CN1268722C - Hydrogenating catalyst for petroleum wax and its preparation process - Google Patents
Hydrogenating catalyst for petroleum wax and its preparation process Download PDFInfo
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- CN1268722C CN1268722C CN 03133997 CN03133997A CN1268722C CN 1268722 C CN1268722 C CN 1268722C CN 03133997 CN03133997 CN 03133997 CN 03133997 A CN03133997 A CN 03133997A CN 1268722 C CN1268722 C CN 1268722C
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Abstract
The present invention discloses a hydrogenating catalyst for petroleum wax and a preparation process thereof. The present invention is characterized in that aluminium hydroxide containing silicon and phosphorus, which is prepared by a CO2 neutralization method, is used as a carrier material of the catalyst, wherein a silicon auxiliary agent and a phosphorus auxiliary agent in the aluminium hydroxide containing the silicon and the phosphorus are added step by step; part of compound containing the silicon and the phosphorus forms glue after mixed with sodium metaaluminate solution; part of the compound containing the silicon is added after glue formation or the ageing process; most of the compound containing the phosphorus is added after the aluminium hydroxide is generated to be washed in the peptization or pulping process. Thus, most of silicon and phosphorus are distributed to the surface of the aluminium hydroxide to effectively perform a function on coordinately regulating the surface physicochemical property and a hole structure of the catalyst. The catalyst has the advantages of simple preparation technology and low cost. The catalyst has good activity and selectivity when processing petroleum wax materials comprising high melting point petroleum wax.
Description
Technical field
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, particularly a kind of mean pore size is big, pore distribution high concentration and active high catalyst for hydrorefining pertroleum wax and preparation method thereof.
Background technology
The main component of paraffin raw material is a normal paraffin, and isoparaffin content is very low.And the content of isoparaffin is more a lot of than the height in the paraffin raw material in the Microcrystalline Wax class raw material, and its composition carbon number is higher.Microcrystalline Wax class raw material has following character: crystallization is little, the fusing point height, and the viscosity of molten state is big, and the oiliness retentivity is good, oil-contg height, sulphur, nitrogen and condensed-nuclei aromatics content height.The hydrorefined purpose of oil wax material is intended to keep paraffinic components, removes with 3, and the 4-benzopyrene is sulphur, nitrogen and the oxygen of carcinogenic substances such as the condensed-nuclei aromatics of representative and non-hydrocarbons.The singularity of Microcrystalline Wax class raw material just requires catalyzer must have the physico-chemical property corresponding with it, such as having big pore volume, aperture and specific surface area, smaller particles degree and high physical strength etc., just require catalyzer to have good depth desulfurization, nitrogen and condensed-nuclei aromatics saturability, and good activity, selectivity and stability.Simultaneously, also require catalyzer to have to try one's best few solid acid and based on slightly acidic, reason is that this process does not allow to take place cracking reaction, otherwise will cause the increase of wax material oleaginousness and penetration degree.
At present, most Wax hydrofining catalyst generally adopts Mo-Ni/A1
2O
3Form, also contain two or more auxiliary agent, as silicon, phosphorus, titanium, boron, fluorine, basic metal and alkaline-earth metal (as magnesium) etc.Regulate the porous and the surface acid property of catalyzer by the collaborative regulating effect of two or more auxiliary agent, improve the interaction between active ingredient and carrier, to be fit to of the requirement of oil wax material unifining process the catalyzer physico-chemical property.
Wax hydrofining catalyst is general to be adopted siliceous and phosphorus oxidation aluminium is carrier, and the method for introducing silicon and phosphorus in alumina supporter is more, but adds siliceous mostly in becoming the glue process and material phosphorus prepares.CN 1048651C and CN 1048037C have announced a kind of preparation method of aluminum oxide of siliceous and phosphorus of macropore, in the preparation process of this aluminum oxide, silicon becomes the glue method to add with phosphorus with substep, can make silicon and phosphorus major part be dispersed in alumina surface like this, but this aluminum oxide peptization is relatively poor, in catalyzer or preparing carriers process, have only the aluminum oxide of the siliceous and phosphorus of a blending part, remaining adopt peptization preferably aluminum oxide so just can help moulding; Simultaneously its to contain silica volume low, only be 0.1w%～5w%, this becomes glue process employing Al
2(SO
4)
3, AlCl
3Or Al (NO
3)
3Be raw material, with ammoniacal liquor or NaAlO
2The solution neutralization is carried out to glue, can make its cost higher like this, and has a large amount of pollutents to discharge.
What CN 1032408C narrated is 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%, NiO
4～6wt%.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.
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%, NiO 8～12%, 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 CN 1032408C method) complexity and the preparation process, causes the raising of environmental pollution and catalyzer cost.
Summary of the invention
The object of the present invention is to provide that a kind of pore structure is reasonable, surface acid property is suitable and active high petroleum wax hydrogenation catalyst, the invention provides a kind of with low cost, simple above-mentioned Preparation of catalysts method of preparation flow that has simultaneously.
In the petroleum wax hydrogenation catalyst of the present invention, reactive metal is at least a group vib metal and at least a group VIII metal, wherein the group vib metal is preferably tungsten, molybdenum, preferred tungsten, the group VIII metal is preferably nickel, cobalt, preferred nickel, its composition comprises: the weight with catalyzer is benchmark, the content of group vib metal oxide is 15.0%～45.0%, the content of group VIII metal oxide is 3.0%～10.0%, dioxide-containing silica is 2.0%～15.0%, is preferably 4.0%～10.0%, is preferably 4.0%～8.0%; Phosphorous oxides content is 0.5%～6.0%, is preferably 1.0%～5.0%, is preferably 1.5%～4.0%.The pore volume of this catalyzer is 0.30ml/g～0.60ml/g, is preferably 0.40ml/g～0.50ml/g; Specific surface area is 120m
2/ g～250m
2/ g is preferably 160m
2/ g～240m
2/ g; Mean pore size is 6.0nm～14.0nm, is preferably 8.0～12.0nm; Pore volume integration rate at 4～15nm reaches more than 85%, is 85v%～95v%.
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 250 μ mol/g～400 μ mol/g, wherein protonic acid (also can be called B acid) acid amount is 20 μ mol/g～120 μ mol/g, be preferably 20 μ mol/g～100 μ mol/g, be preferably 30 μ mol/g～90 μ mol/g; Total acid content in the time of 250 ℃ is 100 μ mol/g～350 μ mol/g, is preferably 190 μ mol/g～300 μ mol/g, and wherein protonic acid acid amount is 10 μ mol/g～80 μ mol/g, is preferably 10 μ mol/g～70 μ mol/g; Total acid content in the time of 350 ℃ is 30 μ mol/g～140 μ mol/g, is preferably 40 μ mol/g～100 μ mol/g, and wherein protonic acid acid amount is 0 μ mol/g～30 μ mol/g, is preferably 0 μ mol/g～20 μ mol/g.The acid matter of catalyst surface mainly is made up of L acid, and protonic acid accounts for 5～30% of total acid content.
Preparation of catalysts method of the present invention comprises adding peptization acid and deionized water is mixed pinches into plastic in siliceous and phosphorus aluminium hydroxide, makes the alumina supporter of siliceous and phosphorus again after extruded moulding, drying and roasting; After the alumina supporter dipping of the siliceous and phosphorus of gained contains the aqueous solution of above-mentioned group vib and group VIII metal, make catalyzer of the present invention after drying and the roasting.
The preparation method of the siliceous and phosphorus aluminium hydroxide that 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, a part of P contained compound solution and carbon dioxide are reacted into glue, stop to feed carbon dioxide after one-tenth glue is finished, aging then, filtration; Wherein the silicon-containing compound add-on accounts for 0%～70% of total adding weight, and is preferred 5%～50%, and the P contained compound add-on accounts for 0%～50% of total adding weight, and preferred 5%～40%;
(3) with adding the silicon-containing compound solution of remainder behind (2) the step gained filter cake pulping again, wear out again, filter filter cake washing;
(4) with behind (3) the step gained filter cake pulping, the P contained compound solution that adds remainder carries out pulp or peptization, aging, makes the P contained compound uniform deposition in surface of aluminum hydroxide, and filtration, filtration cakes torrefaction obtain siliceous and aluminium hydroxide phosphorus then.
The above-mentioned siliceous and concrete preparation process phosphorus oxidation alumina supporter is as follows: will be of the present invention siliceous and aluminium hydroxide phosphorus the shape of claying into power, add peptization acid and deionized water then, mix, in kneading machine, mix and pinch, the mixed time of pinching should be controlled at and be not less than 1.0 hours, be preferably 1.5～3.0 hours, until siliceous mixing with phosphorus aluminium hydroxide pinched into plastic, extruded moulding in banded extruder then, the acidic aqueous solution that in this process, also can add titaniferous or zirconium, so more help the moulding of carrier and the improvement of surface physicochemical property, make the pore distribution of carrier more concentrated in required pore diameter range.The wet bar of moulding descended dry 2.0～8.0 hours at 60～200 ℃, 500～700 ℃ of following roastings 2.0～5.0 hours, promptly got siliceous and alumina supporter phosphorus.Peptization acid wherein is one or more in nitric acid, acetate, hydrochloric acid and the phosphoric acid, is preferably acetate and hydrochloric acid.
The above-mentioned preparation process that contains group vib and group VIII metal water solution is as follows: will contain the group vib metallic compound and contain the group VIII metallic compound and join in a certain amount of deionized water stirring and dissolving.Catalyst specific surface that stabilizes and increases and the dispersion that promotes reactive metal at catalyst surface for solution, suitable increase can form the carboxylic-acid substance of complex compound with reactive metal in the solution, the carboxylic-acid substance who adds is compounds such as citric acid, tartrate, oxalic acid, and the weight concentration of this type of material in solution is 2.0%～20.0%.
Catalyzer physico-chemical property of the present invention is good, has bigger aperture and pore volume, concentrated pore distribution and suitable surface acid amount and acid matter.When catalyzer of the present invention is used for oil wax material hydrogenation, has the ability of the saturated performance of good aromatic hydrocarbons and deep removal sulphur and nitrogen, but also have good selectivity, scission reaction does not take place in reaction process.Catalyst preparation process of the present invention is simple, and preparation cost is lower.
Siliceous and phosphorus aluminium hydroxide of the present invention is to adopt Carbonization Preparation, and siliceous compound and the P contained compound introduced are cheap, and cost is low, and preparation technology is simple, does not have the discharge of pollutent, non-environmental-pollution; Silicon-dioxide is uniformly dispersed at alumina surface simultaneously, has prevented the influence of process to the aluminum oxide microtexture; The present invention is siliceous to have good peptization with phosphorus aluminium hydroxide, particularly improved the silicon content shortcoming of its peptization variation more for a long time, make that moulding is easy when adopting the present invention siliceous and phosphorus preparation of aluminium hydroxide support of the catalyst or catalyzer, and then the Preparation of Catalyst cost is reduced.
The present invention is in the process for preparing siliceous and phosphorus aluminium hydroxide, siliceous and compound phosphorus is to adopt the substep addition method to add, the compound of the siliceous and phosphorus of part be carried out to glue after sodium aluminate solution mixes, the part silicon-containing compound is after becoming glue or add in the weathering process, and most of P contained compound is to add in peptization or pulp process after washing at the aluminium hydroxide that generates.Can reach with try one's best few silicon and phosphorus content like this and regulate the acid matter of surface of aluminum hydroxide, most silicon and phosphorus are distributed in the surface of aluminium hydroxide, the effectively collaborative effect of regulating the surface of aluminum hydroxide physico-chemical property of performance silicon and phosphorus, the effect that has the adjustment hole structure simultaneously.Be that the physico-chemical property of the support of the catalyst made of raw material is with close when not adding silicon and phosphorus or silicon and phosphorus content aluminium hydroxide seldom and be raw material by siliceous and phosphorus aluminium hydroxide of the present invention, even further having improved the physical and chemical performance of carrier, pore distribution is concentrated more, mean pore size further strengthens.The present invention has maximally utilised cheap silicon resource, and as auxiliary agent, has weakened the competition of silicon and phosphorus and reactive metal effectively, has improved the utilization ratio of reactive metal.
Embodiment
The concrete preparation process of catalyzer of the present invention is as follows:
One, the preparation of siliceous and phosphorus aluminium hydroxide
In the preparation of aluminium hydroxide process of the siliceous and phosphorus of the present invention, the concentration of used sodium aluminate solution is 5gAl
2O
3/ l～60gAl
2O
3/ l.Silicon-containing compound is acidifying water glass (being commonly called as water glass) solution preferably, also can be sodium silicate solution, for aluminium hydroxide after becoming glue is easy to Na
+Washing can also be low sodium silicon sol solution, and containing silicon-dioxide in the adjusting silicon-containing compound solution is 5g/l～40g/l.Acidifying water glass is to add acidic solution such as dilute hydrochloric acid solution or salpeter solution in water glass solution, is mixed with the acidified sodium silicate solution of as clear as crystal good fluidity, and helping silicon-containing compound is that camber disperses becoming colloid, and its pH value is 1～3; P contained compound is ammonium phosphate salt material preferably, also can be that the mixing solutions water of phosphoric acid solution or phosphoric acid and nitric acid is mixed with the phosphorous dilute solution of 1.0g/l～10.0g/l that is.The adding mode of silicon-containing compound solution and P contained compound solution preferably with and stream mode join in the aluminum contained compound solution, or three kinds of liquors join in the glue jar with certain flow respectively and carry out neutralization reaction with carbonic acid gas.Become the glue temperature to be controlled at 15 ℃～35 ℃, be preferably between 18 ℃～30 ℃, be preferably between 18 ℃～25 ℃ according to needed siliceous and porous phosphorus aluminium hydroxide.Concentration of carbon dioxide is controlled at 10v%～50v% (20v%～40v%) preferably.Be controlled to the glue slurry pH value and be at 9～12 o'clock and stop logical carbonic acid gas.Can wear out and also can not wear out, digestion time is 0 minute～60 minutes, and preferred digestion time is 10 minutes～60 minutes.Filter cake behind the dope filtration is pulled an oar after adding entry, adds the remainder silicon-containing compound of calculated amount under whipped state, and the silicon-containing compound of this moment can be the silicon sol solution of water glass solution or low sodium, and the silicon sol solution that adds low sodium is for convenient for washing.Aging again 10 minutes～120 minutes, be preferably 40 minutes～80 minutes, be preferably 40 minutes～60 minutes, controlled temperature is at 20 ℃～35 ℃, filter then filter cake.With ordinary method washing 1～6 time, in the aluminium hydroxide of preparation, contain Na
+By weight＜0.05%.The control wash temperature is preferably 20 ℃～30 ℃ at 20 ℃～40 ℃, and washing times is preferably 3 times～6 times, most preferably is 3 times～4 times.Filter cake after the washing is added entry again carry out pulp, the mixing solutions that adds phosphate aqueous solution or phosphoric acid and nitric acid then carries out peptization, or the aqueous solution that adds phosphoric acid ammonium salt class carries out pulp and aging, make the P contained compound uniform deposition in surface of aluminum hydroxide, filtration, filtration cakes torrefaction are then under 80 ℃～180 ℃ then, preferred 100 ℃～150 ℃ dry 2 hours～12 hours down, promptly get the aluminium hydroxide of siliceous and phosphorus of the present invention.
The adding mode of various material solutions can specifically be selected as required, and as adopting following manner: (1) feeds sodium aluminate solution with carbon dioxide, adds silicon-containing compound solution and P contained compound solution with certain flow simultaneously; (2) with adding silicon-containing compound and P contained compound solution in the sodium aluminate solution, feed carbon dioxide then; (3) sodium aluminate solution, silicon-containing compound solution and P contained compound solution join in the glue jar with certain flow respectively, feed carbon dioxide simultaneously; Its order of addition(of ingredients) also can specifically be selected as required, and preferred version is (3).
Two, the preparation of siliceous and phosphorus oxidation alumina supporter of the present invention
In the preparation process of carrier, peptization acid is preferably acetate and hydrochloric acid.Mix with aluminium hydroxide and peptization acid phosphorus siliceous, in kneading machine, mix and pinch, the water yield that the control kneading process adds, proper extension mixes and pinches the time, makes to mix to pinch material plasticizing, and easy moulding also concentrates the carrier hole distribution height of preparation.The mixed time of pinching should be controlled at and be not less than 1.0 hours, is preferably 1.5～3.0 hours.In the preparing carriers process, can also add the auxiliary agent titanium-containing compound, be preferably titanous chloride.Hydrochloric acid of the present invention is the free acid in the Titanium Trichloride Solution preferably, promptly contains acetate, hydrochloric acid and titanous chloride in the peptization acid solution, and wherein the add-on of acetate is 2.0～3.0g/100g aluminum oxide, and the add-on of titanous chloride should make TiO
2Weight content in alumina supporter is controlled at less than 1.0% and is advisable, be preferably 0.5%～0.8%, add an amount of titanium and can improve activity of such catalysts, simultaneously titanium joins with the form of Titanium Trichloride Solution that catalyst pores is distributed is more concentrated, reach the purpose of preparation pore distribution concentration catalyzer, but added pore volume and the specific surface area that too much titanous chloride can reduce carrier.The maturing temperature of shaping carrier should be fit to the influence to the acid matter of catalyst surface of the characteristics of petroleum wax raw material and hydrogenation process, suitably adjust the maturing temperature of carrier, the maturing temperature that process of the present invention is suitable is 550 ℃～700 ℃, be preferably 580 ℃～650 ℃, can prepare the suitable alumina supporter of mean pore size and surface acid amount and acid matter.
The present invention's alumina supporter siliceous and that the moulding of phosphorus aluminium hydroxide prepares after the said temperature roasting has following character: dioxide-containing silica is 2.0%～20.0% by weight, phosphorous oxides content is 0.5%10.0% by weight, pore volume is 0.6ml/g～1.2ml/g, and specific surface area is 300m
2/ g～400m
2/ g, mean pore size is 6.0nm～20.0nm.
In order to adopt the deployment conditions of two kinds of auxiliary agents of sem test Si, P at alumina surface, siliceous and the phosphorus aluminium hydroxide of the present invention is prepared into cylindrical strip thing through moulding process, by Si, the 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 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 SiO
2Content is 8.0wt%, P
2O
5Content is that 3.5wt% is an example).As can be seen from Table 1, the average content height of two kinds of auxiliary agents of silicon and phosphorus each point in the square section is consistent, can illustrate that silicon and phosphate builder are in the alumina surface high dispersing.
The distribution situation of silicon and phosphorus in the alumina supporter that table 1 scanning electron microscope method is analyzed
| The auxiliary agent average content | Center 0.0R * | 0.25R | 0.5R | 0.75R | R |
| SiO 2/wt％ | 8.21 | 8.20 | 8.19 | 8.21 | 8.22 |
| P 2O 5/wt％ | 3.53 | 3.55 | 3.51 | 3.54 | 3.56 |
| Al 2O 3/wt％ | 88.26 | 88.25 | 88.30 | 88.25 | 88.22 |
Annotate:
*R be cylinder strip cross section radius.
Three, the preparation of the reactive metal aqueous solution
The group vib metal is preferably tungsten, and the group VIII metal is preferably nickel.Tungstenic compound and nickel compound containing used in tungstenic-nickel aqueous solution process for preparation are water miscible inorganic salt, Tungstenic compound can be one or more in ammonium metawolframate, ethyl ammonium metawolframate and the tungstate, and nickel compound containing is one or more in nickelous nitrate, nickelous chloride and the nickelous acetate.It is ammonium metawolframate that the present invention mainly selects Tungstenic compound, and the selection nickel compound containing is a nickelous nitrate, and used carboxylic-acid substance is preferably citric acid and two kinds of materials of oxalic acid.Earlier citric acid and the oxalic acid with calculated amount joins in a certain amount of deionized water, and stirring and dissolving adds the ammonium metawolframate stirring and dissolving of calculated amount again, adds the nickelous nitrate of calculated amount at last, and the solution that is prepared into contains WO
3Concentration be 200～650g/l, be preferably 400～550g/l, the concentration that contains NiO is 50～150g/l, be preferably 80～120g/l, the total concn that contains citric acid and oxalic acid is 2.0wt%～20.0wt%, be preferably 5.0wt%～15.0wt%, the mol ratio of oxalic acid and citric acid is 1: 1～4: 1, is preferably 1: 1～2: 1.
Four, Preparation of catalysts
The aqueous solution of tungstenic-nickel is flooded the alumina supporter of siliceous and phosphorus, employing ordinary method dipping, drying is 3～12 hours under 60 ℃～150 ℃, be preferably at 80～120 ℃ following dry 4～6 hours, 400 ℃～550 ℃ following roastings 2～6 hours, be preferably 450～520 ℃ of roastings 3～5 hours, get final catalyst prod.
Further specify technical solution of the present invention by the following examples.
Embodiment 1
(1) preparation of siliceous and phosphorus aluminium hydroxide
1) solution preparation
Preparation concentration is 30gAl
2O
3The sodium aluminate solution of/l; Add sodium silicate solution in dilute nitric acid solution, stir fast, be prepared into the acidifying sodium silicate solution, the concentration that makes the acidifying sodium silicate solution is 20gSiO
2/ l, the pH value of final solution is 1; Compound concentration is 20.0gSiO
2The low sodium silicon sol solution of/l; Compound concentration is the ammonium dihydrogen phosphate of 5.0gP/l.
2) become glue
Sodium aluminate solution is placed in the glue jar, and 20 ℃ of controlled temperature slowly add the acidifying sodium silicate solution with certain flow, stir fast, and the water glass of adding is with SiO
2The content of meter in aluminium hydroxide is 4.0% by weight, and feeding concentration is 30% (volumetric concentration) carbon dioxide down together, until slurry pH value is to stop logical carbon dioxide at 11 o'clock, and slurries are aging 0.5hr under whipped state, filters then, washing makes to contain Na in the carrier
+By weight＜0.05%.Filter cake adds the deionized water reslurry and stirs, and adds the low sodium silicon sol solution of calculated amount then, makes silicon-containing compound with SiO
2The final content of meter in siliceous and phosphorus aluminium hydroxide is 8.0wt%, add ammonium dihydrogen phosphate simultaneously, the ammonium dihydrogen phosphate that adds is 3.0% in the content of P in aluminium hydroxide by weight, and then aging 0.5 hour, filter, filter cake descended dry 8 hours at 150 ℃, was crushed to 180 orders again, promptly made siliceous and aluminium hydroxide product A 1 phosphorus.
(2) preparation of siliceous and phosphorus oxidation alumina supporter
20g acetate, 30g Titanium Trichloride Solution (are contained TiCl
3Be 15wt%) join in the 700g deionized water, stir, make acidic solution.Take by weighing the above-mentioned siliceous and phosphorus aluminium hydrate powder (contents on dry basis is 70wt%) of 1000g, add 20.0g sesbania powder as extrusion aid, adding above-mentioned acidic solution again mixes, in small-sized kneading machine, mix then and pinch 2.0 hours, when material becomes plastic, in banded extruder, be extruded into stripe object, under 120 ℃ condition dry 6 hours then, roasting is 4 hours under 620 ℃ condition, is prepared into siliceous and alumina supporter A2 phosphorus.
(3) Preparation of catalysts
The water-intake rate of the prepared carrier of measuring process (2), prepare the tungstenic-nickel solution of respective concentration according to the metal component content of water-intake rate and catalyzer requirement, in 400g water, add 15g citric acid and 15g oxalic acid, add the 360g ammonium metawolframate after the stirring and dissolving, after the stirring and dissolving, add the 220g nickelous nitrate again, dissolving, filter, make 600ml tungstenic-nickel solution, WO in the solution
3Concentration be 50.0g/100ml, the concentration of NiO is 9.1g/100ml.
With the prepared siliceous and phosphorus oxidation alumina supporter of this solution impregnation step (2), impregnated carrier in changeing pot, adopt saturated impregnation method, solution is impregnated on the carrier with vaporific form, the dipping back that finishes is changeed pot and is rotated further 20～40 minutes, with the wet feed homogenize, with wet feed 110 ℃ dry 4 hours down, 500 ℃ of calcination activations 4 hours, promptly get product A of the present invention.
Embodiment 2
(1) preparation of siliceous and phosphorus aluminium hydroxide
Compare with embodiment 1 (1), be mixed with the phosphoric acid solution of phosphorous 8.0g/l, slurries add phosphoric acid solution and carry out peptization, and aging 1.0 hours then, all the other were identical with embodiment 1 (1), promptly got siliceous and aluminium hydroxide product B 1 phosphorus.
(2) siliceous preparation with the phosphorus oxidation alumina supporter is identical with embodiment 1 (2).
(3) Preparation of catalysts is identical with embodiment 1 (3).Be cost routine product B of the present invention.
Embodiment 3
(1) preparation of siliceous and phosphorus aluminium hydroxide
Compare with embodiment 1 (1), be mixed with phosphoric acid and the salpeter solution of phosphorous 3.0g/l, becoming the glue process not add solution containing phosphate, after becoming the glue filter cake washing, add phosphoric acid after with the filter cake pulp and salpeter solution carries out peptization, all the other are identical with embodiment 1 (1), promptly get siliceous and aluminium hydroxide products C 1 phosphorus.
(2) siliceous preparation with the phosphorus oxidation alumina supporter is identical with embodiment 1 (2).
(3) Preparation of catalysts
Compare with embodiment 1 (3), in the dipping solution, adjust active metal W O
3Concentration be 30.0g/100ml, the concentration of NiO is 6.5g/100ml, all the other are identical with embodiment 1 (3), i.e. cost example, products C of the present invention.
Embodiment 4
(1) preparation of siliceous and phosphorus aluminium hydroxide
Compare with embodiment 1 (1), be mixed with phosphoric acid and the salpeter solution of phosphorous 6.0g/l, the primary ammonium phosphate amount that adds in becoming the glue process is 2.0wt% in the content of P in aluminium hydroxide, phosphoric acid amount reduces in becoming glue rear slurry peptization course, make that the content of P reaches 3.0% in the finished product, all the other are identical with embodiment 1 (1), promptly get siliceous and aluminium hydroxide product D1 phosphorus.
(2) siliceous preparation with the phosphorus oxidation alumina supporter is identical with embodiment 1 (2).
(3) Preparation of catalysts
Compare with embodiment 1 (3), in the dipping solution, adjust active metal W O
3Concentration be 40.0g/100ml, the concentration of NiO is 12.0g/100ml, all the other are identical with embodiment 1 (3), promptly get product D of the present invention.
Embodiment 5
(1) preparation of siliceous and phosphorus aluminium hydroxide
Compare with embodiment 1 (1), sodium aluminate solution, acidified sodium silicate solution joins in the glue jar with the flow that calculates respectively with ammonium dihydrogen phosphate, and stir fast, and the mixing solutions in becoming the glue jar feeds the carbon dioxide of 30% concentration, all the other are identical with embodiment 1 (1), promptly get siliceous and aluminium hydroxide product E 1 phosphorus.
(2) siliceous preparation with the phosphorus oxidation alumina supporter is identical with embodiment 1 (2).
(3) Preparation of catalysts
Compare with embodiment 1 (3), in the dipping solution, adjust active metal W O
3Concentration be 60.0g/100ml, the concentration of NiO is 12.0g/100ml, all the other are identical with embodiment 1 (3), i.e. cost example, product E of the present invention.
Embodiment 6
(1) preparation of siliceous and phosphorus aluminium hydroxide
Compare with embodiment 1 (1), change acidifying sodium silicate solution and low sodium silicon sol solution into common sodium silicate solution, the concentration that makes solution is 20gSiO
2/ l changes ammonium dihydrogen phosphate into phosphoric acid solution, is becoming the glue after-filtration, and the remainder sodium silicate solution with behind the filter cake reslurry makes silicon-containing compound with SiO
2The content of meter in aluminium hydroxide is 12.0wt%.Filtration washing then, washing times is 5 times, makes to contain Na in the carrier
+By weight＜0.05%.And then the filter cake pulp after will washing, the dilute solution that adds phosphoric acid is carried out peptization, and aging 1.5 hours, the unclassified stores consumption was identical with embodiment 1 (1) with operational condition, promptly got siliceous and aluminium hydroxide product F 1 phosphorus.
(2) siliceous preparation with the phosphorus oxidation alumina supporter is identical with embodiment 1 (2).
(3) Preparation of catalysts
Compare with embodiment 1 (3), in the dipping solution, add the carboxylic-acid substance and measure raising (each 30g of citric acid and oxalic acid), all the other are identical with embodiment 1 (3), and promptly the cost example gets product F of the present invention.
Embodiment 7
(1) preparation of siliceous and phosphorus aluminium hydroxide
Becoming the glue after-filtration, silicon-containing compound solution will do not added behind the filter cake washing reslurry, reduce the add-on of P contained compound solution, in the content of P in aluminium hydroxide is 1.5% by weight, the unclassified stores consumption is identical with embodiment 1 (1) with operational condition, promptly gets siliceous and aluminium hydroxide product G 1 phosphorus.
(2) preparation of siliceous and phosphorus oxidation alumina supporter
Compare with embodiment 1 (2), do not add Titanium Trichloride Solution in the acidic solution, only add acetate, the acetate amount is brought up to 40.0g, and will mix and pinch the time proper extension, pinch into plastic up to material is mixed, all the other are identical with embodiment 1 (2).
(3) Preparation of catalysts is identical with embodiment 1 (3).Be cost routine product G of the present invention.
Embodiment 8
(1) preparation of siliceous and phosphorus aluminium hydroxide
Compare with embodiment 1 (1), becoming the glue after-filtration, the low sodium silicon sol solution add-on that adds behind the filter cake washing reslurry is improved, make silicon-containing compound with SiO
2The content of meter in siliceous aluminium hydroxide is 16.0wt%, improve the add-on of P contained compound simultaneously, making in the content of P in aluminium hydroxide is 5.0wt%, digestion time changes 2.0 hours into, the unclassified stores consumption is identical with embodiment 1 (1) with operational condition, promptly gets siliceous and aluminium hydroxide product H1 phosphorus.
(2) siliceous preparation with the phosphorus oxidation alumina supporter is identical with embodiment 1 (2).
(3) Preparation of catalysts is identical with embodiment 1 (3).Be the routine product H of the present invention of getting of cost.
Comparative example 1
(1) preparation of siliceous and phosphorus aluminium hydroxide
Prepare the siliceous and phosphorus aluminium hydroxide of macropore by the described method of CN 1048037C.
Add 1000ml water in a container, be warming up to 67 ℃, add the 3700ml solution that contains aluminum chloride 330g, adding concentration simultaneously is 10g NH
3The ammonia soln of/100ml, control PH is 8.0, and temperature is 60 ℃, and the reinforced time is 120 minutes.The aging 80ml solution that adds the water glass that contains 6.4g after 30 minutes, filtration washing is to Cl
-/ Al
2O
3＜0.3wt%.After then filter cake being pulled an oar with deionized water, add the phosphoric acid 3.75ml of 85v%, stir 30 minutes after-filtration, filter cake is crushed to 180 orders with it 130 ℃ of dryings after 8 hours, get siliceous and phosphorus aluminium hydroxide I1.
(2) preparation of siliceous and phosphorus oxidation alumina supporter
40g acetate, 40g Titanium Trichloride Solution (are contained TiCl
3Be 15wt%) join in the 700g deionized water, stir, make acidic solution.(the SB aluminium hydroxide of German import, pore volume are 0.56ml/g, and specific surface is 340m to take by weighing the aluminium hydrate powder of the good less pore volume of above-mentioned siliceous and phosphorus aluminium hydrate powder (contents on dry basis is 70wt%) of 800g and 400g peptization
2/ g, contents on dry basis is 70wt%), add 60.0g sesbania powder as extrusion aid, add above-mentioned acidic solution again and mix, in small-sized kneading machine, mix then and pinch 3.0 hours, when material becomes plastic, in banded extruder, be extruded into stripe object, under 120 ℃ condition dry 6 hours then, roasting was 4 hours under 620 ℃ condition, is prepared into siliceous and alumina supporter I2 phosphorus.
(3) Preparation of catalysts promptly makes the comparative example product I with embodiment 1 (3).
Embodiment 9
The physico-chemical property of each embodiment and comparative example catalyst prod is listed in table 3.Each embodiment activity rating of catalyst the results are shown in table 4.
As can be seen from Table 2, the pore structure of catalyzer of the present invention is reasonable, and acidity is suitable.Regulating effect by silicon and two kinds of auxiliary agents of phosphorus, can realize the adjusting of catalyzer pore volume and surface acid amount and acid matter, and along with the raising of silicone content, catalyst surface acid amount improves, strength of acid increases, along with the increase of phosphate builder content, surface of aluminum hydroxide acid amount and strength of acid reduce, and the pore distribution dispersity increases.Therefore,, Si and P are evenly distributed at catalyst surface, should are becoming glue to finish the compound that the back adds most siliceous and phosphorus in order to regulate the physico-chemical property of catalyzer.
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, all, illustrate that catalyzer of the present invention has good hydrorefining paraffin wax and aromatic hydrocarbons saturability far below the requirement of national standard to condensed-nuclei aromatics content.
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 and phosphorus oxidation aluminium) 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％ | NiO /wt％ | 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 | 30.5 | 4.5 | 5.0 | 1.8 | 0.42 | 190 | 0.90 | 9.5 | 90 | 344/80 | 246/37 | 85/21 |
| B | 30.6 | 4.6 | 5.2 | 1.9 | 0.41 | 185 | 0.91 | 9.3 | 92 | 335/72 | 255/33 | 90/12 |
| C | 18.5 | 4.0 | 6.0 | 2.0 | 0.48 | 210 | 0.84 | 9.1 | 87 | 365/85 | 263/40 | 85/20 |
| D | 24.0 | 6.2 | 5.5 | 1.9 | 0.45 | 184 | 0.87 | 9.8 | 88 | 350/70 | 265/33 | 75/11 |
| E | 35.1 | 5.8 | 4.5 | 1.7 | 0.37 | 169 | 0.96 | 8.8 | 86 | 365/71 | 255/40 | 75/10 |
| F | 30.2 | 4.5 | 7.7 | 1.8 | 0.44 | 225 | 0.91 | 7.8 | 85 | 385/90 | 295/50 | 95/30 |
| G | 30.4 | 4.6 | 5.0 | 1.0 | 0.45 | 210 | 0.88 | 8.6 | 89 | 366/77 | 284/40 | 90/24 |
| H | 29.0 | 4.5 | 9.5 | 3.1 | 0.46 | 234 | 0.89 | 7.9 | 86 | 342/66 | 245/20 | 70/6 |
| I | 30.4 | 4.5 | 1.5 | 1.8 | 0.52 | 234 | 0.80 | 8.9 | 88 | 315/30 | 205/15 | 60/5 |
During evaluate catalysts, adopting paraffin is No. 59 ketone benzin system waxes.Processing condition are: hydrogen dividing potential drop 6.0MPa, temperature is 260 ℃, volume space velocity 1.5h
-1, hydrogen wax than 120 (v)
Each routine catalyst activity evaluation result of table 3
Each routine catalyzer is used for the Microcrystalline Wax unifining process.Under the processing condition of table 5, handle 75
#Microcrystalline Wax (its character sees Table 4), as can be seen from Table 6, product reaches the food grade Microcrystalline Wax standard of the industry standard SH/T0013-1999 of China Petrochemical Industry behind its hydrogenation, condensed-nuclei aromatics content meets the U.S. FDA standard, the product of producing can meet developed country's standard, compare with comparative example, high 3～4 units of each embodiment color, condensed-nuclei aromatics content also is significantly less than the level of comparative example catalyzer, sulphur and nitrogen content are very low, all below 10ppm, illustrate that the present invention's catalyzer siliceous and that phosphorus aluminium hydroxide is made has the good depth desulfurization, nitrogen activity and arene saturating activity.
Table 4 75
#The Microcrystalline Wax feedstock property
| Project | Data |
| Melt drop temperature/℃ | 78.4 |
| Penetration degree/1/10mm | 21 |
| Viscosity/mm 2·s -1 | 16.77 |
| Oil-containing/wt% | 2.23 |
| Sulphur/ugg -1 | 453 |
| Nitrogen/ugg -1 | 62 |
| Flash-point/℃ | 294 |
| Color/Sai Shi number | ＜-16 |
Table 5 75
#Microcrystalline Wax hydrofining test technology condition (adopting the one-stage serial two reactor system)
| Reactor | One is anti- | Two is anti- |
| Reaction pressure (hydrogen dividing potential drop), MPa | 15.0 | 15.0 |
| Temperature of reaction, ℃ | 340 | 270 |
| Hydrogen wax volume ratio | 700 | 700 |
| Volume space velocity, h -1 | 1.0 | 1.0 |
| Total air speed, h -1 | 0.5 | |
Each routine catalyst activity evaluation result of table 6
Claims (16)
1, a kind of petroleum wax hydrogenization catalyst preparation method comprises and mixes alunite after adding peptization acid in the aluminium hydroxide of siliceous and phosphorus, makes the alumina supporter of siliceous and phosphorus again through extruded moulding, drying and roasting; After the gained carrier impregnation contained the aqueous solution of at least a group vib metal and at least a group VIII metal, drying and roasting made final catalyzer, it is characterized in that siliceous and aluminium hydroxide phosphorus is prepared by following method:
(1) preparation sodium aluminate solution, silicon-containing compound solution;
(2) under agitation condition, sodium aluminate solution, a part of silicon-containing compound solution, a part of P contained compound solution and carbon dioxide are reacted into glue, becoming the glue temperature is 15 ℃～35 ℃, becoming the glue slurry pH value is to stop logical carbonic acid gas at 9～12 o'clock, aging then or not aging, digestion time 0～60 minute is filtered; Wherein the silicon-containing compound add-on accounts for its total 5%～70% of weight that adds, and the P contained compound add-on accounts for its total 0%～50% of weight that adds;
(3) will add the silicon-containing compound solution of remainder behind (2) the step gained filter cake pulping again, wore out 10 minutes～120 minutes at 20 ℃～35 ℃ again, filter filter cake washing;
(4) with behind (3) the step gained filter cake pulping, the P contained compound solution that adds remainder carries out pulp or peptization, aging, makes the P contained compound uniform deposition in surface of aluminum hydroxide, and filtration, filtration cakes torrefaction obtain siliceous and aluminium hydroxide phosphorus then;
The add-on of group vib metal and group VIII metal is respectively 15.0%～45.0% and 3.0%～10.0% with the weight content of its metal oxide in final catalyzer and is as the criterion.
2, in accordance with the method for claim 1, it is characterized in that the silicon-containing compound add-on accounts for its total 5%～50% of weight that adds in the step (2), the P contained compound add-on accounts for its total 5%～40% of weight that adds, the silicon-containing compound that adds in the step (2) is the acidifying sodium silicate solution, its pH value is 1～3, and containing silicon-dioxide in the solution is 5g/l～40g/l.
3, in accordance with the method for claim 1, the concentration that it is characterized in that described sodium aluminate solution is 5gAl
2O
3/ l～60gAl
2O
3/ l, the P contained compound strength of solution is phosphorous 1.0g/l～10.0g/l.
4, in accordance with the method for claim 1, it is characterized in that concentration of carbon dioxide is 10v%～50v%; The described silicon-containing compound of step (3) is water glass solution or silicon sol solution, and described washing is 20 ℃～40 ℃ washings 1～6 time; The described drying of step (4) is under 80 ℃～180 ℃, dry 2 hours～12 hours.
5, in accordance with the method for claim 1, the adding method that it is characterized in that the described sodium aluminate solution of step (2), silicon-containing compound solution, P contained compound solution is selected one of following form: (1) feeds sodium aluminate solution with carbon dioxide, adds silicon-containing compound solution and P contained compound solution simultaneously; (2) with adding silicon-containing compound and P contained compound solution in the sodium aluminate solution, feed carbon dioxide then; (3) sodium aluminate solution, silicon-containing compound solution and P contained compound solution join in the glue jar with certain flow respectively, feed carbon dioxide simultaneously.
6, in accordance with the method for claim 1, it is characterized in that described peptization acid for acetate and hydrochloric acid, also adds the auxiliary agent titanium-containing compound, wherein the add-on of acetate is 2.0～3.0g/100g aluminum oxide, and the add-on of titanium is with TiO
2The weight content of meter in alumina supporter is less than 1.0wt%; The mixed time of pinching was controlled at 1.0～3.0 hours in the kneading process; The wet bar of moulding descended dry 2.0～8.0 hours at 60 ℃～200 ℃, 500～700 ℃ of following roastings 2.0～5.0 hours.
7, in accordance with the method for claim 6, the add-on that it is characterized in that titanium is for TiO
2The weight content of meter in alumina supporter is 0.5%～0.8%, and titanium-containing compound is a titanous chloride.
8, in accordance with the method for claim 1, it is characterized in that adding can form the carboxylic-acid substance of complex compound with reactive metal in the described preparation process that contains group vib and group VIII metal water solution, the weight concentration in solution is 2.0%～20.0%.
9, in accordance with the method for claim 8, it is characterized in that the weight concentration of described carboxylic-acid substance in solution is 5.0%～15.0%, described carboxylic-acid substance is one or more in citric acid, tartrate, the oxalic acid.
10, according to claim 8 or 9 described methods, it is characterized in that described carboxylic-acid substance is oxalic acid and citric acid, its mol ratio is 1: 1～4: 1.
11, in accordance with the method for claim 10, the mol ratio that it is characterized in that described oxalic acid and citric acid is 1: 1～2: 1.
12, in accordance with the method for claim 1, it is characterized in that described group vib metal is a tungsten or/and molybdenum, the group VIII metal is that nickel is or/and cobalt.
13, in accordance with the method for claim 12, it is characterized in that the group vib metal is a tungsten, the group VIII metal is a nickel.
14, the petroleum wax hydrogenation catalyst of the arbitrary described method preparation of claim 1～13, the composition that it is characterized in that this catalyzer comprises: the weight with catalyzer is benchmark, the content of group vib metal oxide is 15.0%～45.0%, the content of group VIII metal oxide is 3.0%～10.0%, dioxide-containing silica is 2.0%～15.0%, and phosphorous oxides content is 0.5%～6.0%; The pore volume of this catalyzer is 0.30ml/g～0.60ml/g, and specific surface area is 120m
2/ g～250m
2/ g, mean pore size is 6.0nm～14.0nm, reaches more than 85% at the pore volume integration rate of 4～15nm.
15, according to the described catalyzer of claim 14, it is characterized in that the weight with catalyzer is benchmark, dioxide-containing silica is 4.0%～8.0%; Phosphorous oxides content is 1.5%～4.0%; The pore volume of this catalyzer is 0.40ml/g～0.50ml/g, and specific surface area is 160m
2G～240m
2/ g.
16, according to the described catalyzer of claim 14, it is characterized in that this 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 20 μ mol/g～120 μ mol/g; Total acid content in the time of 250 ℃ is 100 μ mol/g～350 μ mol/g, and wherein protonic acid acid amount is 10 μ mol/g～80 μ mol/g; Total acid content in the time of 350 ℃ is 30 μ mol/g～140 μ mol/g, and wherein protonic acid acid amount is 0 μ mol/g～30 μ mol/g.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133997 CN1268722C (en) | 2003-09-15 | 2003-09-15 | Hydrogenating catalyst for petroleum wax and its preparation process |
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| CN1268722C true CN1268722C (en) | 2006-08-09 |
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| CN105983445B (en) * | 2015-02-03 | 2019-08-02 | 中国石油天然气股份有限公司 | A kind of catalyst carrier for hydrgenating and preparation method thereof |
| CN106140284B (en) * | 2015-03-27 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of carrier of hydrocracking catalyst and preparation method thereof |
| CN106140251B (en) * | 2015-03-27 | 2018-07-20 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and preparation method thereof |
| CN106140249B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method of carrier of hydrocracking catalyst |
| CN106140281B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method of middle oil type hydrocracking catalyst |
| CN106140287B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106140280B (en) * | 2015-03-27 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN106140250B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN106140286B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | The preparation method of carrier of hydrocracking catalyst |
| CN114471508B (en) * | 2020-10-27 | 2023-07-11 | 中国石油化工股份有限公司 | Silicon-containing aluminum oxide molding carrier and preparation method and application thereof |
| CN116060087B (en) * | 2021-10-29 | 2024-05-07 | 中国石油化工股份有限公司 | Grading method of hydrogenation catalyst and application of grading method in refining microcrystalline wax |
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