CN1088087C - Preparation of hydrogenation catalyst - Google Patents
Preparation of hydrogenation catalyst Download PDFInfo
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- CN1088087C CN1088087C CN99120515A CN99120515A CN1088087C CN 1088087 C CN1088087 C CN 1088087C CN 99120515 A CN99120515 A CN 99120515A CN 99120515 A CN99120515 A CN 99120515A CN 1088087 C CN1088087 C CN 1088087C
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Abstract
The present invention describes a hydrofining catalyst and a preparation method thereof. The catalyst uses alumina containing silicon as a carrier and metallic elements of the VIII group (Fe, Co and Ni) and the VI B group (Mo and W) as active components, adds boron as an auxiliary agent and particularly contains three active components of tungsten, molybdenum and nickel. In the preparation method of the catalyst, ammonia solution containing molybdenum and boron and water solution containing tungsten and nickel are respectively prepared, then, the formed carrier is immersed in two stages, and the catalyst is manufactured through the operation of drying and segmenting calcining.
Description
The present invention relates to a kind of hydrogenization catalyst preparation method, particularly support the hydrogenization catalyst preparation method of auxiliary agent.
Catalyst used for hydrogenation of distilled oil fraction is carrier usually with the aluminum oxide, with group vib (Mo, W) and VIII family (Fe, Co, Ni) metallic element is the hydrogenation activity component, add auxiliary agent and improve the acidity, active ingredient of carrier dispersiveness, reductibility and curability at carrier surface, the effect that prolongs catalyzer work-ing life, improves selectivity and stability is played in the adding of auxiliary agent toward contact, the auxiliary agent that hydrogenation catalyst is commonly used has fluorine, phosphorus, boron, silicon etc.It is best for example all to have reported when containing three kinds of active ingredients of tungsten nickel and boron additive in the hydrogenation catalyst its hydrogenation performance in patent of invention CN1052501A and CN1086534A, the Preparation of catalysts method is to make the molybdenum boron ammonia soln and the tungsten nickel aqueous solution earlier, and respectively the carrier of moulding is sprayed, need carry out drying and roasting after spraying at every turn.So in these two pieces of patents of invention, load active component tungsten, molybdenum, nickel and boron additive, at least through twice dipping, drying and roasting, so the catalyst preparation process complexity.
The objective of the invention is to keep with under the suitable prerequisite of the catalyst activity of prior art for preparing, simplify the Preparation of catalysts flow process, reduce the cost of catalyzer.
Technical key point of the present invention is to make earlier the tungsten nickel aqueous solution and molybdenum boron ammonia soln respectively, is rationally controlling under the prerequisite of two kinds of solution acid alkalinities, with the method supported catalyst component of segmentation dipping, adopts the technology of segmentation roasting.More specifically saying so and getting volume earlier is that 50～55% solution of carrier saturated extent of adsorption spray, and second section dipping volume is that 50～55% another kind of solution of carrier saturated extent of adsorption sprays or carries out the supersaturation dipping with this solution; The technology of segmentation roasting is: earlier 150～350 ℃ of following roastings 2～6 hours, then 400～550 ℃ of following roastings 2～6 hours.
In the industrial implementation process, often adopt ammonium metawolframate and the nickelous nitrate preparation tungsten nickel aqueous solution, so the tungsten nickel aqueous solution is acid; General adopt ammonium molybdate (or molybdic oxide) and boric acid (or ammonium borate) to add in the ammonia soln heating and make Mo-B solution, so molybdenum boron ammonia soln is alkaline.If adopt segmentation to spray tungsten nickel solution and Mo-B solution simply, there are the following problems: tart solution and basic solution segmentation are impregnated on the identical carrier, and the Mo-B solution of the tart tungsten nickel aqueous solution and alkalescence can not all be adsorbed the component of solution taking place neutralization reaction to have precipitation to separate out on the carrier, block the duct of catalyzer, cause that activity of such catalysts component and auxiliary agent build up on carrier.So the key that adopts segmentation to spray technology be to avoid carrier surface generate precipitation and resolve the activity of such catalysts component and auxiliary agent in the finely dispersed problem of carrier surface.Will make solution component not generate precipitation at carrier surface for the segmentation pickling process, potential of hydrogen, the impregnation sequence of two kinds of solution, the interlude that found through experiments the reasonable control molybdenum boron ammonia soln and the tungsten nickel aqueous solution in the present invention is crucial technology.More detailed is illustrated as:
If spray Mo-B solution, back dipping tungsten nickel solution earlier, require the alkalescence of Mo-B solution lower, its pH value is preferably between 6～9.When Mo-B solution alkalescence is too strong, can makes the tungsten nickel solution neutralization of back dipping and cause that tungsten nickel component generates precipitation and builds up at carrier surface.The pH value of Mo-B solution can be controlled by the add-on of ammoniacal liquor, Mo-B solution alkalescence cross when strong can be with organic acid or/and mineral acid regulate, such as nitric acid, oxalic acid, formic acid, acetate, hydrochloric acid etc.
If spray tungsten nickel solution, back dipping Mo-B solution earlier, require the alkalescence of Mo-B solution stronger, its pH value is preferably between 9～12, could guarantee like this when Mo-B solution is impregnated on the carrier, can not make molybdenum boron component coagulation on the surface of support of the catalyst with the neutralization of the acid in the tungsten nickel solution, the pH value of regulating Mo-B solution can realize by the ammonia vol that control is added.
Similarly, can regulate tungsten nickel pH value of aqueous solution and solve the problem that the solute precipitation is separated out in the dipping solution in the segmentation steeping process, regulate tungsten nickel aqueous solution potential of hydrogen, adding acid makes the pH value reduce to be easy to, but add alkali and make difficulty of tungsten nickel pH value of water solution increase, because the tungsten nickel solution pH value of high density has precipitation and generates when increasing, carry out easily so be not so good as the potential of hydrogen of adjusting Mo-B solution.
Two sections dipping interludes flood (spraying) second kind of solution after requiring to guarantee that first kind of solution component is adsorbed onto on the carrier again.For alumina supporter, got final product pitch time between 10～30 minutes.The too short homodisperse of dipping solution component on support of the catalyst that be unfavorable for of interlude.
By take to control impregnating speed (or time), suitably means such as excessive dipping solution and segmentation roasting technology can further improve the activity of such catalysts component and auxiliary agent is uniformly dispersed at carrier surface.Say so in more detail: control impregnating speed (or time) refers to and requires dipping solution to be vaporific to spray on carrier; Suitably to refer to the overall solution volume that requires to spray (dipping) be 105～110% of carrier saturated extent of adsorption to excessive dipping solution;
When catalyzer adopted the segmentation roasting, first maturing temperature should be preferably between 200～250 ℃ between 150～350 ℃.
Say that in more detail the segmentation roasting technology refers to earlier 150～350 ℃ of following roastings 2～6 hours, then 400～550 ℃ of following roastings 2～6 hours.Because between 150～350 ℃ be the temperature range that the compound decomposition of hydrogenation catalyst component forms its oxide compound, the oxide compound of these catalyst components is comparatively active in this decomposition temperature scope, and it is not strong in conjunction with getting with carrier (aluminum oxide), under this temperature, stay for some time, help of diffusion and the infiltration of these oxide compounds, help it and be uniformly dispersed in catalyzer inside.And be the common maturing temperature of hydrogenation catalyst between 400～550 ℃, under this temperature, keep for some time, improve the intensity of catalyzer easily, make active ingredient and carrier firmly be difficult for running off, more help making active ingredient to change into needed crystalline phase in conjunction with getting.
The concrete preparation process of catalyzer of the present invention is:
(1) get the aluminum hydroxide solid elastomer powder and low sodium silicon solution (Na ion concentration is less than 1000ppm) mixes, add entry and peptizing agent etc., siliceous alumina supporter is made in moulding drying, roasting.
(2) tungsten salt and nickel salt are added make the tungsten nickel aqueous solution in the entry.Molybdenum compound and boron compound are added in the ammonia soln, make stable Mo-B solution.
(3) get above-mentioned siliceous alumina supporter (rotary drum) in rotary container, be that 50～55% tungsten nickel solution of carrier saturated extent of adsorption sprays earlier with volume, rotated 10～30 minutes, and then be that 50～55% Mo-B solutions of carrier saturated extent of adsorption carry out second section and spray or carry out the supersaturation dipping with this solution with volume, the pH value that requires Mo-B solution is between 9～12.
(3`) or: get a certain amount of above-mentioned siliceous alumina supporter in rotary drum, be that 50～55% Mo-B solution of carrier saturated extent of adsorption sprays earlier with volume, requiring the pH value of Mo-B solution is between 6～9, rotated 10～30 minutes, and then be that 50～55% tungsten nickel solutions of carrier saturated extent of adsorption carry out second section and spray or carry out the supersaturation dipping with this solution with volume.
(4) catalyzer that finishes of dipping earlier 150～350 ℃ of following roastings 2～6 hours, 400～550 ℃ of following roastings 2～6 hours, makes catalyzer of the present invention through 100～130 ℃ of dryings 2～6 hours then.
The moulding of described siliceous alumina supporter adopts the forming technique of existing support of the catalyst to realize, such as: drip ball forming, extruded moulding, roller forming, compression molding etc.Wherein more specifically explanation is:
1. dripping ball forming is: after getting required aluminum hydroxide solid elastomer powder and low sodium silicon sol (Na ion concentration is less than 1000ppm) and mixing, with mineral acid or/and organic acid is made false colloidal sol, through oil ammonia column balling-up and curing, drying is 1～10 hour under 90～130 ℃, 500～700 ℃ of roasting temperatures 2～6 hours, make siliceous alumina supporter.
2. extruded moulding is: after getting required aluminum hydroxide solid elastomer powder and low sodium silicon sol and mixing earlier, pinch into plastic paste, extruded moulding on banded extruder with mixing as the mineral acid of peptizing agent and/or organic acid (for example nitric acid, hydrochloric acid, citric acid, oxalic acid, formic acid, acetate etc.), water, extrusion aid (as sesbania powder, Mierocrystalline cellulose, starch, gac etc.).The shape of carrier can change with the method for changing the banded extruder orifice plate, can be cylindrical, also can be special-shaped bar, carrier adopts the dry and roasting of condition same as described above to make siliceous alumina supporter after the moulding.
The physico-chemical property of siliceous alumina supporter is as follows: specific surface area 200～400m
2/ g, average pore diameter is 4.0～14nm, pore volume 0.4～0.8ml/g, the silicon-dioxide content in carrier is 5～20m%.Wherein the physico-chemical property of siliceous alumina supporter can be according to the requirement to finished catalyst, select different aluminum hydroxide solid elastomer powder raw materials and carrier condition of molding such as: factors such as the consumption of peptizing agent, maturing temperature and time are adjusted, and get final product according to a conventional method.
Owing to adopt the segmentation dipping technique, therefore require the concentration of dipping solution higher.It is that raw material adds the tungsten nickel solution that promptly can be made into high density in the entry that the described tungsten nickel aqueous solution preferably adopts ammonium metawolframate and nickelous nitrate.It consists of WO
31.0～3.5mol/l, NiO 1.0～2.5mol/l.
The preparation of described Mo-B solution, wherein molybdenum compound is preferably ammonium molybdate or molybdic oxide, boron compound is boric acid or ammonium borate preferably, its preparation process is that the ammonium molybdate (or molybdic oxide) that takes by weighing aequum and boric acid (or ammonium borate) add in the ammoniacal liquor and dissolves, heated 1～8 hour down at 40～90 ℃, between 30～40 ℃, placed 50～300 hours then, make it to become stable solution.Can pass through to add the pH value of ammoniacal liquor regulator solution between 9～12; The method that reduces Mo-B solution pH value is to carry out acidifying by concentration that reduces ammonia in the ammonia soln or adding acid, regulates Mo-B solution pH value between 6～9, and these acid can be nitric acid, oxalic acid, formic acid, acetate, hydrochloric acid etc.By the Mo-B solution that above-mentioned steps makes, it consists of MoO
31.0～2.5mol/l, B
2O
30.7～2.2mol/l.
Described supersaturation dipping refers to the solution impregnation of 1.5～3.0 times of volumes of carrier saturated extent of adsorption 0.5～2.0 hour.Zhi Bei catalyst used for hydrogenation of distilled oil fraction according to the method described above, with VIII family (as Fe, Co and/or Ni) and group vib (as Mo and/or W) metallic element is active ingredient, adds boron additive, is carrier with siliceous aluminum oxide, the pore volume of catalyzer is 0.2～0.5ml/g, and specific surface area is 100～200m
2/ g is a benchmark with the quality of catalyzer, and each components contents is SiO
23～10m%, WO
315～20m%, MoO
36～10m%, NiO 3～5m%, B
2O
32～5m%, all the other are aluminum oxide.This catalyzer can be used for the fraction oil hydrogenation refining process after sulfuration.
In a word, make catalyzer with roasting and compare through single-steeping, drying with the prior art that just makes catalyzer through twice dipping, drying and roasting at least by provided by the invention, simplified the Preparation of catalysts flow process, and activity of such catalysts is suitable with the catalyst activity of prior art for preparing, has therefore reduced the cost of catalyzer.Among the present invention rationally between control dipping solution acid-basicity, impregnating speed (or time), two sections dippings at regular intervals, suitably under the prerequisite of excess impregnation solution volume, after adopting two sections dipping methods, further adopt the segmentation roasting technology to make that activity of such catalysts component and auxiliary agent are uniformly dispersed at catalyst surface, the active maintenance do not descend, and the Preparation of catalysts flow process obtain simplifying.
Further specify advantage of the present invention and technical characterictic below by embodiment and Comparative Examples, but the present invention is confined to not only among this embodiment.
Embodiment 1
Present embodiment has been introduced the preparation process and the method for siliceous alumina supporter.
(Liaoning Province No.3 Petroleum Factory, Fushun Petroleum Chemical Industry Co. catalyst plant is produced, and contains Al to get aluminum hydroxide solid elastomer powder 1000g
2O
366.0m%) (the new light remover in Shenyang City factory produces, and the pH value is 9.3, contains SiO with the 160ml silicon sol
2: 30.0m%, Na
+Concentration is 300ppm) mix after, adding 1800ml concentration is in the salpeter solution of 1.25mol/l, false colloidal sol is made in stirring, drip ball, be solidified into the ball-type carrier through oil ammonia column then, through 90 ℃ of dryings 8 hours, siliceous alumina supporter A was made in 550 ℃ of following roastings in 4 hours, and its physico-chemical property is listed in the table 1.
(Shandong Province Chemical Fertilizer Factory No.1, Qilu Petrochemical Co. produces, and contains Al to get aluminum hydroxide solid elastomer powder 1000g
2O
366.0m%) mix earlier with the 300ml silicon sol, add 680ml again and contain the mixing solutions of nitric acid and acetic acid, wherein concentration of nitric acid is 0.80mol/l, acetate concentration is 0.50mol/l, mix and pinch even one-tenth paste plastic, be extruded into the cloverleaf pattern bar of 1.2mm on banded extruder, drying is 4 hours under 120 ℃, 550 ℃ of following roastings made siliceous alumina supporter B in 4 hours, and its physico-chemical property is listed in the table 1.
The physico-chemical property carrier S iO of the siliceous alumina supporter of table 1
2Specific surface area pore volume mean pore size shape and diameter
M% m
2/ g ml/g nm mmA 8.6 310 0.65 8.4 spheries 1.5～2.5B 14.1 230 0.67 11.7 trifolium, 1.2
The saturated water absorption that records baked siliceous alumina supporter A and B is every 100g carrier suction 80ml.
Embodiment 2
Present embodiment has been introduced the compound method of the tungsten nickel aqueous solution and molybdenum boron ammonia soln.
(1) measure ammonia soln, (technical grade contains MoO to add ammonium molybdate successively
382.7%) and boric acid (technical grade),, measures the pH value of solution value, placed 100 hours down, make and stablize Mo-B solution D, E, the results are shown in Table 2 at 40 ℃ 70 ℃ of heating 6 hours down.
Table 2 numbering ammonia soln heptamolybdate tetrahydrate pH value is formed (mol/l)
ml，mol/L g g MoO
3 B
2O
3D 785，6.70 370 180 8.5 2.13 1.47E 785，3.43 370 180 6.5 2.12 1.46
(2) measure 230ml water, (technical grade contains WO to add the 420g ammonium metawolframate successively
385.2m%) with 332g nickelous nitrate (technical grade, chemical industry four factories in Fushun, Liaoning Province produce), make tungsten nickel solution G after the stirring and dissolving, recording the pH value of solution value is 2.5, and it consists of WO
33.09mol/L, NiO 2.20mol/L.
Embodiment 3
Present embodiment has been introduced the dipping, drying, roasting process of catalyzer and to the influence of catalyst property.
(1) siliceous alumina supporter A and the B that gets among the embodiment 1 places rotary container (rotary drum) respectively, the Mo-B solution of getting earlier among the embodiment 2 sprays (with 10 minutes time), rotated 15 minutes after finishing, the tungsten nickel solution of getting again among the embodiment 2 sprays (with 10 minutes time), then through 120 ℃ of dryings 3 hours, with 60 ℃/hour of heat-up rates rise to different temperature, roasting makes catalyst I, I in air atmosphere
1, J, J
1, K, L, the preparation condition that it is concrete and catalyzer are formed and are listed in the table 3.
The table 3 catalytic carrier 1. molten roasting of the molten 2. tungsten of molybdenum boron nickel is formed (m%) agent g liquid, ml liquid, ml ℃ of/hour MoO
3, WO
3, NiO, B
2O
3I A/200 D/85 85 20,0/4 43,0/4 8.9 18.5 4.2 2.2I
1A/200 D/85 85--43,0/4 8.9 18.5 4.2 2.2J A/200 E/85,85 30,0/2 50,0/2 9.1 18.7 4.3 2.3J
1A/200 E/85 85--50,0/2 9.1 18.7 4.3 2.3K B/200 D/85,85 20,0/4 43,0/4 8.1 18.6 4.2 2.1L B/200 E/85 85 25,0/3 45,0/3 8.4 18.9 4.3 2.2
(2) get siliceous alumina supporter A among the embodiment 1 in rotary drum, the tungsten nickel solution of getting earlier among the embodiment 2 sprays (with 10 minutes time), rotated 15 minutes after finishing, the Mo-B solution of getting again among the embodiment 2 sprays (with 10 minutes time), then through 120 ℃ of dryings 3 hours, with 60 ℃/hour of heat-up rates rise to different temperature, roasting makes catalyst I in air atmosphere
2, J
2, preparation condition that it is concrete and catalyzer composition are listed in the table 4.
The table 4 catalytic carrier 1. molten roasting of the molten 2. molybdenum of tungsten nickel boron is formed (m%) agent g liquid, ml liquid, ml ℃ of/hour MoO
3, WO
3, NiO, B
2O
3I
2A/200 85 D/85 20,0/4 43,0/4 5.3 19.5 4.1 2.4J
2A/200 85 E/85 30,0/2 50,0/2 4.8 19.7 4.1 2.1
Because the saturated water absorption of baked siliceous alumina supporter A and B is every 100g carrier suction 80ml among the embodiment 1, so present embodiment sprays in the solution process every section and sprays used solution and all account for 53% of carrier saturated extent of adsorption.
For catalyst I and I
2, J and J
2, just tungsten nickel solution and Mo-B solution spray reversed in order, and all the other preparation conditions are all identical.From the compositional analysis result of catalyzer (see Table 3 and table 4) as can be seen: catalyst I
2, J
2Middle MoO
3Content on the low side.This is because tungsten nickel solution acidity strong (the pH value is 2.5), in catalyst I
2, J
2After spraying the tungsten nickel solution earlier in the preparation process, do not adsorb because of the component that sprays after making part in catalyst surface generation precipitin reaction when spraying Mo-B solution again.This embodiment explanation is if require when spraying the tungsten nickel solution earlier its acidity its alkalescence of Mo-B solution weak, that spray after requiring stronger, otherwise the catalyst activity components contents does not reach desired numerical value.
Embodiment 4
Present embodiment has been introduced the activity rating result of the catalyzer minisize reaction among the embodiment 3.
Is raw material to contain 50m% than the cyclohexane solution of pyridine, under identical condition, to catalyst I, I
1, I
2, J, J
1, J
2Carry out active contrast experiment, be reflected on the little anti-chromatographic system and carry out.Catalyzer is packed into behind the reactor, at first under 400 ℃ of hydrogen with hydrogen sulfide prevulcanized 2 hours, feed reaction raw materials then, be 4.0h in 330 ℃ of temperature of reaction, pressure 4.0MPa, air speed
-1, hydrogen-oil ratio (v/v) is to begin reaction under 2000 the condition, stable reaction was taken a sample after 3 hours, chromatography analysis, the thermal conductivity cell detection signal, reaction result is listed in the table 5.
Table 5 catalyzer micro-activity evaluation result catalyst I I
1I
2J J
1J
2Transformation efficiency % 57.8 55.3 47.1 58.3 53.4 45.7 denitrification percent % 26.4 20.5 15.2 26.5 19.8 14.3
From the data of table 5 as can be seen: the specific activity catalyst I of catalyst I
1Active high, the specific activity catalyzer J of catalyzer J
1Active high, illustrate and adopts after the segmentation roasting technology, the activity of such catalysts raising; Catalyst I
2And J
2Active minimum, the impregnation sequence of the potential of hydrogen that adopts rationally control Mo-B solution and tungsten nickel solution, solution is described after, activity of such catalysts does not more adopt the catalyst activity of this technology to improve.Thereby further proved that by present embodiment the impregnation sequence of Mo-B solution and tungsten nickel solution, the potential of hydrogen and the segmentation roasting of solution are the key factors that influences catalyst activity.
Comparative Examples 1
This Comparative Examples has compared by the catalyzer of the present invention's preparation with by patent of invention CN1052501A, the activity of such catalysts of CN1086534A preparation.
Method according to Chinese invention patent CN1052501A makes catalyzer M, makes catalyst n by the described method of CN1086534A, and the physico-chemical property of this reference catalyst and the catalyst I that is made by the inventive method, K is listed in the table 6.
The physico-chemical property catalyzer of table 6 catalyzer is formed (m%) pore volume specific surface area
SiO
2WO
3MoO
3NiO B
2O
3Ml/g m
2/ gM (reference 4.7 18.6 7.8 4.3 2.1 0.30 150N (reference 10.5 18.0 8.0 4.1 3.8 0.37 131 I 5.6 18.5 9.1 4.2 2.2 0.38 174 K 9.5 18.9 8.1 4.3 2.1 0.40 129
Getting catalyst I of the present invention and reference catalyst M after carrying out prevulcanized respectively on the 100ml small hydrogenation device, is raw material with the grand celebration coker gas oil, and character is listed in the table 7, is 400 at 360 ℃, hydrogen-oil ratio (v/v), volume space velocity is 2.0h
-1, total pressure is under the condition of 6.0MPa catalyzer to be carried out activity rating, the results are shown in Table 8.
Getting catalyzer K of the present invention and reference catalyst N after carrying out prevulcanized respectively on the 100ml small hydrogenation device, is raw material with triumph wax tailings (CGO), and character is listed in the table 7, is 800 at 350 ℃, hydrogen-oil ratio (v/v), volume space velocity is 0.8h
-1, total pressure is under the condition of 8.0MPa catalyzer to be carried out activity rating, the results are shown in Table 8.
Table 7 stock oil character stock oil title grand celebration coker gas oil triumph CGO density, (20 ℃) kg.m
-3826 913 boiling ranges, ℃ initial boiling point 202 25810% 232 37450% 278 41290%---47695% 336 512 does 342 539 sulphur, ppm 1,000 9800 nitrogen, ppm 1,095 6600
Table 8 catalyst activity evaluation result catalyst desulfurizing rate, the % denitrification percent, %I 98.2 93.6M (reference) 98.0 93.2K, 88.0 43.1N (reference) 87.4 42.5
By catalyst activity evaluation result in the table 8 as can be seen, catalyzer of the present invention is compared with reference catalyst, desulfurization under the identical operations condition, denitrification activity are suitable, and the present invention controls under the prerequisite of dipping solution acid-basicity rationally, after adopting two sections dipping methods, further adopt the segmentation roasting technology, simplified the Preparation of catalysts flow process, reduced the cost of catalyzer.
Claims (8)
1, a kind of preparation method of catalyst used for hydrogenation of distilled oil fraction is characterized in that adopting the technology of segmentation dipping, segmentation roasting, and concrete steps are:
(1) get the aluminum hydroxide solid elastomer powder and low sodium silicon solution mixes earlier, add entry and peptizing agent, siliceous alumina supporter is made in moulding drying, roasting;
(2) tungsten salt and nickel salt are added make the tungsten nickel aqueous solution in the entry, get molybdenum compound and boron compound and add in the ammonia soln, make stable Mo-B solution;
(3) get above-mentioned siliceous alumina supporter in rotary drum, be that 50～55% Mo-B solution of carrier saturated extent of adsorption sprays earlier with volume, requiring the pH value of Mo-B solution is between 6～9, rotated 10～30 minutes, and then be that 50～55% tungsten nickel solutions of carrier saturated extent of adsorption carry out second section and spray or carry out the supersaturation dipping with this solution with volume;
(4) catalyzer that finishes of dipping earlier 150～350 ℃ of following roastings 2～6 hours, 400～550 ℃ of following roastings 2～6 hours, makes catalyzer of the present invention through 100～130 ℃ of dryings 2～6 hours then.
2, according to the described preparation method of claim 1, it is characterized in that step (3) is for getting above-mentioned siliceous alumina supporter in rotary drum, earlier 50～55% tungsten nickel solution with the carrier saturated extent of adsorption sprays, rotated 10～30 minutes, and then be that 50～55% Mo-B solution of carrier saturated extent of adsorption carries out second section and sprays or carry out the supersaturation dipping with this solution with volume, require the pH value of Mo-B solution this moment is between 9～12.
3, according to claim 1 or 2 described preparation methods, it is characterized in that the tungsten nickel aqueous solution is the aqueous solution of ammonium metawolframate and nickelous nitrate, its concentration is WO
31.0～3.5mol/l, NiO 1.0～2.5mol/l.
4, according to claim 1 or 2 described preparation methods, the compound method that it is characterized in that molybdenum boron ammonia soln is that ammonium molybdate or molybdic oxide and boric acid or ammonium borate are joined in the ammoniacal liquor, heated 1～8 hour down at 40～90 ℃, between 30～40 ℃, placed 50～300 hours then, make and stablize molybdenum boron ammonia soln, its concentration is MoO
31.0～2.5mol/l, B
2O
30.7～2.2mol/l.
5,, it is characterized in that the supersaturation dipping described in the step (3) refers to the solution impregnation of 1.5～3.0 times of volumes of carrier saturated extent of adsorption 0.5～2.0 hour according to claim 1 or 2 described preparation methods.
6, a kind of catalyst used for hydrogenation of distilled oil fraction according to claim 1 or 2 described method preparations, it is characterized in that with VIII family and group vib metallic element be active ingredient, add boron additive, is carrier with siliceous aluminum oxide, the pore volume of catalyzer is 0.2～0.5ml/g, and specific surface area is 100～200m
2/ g is a benchmark with the quality of catalyzer, and each components contents is SiO
23～10%, WO
315～20%, MoO
36～10%, NiO 3～5%, B
2O
32～5%, all the other are aluminum oxide.
7,, it is characterized in that said group VIII metallic element is Fe, Co and/or Ni according to the described catalyzer of claim 6; The group vib metallic element is Mo and/or W.
8,, it is characterized in that can be used for the fraction oil hydrogenation refining process after this catalyst vulcanization according to the described catalyzer of claim 6.
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| CN99120515A CN1088087C (en) | 1999-09-17 | 1999-09-17 | Preparation of hydrogenation catalyst |
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|---|---|---|---|
| CN99120515A CN1088087C (en) | 1999-09-17 | 1999-09-17 | Preparation of hydrogenation catalyst |
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| CN1088087C true CN1088087C (en) | 2002-07-24 |
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| CN100441272C (en) * | 2002-11-06 | 2008-12-10 | 中国石油化工股份有限公司 | Catalyzer for hydrogenation on tail gas of sulphur and its prepn. method |
| KR100725216B1 (en) | 2003-05-15 | 2007-06-07 | 후아웨이 테크놀러지 컴퍼니 리미티드 | A system and method for providing rbt in communication network |
| CN1840618B (en) * | 2005-03-31 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst with silicon oxide-alumina as carrier and its preparation |
| CN103537287B (en) * | 2012-07-12 | 2015-12-09 | 中国石油化工股份有限公司 | Concentrate pore size distribution nickel-base catalyst and preparation method thereof |
| CN105642269B (en) * | 2016-02-26 | 2018-07-27 | 江西国瓷博晶新材料科技有限公司 | A kind of compound cerium zirconium sosoloid and preparation method thereof |
| CN113042048B (en) * | 2021-03-23 | 2024-01-30 | 江苏三一环境科技有限公司 | VOCs (volatile organic compounds) treatment catalyst and preparation method and application thereof |
| CN114471553A (en) * | 2022-01-26 | 2022-05-13 | 厦门怡烁氢能源科技有限公司 | Preparation and application of rare earth modified catalyst for ammonia decomposition hydrogen production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052501A (en) * | 1989-12-11 | 1991-06-26 | 中国石油化工总公司抚顺石油化工研究院 | Hydrobon catalyst and method for making |
| CN1086534A (en) * | 1992-11-05 | 1994-05-11 | 中国石油化工总公司抚顺石油化工研究院 | A kind of heavy-oil hydrogenation denitrification catalyst |
-
1999
- 1999-09-17 CN CN99120515A patent/CN1088087C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052501A (en) * | 1989-12-11 | 1991-06-26 | 中国石油化工总公司抚顺石油化工研究院 | Hydrobon catalyst and method for making |
| CN1086534A (en) * | 1992-11-05 | 1994-05-11 | 中国石油化工总公司抚顺石油化工研究院 | A kind of heavy-oil hydrogenation denitrification catalyst |
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| CN1288935A (en) | 2001-03-28 |
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