Hydrotreating catalyst adopts immersion process for preparing usually.Promptly, flood certain carrier (as Al with the solution that contains required active ingredient (as Mo, Ni, Co, P etc.)
2O
3, SiO
2-Al
2O
3Deng).In preparation high reactivity immersion type hydrotreating catalyst process, ran into many difficulties, and these difficulties are almost all relevant with steeping fluid.For example, especially the steeping fluid of ultrahigh concentration is usually unstable or very unstable for high density.Mo-Ni (the Co)-P/Al that therefore, prepare the superelevation metal content
2O
3Hydrotreating catalyst is difficult to adopt " a step pickling process " once to finish.And adopt two step or multistep pickling process or other methods, not only make the preparation process complexity, and may bring detrimentally affect some physical and chemical performance (as physical strength) of catalyzer.
United States Patent (USP) 4,392,985 disclose the preparation method of a kind of Mo, Co, P solution.The main points of this method are: at first under agitation with ammonium molybdate (NH
4)
6Mo
7O
244H
2O is partially soluble in the water.Not dissolving part adds H under slowly stirring
3PO
4(85%) dissolving adds Xiao Suangu Co (NO again
3)
26H
2O.The solution that adopts this invention to make, every 100ml can contain 33.6g MoO
3, 6.3g CoO and 8.6g P.The solution pH value is lower than 1.2.United States Patent (USP) 4,444,905 have introduced a kind of Mo, the Ni of higher molybdenum concentration, method of P solution of preparing.These method main points are: by a certain percentage with MoO
3, H
2O and H
3PO
4(75%) makes pulpous state.Add a certain amount of nickelous carbonate in during>15 minutes, be warming up to 93 ℃ and heating 2 hours under this temperature.Make bright green solution.According to the prepared solution of this method, every 100ml can contain 12-34gMoO
3, 2.0-5.6gNiO, 2.3-6.4g P.This solution at room temperature can be stablized 6 months.Such strength of solution for the high metal content of preparation, high-activity hydrogenation catalyst, still can not be finished in a step.
The objective of the invention is: (1) preparation high stability, Mo, the Ni (Co) of high density, P solution; (2) simplify the Catalyst Production process, reduce cost; (3) improve catalyst activity and physical strength.
Mo of the present invention, Ni (Co), P solution, every 100ml solution contains 45-80g MoO
3, 8-20g NiO, 0-15g CoO, P/MoO
3Weight ratio is 0.08-0.18.
High strong solution compound method of the present invention is: by the strength of solution requirement required phosphoric acid is added in the entry, make phosphate aqueous solution.Above-mentioned phosphate aqueous solution is joined in the molybdenum oxide of aequum.This system under agitation is heated to little boiling, makes the whole or most of dissolvings of molybdenum oxide.System temperature is reduced to 60-70 ℃, add the basic nickel carbonate of requirement, be warming up to little boil and heated and stirred is all dissolved basic nickel carbonate once more.Last heating evaporation is removed redundant moisture and is made solution concentration, makes Mo, Ni, the P solution of high density, high stability.In addition, can also be as required, before solution evaporation concentrates, add nickelous nitrate and/or Xiao Suangu in above-mentioned solution, stirring and dissolving is with the pH value of regulator solution, and increase Ni content or introduce the Co component, revaporization concentrates Mo, Ni (Co), the P solution that makes high density, high stability.
The preparation process of solution of the present invention is as follows:
(1). phosphate aqueous solution is added in the molybdenum oxide, stir, slowly heat temperature raising is to little boiling, and is heated to molybdenum oxide all or most of dissolving.
(2). after above-mentioned solution is cooled to 60-70 ℃, slowly add basic nickel carbonate, place and be warming up to little boiling again after 15 minutes, be heated to throw out and dissolve substantially.(this impurity is brought into by impure raw material to remove insoluble impurities to reduce to the room temperature after-filtration.If use pure raw material, can save filtration step).
(3). as required, can in above-mentioned filtrate, add nickelous nitrate and/or Xiao Suangu, with Mo, Ni, P or Mo, Ni, Co, the P solution that makes required PH.
(4). above-mentioned solution heating is concentrated into needed concentration.Prepared Mo, Ni (Co), P solution according to the present invention have following character:
(1). every 100ml solution can contain MoO
345-80g, NiO 8-20g, CoO 0-15g, P/MoO
3Weight ratio is 0.08-0.18.
(2). can prepare the solution of different PH as required.Solution pH value variation range is 0-3.8.
(3). this solution at room temperature can be stablized more than 3 years.
Advantage of the present invention is:
(1) Mo of the present invention, Ni (Co), P solution, preparation process is simple, easily row.
(2) Mo of the present invention, Ni (Co), P solution, metal M o and Ni (Co) concentration can be very.The hydrotreating catalyst that just can prepare high metal content through the single-steeping process.
(3). Mo of the present invention, Ni (Co), P solution, even also very stable under very high metal concentration.At room temperature can stablize and not produce muddiness or precipitation more than 3 years.
(4). catalyzer of the present invention, the catalyzer that its hydrotreatment reactivity ratio makes with usual way wants high.
For further specifying the present invention, enumerate following examples and comparative example.(A) the preparation embodiment 1 of .Mo, Ni (Co), P solution
20ml phosphoric acid (85%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 60-70 ℃.Under agitation slowly add basic nickel carbonate 35g, be warming up to again and littlely boil and heated 3 hours, dissolve substantially to throw out.Filter.Filtrate is concentrated into 250ml.Embodiment 2
17ml phosphoric acid (85%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to little boil and heat all dissolved to molybdenum oxide in 4 hours.Filter.In filtrate, add the 87g nickelous nitrate.Be concentrated into 250ml after the dissolving.Embodiment 3
The 10g nickelous nitrate is joined in embodiment 1 prepared solution.Dissolving.The solution heating is concentrated into 200ml.Embodiment 4
The 15g Xiao Suangu is joined in embodiment 1 prepared solution.Dissolving.The solution heating is concentrated into 200ml.Make Mo, Ni, Co, P solution.Embodiment 5
To be concentrated into 160ml by embodiment 3 prepared solution heating.Embodiment 6
To be concentrated into 130ml by embodiment 3 prepared solution heating.Embodiment 7
40ml phosphoric acid (85%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 60-70 ℃, under agitation slowly add the 45g basic nickel carbonate.Be warming up to again and littlely boil and heated 3 hours, dissolve substantially to throw out.Filter.Filtrate is concentrated into 200ml.Comparative example 1
With 313ml water (21 ℃), 5.0ml phosphoric acid (75%) and 100g molybdenum oxide are made pulpous state.Slowly add 28.5g nickelous carbonate (adding more than 15 minutes).With mixture heating up to 93 ℃, stir then, and under this temperature, kept 2 hours.With the solution concentration that makes to 347ml.Comparative example 2
Comparative example 1 prepared solution heating is concentrated into 200ml.More than Mo, Ni, P and Mo, Ni, Co, the physico-chemical property of P solution of each routine gained list in the table 1.
The character of each routine solution of table 1
Strength of solution, g/100ml
PH MoO
3NiO CoO P P/MoO
3Weight ratio stability * embodiment 1 3.0 40.0 8.0---3.6 are embodiment 2 0.1 40.0 8.9---3.0 embodiment 3 1.9 50.0 11.2---4.5 embodiment embodiment 5 1.6 62.5 14.0---5.6 embodiment 6 1.4 76.9 17.2---6.9 embodiment 7 1.3 50.0 12.9---9.0 0.05 0.5 years comparative example 2 2.1 39.5 8.3---2.1 of comparative example 1 3.0 22.8 4.8---1.2,0.05 concentration process more than 0.18 3 more than 0.09 3 more than 0.09 3 more than 4 1.8 50.0 10.0 1.9 4.5 0.09 3 years more than 0.09 3 more than 0.08 3 more than 0.09 3
Precipitation appears
*At room temperature place
As can be seen from Table 1, not only concentration is high but also extremely stable for the solution of embodiment 1-7.Solution in the comparative example, concentration have raising precipitation just to occur slightly, become unstable.
(B). verify beneficial effect embodiment 8 of the present invention by the preparation hydrotreating catalyst
Take by weighing 100g γ-Al
2O
3, add Mo, Ni, the P solution of 130ml according to (A) embodiment 3 preparations, at room temperature flood 4 hours after, leach redundant solution.Moist catalysis was dried 3 hours down at 105-115 ℃ after air drying spends the night.Dried sample is warming up to 190 ℃ with 3-5 ℃ of/minute speed, constant temperature 0.5 hour.Be warming up to 368 ℃ with 3-5 ℃ of/minute speed again, constant temperature 1 hour.Be warming up to 470 ℃ with 3-5 ℃ of/minute speed at last, constant temperature calcining 3 hours.Embodiment 9
Employing is a steeping fluid according to the solution of (A) embodiment 5 preparations.Method for preparing catalyst and step are with embodiment 8.Comparative example 3
Employing is a steeping fluid according to the solution of (A) comparative example 1 preparation.Method for preparing catalyst and step are with embodiment 8.Comparative example 4
The catalyzer that comparative example 1 is made is used according to the solution impregnation of (A) comparative example 1 preparation the 2nd time.Dipping, drying, roasting condition are with embodiment 8.More than each routine prepared MoNiP/Al
2O
3Catalyzer and used γ-Al
2O
3Physico-chemical property list in table 2 and the table 3 respectively.Raw materials used oil properties of evaluation of catalyst activity and reaction process condition see Table 4 and table 5.
Evaluate catalysts was vulcanized respectively under 260 ℃ and 370 ℃ 8 hours with the grand celebration aviation kerosene cut that contains dithiocarbonic anhydride 1.5% (V).Sulfuration finishes, and swap-in stock oil is stablized after 8 hours and begun to test.When estimating each routine catalyzer, by the conditioned reaction temperature, make total denitrification percent reach 95w%, promptly generating oily nitrogen content is 0.06w%.When catalyzer than low reaction temperatures the time, just can reach this denitrification percent, show that this catalyzer has higher activity.Vice versa.
Table 6 is listed each routine catalyst hydrogenation denitrification reaction activity rating result.
From table 3 and table 6 result as can be seen: the catalyzer that adopts the present invention's preparation, hydrodenitrogenationactivity activity is much higher, compares temperature of reaction with common single-steeping method and will hang down 13 ℃ (embodiment 8 compares with comparative example 3) or low 19 ℃ (embodiment 9 compares with comparative example 3).Compare with common secondary dipping process, although step is simple, temperature of reaction still will be hanged down 7 ℃ (embodiment 9 compares with comparative example 3).In addition, hydrotreating catalyst of the present invention, aspect physico-chemical property, physical strength for example, aspects such as specific surface area and pore volume all are better than common secondary dipping process.
Used γ-the Al of table 2 each routine catalyzer of preparation
2O
3The physico-chemical property specific surface area, M
2/ g 308 pore volume, ml/g 0.607 average pore diameter, nm 7.76 physical strengths, N/mm
*17.3* Φ 1.0mm strip
The physico-chemical property of each routine catalyzer of table 3
Embodiment 8 embodiment 9 comparative examples 3 comparative examples 4 specific surfaces, m
2/ g 162 138 195 127 pore volumes, ml/g 0.320 0.300 0.380 0.290 average pore diameter, nm 8.16 8.23 7.93 8.19 chemical constitutions, w%MoO
324.1 29.6 16.8 28.9NiO, 4.31 5.60 3.71 6.32P, 2.60 2.70 0.35 1.38Al
2O
3Surplus surplus surplus surplus bulk density, g/ml 0.930 0.952 0.870 0.897 physical strength, N/mm
*19.6 18.9 17.6 8.3* φ 1.0mm strips
Table 4 stock oil character stock oil triumph VGO proportion d (20 ℃), g/ml 0.903 sulphur, w% 0.46 nitrogen, w% 0.12 condensation point, ℃ 36 carbon residues, w% 0.05 boiling range, ℃ IBP/10% 290/34930%/50% 375/39270%/90% 406/43695%/EBP 446/467
Table 5 reaction process condition reaction pressure, MPa 6.37LHSV, h
-11.00 hydrogen/oil volume is than 1,000
The hydrodenitrification reactive behavior of each routine catalyzer of table 6 is catalyzer embodiment 8 embodiment 9 comparative examples 3 comparative examples 4 temperature of reaction relatively, and ℃ 380 372 393 379