CN1597869A - Hydrogenating refining catalyst for petroleum wax stuff and its preparation process - Google Patents

Abstract

The invention discloses a petroleum wax hydrofining catalyst and its preparing method, using Wu, Mo and Ni (or Co) as active metals and using the aluminum oxide containing Si and P auxiliaries to act as a carrier and its preparing method: it dips the aluminum oxide carrier in the Wu-Ni/Co water solution and the Mo-B water solution, respectively, so as to make it. The aluminum oxide carrier is prepared by using the Si-containing aluminum hydroxide prepared by CO2 neutralization process and then adding in the P-containing compound in the forming process. Its preparing process is simple and low-cost. The invention can effectively regulate the physico-chemical property of a catalyst by the cooperative regulation of the two compound auxiliaries, making the catalyst have reasonable aperture structure and proper surface acidic property. This catalyst can process the petroleum waxes including high-melting point petroleum wax and produce food-grade petroleum wax products.

Description

A kind of oil wax material Hydrobon Catalyst And Its Preparation Method

Technical field

The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, particularly a kind of oil wax material Hydrobon Catalyst And Its Preparation Method.

Background technology

The Wax hydrofining purpose is intended to keep the essentially consist of normal paraffin, removes with 3, and the 4-benzopyrene is sulphur, nitrogen and the oxygen etc. of carcinogenic substances such as the condensed-nuclei aromatics of representative and non-hydrocarbons.In order to make the wax material molecule fully carry out chemical reaction in catalyst active center, catalyzer must have big specific surface, large pore volume and unimpeded duct, for reactant and product molecule provide ideal reacting environment.In addition, the hydrorefining paraffin wax process is the very strong reaction process of selectivity, and it is saturated to make unsaturated components such as impurity removals such as sulphur, nitrogen and oxygen in the paraffin and condensed-nuclei aromatics be able to hydrogenation.Simultaneously, this process does not allow to take place cracking reaction, otherwise will cause the increase of wax material oleaginousness and penetration degree.For this reason, catalyzer should have the few solid acid and based on slightly acidic of trying one's best.

At present, most Wax hydrofining catalyst all adopts Mo-Ni/Al ₂O ₃Form, promoter material is generally siliceous and phosphorus, and what have also contains basic metal and alkaline-earth metal.The purpose of introducing auxiliary agent in the catalyzer be regulate the porous and the surface acid property of catalyzer and/or improve active ingredient and carrier between interaction, to be fit to of the requirement of oil wax material unifining process to the catalyzer physico-chemical property.

CN1210882A relates to a kind of nickelic tungsten type catalyst for hydrogenation refining of Vaseline, and its Ni/W (mole) value is 0.90～1.10, and the metal content of catalyzer is WO by weight ₃26～32%, NiO8～12%, Ni/W (mol ratio) is 0.90～1.10, its WO ₃The content height helps the aromatic hydrocarbons saturated reaction.Method for preparing catalyst also is at P ₂O ₅-SiO ₂-Al ₂O ₃Dipping W-Ni solution on the carrier owing to have a large amount of pollutents to discharge in its preparing carriers process (by the preparation of CN1032408C method) complexity and the preparation process, causes the raising of environmental pollution and catalyzer cost.

US4186078 has narrated a kind of Wax hydrofining catalyst, wherein contains 5wt%～25wt% silicon-dioxide in the alumina supporter, the basic metal of 0.2wt%～5.0wt%.Add alkaline components on the carrier,,, prevent that acid from measuring and strength of acid is excessive and the wax material overcracking generates oil so that be fit to the Wax hydrofining process to regulate the acid matter of catalyzer.But cause alkali-metal loss easily, make and contain basic metal in the product or pollute corrosion device, influence the life-time service of device.

CN 1032408C has narrated a kind of Wax hydrofining catalyst, is active ingredient with Mo, Ni, with P ₂O ₅-SiO ₂-Al ₂O ₃Be carrier.This catalyzer contains MoO ₃18～24wt%, NiO4～6wt%.This Preparation of catalysts process: use in the ammoniacal liquor and the silicon behind low temperature aging-aluminium mixed sols, after filtering, washing, with phosphoric acid and nitric acid peptization, by the oil ammonia column moulding, drying and roasting get P more then ₂O ₅-SiO ₂-Al ₂O ₃Carrier with the aqueous solution dipping that contains molybdenum and nickel, makes catalyzer then.When the wet gel peptization, introduce phosphoric acid, with strong acid center and the minimizing total acid content of eliminating carrier; Carrier just can only be prepared into ball type carrier by the oil ammonia column moulding, and this balling-up process complexity, causes yield low through overmolding, drying, screening process, preparing carriers cost height.Though when the dipping reactive metal, use measures such as vacuum impregnation or reduction impregnating speed, cause the spheroidal particle fragmentation inevitably, make yield low, cause catalyzer cost height.

Summary of the invention

The object of the present invention is to provide a kind of oil Wax hydrofining catalyst that porous is good, surface acid property suitable, activity is high that has, the invention provides a kind of with low cost, simple above-mentioned Preparation of catalysts method of preparation flow that has simultaneously.

Oil Wax hydrofining catalyst of the present invention has following character, and the activity of such catalysts metal component is two or more in vib metal and the group VIII metal, is preferably tungsten, molybdenum and nickel or cobalt, and auxiliary agent contains Si and P.The composition of catalyzer of the present invention comprises: the weight with catalyzer is benchmark, and tungstic oxide content is 10.0%～40.0%, is preferably 12.0%～30.0%, is preferably 15.0%～25.0%; Molybdic oxide content is 4.0%～30.0%, is preferably 5.0%～20.0%, is preferably 6.0%～15.0%; Nickel oxide or cobalt contents are 5.0%～16.0%, are preferably 6.0%～14.0%, are preferably 8.0%～12.0%; SiO ₂Content is 2.0%～10.0%, is preferably 3.0%～8.0%, and P content is 1.0%～5.0%, is preferably 1.0%～3.0%, and the content of boron oxide is 0%～2.0%, is preferably 0～1.0%.The mol ratio of (Ni or Co)/(W+Mo+Ni or Co) is 0.40～0.60, and wherein the mol ratio of W/Mo is 0.50～2.00.Be preferably (Ni or Co)/mol ratio of (W+Mo+Ni or Co) is 0.40～0.50, wherein the mol ratio of W/Mo is 0.80～1.50.The mean pore size of this catalyzer is 7.0～12.0nm, and specific surface is 150～260m ²/ g, pore volume are 0.30～0.55cm ³/ g, tap density is 0.80～1.00g/ml, at the pore volume integration rate of 4～15nm is＞85v%.

Catalyzer of the present invention by the measured acid amount of meleic acid distribution is: the total acid content in the time of 160 ℃ is 200 μ mol/g～500 μ mol/g, be preferably 300 μ mol/g～400 μ mol/g, wherein protonic acid (B acid) acid amount is 30 μ mol/g～100 μ mol/g, be preferably 30 μ mol/g～90 μ mol/g, be preferably 30 μ mol/g～70 μ mol/g.Total acid content in the time of 250 ℃ is 150 μ mol/g～350 μ mol/g, is preferably 190 μ mol/g～250 μ mol/g, and wherein protonic acid (B acid) acid amount is 20 μ mol/g～60 μ mol/g, is preferably 30 μ mol/g～50 μ mol/g; Total acid content in the time of 350 ℃ is 70 μ mol/g～140 μ mol/g, is preferably 80 μ mol/g～120 μ mol/g, and wherein protonic acid (B acid) acid amount is 0 μ mol/g～40 μ mol/g, is preferably 0 μ mol/g～30 μ mol/g.Its infrared acidity changes along with the variation of auxiliary agent Si and P content.

Reactive metal and phosphorus, silicon are uniformly dispersed at alumina surface.Deployment conditions for reactive metal in the detecting catalyst and auxiliary agent, adopt sem test reactive metal and two kinds of auxiliary agents of Si, P deployment conditions at alumina surface, Preparation of Catalyst of the present invention is become cylindrical strip thing, by reactive metal and the Si, P two kind auxiliary agent content distribution situation of scanning electron microscope analysis from the cross section center of bar to outside surface, can find out reactive metal and Si, the P distribution situation at alumina surface effectively, scanning electron microscope analysis of the present invention the results are shown in table 1 (with colorimetrically analysing WO ₃Content is 20.0wt%, MoO ₃Content is 9.0wt%, and NiO content is 6.0%, SiO ₂Content is 6.0wt%, P ₂O ₅Content is that 3.0wt% is an example).As can be seen from Table 1, the average content height of two kinds of auxiliary agents of reactive metal and silicon and phosphorus each point in the square section is consistent, can illustrate that reactive metal and silicon and phosphate builder are in the alumina surface high dispersing.

The alumina carrier surface reactive metal that table 1 scanning electron microscope method is analyzed and the distribution situation of auxiliary agent

	Center 0.0R *	????0.25R	????0.5R	????0.75R	????R
						??WO 3/wt％	????19.90	????19.92	????19.96	????20.00	????20.12
??MoO 3/wt％	????8.90	????8.95	????9.00	????9.05	????9.10
						??NiO/wt％	????5.97	????5.98	????6.01	????6.05	????6.03
??SiO 2/wt％	????6.05	????6.03	????5.98	????6.03	????6.01
						??P 2O 5/wt％	????2.95	????2.99	????3.01	????3.04	????3.02
??Al 2O 3/wt％	????56.23	????56.13	????56.04	????55.85	????55.72

Annotate: ^*R be cylinder strip cross section radius.

Preparation of catalysts method of the present invention may further comprise the steps:

(1) in siliceous aluminium hydroxide, add the phosphorated compound mix pinch, moulding, drying, roasting, make siliceous and phosphorus oxidation alumina supporter;

(2) aqueous solution of preparation tungstenic-nickel or cobalt and the alkaline aqueous solution that contains molybdenum-boron;

(3) with the aqueous solution of (1) prepared alumina supporter dipping tungstenic-nickel or cobalt, after drying, the roasting, make catalyst intermediate;

(4) flood the solution that contains molybdenum-boron with (3) prepared catalyst intermediate, after drying, the roasting, get final catalyst prod.

The preparation process of the siliceous aluminium hydroxide carrier that catalyzer of the present invention is used may further comprise the steps:

(1) preparation sodium aluminate solution, silicon-containing compound solution;

(2) under agitation condition, sodium aluminate solution, a part of silicon-containing compound solution (or not adding silicon-containing compound solution) are reacted into glue with carbon dioxide, material solution or slurries mix the back and feed carbon dioxide and become glue or wherein one or both to add into glue continuously when feeding carbonic acid gas, stop to feed carbon dioxide after becoming glue to finish, aging then, filtration; Wherein the add-on of silicon-containing compound solution is 0%～50% of its total add-on;

(3) with adding remainder (or wholes') silicon-containing compound solution behind step (2) the gained filter cake pulping again, wear out again, filter, filter cake washing, drying gets siliceous aluminium hydroxide.

Catalyzer of the present invention has rational pore structure, promptly has the pore distribution of suitable pore volume and specific surface area and high concentration; Catalyzer of the present invention contains three kinds of active metal components, and has suitable reactive metal molar ratio, can allocate of the interaction of each active ingredient effectively at alumina surface, especially suitably improve nickel or the cobalt mol ratio in whole reactive metals, can effectively improve the anti-coking performance of activity of such catalysts level and catalyzer; This catalyzer has suitable surface acid property and strength of acid, and the paraffin cracking of having avoided taking place when using this catalyzer takes place, and makes catalyzer have good selectivity; In a word, catalyzer of the present invention has the saturated performance of good activity, selectivity and aromatic hydrocarbons.

Siliceous and phosphorus composite assistant alumina supporter of the present invention is siliceous aluminium hydroxide and the P contained compound mixing extruded moulding that adopts Carbonization Preparation, and silicon and phosphorus are uniformly dispersed at carrier surface, do not influence the pore structure of aluminum oxide.Siliceous aluminium hydroxide of the present invention is to introduce cheap siliceous compound in the process of Carbonization Preparation aluminium hydroxide, and this preparation technology is simple, does not have pollutent to discharge, non-environmental-pollution, and cost is low; Silicon-dioxide is uniformly dispersed at alumina surface simultaneously, has prevented the influence of process to the aluminum oxide microtexture.The siliceous aluminium hydroxide of the present invention has good peptization, particularly improved the silicon content shortcoming of its peptization variation more for a long time, make that moulding is easy when using siliceous preparation of aluminium hydroxide support of the catalyst of the present invention or catalyzer, and then the Preparation of Catalyst cost is reduced.

Two kinds of auxiliary agents of silicon of the present invention and phosphorus add in the preparation process of the building-up process of raw material and carrier respectively, can effectively regulate the porous and the surface acid property of carrier by the collaborative regulating effect of these two kinds of auxiliary agents, add phosphate builder, can effectively reduce separately surface acid amount and strength of acid by the siliceous alumina supporter of siliceous preparation of aluminium hydroxide, can effectively regulate the pore volume and the specific surface area of carrier, more effectively regulate simultaneously the activity of such catalysts metal of preparing carriers and the interaction strength of aluminum oxide thus, more help the sulfuration of catalyst activity metal and the performance of catalyst activity.High activated catalyst of the present invention also can be used as the deep desulfuration denitrification catalyst and falls the Hydrobon catalyst of arenes catalytic agent etc., according to different processing purpose, the mole of suitably regulating the content of silicon and two kinds of auxiliary agents of phosphorus in the carrier and silicon and phosphorus is the porous and the surface acid property of carrier when.

Embodiment

The concrete preparation process of catalyzer of the present invention is as follows:

(1), the preparation of siliceous aluminium hydroxide, may further comprise the steps:

A, preparation sodium aluminate solution, its concentration is 5gAl ₂O ₃/ l～60gAl ₂O ₃/ l; Preparation silicon-containing compound solution, sodium silicate solution (being commonly called as water glass) preferably, its concentration is 5gSiO ₂/ l～40gSiO ₂/ l.

B, under agitation condition, with sodium aluminate solution, a part of silicon-containing compound solution (add-on account for its total add weight 0%～50%) with concentration be that (preferably the carbon dioxide of 20v%～40v%) is reacted into glue to 10v%～50v%, material solution or slurries mix the back and feed carbon dioxide and become glue or wherein one or both to add into glue continuously when feeding carbonic acid gas, when being 9～12, the pH value stops logical carbonic acid gas, aging then, filtration.Wherein said one-tenth glue temperature is controlled at 15 ℃～35 ℃ according to the porous of needed siliceous aluminium hydroxide, is preferably between 15 ℃～30 ℃, is preferably between 18 ℃～25 ℃; Can wear out and also can not wear out, digestion time is 0 minute～60 minutes, preferably aging 10 minutes～60 minutes.

Wherein, the adding mode of various material solutions can specifically be selected as required among the step b, as adopting following manner: carbon dioxide is fed sodium aluminate solution, add silicon-containing compound solution with certain flow simultaneously; Or, feed carbon dioxide then with adding silicon-containing compound in the sodium aluminate solution; Other order of addition(of ingredients) also can specifically be selected as required.

C, with behind the step b gained filter cake pulping, under whipped state, add the silicon-containing compound solution of remainder again, be preferably 40 minutes～80 minutes, be preferably 40 minutes～60 minutes, aging again 10 minutes～120 minutes, control reaction temperature was 20 ℃～35 ℃, filter then filter cake.With ordinary method washing 1～6 time, or add volatile salt salt material, carry out ammonium radical ion and Na ion-exchange, make Na ⁺Washing be more prone to, washing effect is better, until the preparation aluminium hydroxide in contain Na ⁺By weight＜0.05%.The control wash temperature is at 40 ℃～80 ℃, and washing times is preferably 3 times～6 times.Under 80 ℃～180 ℃, preferred 100 ℃～150 ℃ following dryings 2 hours～12 hours promptly get siliceous aluminium hydroxide then.

(2) preparation of siliceous and phosphorus oxidation alumina supporter

A, take by weighing a certain amount of siliceous aluminium hydroxide, add a kind of phosphorated compound and mix, add the peptization acid of calculated amount and deionized water then and mix and pinch, the mixed plastic of pinching into of material;

B, then with the moulding on shaper of above-mentioned plastic, be prepared into bar, again with bar under 80～150 ℃ condition dry 2～8 hours, roasting 2～6 hours under 500～800 ℃ condition then makes siliceous and the phosphorus oxidation alumina supporter.

Wherein, the P contained compound described in the step a is ammonium phosphate salt or phosphoric acid.In order to prepare than large pore volume and phosphorus solid support material in the carrier surface high dispersing, can select ammonium phosphate salt material to mix kneading fully with the form and the siliceous aluminium hydroxide of the aqueous solution, also can adopt phosphoric acid, phosphoric acid is mixed the preparation of pinching bar as the part of peptization acid, phosphoric acid is a kind of mineral acid of medium tenacity, the dilute aqueous soln of phosphoric acid can fully contact with aluminum oxide, can reach the effect of phosphorus in the alumina surface high dispersing.Remaining peptization acid can be one or more of acetate, nitric acid, hydrochloric acid etc., and is less for the influence that the pore volume that makes carrier is subjected to, and should select acid more weak acetate as peptization acid.

The prepared siliceous and phosphorus oxidation alumina supporter of the present invention has following character: pore volume is 0.50～1.00ml/g, and specific surface area is 260～350m ²/ g, pore distribution concentration accounts for more than the 85v% of total pore volume at the pore volume integration rate of 6～20nm, and mean pore size is 8.0nm～14.0nm.

(3) Preparation of catalysts

The process for preparation of tungstenic-nickel aqueous solution is: water miscible Tungstenic compound is added in the deionized water, stir and dissolve, add nickel compound containing again after the Tungstenic compound dissolving finishes, stirring and dissolving is filtered then, filters insolubles in the compound, filtrate is placed stand-by, WO in the solution ₃Concentration and the concentration of NiO can decide according to the water-intake rate of carrier and the component concentration of design catalyzer, W-Ni solution.

Tungstenic compound is ammonium tungstate or ammonium metawolframate in tungsten-nickel solution, and nickel compound containing is water-soluble nickel salts such as nickelous nitrate, nickelous chloride or nickelous acetate, and cobalt compound is Xiao Suangu or cobalt chloride etc.

The process for preparation that contains molybdenum-boron aqueous solution is: ammonium molybdate is dissolved in the ammonia soln, and stirring and dissolving in encloses container, and to make the temperature of solution be 50～80 ℃, after the ammonium molybdate dissolving, adds boron-containing compound, stirring and dissolving.MoO in the solution ₃Content can reach 38.0g/100ml, according in the variation of support of the catalyst water-intake rate and the catalyzer to MoO ₃MoO in the solution is suitably adjusted in the requirement of content ₃Concentration, Mo-B solution.

Ammonium molybdate is ammonium tetramolybdate or water miscible Ammonium Heptamolybdate in the Mo-B solution, and the concentration of ammoniacal liquor is 3.0g～14.0g/100g solution, according to MoO ₃The concentration of ammonia in the ammoniacal liquor is suitably adjusted in the variation of concentration.Boron-containing compound is a boric acid, and one of purpose that adds boric acid in this solution is the stability that keeps solution, and another purpose is to make molybdenum compound more even in the catalyzer dispersion, sometimes for needs, can not add boron-containing compound in the solution.

The preparation of catalyst intermediate: with the siliceous and phosphorus oxidation alumina supporter dipping tungstenic-nickel of gained in the step (2) or the aqueous solution of cobalt, following dry 3～12 hours at 50 ℃～150 ℃ then, 400 ℃～500 ℃ following roastings 2～6 hours, the preparation catalyst intermediate.

Final Preparation of catalysts: above-mentioned catalyst intermediate dipping is contained the aqueous solution of molybdenum-boron, then 60 ℃～190 ℃ dry 2～8 hours down, 450 ℃～600 ℃ following roastings 2～5 hours, final catalyst prod.

Further specify technical solution of the present invention by the following examples.

Embodiment 1

(1) preparation of siliceous aluminium hydroxide

With concentration is 30gAl ₂O ₃The sodium aluminate solution of/l places in the glue jar, 20 ℃ of controlled temperature, and adding concentration is 20gSiO ₂The sodium silicate solution of/l stirs, and the water glass of adding is with SiO ₂The content of meter in siliceous aluminium hydroxide is 2.0% by weight, feeding concentration is the carbon dioxide of 30v%, until slurry pH value is to stop logical carbon dioxide at 11 o'clock, slurries are aging 0.5hr under whipped state, filter then, filter cake adds the deionized water reslurry and stirs, and adds the remainder sodium silicate solution of calculated amount then, makes silicon-containing compound with SiO ₂The final content of meter in siliceous aluminium hydroxide is 8.0wt%, and then aging 0.5 hour, filter, wash 4 times, make to contain Na in the carrier ⁺By weight＜0.05%, dry (110 ℃) 4 hours are crushed to 180 orders again, promptly make siliceous aluminium hydroxide Al.

(2) preparation of the alumina supporter of siliceous phosphorus composite assistant

Get the prepared Powdered siliceous aluminium hydroxide of 1000g step (1) (contents on dry basis is 70wt%), the phosphate aqueous solution of 500g 10wt% is mixed with 25g acetic acid solution and 400g deionized water, mixing solutions joins in the siliceous aluminium hydrate powder, in small-sized kneader, mediated 2.0 hours, material mixed pinch into plastic, in banded extruder, be prepared into bar then, then 100 ℃ of dryings 6.0 hours, and roasting 4.0 hours under 600 ℃ condition, carrier A 2.

(3) Preparation of catalysts

Catalyst intermediate preparation: record the water-intake rate of carrier A 2, prepare the aqueous solution of tungstenic and nickel according to water-intake rate, the siliceous and phosphorus oxidation aluminium that step (2) is made floods this solution then, makes content in final catalyzer in oxide weight, WO ₃Be 19.5%, NiO is 7.5%.Under 150 ℃ condition dry 6 hours, roasting 4 hours under 400 ℃ condition then, catalyst intermediate A3.

Final Preparation of catalysts: record the water-intake rate of carrier A 3, preparation contains the alkaline aqueous solution of molybdenum and boron according to water-intake rate, and above-mentioned catalyst intermediate is flooded this solution, makes content in final catalyzer in oxide weight, MoO ₃Be 9.5%, B ₂O ₃Be 1.0%, under 180 ℃ condition dry 6 hours, roasting 3 hours under 500 ℃ condition then, final catalyst prod A.

Embodiment 2

(1) preparation of siliceous aluminium hydroxide is identical with embodiment 1 (1);

(2) preparation of the alumina supporter of siliceous and phosphorus composite assistant is identical with embodiment 1 (2);

(3) Preparation of catalysts

Compare with (3) among the embodiment 1, increase WO in the solution ₃Concentration, make in the final catalyzer, in oxide weight, WO ₃Content is 25.6%; NiO content is 7.6%.Reduce MoO in molybdenum-B solution ₃Content, make MoO in the final catalyzer ₃Content is 6.5%, and all the other are identical with (3) among the embodiment 1.Promptly get final catalyst prod B.

Embodiment 3

(1) preparation of siliceous aluminium hydroxide is identical with embodiment 1 (1);

(2) preparation of the alumina supporter of siliceous and phosphorus composite assistant is identical with embodiment 1 (2);

(3) Preparation of catalysts

Compare with (3) among the embodiment 1, reduce WO in the solution ₃Concentration, suitably increase the concentration of NiO in the solution, make in the final catalyzer, in the weight of oxide compound, WO ₃Content is 15.6%, and NiO content is 8.5%; Increase MoO in molybdenum-B solution ₃Content, make MoO in the final catalyzer ₃Content is 14.5%, and all the other are identical with (3) among the embodiment 1.Promptly get final catalyst prod C.

Embodiment 4

(1) preparation of siliceous aluminium hydroxide is identical with embodiment 1 (1);

(2) preparation of the alumina supporter of siliceous and phosphorus composite assistant

Compare with embodiment 1 (2), change maturing temperature into 700 ℃, roasting 3 hours, all the other are identical with embodiment 1 (2), get carrier D2.

(3) Preparation of catalysts is compared with (3) among the embodiment 1, makes that in the weight of oxide compound, the content of NiO is 7.8% in the final catalyzer, and all the other are identical with (3) among the embodiment 1, promptly get final catalyst prod D.

Embodiment 5

(1) preparation of siliceous aluminium hydroxide is identical with embodiment 1 (1);

(2) preparation of the alumina supporter of siliceous and phosphorus composite assistant

Compare with (2) among the embodiment 1, choose phosphorated ammonium salt class material and replace phosphoric acid, taking by weighing primary ammonium phosphate 60.0g is dissolved in the 450g deionized water, acetic acid solution changes 50.0g into and joins in the 380g deionized water, earlier ammonium dihydrogen phosphate aqueous solution is joined and carry out premix in the siliceous aluminium hydrate powder and pinched 1.5 hours, add acetic acid aqueous solution then, carry out fully mixing pinching into plastic.All the other are identical with (2) among the embodiment 1, get carrier E2.

(3) Preparation of catalysts

Compare with embodiment 1 (3), make in the final catalyzer, in the weight of oxide compound, WO ₃Content is 19.6%, MoO ₃Content is 9.9%, and should be Xiao Suangu with the nickelous nitrate in the solution, and to make the content of CoO on catalyzer be 8.0%, and all the other are identical with (3) among the embodiment 1, promptly get final catalyst prod E.

Embodiment 6

(1) preparation of siliceous aluminium hydroxide

Compare with embodiment 1 (1),, the remainder sodium silicate solution add-on behind the filter cake reslurry is improved, make silicon-containing compound with SiO becoming the glue after-filtration ₂The content of meter in siliceous aluminium hydroxide is 12.0wt%, and the unclassified stores consumption is identical with embodiment 1 (1) with operational condition, gets siliceous aluminium hydroxide F1.

(2) preparation of the alumina supporter of siliceous and phosphate builder is identical with embodiment 1 (2), carrier F2.

(3) Preparation of catalysts

Compare with embodiment 1 (3), make in the final catalyzer, in the weight of oxide compound, NiO content brings up to 11.5%, WO ₃Content is 19.7%, MoO ₃Content is 10.1%, and the mol ratio that makes Ni/ (W+Mo+Ni) is 0.50, and other is identical with embodiment 1 (3), promptly gets final catalyst prod F.

Embodiment 7

(1) preparation of siliceous aluminium hydroxide

Compare with embodiment 1 (1),, the remainder sodium silicate solution add-on behind the filter cake reslurry is improved, make silicon-containing compound with SiO becoming the glue after-filtration ₂The content of meter in siliceous aluminium hydroxide is 16.0wt%, and the unclassified stores consumption is identical with embodiment 1 (1) with operational condition, gets siliceous aluminium hydroxide G1.

(2) preparation of the alumina supporter of siliceous and phosphate builder is identical with embodiment 1 (2), carrier G2.

(3) Preparation of catalysts is compared with embodiment 1 (3), makes in the final catalyzer, and in the weight of oxide compound, NiO content is 7.6%, WO ₃Content is 19.4%, MoO ₃Content is 9.3%, and other are with real

Execute example 1 (3), promptly get final catalyst prod G.

Embodiment 8

(1) preparation of siliceous aluminium hydroxide

Compare with embodiment 1 (1), will become the add-on of glue process mesosilicic acid sodium solution to improve, the water glass that makes adding be with SiO ₂The content of meter in siliceous aluminium hydroxide is 4.0% by weight, and the unclassified stores consumption is identical with embodiment 1 with operational condition, gets siliceous aluminium hydroxide H1.

(2) preparation of the alumina supporter of siliceous and phosphorus composite assistant is identical with embodiment 1 (2), carrier H2.

(3) Preparation of catalysts is compared with embodiment 1 (3), makes in the final catalyzer, in the weight of oxide compound, WO ₃Content is 19.7%, and NiO content is 8.5%, and other is identical with embodiment 1 (3), promptly gets final catalyst prod H.

Comparative example 1

Employing is according to the commercially available hydrorefining paraffin wax special-purpose catalyst 481-2B of patent CN 1032408C method preparation, and this catalyst activity metal component is Mo-Ni, has bigger pore volume and specific surface area.

Embodiment 9

Present embodiment is that the carrier physico-chemical property of above embodiment and comparative example characterizes and activity rating result and comparison.During evaluate catalysts, raw materials used wax is No. 59 ketone benzin system waxes, and processing condition are: hydrogen dividing potential drop 6.0MPa, temperature is 260 ℃, volume space velocity 1.5h ^-1, (v), evaluation result sees Table 3 to hydrogen wax than 120.

The physico-chemical property of the catalyzer that each embodiment and comparative example are prepared is listed in table 2.The measuring method of meleic acid is to adopt the acid matter of infrared spectroscopic determination.The method that the present invention adopts is to utilize pyridine (C ₅H ₅N) lip-deep L acid of determining adsorption oxide compound (the present invention refers to siliceous aluminum oxide) and B acid promptly utilize at 1640cm ^-1～1500cm ^-1And 1500cm ^-1～1440cm ^-1Difference on the range of spectra can be distinguished the physical adsorption pyridine and be coordinated to the pyridine at L acid position and the pyridine that is adsorbed on B acid position, according to the amount of how much coming to determine oxide surface L acid and B acid of absorption pyridine amount.

The physico-chemical property of catalyzer among each embodiment of table 2

Physico-chemical property	??WO 3?/wt％	???MoO 3???/wt％	??NiO ??/wt％	Ni or the Co mol ratio in the gross activity metal	?SiO 2?/wt％	???P ?/wt％	Pore volume/cm 3·g -1	Specific surface area/m 2·g -1	Bulk density/gml -1	Mean pore size/nm	4～15nm pore volume integration rate/%	Meleic acid distribution/μ molg -1
															160 ℃ of total acid/B acid	250 ℃ of total acid/B acid	350 ℃ of total acid/B acid
												?A	?19.5	????9.5				??7.5	????0.40	??5.0	??1.0	????0.45	????190	????0.90	????9.5	????90	??350/85	??256/35	???85/20
?B	?25.6	????6.5	??7.6	????0.40	??5.2	??1.1	????0.43	????185	????0.93	????9.3	????92				??325/70	??245/30	???90/10
												?C	?15.6	????14.5				??8.5	????0.40	??5.1	??1.2	????0.48	????210	????0.84	????9.1	????87	??375/89	??273/45	???85/23
?D	?19.5	????9.5	??7.8	????0.41	??5.0	??1.0	????0.53	????184	????0.91	????11.5	????88				??340/66	??255/35	???75/10
												?E	?19.6	????9.9				??8.0 ??(CoO)	????0.41	??4.9	??0.9	????0.45	????199	????0.86	????9.0	????86	??355/65	??245/40	???78/12
?F	?19.7	????10.1	??11.5	????0.50	??7.5	??1.1	????0.44	????201	????0.87	????8.8	????87				??395/95	??285/55	???95/25
												?G	?19.4	????9.3				??7.6	????0.41	??9.5	??1.0	????0.45	????210	????0.88	????8.6	????89	??376/76	??274/30	???94/21
?H	?19.7	????9.5	??8.5	????0.43	??2.5	??1.1	????0.42	????194	????0.89	????8.7	????86				??342/76	??255/23	???80/10
												Comparative example 1	?-	????17.5				??4.2	????0.32	??4.5	??1.8	????0.52	????234	????0.80	????8.9	????88	??305/20	??175/12	???50/10

Each routine catalyst activity evaluation result of table 3

The catalyzer numbering	Raw material	????A	????B	????C	????D	????E	????F	????G	????H	Comparative example 1
											Fusing point/℃	?59.2	??59.2	???59.3	???59.1	??25.2	??58.4	??59.3	???59.3	???59.3	???58.1
Oleaginousness/% (m/m)	?0.21	??0.22	???0.22	???0.23	??0.21	??0.21	??0.23	???0.23	???0.23	???0.24
											Color/(Sai Shi) number	?+10	??＞+30	???＞+30	???＞+30	??＞+30	??＞+30	??＞+30	???＞+30	???＞+30	???+30
Light stability/number	?5～6	??2～3	???2～3	???2～3	??2～3	??2～3	??2～3	???2～3	???2～3	???3～4
											Heat-resistant quality/(Sai Shi) number	?+5	??+28	???+29	???+28	??+28	??+28	??+29	???+28	???+28	???+27
Readily carbonizable substance	Do not pass through	By	By	By	By	By	By	By	By	By
											Condensed-nuclei aromatics, ultraviolet absorptivity/cm
280～289nm is not more than	?1.810	??0.025	???0.014	???0.019	??0.025	??0.023	??0.020	???0.022	???0.026	???0.048
											290～299nm is not more than	?1.385	??0.017	???0.008	???0.017	??0.018	??0.016	??0.014	???0.018	???0.019	???0.039
300～359nm is not more than	?0.998	??0.013	???0.005	???0.013	??0.014	??0.015	??0.012	???0.014	???0.015	???0.021
											360～400nm is not more than	?0.080	??0.005	???0.001	???0.006	??0.006	??0.005	??0.001	???0.006	???0.004	???0.010

As seen from Table 2, catalyzer of the present invention contains three kinds of reactive metal tungsten, molybdenum and nickel (or cobalt), and (Ni or Co)/(W+Mo+Ni or Co) mol ratio is higher, and pore structure is reasonable, and the acid matter of catalyst surface and strength of acid are suitable.From the evaluation result of table 3 catalyzer as seen, the embodiment catalyzer has good hydrorefining paraffin wax performance, catalyzer is at low-temp low-pressure, low hydrogen wax when has good activity under the high-speed condition, make hydrogenation paraffin reach slab wax standard (GB7189-94) fully, heat-resistant quality is higher 1～2 number than comparative example, low 1 number of light stability, and condensed-nuclei aromatics ultraviolet absorptivity value is also low than comparative example, illustrates that catalyzer of the present invention has good hydrorefining paraffin wax and aromatic hydrocarbons saturability.

Claims (13)

1, a kind of oil Wax hydrofining catalyst, with group vib and group VIII metal is reactive metal, auxiliary agent contains silicon and phosphorus, with the aluminum oxide is carrier, the composition that it is characterized in that described catalyzer comprises: the weight with catalyzer is benchmark, tungstic oxide content is 10.0%～40.0%, molybdic oxide content is 4.0%～30.0%, nickel oxide or cobalt oxide content are 5.0%～16.0%, dioxide-containing silica is 2.0%～10.0%, phosphorus content is 1.0%～5.0%, and boron oxide content is 0～2.0%; The mol ratio of wherein (Ni or Co)/(W+Mo+Ni or Co) is 0.40～0.60, and wherein the mol ratio of W/Mo is 0.50～2.00.

2, catalyzer according to claim 1, it is characterized in that, weight with catalyzer is benchmark, tungstic oxide content is 15.0%～25.0%, molybdic oxide content is 6.0%～15.0%, and nickel oxide or cobalt oxide content are 8.0%～12.0%, and dioxide-containing silica is 3.0%～8.0%, phosphorus content is 1.0%～3.0%, and boron oxide content is 0～1.0%.

3, catalyzer according to claim 1 is characterized in that the mol ratio of (Ni or Co) in the described catalyzer/(W+Mo+Ni or Co) is 0.40～0.50, and wherein the mol ratio of W/Mo is 0.80～1.50.

4, catalyzer according to claim 1, it is characterized in that described catalyzer by the measured acid amount of meleic acid distribution is: the total acid content in the time of 160 ℃ is 200 μ mol/g～500 μ mol/g, and wherein protonic acid acid amount is 30 μ mol/g～100 μ mol/g; Total acid content in the time of 250 ℃ is 150 μ mol/g～350 μ mol/g, and wherein protonic acid acid amount is 20 μ mol/g～60 μ mol/g; Total acid content in the time of 350 ℃ is 70 μ mol/g～140 μ mol/g, and wherein protonic acid acid amount is 0 μ mol/g～40 μ mol/g.

5, catalyzer according to claim 1, it is characterized in that described catalyzer by the measured acid amount of meleic acid distribution is: the total acid content in the time of 160 ℃ is 300 μ mol/g～400 μ mol/g, and wherein protonic acid acid amount is 30 μ mol/g～70 μ mol/g; Total acid content in the time of 250 ℃ is 190 μ mol/g～250 μ mol/g, and wherein protonic acid acid amount is 30 μ mol/g～50 μ mol/g; Total acid content in the time of 350 ℃ is 80mol/g～120 μ mol/g, and wherein protonic acid acid amount is 0 μ mol/g～30 μ mol/g.

6, catalyzer according to claim 1, the mean pore size that it is characterized in that described catalyzer is 7.0～12.0nm, specific surface area is 150～260m ²/ g, pore volume are 0.30～0.55cm ³/ g, tap density is 0.80～1.00g/ml, accounts for more than the 85v% of total pore volume at the pore volume integration rate of 4～15nm.

7, the arbitrary described Preparation of catalysts method of claim 1～6 may further comprise the steps:

(1) in siliceous aluminium hydroxide, add the phosphorated compound mix pinch, moulding, drying, roasting, make siliceous and phosphorus oxidation alumina supporter;

(2) aqueous solution of preparation tungstenic and nickel or cobalt and the alkaline aqueous solution that contains molybdenum-boron;

(3) the prepared alumina supporter of step (1) floods the aqueous solution of tungstenic and nickel or cobalt, after drying, the roasting, makes catalyst intermediate;

(4) the prepared catalyst intermediate dipping of step (3) contains the aqueous solution of molybdenum-boron, after drying, the roasting, gets final catalyst prod.

8, preparation method according to claim 7 is characterized in that the siliceous aluminium hydroxide described in the step (1) is prepared by following method:

(1) preparation sodium aluminate solution, silicon-containing compound solution;

(2) under agitation condition, sodium aluminate solution, silicon-containing compound solution and carbon dioxide are reacted into glue, material solution mixes the back and feeds carbon dioxide and become glue or wherein one or both to add into glue continuously when feeding carbonic acid gas, stop to feed carbon dioxide after becoming glue to finish, aging then, filtration; Wherein the add-on of silicon-containing compound is its total 0%～50% of weight that adds;

(3) with adding the silicon-containing compound solution of remainder behind step (2) the gained filter cake pulping again, wear out again, filter filter cake washing, drying.

9, preparation method according to claim 8, the concentration that it is characterized in that the sodium aluminate solution described in the step (1) is 5gAl ₂O ₃/ l～60gAl ₂O ₃/ l, silicon-containing compound are water glass, and the concentration of silicon-containing compound is 5gSiO ₂/ l～40gSiO ₂/ l; One-tenth glue temperature described in the step (2) is controlled at 15 ℃～35 ℃, and concentration of carbon dioxide is controlled at 10v%～50v%, is controlled to the glue slurry pH value and is at 9～12 o'clock and stop logical carbonic acid gas, and digestion time is 0 minute～60 minutes; Digestion time in the step (3) is 10 minutes～120 minutes, and control reaction temperature is 20 ℃～35 ℃, and the control wash temperature is at 40 ℃～80 ℃, and washing times is 1 time～6 times, and described drying is following dry 2 hours～12 hours at 80 ℃～180 ℃.

10, preparation method according to claim 9 is characterized in that the one-tenth glue temperature described in the step (2) is controlled at 18 ℃～25 ℃, and concentration of carbon dioxide is controlled to be 20v%～40v%, and digestion time is 10 minutes～60 minutes; Digestion time described in the step (3) is 40 minutes～60 minutes.

11, preparation method according to claim 7 is characterized in that described P contained compound is ammonium phosphate salt or phosphoric acid.

12, preparation method according to claim 7, the drying that it is characterized in that the alumina supporter precursor described in the step (1) is under 80～150 ℃ condition dry 2～8 hours, roasting is roasting 2～6 hours under 500～800 ℃ condition.

13, preparation method according to claim 7 is characterized in that the drying described in the step (3) is to descend dry 3～12 hours at 50 ℃～150 ℃, and described roasting is 400 ℃～500 ℃ following roastings 2～6 hours; Drying described in the step (4) is to descend dry 2～8 hours at 60 ℃～190 ℃, and described roasting is 450 ℃～600 ℃ following roastings 2～5 hours.