CN1325942A - Hydrorefining catalyst for hydrocarbons and its preparing process - Google Patents
Hydrorefining catalyst for hydrocarbons and its preparing process Download PDFInfo
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Abstract
A hydrorefining catalyst for hydrocarbons contains gamma-Al2O3 as carrier, metals in VIB and VIII families as active component and assistant B, and is prepared through immersing in the solution containing said metals, mixed complexing agent of organic carboxylic acid and polyol, and assistant B, drying and calcining. It is especially suitable for hydrodenitrifying hydrocarbons.
Description
The present invention relates to a kind of hydrorefining catalyst for hydrocarbon and preparation method thereof.
Hydrocarbons hydrogenation is made with extra care the important process process that is absolutely necessary in petrochemical complex, its objective is in order to remove organic sulfide contained in the stock oil and organic nitrogen compound, to satisfy requirement on environmental protection.Need a kind of effective catalyzer in this process, used catalyzer is the catalyzer that is loaded with molybdenum or tungsten, cobalt or nickel isoreactivity component on the aluminum oxide in the traditional technology.In order to improve the performance of catalyzer, usually add various auxiliary agents such as P, B, F, Ti, Zr etc.
United States Patent (USP) 4,724,226 disclose a kind of auxiliary agent B catalyzer that contains, its carrier is to contain the aluminum oxide that boron oxide is 0.1～5wt%, the boracic carrier adopts Tai-Ace S 150 and sodium metaaluminate and the preparation of sodium metaborate coprecipitation method, active ingredient still as previously mentioned, the characteristics of this catalyzer are that hydrodesulfurization activity and hydrodemetallation (HDM) activity are higher, and the macropore volume of catalyzer can be controlled as required.But this catalyzer also has its weak point, and promptly in the preparation process of carrier, the utilization ratio of boron is low, and the loss when washing of most of boron causes production cost to increase.This catalyzer makes the specific surface area of catalyzer less because boron enters the aluminum oxide skeleton.
Contain the B catalyzer and aspect the raising boron oxide content, carrying out many work.As disclosing in the Chinese patent prospectus (publication number 1052501A) with boric acid ammonia soln impregnated alumina, obtained containing the higher alumina supporter of boron oxide content, this catalyst activity component still as previously mentioned, the characteristics of this catalyzer are to have higher hydrodenitrogenationactivity activity and satisfactory stability.But the place that this catalyzer also haves much room for improvement.Owing to used ammoniacal liquor in adding the B process, ammonia is volatile in storage process, makes the solution instability, and in use, along with the deposition of metal makes ammonia volatilization, this must make Working environment worsen.And because the steeping fluid instability, in the catalyzer drying process, boron is assembled easily, and metal dispersity is reduced.Japanese Patent 54-096489 then adopts following method to improve B content: soak catalyzer with excessive boric acid aqueous solution, by heating moisture evaporation is fallen.But this method also has certain shortcoming.During heating evaporation moisture the operating time oversize, be unfavorable for the suitability for industrialized production of catalyzer, and evaporate to dryness solution will cause catalyzer outside surface accumulation of metal, the intensity of catalyzer also will be subjected to certain influence.Disclose in the Chinese patent prospectus (publication number 1070418A) with boric acid and the mixed method of pinching of alumina dry glue and added B, the characteristics of this method are that the amount of B can be added arbitrarily as required, but it is relatively poor with the B dispersity that this method adds, when B content was above above 2wt%, major part was converted into inactive tetrahedral coordination B.United States Patent (USP) 4,139,492 disclose a kind of preparation method of hydrotreatment catalyst that contains auxiliary agent B, and B adopts HBF
4Add.The shortcoming of this patent is HBF
4With strongly-acid with the intensity and the specific surface area of heavy losses catalyzer, activity of such catalysts will reduce greatly.And fluoroboric acid is poisonous, and Working environment is worsened.
In sum, also has the following improved place for the treatment of about containing B catalyzer patent.1, adopt ammoniacal liquor or amine to improve the concentration of adding B, unfavorable to Working environment, the dispersity of catalyzer boron and metal is reduced.2, it is too strong to contain the acidity of B reagent, and with the intensity and the specific surface area of heavy losses catalyzer, activity of such catalysts will reduce greatly.3, the activity of hydrorefining catalyst for hydrocarbon can also further improve.
Purpose of the present invention is just in order to solve above-mentioned three aspect problems.A kind of Hydrobon catalyst that contains the B auxiliary agent with greater activity is provided on the one hand.A kind of preparation method of Hydrobon catalyst is provided on the other hand, this method has simplified Preparation of catalysts technology, reduced catalyst production cost and avoided, avoided simultaneously because of adopting of the loss of strong acid steeping fluid to catalyst strength and specific surface area because of adopting the environmental pollution that ammonia or amine brought.
Catalyzer of the present invention is with Al
2O
3Be carrier, preferably with γ-Al
2O
3Carrier is active ingredient with group VIII metal and group VIB metal, and contains auxiliary agent B that boron content is counted 0.5wt%～10wt% with boron oxide.
The specific surface area of catalyzer of the present invention is 150～300m
2/ g, recording total pore volume with nitrogen adsorption method is 0.1～0.50ml/g, and mean pore size is 2～10nm, and 5～10nm hole accounts for 75% of total pore volume at least, accounts for 5% of total pore volume at least greater than the 10nm hole, and side pressure strength is 18～30N/mm.
Wherein the group VIB metal is preferably aluminium and/or tungsten, is 5wt%～35wt% in its content of oxide compound; Group VIII metal is nickel and/or cobalt, is 2wt%～10wt% in its content of oxide compound.
Preparation of catalysts process of the present invention is:
1, produces Al
2O
3Carrier;
2, preparation dipping solution: group VIB metallic compound, organic carboxyl acid and polyvalent alcohol mixed twine mixture, boron-containing compound are mixed, add deionized water dissolving, add the group VIII metal compound then, be mixed with dipping solution.3, Preparation of Catalyst: the dipping solution that obtains with the 2nd step floods the carrier that the 1st step obtained, and dry then, roasting makes the catalyzer finished product.
Al in the above-mentioned steps 1
2O
3Carrier is γ-Al preferably
2O
3Carrier, specific surface area are 200～400m
2/ g, recording total pore volume with nitrogen adsorption method is 0.1～1.5ml/g, mean pore size is 2～15nm.
This alumina supporter can prepare with following method:
Press W
HNO3/ W
The dry sample of aluminium hydroxide=0.010～0.025, W
H2O/ W
The dry sample of aluminium hydroxide=0.50～1.0 are extruded into various suitable shapes (as cloverleaf pattern, bar shaped, sphere etc.) after pinching with dry sample of aluminium hydroxide and aqueous nitric acid are fully mixed; Dry in the shade in room temperature, 100～150 ℃ of oven dry 2～8 hours, progressively be warming up to 450～650 ℃, roasting 4～8 hours makes γ-Al
2O
3Carrier.The dry sample of wherein said aluminium hydroxide preferably is can be converted into γ-Al through roasting
2O
3Aluminum hydroxide solid elastomer.
Dipping solution described in the above-mentioned steps 2 is the dipping solution of boracic and hydrogenation activity component, contains B by weight
2O
31%～10%, contain organic carboxylic acid 5%～30%, contain polyvalent alcohol 1～10%, contain P
2O
50～10%, preferably contain P
2O
50.1～5%, the pH value of solution is 0～6.
The hydrogenation activity component of above-mentioned dipping solution is selected from VI B family's metallic element and/or VIII family metallic element, and the group VIB metal oxide contains 5%～25% by weight in the dipping solution, and the VIII family metal oxide contains 1%～10% by weight.Wherein the group VIB metallic element is preferably molybdenum and/or tungsten, and VIII family metallic element is preferably cobalt and/or nickel.
Organic carboxyl acid in the above-mentioned dipping solution is selected from alcohol acid, amino acid or its mixture.Wherein amino acid is selected from nitrilotriacetic acid, ethylenediamine tetraacetic acid (EDTA), and alcohol acid is selected from citric acid, tartrate.
Polyvalent alcohol in the above-mentioned dipping solution contains the compound of two or more hydroxyls for one or more, as N.F,USP MANNITOL, ethylene glycol, glycerol etc., is preferably N.F,USP MANNITOL.
The employed group VIB metallic compound of preparation dipping solution is ammonium molybdate or ammonium metawolframate, and VIII family metallic compound is nickelous nitrate or Xiao Suangu; Boron-containing compound is selected from one or more in boric acid, ammonium borate, ammonium metaborate, the tetraboric acid ammonium, is preferably boric acid.
The employed dipping solution of the inventive method can add P contained compound, can when adding the group VIII metal compound, add P contained compound, described P contained compound can be selected from one or more in phosphoric acid, ammonium phosphate, Hypophosporous Acid, 50, phosphorous acid, ammonium hydrogen phosphate, the primary ammonium phosphate, is preferably phosphoric acid.
Preparation of catalysts process of the present invention can adopt equi-volume impregnating, and the drying and roasting condition of dipping rear catalyst carrier is: drying conditions is to descend dry 2～8 hours at 100 ℃～150 ℃, and roasting condition is 450 ℃～650 ℃ following roastings 4～8 hours.
Fig. 1 is the x-ray diffraction spectra of catalyzer D of the present invention and contrast medium X.
As can be seen from the figure, catalyst D of the present invention does not find β-NiMoO4Feature X-ray diffraction maximum (2 Theta angles are 26.4deg), and in contrast medium X, this peak is very obvious. The metal active constituent decentralization that catalyst of the present invention is described is high than contrast medium, thereby has higher catalytic reaction activity.
Compared with prior art, catalyst of the present invention has higher boron and metal dispersity, and the pore size distribution that has larger specific area, pore volume and concentrate. In the suitable situation of tenor, catalyst of the present invention has higher hydrodesulfurization and hydrodenitrogenationactivity activity.
The preparation method of catalyst of the present invention uses the dipping solution of a kind of boracic, phosphorus and hydrogenation activity component, and this dipping solution stability is high, boron concentration is high, acidity is suitable, and the preparation method is simple, and is more friendly to environment. Specifically, the employed dipping solution of catalyst of the present invention has the following advantages:
1, the employed dipping solution of the inventive method is not owing to contain the material such as volatile Ammonia, in preparation, storage process, do not produce volatile substance, solution is more stable, and the ammonia that do not volatilize in the catalyst soakage process produces, working environment and atmospheric environment are not polluted, and can make boron and hydrogenation active metals that higher decentralization is arranged.
2, the employed dipping solution of the inventive method makes boron and the organic combination of hydrogenation active metals component owing to use organic carboxyl acid and polyhydric alcohol complex agent, has improved the content of boron in maceration extract, can prepare the high Hydrobon catalyst of boron content.
3, the acidity of the employed dipping solution of the inventive method is suitable, and can regulate as required, therefore can keep to greatest extent and adjust every physical and chemical indexes of catalyst carrier, make the catalyst of producing satisfy the preparation requirement of all kinds Hydrobon catalyst. The specific area that can effectively keep carrier such as the employed dipping solution of the inventive method.
4, the preparation method of the employed dipping solution of the inventive method is simple, raw material be easy to get and price low, the production cost of catalyst is reduced greatly.
The purposes of catalyst of the present invention is in hydrocarbons hydrogenation transforms HDN and HDS process to be played catalytic action simultaneously. Operating condition is: presulfided catalyst, cool the temperature to 200 ℃, and pass into feedstock oil (boiling range is 200 ℃～350 ℃, sulfur content 5 μ g/g～1500 μ g/g, nitrogen content 5 μ g/g～1500 μ g/g); 300～360 ℃ of temperature, liquid hourly space velocity (LHSV) is 0.5～4h-1, hydrogen pressure is 2～10MPa, hydrogen-oil ratio (volume) is under 400～1000 the reaction condition, can obtain good refining effect.
In order to further specify the present invention, enumerate following examples and Comparative Examples, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
1, the preparation of carrier
Restrain aluminum hydroxide solid elastomers and contain HNO 133
32.5 the 100ml aqueous solution of gram fully mixes and pinches, and is extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, 120 ℃ of oven dry 4 hours, progressively be warming up to 500 ℃, roasting 5 hours makes γ-Al
2O
3Carrier.The specific surface area of this carrier, total pore volume, mean pore size and pore distribution see Table 3.
2, the preparation of dipping solution
8.783 gram Ammonium Heptamolybdates, 9 gram citric acids, 2 gram N.F,USP MANNITOL and 1.856 gram boric acid are put into same beaker, add the 12ml deionized water, under agitation be heated to 70 ℃ of dissolvings, the dissolving back adds 0.41ml phosphoric acid and 4.655 grams, six water nickelous nitrates, make a stable dipping solution, its pH value is 1.2.
3, Preparation of catalysts method
With the equivalent impregnation method above-mentioned dipping solution is sprayed on the above-mentioned carrier of 20 grams, in 120 ℃ of oven dry 4 hours, 500 ℃ of roastings 4 hours, can make the catalyzer that contains boron oxide, wherein molybdenum oxide content is 24wt%, and nickel oxide content is 4wt%, and boron oxide content is 3.5wt%, phosphorus pentoxide content is 1.5wt%, and all the other are aluminum oxide.This catalyzer represents that with A the specific surface area of A, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 21, carrier
With embodiment 1.2, the preparation of dipping solution
With embodiment 1, just ammonium molybdate is 5.885 grams, and boric acid is 1.185 grams, and six water nickelous nitrates are 3.119 grams, primary ammonium phosphate 0.76ml, and citric acid 6 grams, N.F,USP MANNITOL is 1.5 grams, its pH value is 1.6.2, Preparation of catalysts method
The Preparation of catalysts method is with the embodiment I, and just in the oxidized catalyst that makes, molybdenum oxide content is 18% (weight), nickel oxide content is 3% (weight), boron oxide is 2.5% (weight), and phosphorus pentoxide content is 1.5wt%, and all the other are aluminum oxide.This catalyzer represents that with B the specific surface area of B, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 31, carrier
With embodiment 1.2, the preparation of dipping solution
With embodiment 1, just ammonium molybdate is 3.567 grams, and boric acid is 0.861 gram, and six water nickelous nitrates are 1.891 grams, phosphoric acid 0.32ml, and nitrilotriacetic acid 2 grams, N.F,USP MANNITOL is 1 gram, its pH value is 1.4.3, Preparation of catalysts method
The Preparation of catalysts method is with embodiment 1, and just in the oxidized catalyst that makes, molybdenum oxide content is 12% (weight), and nickel oxide content is 2% (weight), and boron oxide is 2% (weight), and phosphorus pentoxide content is 1.5wt%.This catalyzer represents that with C the specific surface area of C, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 41, carrier
With embodiment 1.2, the preparation of dipping solution
With embodiment 1, just ammonium molybdate is 6.216 grams, and boric acid is 1.751 grams, and six water nickelous nitrates are 6.588 grams, phosphoric acid 0.38ml, and citric acid 6.5 grams, its pH value is 1.5.3, Preparation of catalysts method
The Preparation of catalysts method is with embodiment 1, and just in the oxidized catalyst that makes, molybdenum oxide content is 18% (weight), and nickel oxide content is 6% (weight), and boron oxide is 3.5% (weight), and phosphorus pentoxide content is 1.5wt%.This catalyzer represents that with D the specific surface area of D, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 51, carrier
With embodiment 1.2, the preparation of dipping solution
With embodiment 1, just ammonium molybdate is 6.173 grams, and the tetraboric acid ammonium is 2.3 grams, and six water nickelous nitrates are 3.27 grams, phosphoric acid 0.37ml, and citric acid and ethylenediamine tetraacetic acid (EDTA) mixture (volume ratio is 2: 1) 3.5 grams, N.F,USP MANNITOL is 3 grams, its pH value is 1.5.3, Preparation of catalysts
The Preparation of catalysts method is with embodiment 1, and just in the oxidized catalyst that makes, molybdenum oxide content is 18% (weight), and nickel oxide content is 3% (weight), and boron oxide is 6% (weight), and phosphorus pentoxide content is 1.5wt%.This catalyzer represents that with E the specific surface area of E, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 61, carrier
Same embodiment.2, the preparation of dipping solution
With embodiment 1, just ammonium molybdate is 6.047 grams, and boric acid is 1.460 grams, and six water nickelous nitrates are 3.204 grams, phosphatase 11 .53ml, and citric acid 6.5 grams, the mixture of N.F,USP MANNITOL and ethylene glycol (volume ratio is 1: 1) is 2 grams, its pH value is 1.0.3, Preparation of catalysts
The Preparation of catalysts method is with embodiment 1, and just in the oxidized catalyst that makes, molybdenum oxide content is 18% (weight), and nickel oxide content is 3% (weight), and boron oxide is 3% (weight), and phosphorus pentoxide content is 3wt%.This catalyzer represents that with F the specific surface area of F, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 71, carrier
With embodiment 1.2, the preparation of dipping solution
With embodiment 1, just ammonium molybdate is 6.306 grams, and boric acid is 1.522 grams, and six water nickelous nitrates are 3.340 grams, phosphoric acid 0.73ml, and citric acid 6.5 grams, N.F,USP MANNITOL is 1.5 grams, its pH value is 1.2.3, Preparation of catalysts
The Preparation of catalysts method is with embodiment 1, and just in the oxidized catalyst that makes, molybdenum oxide content is 18% (weight), and nickel oxide content is 3% (weight), and boron oxide is 3% (weight), and phosphorus pentoxide content is 6wt%.This catalyzer represents that with G the specific surface area of G, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 81, carrier
With embodiment 1.2, the preparation of dipping solution
With embodiment 1, just ammonium molybdate is 13.019 grams, and boric acid is 2.83 grams, and six water nickelous nitrates are 6.9 grams, phosphatase 11 .26ml, and citric acid 13 grams, N.F,USP MANNITOL is 3 grams, and water is 24ml, and its pH value is 0.5.3, Preparation of catalysts
Above-mentioned dipping solution is impregnated at twice prepares catalyzer on the carrier, in the oxidized catalyst that makes, molybdenum oxide content is 30% (weight), and nickel oxide content is 5% (weight), and boron oxide is 4.5% (weight), and phosphorus pentoxide content is 4wt%.This catalyzer represents that with H the specific surface area of H, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of embodiment 91, carrier
With embodiment 1.2, the preparation of dipping solution
5.6 gram ammonium molybdates, 12 gram tartrate, 2 gram glycerol and 2 gram boric acid are put into same beaker, add the 12ml deionized water, under agitation be heated to 70 ℃ of dissolvings, the dissolving back adds 3.5 gram nickelous nitrates, makes the stable solution that soaks altogether, and its pH value is 0.6.3, Preparation of catalysts
Above-mentioned dipping solution is impregnated at twice prepares catalyzer on the carrier, in the oxidized catalyst that makes, alumina content is 17.5% (weight), and nickel oxide content is 2% (weight), and boron oxide is 4.3% (weight).This catalyzer represents that with I the specific surface area of I, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The preparation of Comparative Examples 11, carrier
The preparation method of carrier is with embodiment 1.2, the preparation of dipping solution.
It is as follows to prepare dipping solution by disclosed method in the U.S. Patent Publication specification sheets (publication number 4,139,492): with 33.8 gram ammonium molybdates, 21.5 gram six water nickelous nitrates and 12.1 gram HBF
4Mix, add in the 70ml water, stir dissolving in 1 minute, make molybdenum nickel boron mixing solutions.3, Preparation of catalysts method: above-mentioned dipping solution is sprayed 100 gram γ-Al with the equivalent impregnation method
2O
3On the carrier, in 110 ℃ of oven dry 4 hours, 500 ℃ of roastings 4 hours can make the catalyzer that contains B, and wherein molybdenum oxide content is 20wt%, and nickel oxide content is 4wt%, B
2O
3Content is 35wt%, and all the other are aluminum oxide.This catalyzer represents that with X the specific surface area of X, total pore volume, mean pore size and pore distribution see Table 3, and side pressure strength sees Table 2.
The application of embodiment 10 catalyzer in the hydrocarbon conversion
Catalyst A, B, C, D, E, F, G, H, I and X are tested as hydrogenating desulfurization and denitrogenation.Catalyzer X is as the contrast experiment.Catalyst A, B, C, D, E, F, G, H, I and X operation condition are identical.
Get catalyzer 20.0 gram and pack in the fixed-bed reactor, cool the temperature to 200 ℃ after the prevulcanized, feed stock oil (boiling range is that 200～350 ℃, sulphur content 1000 μ g/g, total nitrogen content are that 1500 μ g/g, alkali nitrogen content are 870 μ g/g); 360 ℃ of temperature, air speed is 1.5/ o'clock, and reaction pressure is 5MPa, and hydrogen-oil ratio (volume) is to react under 600 the condition.
The activity of invention catalyst A～I is represented with relative reactivity, is 100 with 200 hours activity of comparative catalyst X running promptly, the relative reactivity of the more resulting by comparison active expression invention catalyzer of catalyst A～I of the present invention.Desulphurizing activated relatively by following formula calculating:
Desulphurizing activated relatively=100 * [(1/S
p)
1/2-((1/S
f)
1/2]/[(1/S
Pr)
1/2-((1/S
Fr)
1/2] S in the formula
Fr, S
PrThat represents raw materials used oil of reference catalyst X and the product after reference agent hydrotreatment respectively contains sulphur concentration, S
f, S
pRepresent respectively the invention catalyzer (the raw materials used oil of A～I) and through the invention catalyzer (product after the hydrotreatment of A～I) contain sulphur concentration.Denitrification activity calculates by following formula relatively:
Relative denitrification activity=100 * ln (N
f/ N
p)/ln (N
Fr/ N
Pr) N in the formula
Fr, N
PrThat represents the raw materials used and product after reference agent hydrotreatment of reference catalyst X respectively contains nitrogen concentration, N
f, N
pRepresent respectively the invention catalyzer (the raw materials used oil of A～I) and through the invention catalyzer (product after the hydrotreatment of A～I) contain nitrogen concentration.The living-article comparing result is as shown in table 1.
The active comparing result of table 1
Table 1 is the result show, compares with the reference agent, and catalyzer of the present invention has higher hydrogenating desulfurization and denitrification activity when active metallic content is suitable; When adding B, too high P content is to activity unfavorable (F catalyzer).The catalyst strength experiment is as shown in table 2.
| Catalyzer | Reaction times (hour) | Relative dealkalize nitrogen activity | Relative removing total nitrogen activity | Desulphurizing activated relatively |
| ???A | ????200 | ????108 | ?????112 | ???110 |
| ???B | ????200 | ????121 | ?????129 | ???120 |
| ???C | ????200 | ????88 | ?????94 | ???90 |
| ???D | ????200 | ????108 | ?????113 | ???111 |
| ???E | ????200 | ????104 | ?????112 | ???109 |
| ???F | ????200 | ????101 | ?????106 | ???105 |
| ???G | ????200 | ????125 | ?????134 | ???122 |
| ???H | ????200 | ????119 | ?????124 | ???119 |
| ???I | ????200 | ????102 | ?????110 | ???105 |
| ???X | ????200 | ????100 | ?????100 | ???100 |
Table 2 catalyst strength experimental result
Table 2 is the result show, increases with B content, and invention catalyzer side pressure strength increases, and all is higher than contrast medium.
| Catalyzer | ?A | ?B | ?C | ?D | ?E | ?F | ?G | ?H | ?I | ?X |
| Intensity (N/mm) | ?22 | ?20 | ?23 | ?21 | ?22 | ?18 | ?21 | ?23 | ?22 | ?12 |
Table 3 specific surface area, pore distribution and pore volume
| Aperture (nm) | Carrier PV% | ?A PV％ | ?B PV％ | ?C PV％ | ?D PV％ | ?E PV％ | ?F PV％ | ?G PV％ | ?H PV％ | ?I PV％ | ?X PV％ |
| ＜4 | 0.5 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.0 | 0.3 | 0.1 | 0.2 |
| 4～5 | 3.2 | 1.0 | 1.0 | 0.8 | 0.6 | 0.5 | 1.6 | 1.0 | 2.2 | 1.4 | 2.2 |
| 5～6 | 11.3 | 4.7 | 4.5 | 4.3 | 4.0 | 3.8 | 2.2 | 1.5 | 8.0 | 2.4 | 3.7 |
| 6～7 | 35.1 | 8.6 | 8.4 | 8.2 | 8.0 | 7.5 | 8.6 | 6.5 | 25 | 6.6 | 9.6 |
| 7～8 | 34.0 | 23.0 | 23.2 | 23.5 | 23.8 | 24.5 | 21.0 | 24.0 | 27 | 24.1 | 22.0 |
| 8～9 | 6.8 | 29.0 | 29.2 | 30.1 | 30.5 | 30.5 | 28.2 | 29.0 | 16 | 28.0 | 28.7 |
| 9～10 | 1.1 | 19.6 | 18.6 | 19.7 | 20.0 | 21.0 | 18.5 | 15.0 | 11.5 | 16.0 | 18.6 |
| 10～11 | 1.7 | 6.0 | 6.5 | 6.5 | 6.2 | 5.5 | 8.0 | 11.0 | 4 | 10.5 | 7.0 |
| ＞11 | 6.3 | 7.0 | 7.5 | 7.5 | 7.5 | 5.8 | 9.0 | 12.0 | 6 | 12.5 | 7.0 |
| Total pore volume ml/g | 0.65 | 0.45 | 0.46 | 0.44 | 0.43 | 0.41 | 0.40 | 0.35 | 0.47 | 0.45 | 0.25 |
| Surface-area M 2/g | 310 | 210 | 230 | 220 | 200 | 190 | 170 | 185 | 245 | 200 | 125 |
| Mean pore size (nm) | 8.4 | 8.6 | 8.0 | 8.0 | 8.6 | 8.6 | 9.4 | 7.6 | 7.7 | 9.0 | 8.0 |
Table 4 catalyzer is formed and content
| Catalyzer | MoO 3％ | NiO％ | B 2O 3％ | P 2O 5％ |
| A | 24 | 4 | 3.5 | 1.5 |
| B | 18 | 3 | 2.5 | 1.5 |
| C | 12 | 2 | 2 | 1.5 |
| D | 18 | 6 | 3.5 | 1.5 |
| E | 18 | 3 | 6 | 1.5 |
| F | 18 | 3 | 3 | 6 |
| G | 18 | 3 | 3 | 3 |
| | 30 | 5 | 4.5 | 4 |
| I | 17.5 | 2 | 4.3 | |
| X | 20.0 | 4.0 | 3.5 |
Not only have higher desulfurization removing nitric activity according to the prepared Hydrobon catalyst of the present invention, and the preparation method is simple, friendly more to environment.
Claims (24)
1, a kind of Hydrobon catalyst is with Al
2O
3Be carrier, VI B and group VIII metal are active ingredient, it is characterized in that containing in the catalyzer auxiliary agent B, are 0.5wt%～10wt% in corresponding oxide compound boron content.
2, according to the described catalyzer of claim 1, it is characterized in that described group VIB metal is molybdenum and/or tungsten, it is nickel and/or cobalt that its content is counted 5wt%～35wt% group VIII metal with oxide compound, its content is counted 2wt%～10wt% with oxide compound.
3,, it is characterized in that specific surface area of catalyst is 150～300m according to the described catalyzer of claim 1
2/ g, pore volume are 0.1～0.50ml/g, and mean pore size is 2～10nm, and 5～10nm hole accounts for the ratio of total pore volume more than or equal to 75%, and the ratio that accounts for total pore volume greater than the 10nm hole is more than or equal to 5%, and side pressure strength is 18～30N/mm.
4, the described Preparation of catalysts method of a kind of claim 1 comprises:
(1) preparation Al
2O
3Carrier;
(2) preparation dipping solution: group VIB metallic compound, organic carboxyl acid and polyvalent alcohol mixed twine mixture, boron-containing compound are mixed, add deionized water dissolving, add the group VIII metal compound then, be mixed with dipping solution.
(3) Preparation of Catalyst: the carrier that (1) step of dipping solution dipping that obtains with (2) step obtains, dry then, roasting makes the catalyzer finished product.
5, according to the described preparation method of claim 4, it is characterized in that the Al described in the step (1)
2O
3The specific surface area of carrier is 200～400m
2/ g, pore volume are 0.1～1.5ml/g, and mean pore size is 2～15nm.
6,, it is characterized in that the dipping solution described in the step (2) is the dipping solution of boracic and hydrogenation activity component, contains B by weight according to the described preparation method of claim 4
2O
31%～10%, contain organic carboxylic acid 5%～30%, contain polyvalent alcohol 1～10%, contain P
2O
50～10%.
7,, it is characterized in that described dipping solution contains P according to claim 4 or 6 described preparation methods
2O
50.1～5%.
8,, it is characterized in that described hydrogenation activity component is selected from VI B family's metallic element and/or VIII family metallic element according to claim 4 or 6 described preparation methods.
9, according to the described preparation method of claim 8, it is characterized in that described group VIB metal oxide contains 5%～25% by weight, the VIII family metal oxide contains 1%～10% by weight.
10, according to the described preparation method of claim 9, it is characterized in that described group VIB metallic element is molybdenum and/or tungsten, VIII family metallic element is cobalt and/or nickel.
11,, it is characterized in that described organic carboxyl acid is selected from alcohol acid, amino acid or its mixture according to claim 4 or 6 described preparation methods.
12,, it is characterized in that described amino acid is selected from nitrilotriacetic acid, ethylenediamine tetraacetic acid (EDTA) according to the described preparation method of claim 11.
13,, it is characterized in that described alcohol acid is selected from citric acid, tartrate according to the described preparation method of claim 11.
14,, it is characterized in that described polyvalent alcohol contains the compound of two or more hydroxyls for one or more according to claim 4 or 6 described preparation methods.
15,, it is characterized in that described polyvalent alcohol is selected from N.F,USP MANNITOL, ethylene glycol, glycerol according to the described preparation method of claim 14.
16,, it is characterized in that described polyvalent alcohol is a N.F,USP MANNITOL according to the described preparation method of claim 14.
17, according to the described preparation method of claim 4, it is characterized in that described group VIB metallic compound is selected from ammonium molybdate or ammonium metawolframate, VIII family metallic compound is selected from nickelous nitrate or Xiao Suangu.
18,, it is characterized in that described boron-containing compound is selected from one or more in boric acid, ammonium borate, ammonium metaborate, the tetraboric acid ammonium according to the described preparation method of claim 4.
19,, it is characterized in that described boron-containing compound is a boric acid according to the described preparation method of claim 18.
20,, it is characterized in that when adding the group VIII metal compound, adding P contained compound according to the described preparation method of claim 4.
21,, it is characterized in that described P contained compound is selected from one or more in phosphoric acid, ammonium phosphate, Hypophosporous Acid, 50, phosphorous acid, ammonium hydrogen phosphate, the primary ammonium phosphate according to the described preparation method of claim 20.
22,, it is characterized in that the described P contained compound that contains is a phosphoric acid according to the described preparation method of claim 21.
23,, it is characterized in that step (3) adopts equi-volume impregnating according to the described preparation method of claim 4.
24, according to the described preparation method of claim 4, it is characterized in that the described drying conditions of step (3) is to descend dry 2～8 hours at 100 ℃～150 ℃, roasting condition is 450 ℃～650 ℃ following roastings 4～8 hours.
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| CN00110464A CN1101455C (en) | 2000-05-26 | 2000-05-26 | Hydrorefining catalyst for hydrocarbons and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00110464A CN1101455C (en) | 2000-05-26 | 2000-05-26 | Hydrorefining catalyst for hydrocarbons and its preparing process |
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| Publication Number | Publication Date |
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| CN1325942A true CN1325942A (en) | 2001-12-12 |
| CN1101455C CN1101455C (en) | 2003-02-12 |
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| CN101733119B (en) * | 2008-11-25 | 2012-12-05 | 中科合成油技术有限公司 | Catalyst for hydrogenation of Fischer-Tropsch synthesis oil, preparation method as well as application thereof |
| CN102039203B (en) * | 2009-10-16 | 2013-04-10 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139492A (en) * | 1977-08-10 | 1979-02-13 | American Cyanamid Company | Hydrotreating catalysts |
| CN1019204B (en) * | 1991-06-13 | 1992-11-25 | 北京市石景山区环境保护科技研究站 | Recovery and utilization method of electric furnace powder dust |
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2000
- 2000-05-26 CN CN00110464A patent/CN1101455C/en not_active Expired - Lifetime
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