminum oxide, its character is as follows: specific surface area 220-300m
2/ g, pore volume are 0.45-0.52ml/g.The present invention can adopt extrusion aid during extrusion in the process of Preparation of Catalyst, extrusion aid commonly used can be: one or more in sesbania powder, citric acid, oxalic acid, Mierocrystalline cellulose, starch, the polymeric surface active agent etc.Involved in the present invention to peptizing agent can be: one or more in Tai-Ace S 150, citric acid, nitric acid, acetic acid, the oxalic acid etc.
In the described step (2), also add nano silicon when making tackiness agent with aperture refractory inorganic oxides and peptization acid peptization, the content in catalyzer is 0～10wt%, is preferably 2.5wt%～10wt%, is preferably 5wt%-10wt%.The median size of described nano silicon is 10～100nm.
In the described step (1), contain magnesium-modified aluminum oxide in the refractory porous inorganic oxide, wherein auxiliary agent magnesium is 3wt%～8wt% in the content of oxide compound in modified aluminas, is preferably 2wt%～6wt.The content of described magnesium-modified aluminum oxide in catalyzer is 20wt%-90wt%, is preferably 30wt%-90wt%.
The preparation process of magnesium-modified aluminum oxide is as follows among the present invention:
(1), with alum liquor and the sodium aluminate solution of preparation under agitation condition also stream add in the glue jar, controlled temperature is at 50-65 ℃, between the pH value 7.0-8.5.
(2), after the cemented into bundles, under agitation condition aging 0.5-1 hour.
(3), aging back feed liquid filtration making beating is washed to negatively charged ion/Al
2O
3＜2.0wt%.
(4), filter cake that step 3 is obtained pulls an oar, and water-soluble magnesium-containing compound is made into the aqueous solution, adds then in the above-mentioned slurries, stirs 0.5～1 hour, filter, after the drying magnesium-modified aluminum oxide of the present invention.
Described water-soluble magnesium-containing compound can be one or more in magnesium nitrate, magnesium chloride, the sal epsom.
Catalyst shape after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei).
In the catalyzer of the inventive method gained, preferred main ingredient and content are as follows: the weight with catalyzer is benchmark, and the content of sapphire whisker is 3wt%～10wt%, is preferably 3wt%～8wt%; The group vib metal oxide content is 5wt%～20wt%, preferably 5wt%-17wt%; VIII family metal oxide content is 0.5wt%～6wt%, is preferably 1wt%-6wt%, is preferably 3wt%-6wt%; The content of aluminum oxide is 20wt%-90wt%, is preferably 30wt%-90wt%; Described aluminum oxide preferably adopts magnesium-modified aluminum oxide.
The boiling bed hydrogenation catalyst of the inventive method gained can be handled wax oil, residual oil, coal tar, shale wet goods heavy oil product, can remove heteroatomss such as nitrogen in the heavy oil product, sulphur to greatest extent, reduces its alkene and aromaticity content, improves the stability of product.
Except sapphire whisker, other components all are present in the catalyzer with fine powder sintering shape among the present invention.The aluminum oxide that exists with fine powder sintering shape is referred to as aluminum oxide, is referred to as sapphire whisker with the fibrous aluminum oxide that exists.
Boiling bed hydrogenation catalyst of the present invention has following advantage:
1, preparation method of the present invention adopts complete kneading method, promptly with containing the solution complete wetting refractory porous inorganic oxide of hydrogenation active metals and the mixture of sapphire whisker, and then the adding tackiness agent, fully mix pinch, extruded moulding, drying, roasting, make catalyzer.Hydrogenation active metals ion in this method is not to add in granular metal salt mode, but joins in the catalyzer in the mode of solion, and metal disperses more even, and helps improving the physical strength of catalyzer.
2, the aluminium dihydrogen phosphate that acidity is stronger adds in the tackiness agent of step (2) in this method, sapphire whisker adds in the mixture of step (1), can slow down the strong interaction of acid and refractory porous inorganic oxide and sapphire whisker like this, reduced the loss of pore volume and specific surface area, make final catalyzer have higher pore volume and specific surface area, catalyst activity is high and reduced cost because of simplifying procedures.
3, this preparation method adopts the method that adds sapphire whisker to increase the physical strength of catalyzer, improved the work-ing life of catalyzer, reduced production cost, especially adopt the active oxidation aluminum fiber, when improving catalyzer physical strength and wear resisting property, can also improve the hydrogenation activity and the stability of catalyzer.
4, become in the glue process to add water-soluble magnesium salt at aluminum oxide among this preparation method and modify, can effectively carry out modulation the acid matter and the pore structure of catalyzer.
5, adopt the nanometer grade silica powder among this preparation method, can make the hole wall of catalyzer thin and closely knit, under the prerequisite that has improved catalyzer pore volume, specific surface area, also can improve the physical strength and the wear resisting property of catalyzer.And SiO 2 powder makes tackiness agent earlier and adds, and silicon-dioxide is more evenly distributed in carrier.
6, the reactive metal amount of this catalyst loading is less relatively, and the preparation method is simple, can reduce production costs greatly.
7. because catalyzer adopts the kneading method preparation, catalyzer has higher specific surface area and bigger pore volume.
8. add aluminium dihydrogen phosphate in this method,, have stronger adhesive effect, can effectively improve the physical strength of catalyzer because aluminium dihydrogen phosphate has more oh group.
9. add aluminium dihydrogen phosphate in this hydrogenation catalyst preparation process,, be easy to form complex compound, help improving the interaction of carrier and reactive metal, thereby improve activity of such catalysts with metal because aluminium dihydrogen phosphate contains 6 hydroxyls.
Embodiment
The characteristics of catalyzer of the present invention are described below by specific embodiment.
The specific surface area of product of the present invention and pore volume are to adopt ASAP2400 type low temperature n2 absorption apparatus, calculate according to BET formula.Acid amount and acid matter adopt infrared spectrometer to record, and the sorbent material that uses is pyridine.The median size of nanoparticle is that scanning electron microscope records.
The preparation of Mo, Ni, P dipping solution S-1
Get the technical grade molybdenum oxide respectively and (contain MoO
399wt%) 280g, basic nickel carbonate 110g, phosphoric acid (contain H
3PO
485wt%) 30ml and deionized water are configured to 960ml Mo-Ni-P solution.
The preparation of Mo, Ni, aluminium dihydrogen phosphate dipping solution S-2
Get the technical grade molybdenum oxide respectively and (contain MoO
399wt%) 280g, basic nickel carbonate 110g, aluminium dihydrogen phosphate (P
2O
5Be 33wt%) 48ml and deionized water, be configured to 960ml Mo-Ni-phosphate dihydrogen aluminum solution.
Embodiment 1
The preparation of modified aluminas M-1
A, with concentration for containing 160gAl
2O
3The NaAlO of/L
2Solution (causticity is than 1.25-1.5) and concentration 40gAl
2O
3The Al of/L
2(SO
4)
3Solution under agitation condition and stream join 1L is housed at the bottom of in the one-tenth adhesive dispenser of water, controlled temperature is at 60 ℃, pH value 8.5.
After B, the cemented into bundles, under agitation condition, wore out 0.5-1 hour.
C, aging back feed liquid are filtered making beating washing four times, and the ratio of water and filter cake is 30:1.
D, get 30g magnesium nitrate (Mg (NO
3)
26H
2O) adding distil water dissolving is diluted to 250ml with volumetric flask, is made into Mg-bearing water solution; The magnesium nitrate aqueous solution for preparing is added in the slurries of step C gained and pull an oar, stirred 0.8 hour, filter, must the magnesium aluminum oxide M-1 that contain of the present invention after the drying, its physico-chemical property sees Table 1.
Embodiment 2
The preparation of modified aluminas M-2
A, with concentration for containing 160gAl
2O
3The NaAlO of/L
2Solution (causticity mol ratio 1.25-1.5) and concentration 40gAl
2O
3The Al of/L
2(SO
4)
3Solution under agitation condition and stream join 1L is housed at the bottom of in the one-tenth adhesive dispenser of water, controlled temperature is at 60 ℃, pH value 8.5.
After B, the cemented into bundles, under agitation condition, wore out 0.5-1 hour.
C, aging back feed liquid are filtered making beating washing four times, and the ratio of water and filter cake is 30:1.
D, get 84g magnesium chloride Mg Cl
2The adding distil water dissolving is diluted to 250ml with volumetric flask, is made into Mg-bearing water solution; The magnesium nitrate aqueous solution for preparing is added in the slurries of step C gained and pull an oar, stirred 0.5 hour, filter, must the magnesium aluminum oxide M-2 that contain of the present invention after the drying, its physico-chemical property sees Table 1.
Table 1 sample physico-chemical property
| The embodiment numbering | 1 | 2 |
| Sample number into spectrum | M-1 | M-2 |
| MgO，wt％ | 3.1 | 1.7 |
| Specific surface area, m 2/g | 402 | 411 |
| Pore volume, ml/g | 1.02 | 1.07 |
| Infrared acidity, mmol/g | 0.39 | 0.44 |
Embodiment 3
The preparation that is used for the boiling bed hydrogenation catalyst C-1 of heavy oil product stable hydrogenation of the present invention.
With 206.6 gram M-1 and 22 gram sapphire whisker powder (30 microns of length, 6 microns of diameters, specific surface 183m
2/ g, pore volume 0.08ml/g) carry out evenly wetting with 290ml S-1 solution; To 23 gram nano silicons (the pure nano silicon of branch that chemical industry company limited in Tianjin produces) and 238 gram SB powder (pore volume 0.454ml/g, specific surface area 258m
2/ add the 51g aluminium dihydrogen phosphate in g), add peptization acid and make tackiness agent (butt 30wt%, sour al mole ratio are 0.3); The tackiness agent that makes is added in the above-mentioned wetting compound, puts into rolling machine then, grind to can squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours make catalyzer C-1.The catalyzer physico-chemical property sees Table 2.
Embodiment 4
The preparation that is used for the boiling bed hydrogenation catalyst C-2 of heavy oil product stable hydrogenation of the present invention.
With 155 gram M-2 and 23 gram sapphire whisker (50 microns of length, 10 microns of diameters, specific surface 150m
2/ g, pore volume 0.18ml/g) carry out evenly wetting with 200ml S-1 solution; 18 gram nano silicons (the pure nano silicon of branch that chemical industry company limited in Tianjin produces, median size＜100nm) restrain by SB powder (pore volume 0.454ml/g, specific surface area 258m with 168
2/ add the 30g aluminium dihydrogen phosphate in g), add peptization acid and make tackiness agent (butt 30wt%, sour al mole ratio are 0.3); The tackiness agent that makes is added in the above-mentioned wetting compound, puts into rolling machine then, grind to can squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings made catalyzer C-2 in 3 hours.The catalyzer physico-chemical property sees Table 2.
Embodiment 5
The preparation that is used for the boiling bed hydrogenation catalyst C-3 of heavy oil product stable hydrogenation of the present invention.
At embodiment 3, change the add-on of nano silicon into 32.9 grams by 23 grams, the charging capacity of other each material and operational condition are all identical with embodiment 3, i.e. the cost example.
Embodiment 6
The preparation that is used for the boiling bed hydrogenation catalyst C-4 of heavy oil product stable hydrogenation of the present invention.
At embodiment 4, change the add-on of sapphire whisker into 15.6 grams by 23 grams, the charging capacity of other each material and operational condition are all identical with embodiment 4, i.e. the cost example.
Embodiment 7
The preparation that is used for the boiling bed hydrogenation catalyst C-5 of heavy oil product stable hydrogenation of the present invention.
At embodiment 3, change the add-on of aluminium dihydrogen phosphate into 75 grams by 51 grams, simultaneously dipping solution is changed to S-2 solution, the charging capacity of other each material and operational condition are all identical with embodiment 3, i.e. the cost example.The catalyzer physico-chemical property sees Table 2.
Comparative example-1
This example is the preparation of reference catalyst J-1.Method is basic identical with embodiment 3 with composition, only removes sapphire whisker.The catalyzer physico-chemical property sees Table 2.
Comparative example-2
This example is the preparation of reference catalyst J-2.Method is basic identical with embodiment 3 with composition, just reactive metal is mixed kneading fully with the form of granular metal salt and gets catalyzer (conventional kneading method).The catalyzer physico-chemical property sees Table 2.
Comparative example-3
This example is the preparation of reference catalyst J-3.Method is basic identical with embodiment 3 with composition, only removes aluminium dihydrogen phosphate.The catalyzer physico-chemical property sees Table 2.
The physico-chemical property of table 2 catalyzer
Embodiment 8-12
Present embodiment illustrates the hydrogenation reaction activity of catalyzer provided by the invention.
Adopting isolated island vacuum residuum A is the hydrogenation activity of stock oil evaluate catalysts C-1～C-5.Stock oil character sees Table 3.Be reflected on 31 the boiling bed hydrogenation device and carry out.Reaction conditions is: 400 ℃ of temperature of reaction, hydrogen dividing potential drop 14.6MPa, liquid hourly space velocity 0.25 hour
-1, hydrogen to oil volume ratio 1000:1, the beds rate of expansion is 30v%.Catalyzer is not replaced in the operation process, and 24 hours experimental result of device steady running is listed in table 4.
Comparative example 4-6
The hydrogenation activity of this comparative example explanation reference catalyst.
Adopting isolated island vacuum residuum A is the hydrogenation activity of stock oil evaluate catalysts J-1, J-2, J-3.Stock oil character sees Table 3.Carry out on the boiling bed hydrogenation device of reaction 31.400 ℃ of temperature of reaction, hydrogen dividing potential drop 14.6MPa, liquid hourly space velocity 0.25 hour
-1, hydrogen to oil volume ratio 1000:1, the beds rate of expansion is 30v%.Catalyzer is not replaced in the operation process, and 24 hours experimental result of device steady running is listed in table 4.
Table 3 stock oil character
| Project | Stock oil |
| Density, g/cm 3 | 1.004 |
| Carbon residue, wt% | 14.16 |
| Sulphur, wt% | 2.54 |
| Nitrogen, wt% | 0.83 |
Table 4 evaluating catalyst result
| Numbering | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Catalyzer | C-1 | C-2 | C-3 | C-4 | C-5 | J-1 | J-2 | J-3 |
| Relative desulfurization degree, wt% | 96 | 96 | 100 | 96 | 94 | 93 | 92 | 94 |
| Relative denitrification percent, wt% | 97 | 94 | 100 | 96 | 95 | 91 | 90 | 95 |
Table 5 live catalyst and 24 hours rear catalyst intensity of reaction and abrasion contrast
Claims (13)
1, a kind of preparation method of boiling bed hydrogenation treatment catalyst, this catalyzer comprises refractory inorganic oxides, active metal component, sapphire whisker and auxiliary agent phosphorus, preparation process is as follows:
(1), refractory inorganic oxides mixes wetting with the solution that contains the hydrogenation activity component;
(2), aperture refractory inorganic oxides and peptization acid peptization are made tackiness agent;
(3), the tackiness agent of making in the step (2) is joined in the moistening material of step (1) gained the mixed paste, extruded moulding pinched into;
(4), with the forming composition of step (3) 100～150 ℃ of dryings 0.5～24 hour, at 350～700 ℃ of roasting 1-12 hours, obtain catalyzer;
Wherein auxiliary agent phosphorus partly or entirely comes from aluminium dihydrogen phosphate, described aluminium dihydrogen phosphate adding method adopts following a kind of at least: a, aluminium dihydrogen phosphate add in the solution that contains the hydrogenation activity component of step (1), mix with refractory inorganic oxides then, b, aluminium dihydrogen phosphate are mixed and made into tackiness agent with aperture refractory inorganic oxides and peptization acid;
Wherein sapphire whisker can adopt following at least a method to add:
A, in step (1), in the refractory inorganic oxides preparation process, introduce the sapphire whisker powder;
B, in step (1), sapphire whisker and refractory inorganic oxides powder mix wetting with the solution that contains the hydrogenation activity component;
C, in step (2), sapphire whisker is mixed and made into tackiness agent with aperture refractory inorganic oxides and peptization acid.
2, according to the described preparation method of claim 1, it is characterized in that described sapphire whisker employing method b adds, aluminium dihydrogen phosphate employing method b adds.
3, according to the described preparation method of claim 1, the length that it is characterized in that described sapphire whisker is 4～500 microns, and diameter is 3～100 microns, and the content in catalyzer is 3wt%～10wt%.
4, according to the described preparation method of claim 1, the length that it is characterized in that described sapphire whisker is 10～80 microns, and diameter is 4～50 microns, and the content in catalyzer is 3wt%～8wt%.
5,, it is characterized in that described sapphire whisker selects the active oxidation aluminum fiber for use, its specific surface 120～280m according to the described preparation method of claim 1
2/ g, pore volume are 0.01～0.20ml/g.
6, according to the described preparation method of claim 1, it is characterized in that the add-on of described aluminium dihydrogen phosphate, in phosphorus, account for the 1wt%～4wt% of total catalyst weight.
7,, it is characterized in that the total phosphorus content that described hydrogenation catalyst contains accounts for below the 4wt% of total catalyst weight according to claim 1 or 6 described preparation methods.
8,, it is characterized in that in the described step (2) that also add nano silicon when making tackiness agent with aperture refractory inorganic oxides and peptization acid peptization, the content in catalyzer is 2.5wt%～10wt% according to the described preparation method of claim 1; The median size of described nano silicon is 10～100nm.
9, according to the described preparation method of claim 1, it is characterized in that in the described boiling bed hydrogenation treatment catalyst, described hydrogenation activity component can be selected from one or more in group vib metal and the group VIII metal, that described group vib metal is the most frequently used is Mo and/or W, and the group VIII metal is the most frequently used is among Fe, Ni and the Co one or more; In the optional self-alumina of described refractory porous inorganic oxide, silicon oxide, magnesium oxide, aluminum oxide one magnesium oxide, silicon oxide-aluminum oxide, silicon oxide-magnesium oxide, titanium oxide-magnesium oxide, zirconium white, silicon oxide-aluminum oxide-magnesium oxide and the clay one or more can also contain in auxiliary agent such as phosphorus, the boron one or more.
10, according to the described preparation method of claim 9, it is characterized in that in the hydrotreating catalyst of gained, main ingredient and content are as follows: the weight with catalyzer is benchmark, and the content of sapphire whisker is 3wt%～10wt%; The group vib metal oxide content is 5wt%～20wt%; VIII family metal oxide content is 0.5wt%～6wt%; The content of aluminum oxide is 20wt%-90wt%.
11, according to the described preparation method of claim 9, it is characterized in that in the hydrotreating catalyst of gained, main ingredient and content are as follows: the weight with catalyzer is benchmark, and the content of sapphire whisker is 3wt%～8wt%; The group vib metal oxide content is 5wt%-17wt%; VIII family metal oxide content is 3wt%-6wt%; The content of aluminum oxide is 30wt%-90wt%.
12, according to claim 1,10 or 11 described preparation methods, it is characterized in that in the described step (1), contain magnesium-modified aluminum oxide in the refractory porous inorganic oxide, wherein auxiliary agent magnesium is 3wt%～8wt% in the content of oxide compound in modified aluminas; The content of described magnesium-modified aluminum oxide in catalyzer is 20wt%-90wt%.
13,, it is characterized in that the preparation process of described magnesium-modified aluminum oxide is as follows according to the described preparation method of claim 12:
(1), with alum liquor and the sodium aluminate solution of preparation under agitation condition also stream add in the glue jar, controlled temperature is at 50-65 ℃, between the pH value 7.0-8.5.
(2), after the cemented into bundles, under agitation condition aging 0.5-1 hour.
(3), aging back feed liquid filtration making beating is washed to negatively charged ion/Al
2O
3＜2.0wt%.
(4), with in the step (3) repeatedly after the washing filter cake that obtains pull an oar, and water-soluble magnesium-containing compound is made into the aqueous solution, add then in the above-mentioned slurries, stirred 0.5～1 hour, filter, must magnesium-modified aluminum oxide of the present invention after the drying; Described water-soluble magnesium-containing compound can be one or more in magnesium nitrate, magnesium chloride, the sal epsom.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710012667A CN101376832B (en) | 2007-08-27 | 2007-08-27 | Preparation of bubbling bed hydrotreating catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710012667A CN101376832B (en) | 2007-08-27 | 2007-08-27 | Preparation of bubbling bed hydrotreating catalyst |
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| Publication Number | Publication Date |
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| CN101376832A true CN101376832A (en) | 2009-03-04 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942334A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Production method of molecular sieve dewaxing raw material |
| CN102443414A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Heavy raw material oil boiling bed hydrogenation treatment method |
| CN102465010A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Heavy and poor raw material hydrotreating method |
| CN106938197A (en) * | 2016-05-25 | 2017-07-11 | 中国科学院过程工程研究所 | A kind of preparation method of vanadium-phosphor oxide catalyst |
| CN108187710A (en) * | 2017-12-15 | 2018-06-22 | 中国第汽车股份有限公司 | Improve the method for integral extruding type honeycomb catalyst mechanical strength |
| US10525448B2 (en) | 2015-07-22 | 2020-01-07 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1282732C (en) * | 2002-10-10 | 2006-11-01 | 中国石油化工股份有限公司 | Hydroprocessing catalyst for heavy oil and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942334A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Production method of molecular sieve dewaxing raw material |
| CN101942334B (en) * | 2009-07-09 | 2013-10-09 | 中国石油化工股份有限公司 | Production method of molecular sieve dewaxing raw material |
| CN102443414A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Heavy raw material oil boiling bed hydrogenation treatment method |
| CN102443414B (en) * | 2010-10-13 | 2014-05-21 | 中国石油化工股份有限公司 | Heavy raw material boiling bed hydrogenation treatment method |
| CN102465010A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Heavy and poor raw material hydrotreating method |
| CN102465010B (en) * | 2010-11-04 | 2014-05-21 | 中国石油化工股份有限公司 | Heavy and inferior raw material hydrotreatment method |
| US10525448B2 (en) | 2015-07-22 | 2020-01-07 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
| US10864500B2 (en) | 2015-07-22 | 2020-12-15 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
| US12064749B2 (en) | 2015-07-22 | 2024-08-20 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
| CN106938197A (en) * | 2016-05-25 | 2017-07-11 | 中国科学院过程工程研究所 | A kind of preparation method of vanadium-phosphor oxide catalyst |
| CN106938197B (en) * | 2016-05-25 | 2019-12-13 | 中国科学院过程工程研究所 | Preparation method of vanadium phosphorus oxide catalyst |
| CN108187710A (en) * | 2017-12-15 | 2018-06-22 | 中国第汽车股份有限公司 | Improve the method for integral extruding type honeycomb catalyst mechanical strength |
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