CN103212432B - Catalyst for hydro-denitrification of inferior heavy distillate oil and preparation method and application of catalyst - Google Patents
Catalyst for hydro-denitrification of inferior heavy distillate oil and preparation method and application of catalyst Download PDFInfo
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Abstract
The invention provides a catalyst for hydro-denitrification of inferior heavy distillate oil and a preparation method and application of the catalyst. The preparation method comprises the following steps of: performing surface acid treatment on aluminum oxide and an HY molecular sieve separately; mechanically compounding the aluminum oxide subjected to the acid treatment and the HY molecular sieve subjected to the acid treatment into a carrier; dipping steeping liquid containing catalyst active components to load the catalyst active components; and drying to obtain the catalyst for hydro-denitrification of heavy distillate oil. In the carrier, the content of the HY molecular sieve subjected to the acid treatment is 5 to 20 percent, the active components comprise Mo and/or W, and Co and/or Ni, the steeping liquid also comprises a complexing agent, the Mo and/or W oxide content of the catalyst is 10 to 30 percent, and the Co and/or Ni oxide content of the catalyst is 1 to 10 percent. The catalyst has the characteristics of reasonable acidic distribution, a large number of active metal stacking piles and complete metal vulcanization, has a high hydro-denitrification activity to the inferior heavy distillate oil, and has high hydro-desulfurization performance.
Description
Technical field
The present invention relates to a kind of bad heavy distillate hydrodenitrogenation catalyst and preparation method thereof and application, specifically relate to and a kind of the method for carrying metal Kaolinite Preparation of Catalyst after low-kappa number and preparation-obtained catalyst and application thereof are carried out to carrier, after particularly corresponding classification vulcanization being carried out to it, be applied to bad heavy distillate hydrodenitrogeneration.
Background technology
Along with the aggravation of crude oil heaviness trend and the exploitation of non-conventional oil resource, heavy oil (heavy distillate) will become the main object of following PETROLEUM PROCESSING.The main feature of heavy oil is that sulphur, nitrogen, metal, polycyclic aromatic hydrocarbon compounds content are high, easily causes the poisoning of catalyst and inactivation, thus have higher requirement to hydrotreating catalyst in heavy-oil hydrogenation processing procedure.
The sulphur, nitrogen, metal etc. of heavy oil are all in aromatic ring structure, especially difficult with nitrogen compound hydrogenation and removing, and thus the exploitation of bad heavy distillate hydrodenitrogenation catalyst is the key promoting heavy-oil hydrogenation treatment process technical merit.Having developed multiple both at home and abroad at present take aluminium oxide as carrier hydrogenation pretreatment catalyst, but because aluminium oxide itself has the shortcomings such as surface acidity distribution is comparatively single, Support-metal strong interaction is stronger, cause catalyst metal components state of cure (vulcanization) not high, in heavy oil feedstock nitrogen compound molecule the absorption of catalyst surface and conversion performance poor.For this reason, domestic and international researcher has carried out certain work in carrier surface modification, raising catalyst metal components state of cure (vulcanization) etc.
US4459367 discloses a kind of method adopting HCl treatment aluminium oxide and molecular sieve.The method uses HCl treatment again by after aluminium oxide and molecular sieve mixed-forming, this processing mode can the macropore of production some and mesoporous, but certain destruction and peptization are also existed to aluminium oxide itself, stronger dealuminization is also existed to molecular sieve simultaneously, shaping not only bad for carrier, and the acidity of complex carrier is weakened, molecular sieve crystallinity declines, and is unfavorable for the preparation of high performance catalyst.
US4443558 adopts complete kneading method one-step shaping Kaolinite Preparation of Catalyst, does not introduce other auxiliary agents in its catalyst, just in the preparation engineering of catalyst, first adds acid solution, after add alkaline solution neutralization method.The method is comparatively strong due to the acid that adds and aluminium oxide effect, makes the structural deterioration of aluminium oxide own comparatively serious, after the alkaline solution that adds also can the partially acidic position on catalyst neutralisation surface, make the matching of catalyst surface acidity poor.
CN101433848 adopts the method adding nonionic surface active agent in active metal dipping solution, and obtained catalyst has the good advantage of metal dispersion.But metal is excessively dispersed, be unfavorable for high activity metal phase formation and to the absorption of complicated molecule structure sulphur nitride and hydrogenation and removing reaction.
US2004055936 adopts and add nitrogen-containing compound as dispersant in metal impregnation liquid, and the method can promote the formation of metal component sulfuration phase to a certain extent, and the hydrodenitrogeneration performance of catalyst is made moderate progress.But the method due to the stress efficacy of dispersant low, and dispersant use amount is large.Improve not obvious to the hydrodesulfurization of heavy distillate, denitrification effect.
CN1552794A adopts and add organic carboxyl acid in metal salt solution, stable organic double compound is formed with main metal, metal impregnation solution is made to have good stability, feature that viscosity is low, improve metal component, the particularly dispersiveness of main metal, the activity of catalyst has had raising to a certain degree.But this catalyst is in roasting process, surface is easy to organic acid sintering phenomenon occurs, and metal active centres is partially covered.
Based on problems and shortcomings existing in above-mentioned heavy-oil hydrogenation catalyst and preparation process thereof, be badly in need of that improvement is carried out to correlation technique and improve, to prepare the hydrotreating catalyst of the bad heavy distillate with high hydrodenitrogenationactivity activity.
Summary of the invention
One object of the present invention is to improve for Problems existing and deficiency in heavy distillate hydrotreating catalyst in above-mentioned prior art and preparation process thereof, there is provided a kind of preparation method of heavy distillate hydrodenitrogenation catalyst, to prepare the hydrotreating catalyst of the bad heavy distillate with high hydrodenitrogenationactivity activity.
Another object of the present invention is to provide a kind of hydrotreating catalyst with the bad heavy distillate of high hydrodenitrogenationactivity activity.
Another object of the present invention is to the application that described catalyst is provided, particularly its application in bad heavy distillate hydrodenitrogeneration process.
On the one hand, the invention provides a kind of preparation method of heavy distillate hydrodenitrogenation catalyst, the method comprises:
Respectively surface acid etching is carried out to aluminium oxide and HY molecular sieve, then using the aluminium oxide after acid treatment and the HY molecular sieve after acid treatment machinery compound as carrier, by flooding the maceration extract and catalyst-loaded active component that contain catalyst activity component, drying again, obtained heavy distillate hydrodenitrogenation catalyst; Wherein:
With the gross weight of described carrier for benchmark, the HY molecular sieve content 5wt% ~ 20wt% in carrier after acid treatment;
Described catalyst activity component comprises: main metal M o and/or W and promoter metal Co and/or Ni; Further, also complexing agent is contained in described maceration extract; Described complexing agent be selected from citric acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ethylenediamine one or more, promoter metal and complexing agent mol ratio are 0.1 ~ 5.0: 1;
With the gross weight of gained catalyst for benchmark, with the oxide basis of activity component metal, in catalyst, the content of Mo and/or W oxide is the content of 10wt% ~ 30wt%, Co and/or Ni oxide is 1wt% ~ 10wt%.
In the preparation method of heavy distillate hydrodenitrogenation catalyst of the present invention, by adding the method for organic complexing agent in maceration extract, dispersion and the curability of active metal component can be improved, particularly due to the interaction between aided metal ion and complexing agent, facilitate the formation of high hydrogenation activity phase, thus the hydrotreating catalyst of the heavy distillate with high hydrodenitrogenationactivity activity can be prepared.
According to specific embodiment of the invention scheme, the present invention is to provide one and be applicable to heavy distillate, particularly the preparation method of the bad heavy distillate deep hydrogenation denitrification catalyst of high nitrogen low-sulfur.Alumina carrier surface due to routine only has L acid, and acids type is single, is unfavorable for the fracture of C-N key; Stronger interaction is had between alumina support and metal component, cause active metal in alumina carrier surface high degree of dispersion, make metal component not only difficulty or ease reduction and sulfuration, and the metal stacking number of plies is low, be unfavorable for absorption and the reaction of sterically hindered larger sulphur, nitrogen compound molecule in heavy distillate, make the nitrogen removal performance of catalyst very poor.And in the present invention, adopt the compound of aluminium oxide and HY molecular sieve as carrier, heavy-oil hydrogenation denitrification catalyst performance can be improved.
Inventor finds in further studying, because HY molecular sieve has stronger B acid site, the fracture of C-N key can be promoted, but the remarkable deficiency of aluminium oxide and HY molecular sieve complex carrier is that the L acid of alumina surface is excessively strong, excessively strong, the sour density of B acid of HY molecular sieve surface is comparatively large, pore size is less, very easily in the condensation green coke causing the large molecule of condensed-nuclei aromatics isopolarity on surface, reduce the Activity and stabill of catalyst.Based on the problems referred to above, according to specific embodiment of the invention scheme, present invention further proposes the method for aluminium oxide and HY molecular sieve all being carried out to surface acid etching.Surface acid etching adopts organic acid to carry out pretreatment to aluminium oxide, HY molecular sieve respectively, and aluminium oxide, after organic acid process, reduces the strong L acid site quantity on its surface, increases part B acid site quantity; HY molecular sieve, after sour dealumination treatment, reduces the strong B acid site quantity on surface, and creates part mesopore orbit, makes complex carrier obtain suitable B acid/L acid ratio and good hole link, is conducive to absorption and the reaction of reactant molecule.
According to specific embodiment of the invention scheme, in the preparation method of heavy distillate hydrodenitrogenation catalyst of the present invention, the process of aluminium oxide being carried out to surface acid etching comprises:
Organic acid is mixed with the organic acid soln of concentration range 0.002 ~ 0.5mol/L, under temperature 25 ~ 80 DEG C of conditions, be alumina powder and the organic acid soln mix and blend 20 ~ 120min of 1: 10 ~ 1: 100 by solid-liquid mass ratio, form suspension, filter afterwards, be 7 ~ 9 by washing of precipitate to filtrate pH value, be deposited in 100 ~ 140 DEG C of drying 2 ~ 6h, roasting 2 ~ 6h at 400 ~ 800 DEG C, obtains the alumina powder after acid treatment.
According to more specifically embodiment of the present invention, described alumina powder can be selected from common alumina powder, the fast shedding of aluminium oxide, aluminum oxide dry glue powder, boehmite powder one or more; Preferably, the specific area 200 ~ 380m of selected alumina powder
2/ g, average pore size 5.0 ~ 13.0nm, pore volume 0.6 ~ 1.3mL/g.
According to more specifically embodiment of the present invention, described organic acid can be selected from citric acid, oxalic acid or tartaric acid one or more.
According to specific embodiment of the invention scheme, in the preparation method of heavy distillate hydrodenitrogenation catalyst of the present invention, the process of HY molecular sieve being carried out to surface acid etching comprises:
In the isothermal reactor of 30 ~ 80 DEG C, add citric acid, oxalic acid or tartaric acid solution that concentration is 0.005 ~ 0.5mol/L, drop into HY molecular sieve, wherein solid-liquid mass ratio (molecular sieve and organic acid soln mass ratio) controls in 1: 10 ~ 1: 120 scopes, stir process 30 ~ 100min, after filtration, washing (washing to filtrate pH value is 7 ~ 9 usually), by the molecular sieve after process at 100 ~ 140 DEG C of drying 2 ~ 6h, roasting 2 ~ 8h at 400 ~ 800 DEG C, obtains the HY molecular sieve after acid treatment.
According to specific embodiment of the invention scheme, in the preparation method of heavy distillate hydrodenitrogenation catalyst of the present invention, the process of the aluminium oxide after acid treatment and the machinery of the HY molecular sieve after acid treatment compound is comprised:
Mixed with the HY molecular sieve after acid treatment by alumina powder after acid treatment, through compressing tablet, spin or extruded moulding after kneading, 100 ~ 140 DEG C of drying 12 ~ 20h, roasting 4 ~ 12h at 400 ~ 800 DEG C, obtains the complexes carrier of aluminium oxide and Y molecular sieve.
According to specific embodiment of the invention scheme, in the preparation method of heavy distillate hydrodenitrogenation catalyst of the present invention, be adopt step impregnation method catalyst-loaded active component on carrier, first flood main metal component, and then impregnation aids metal component.Particularly, described step impregnation method comprises:
Prepare the solution of the soluble-salt of main metal as main metal impregnation liquid, adopt the main metal of method load of incipient impregnation on carrier, after placing 4 ~ 14h under the sample normal temperature flooded, dry 2 ~ 6h at 80 ~ 140 DEG C, roasting 2 ~ 6h at 400 ~ 800 DEG C, obtains the catalyst preparation sample containing main metal;
The soluble-salt of the promoter metal of preparation desired concn and the mixed solution of described complexing agent are as promoter metal maceration extract, wherein promoter metal and complexing agent mol ratio are 0.1 ~ 5.0: 1, the promoter metal maceration extract equal-volume prepared is supported on aforementioned containing on the catalyst preparation sample of main metal, obtains the catalyst supporting main metal and promoter metal;
After afterwards the catalyst supporting main metal and promoter metal being placed 4 ~ 14h under normal temperature, at 80 ~ 140 DEG C, drying 10 ~ 30 hours, obtains described heavy distillate hydrodenitrogenation catalyst.
In a specific embodiment of the present invention, when being chosen as Ni-Mo for carried metal, described step impregnation method comprises:
First prepare with the ammonia spirit of 2% ~ 20% salting liquid containing Mo, Mo salt can select molybdenum trioxide or ammonium molybdate, preferably ammonium molybdate, adopt the method dipping of incipient impregnation, after placing 4 ~ 14h (usually placing 6 ~ 10h) under the sample normal temperature flooded, at 80 ~ 140 DEG C, dry 2 ~ 6h, roasting 2 ~ 6h at 400 ~ 800 DEG C, obtain the preparation catalyst sample containing Mo;
Prepare in the nickel nitrate of desired concn and the mixed solution of organic complexing agent, wherein Ni and complexing agent mol ratio are 0.1 ~ 5.0: 1, be preferably 0.1 ~ 2.0: 1, the maceration extract equal-volume prepared be supported on above-mentioned containing on the catalyst preparation product of Mo, obtain the catalyst sample supporting Ni-Mo;
Afterwards by above-mentioned support place 4 ~ 14h under the catalyst sample normal temperature of Ni-Mo after, lower dry 10 ~ 30 hours, obtain Ni-Mo catalyst, it was applicable to heavy distillate hydrodenitrogeneration.
In method of the present invention, the operating procedure do not mentioned in detail, the kneading of such as described carrier, compressing tablet, spin or extruded moulding process, the concrete operations of incipient impregnation etc. all can be carried out according to the routine operation in affiliated field.During concrete enforcement, in kneading process, suitable extrusion aid etc. can also be added.Normal temperature described in the present invention typically refers to 18 ~ 25 DEG C.
On the other hand, present invention also offers the catalyst prepared according to described method, catalyst obtained by the present invention have acid distribution rationally, high, the sufficient feature of metal sulfuration of the active metal stacking number of plies, to bad heavy distillate, there is higher hydrodenitrogenationactivity activity, have higher hydrodesulfurization performance simultaneously concurrently.
According to the preferred specific embodiments of the present invention, the catalyst specific surface prepared by the present invention is 160 ~ 350m
2/ g, average pore size 5.0 ~ 12.0nm, pore volume is 0.3 ~ 0.8ml/g.
Catalyst prepared by the present invention, with the weight of catalyst for benchmark, wherein the content of the oxide of main metal M o and/or W is the content of the oxide of 10wt% ~ 30wt%, Co and/or Ni is 1wt% ~ 10wt%.In addition, preferably, in catalyst of the present invention, the content of aluminium oxide is 65wt% ~ 75wt%.
On the other hand, present invention also offers the application of described catalyst in heavy distillate hydrodenitrogeneration.
Particularly, catalyst of the present invention can be applicable to vacuum distillate, wax tailings, deasphalted oil, de-residue wet goods bad heavy distillate and mixed material thereof, is particularly suitable for high, the low-sulfur content bad heavy distillate raw material of nitrogen content.
On the other hand, present invention also offers a kind of method of heavy distillate hydrodenitrogeneration, the method comprises the application process using catalyst of the present invention as heavy distillate hydrodenitrogenation catalyst.
According to specific embodiment of the invention scheme, the method of heavy distillate hydrodenitrogeneration of the present invention also comprises the process of described catalyst being carried out to presulfurization, described presulfurization adopts hypo-hyperthermia classification vulcanization, conditions of vulcanization is: cryogenic vulcanization temperature is 150 ~ 300 DEG C, high temperature vulcanized temperature is 300 ~ 450 DEG C, the cryogenic vulcanization time is 0.2 ~ 1: 1 with the ratio of high temperature vulcanized time, pressure 4 ~ 6MPa, liquid hourly space velocity (LHSV) 2.0 ~ 10.0h
-1, sulfuration 4 ~ 20h (cryogenic vulcanization and high temperature vulcanized total time), hydrogen-oil ratio 300 ~ 600.
Catalyst of the present invention is for exempting from bake kind, and in order to improve the state of cure (vulcanization) of catalyst, the present invention adopts " hypo-hyperthermia " classification vulcanization.The object of introducing " cryogenic vulcanization " is the state of cure (vulcanization) in order to improve main metal W (or Mo) species, promotes that the metal active of " Ni-W-S (II) or Co-Mo-S (II) " type height hydrogenation activity is formed mutually.This is because the curing capacity of Ni (or Co) is far away higher than W (or Mo), at H
2preferentially can form Ni-S (or Co-S) metal active phase in S atmosphere, thus be unfavorable for the formation of " Ni-W-S (II) (or Co-Mo-S (II)) type " active phase.The present invention introduces complexing agent in maceration extract, and aided metal and complexing agent are had an effect and formed more stable complex compound, under cryogenic conditions, containing Ni
2+(or Co
2+) complex compound to form the speed of " Ni-S (or Co-S) " sulfuration phase suppressed, thus weaken the formation of " Ni-W-S (I) (or Co-Mo-S (I)) type " active phase.Make the same H of main metal W (or Mo) species
2s can fully react, formation as much as possible " Ni-W-S (II) (or Co-Mo-S (II)) type " active phase.Therefore particularly important with the control of the time of " high temperature vulcanized " to " cryogenic vulcanization ".
In sum, the invention provides a kind of heavy distillate hydrodenitrogenation catalyst and preparation method thereof and application, the present invention carries out character and the acidity of the effective modulation carrier surface of pretreatment to aluminium oxide and Y molecular sieve by adopting, and in maceration extract, add the method for organic complexing agent, improve dispersion and the curability of metal component, and the method for calcined catalyst is exempted from further combined with high-low temperature classification sulfuration, make prepared catalyst have higher hydrodenitrogenationactivity activity in heavy distillate hydroprocessing processes, have higher hydrodesulfurization performance simultaneously concurrently.
Detailed description of the invention
In order to the understanding clearly of technical characteristic of the present invention, object and effect, further describe by following examples, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
The first step: alumina surface acid treatment
Take boehmite powder 300g, the oxalic acid solution 6L of preparation 0.04mol/L, in 40 DEG C of waters bath with thermostatic control by boehmite powder dispersion in oxalic acid solution, boehmite and oxalic acid solution mass ratio are 1: 20, continuous stirring 30min, suction filtration, wash to filtrate in neutral, 120 DEG C of dry 4h, 550 DEG C of roasting 3h obtain the alumina powder after acid treatment.
Second step: molecular sieve surface acid treatment
Take 100g HY molecular sieve, the citric acid solution 1.5L of preparation 0.05mol/L, under 45 DEG C of water bath with thermostatic control conditions, HY molecular sieve is dropped in citric acid solution, after mechanical agitation 30min, by suspension suction filtration, filter cake water washing to filtrate is neutral, after 120 DEG C of dry 3h, and 500 DEG C of roasting 3h.Obtain the HY molecular sieve after acid treatment.
3rd step: carrier shaping
Get acid treatment rear oxidation aluminium powder 180g, the HY molecular sieve 20g after acid treatment, fully mixes, after add 9.2g nitric acid (65%), sesbania powder 5g, citric acid 10g, water 150g, kneading extruded moulding.After drying under normal temperature, 120 DEG C of dry 14h, 550 DEG C of roasting 7h, be broken into 20 ~ 40 order particles, takes 70g (water absorption rate 1.25) for subsequent use.
4th step: the preparation of catalyst
Adopt the method for step impregnation, carrying metal Mo and Ni active component.Take 30.6g ammonium molybdate, be dissolved in 87.5g deionized water, adding ammoniacal liquor adjust ph is 9.5, and be stirred to ammonium molybdate particle and all dissolve, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and 550 DEG C of roasting 3h, first make MoO
3/ Al
2o
3sample; Then take 19.5g nickel nitrate, 28.2g citric acid, be dissolved in 87.5g water, by this solution incipient impregnation at above-mentioned MoO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, and 120 DEG C of dry 18h obtain catalyst and are denoted as HDN-1.
Embodiment 2
Adopt the aluminium oxide in embodiment 1 and molecular sieve surface acid treatment mode, get the aluminium oxide 85g after acid treatment respectively, the HY molecular sieve 15g after acid treatment, after abundant mixing, add 4.61g nitric acid (65%), sesbania powder 2.5g, citric acid 5g, water 80g, kneading extruded moulding, after drying under room temperature, 120 DEG C of dry 14h, 550 DEG C of roasting 7h, are broken into 20 ~ 40 order particles, take 21g for subsequent use.Adopt the method for step impregnation, carrying metal W and Ni active component.Take 8.469g ammonium metatungstate, be dissolved in 27.5g deionized water, be stirred to ammonium metatungstate particle and all dissolve, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and 550 DEG C of roasting 3h, first make WO
3/ Al
2o
3sample; Then take 7.008g nickel nitrate, 10.133g citric acid, be dissolved in 27.5g water, by the maceration extract incipient impregnation containing Ni and citric acid at above-mentioned WO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, and 120 DEG C of dry 18h obtain catalyst, are denoted as HDN-2.
Embodiment 3
Adopt the aluminium oxide in embodiment 1 and molecular sieve surface acid treatment mode, get the aluminium oxide 180g after acid treatment respectively, the HY molecular sieve 20g after acid treatment, after abundant mixing, after add 9.2g nitric acid (65%), sesbania powder 5g, citric acid 10g, water 150g, kneading extruded moulding.After drying under normal temperature, 120 DEG C of dry 14h, 550 DEG C of roasting 7h, be broken into 20 ~ 40 order particles, takes 70g (water absorption rate 1.25) for subsequent use.Adopt the method for step impregnation, carrying metal W, Mo and Ni active component.Take 26.64g ammonium metatungstate, 7.57g ammonium molybdate, be dissolved in 87.5g deionized water, be stirred to ammonium metatungstate particle and all dissolve (can suitably heat), normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and 550 DEG C of roasting 3h, first make Mo-WO
3/ Al
2o
3sample; Then take 7.57g nickel nitrate, 10.95g citric acid, be dissolved in 87.5g water, by the maceration extract incipient impregnation containing Ni and citric acid at above-mentioned Mo-WO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, and 120 DEG C of dry 24h obtain catalyst, are denoted as HDN-3.
Embodiment 4
Adopt method in embodiment 1 to carry out surface acid etching to aluminium oxide and molecular sieve, it is shaping that the ratio in employing embodiment 1 carries out complex carrier, gets 20 ~ 40 order complex carrier 70g, adopts the method for step impregnation, carrying metal Mo and Ni active component.Take 30.6g ammonium molybdate, be dissolved in 87.5g deionized water, adding ammoniacal liquor adjust ph is 9.5, and be stirred to ammonium molybdate particle and all dissolve, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and 550 DEG C of roasting 3h, first make MoO
3/ Al
2o
3sample; Then take 19.5g nickel nitrate, 14.1g citric acid, be dissolved in 75g water, by this solution incipient impregnation at above-mentioned MoO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, and 120 DEG C of dry 18h obtain catalyst, are denoted as HDN-4.
Embodiment 5
Adopt method in embodiment 1 to carry out surface acid etching to aluminium oxide and molecular sieve, it is shaping that the ratio in employing embodiment 1 carries out complex carrier, gets 20 ~ 40 order complex carrier 70g, adopts the method for step impregnation, carrying metal Mo and Ni active component.Take 30.6g ammonium molybdate, be dissolved in 87.5g deionized water, adding ammoniacal liquor adjust ph is 9.5, and be stirred to ammonium molybdate particle and all dissolve, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and 550 DEG C of roasting 3h, first make MoO
3/ Al
2o
3sample; Then take 19.5g nickel nitrate, 19.6g ethylenediamine tetra-acetic acid, be dissolved in 87.5g water, by this solution incipient impregnation at above-mentioned MoO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, and 120 DEG C of dry 18h obtain catalyst, are denoted as HDN-5.
Embodiment 6
Adopt method in embodiment 1 to carry out surface acid etching to aluminium oxide and molecular sieve, complex carrier is shaping, gets 20 ~ 40 order complex carrier 70g, adopts the method for step impregnation, carrying metal Mo and Ni active component.Take 30.6g ammonium molybdate, be dissolved in 87.5g deionized water, adding ammoniacal liquor adjust ph is 9.5, and be stirred to ammonium molybdate particle and all dissolve, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and 550 DEG C of roasting 3h, first make MoO
3/ Al
2o
3sample; Then take 19.5g nickel nitrate, 9.8g ethylenediamine tetra-acetic acid, be dissolved in 87.5g water, by this solution incipient impregnation at above-mentioned MoO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, and 120 DEG C of dry 18h obtain catalyst, are denoted as HDN-6.
Embodiment 7
Take boehmite powder 300g, the citric acid solution 6L of preparation 0.02mol/L, adopt the aluminium oxide acid treatment mode in embodiment 1 to obtain citric acid treatment rear oxidation aluminium powder.HY molecular sieve adopts method in embodiment 1 to carry out acid treatment.Take above-mentioned acid treatment rear oxidation aluminium powder 180g, HY molecular sieve 20g respectively, adopt the carrier molding mode in embodiment 1, kneading and compacting.Be broken into 20 ~ 40 order particles, take 70g for subsequent use.Adopt the method for preparing catalyst in embodiment 1, obtain catalyst and be denoted as HDN-7.
Embodiment 8
Take aluminium oxide fast shedding powder 300g, the citric acid solution 6L of preparation 0.02mol/L, adopt the aluminium oxide acid treatment mode in embodiment 1 to obtain citric acid treatment rear oxidation aluminium powder.HY molecular sieve adopts the side in embodiment 1 to carry out acid treatment in fact.Take above-mentioned acid treatment rear oxidation aluminium powder 170g, HY molecular sieve 30g respectively, adopt the carrier molding mode in embodiment 1 to carry out kneading and compacting.Be broken into 20 ~ 40 order particles, take 70g for subsequent use.Adopt the method for step impregnation, carrying metal W and Ni active component.Take 28.23g ammonium metatungstate, be dissolved in 87.5mL deionized water, be stirred to ammonium metatungstate particle and all dissolve, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and 550 DEG C of roasting 3h, first make WO
3/ Al
2o
3sample; Then take 23.36g nickel nitrate, 23.40g ethylenediamine tetra-acetic acid, be dissolved in 87.5g water, by the maceration extract incipient impregnation containing Ni and citric acid at above-mentioned WO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, and 120 DEG C of dry 18h obtain catalyst, are denoted as HDN-8.
Embodiment 9
Take the pretreated Al of oxalic acid that above-described embodiment 1 prepares
2o
3powder 160g.Take 100g HY molecular sieve, the oxalic acid solution 1.2L of preparation 0.07mol/L is placed in 45 DEG C of isothermal reactors, is dropped into by HY molecular sieve in oxalic acid solution, mechanical agitation 0.5h, by suspension suction filtration, filter cake water washing to filtrate is neutral, after 120 DEG C of dry 3h, 500 DEG C of roasting 3h.Obtain required oxalic acid treatment Y molecular sieve.Get the molecular sieve after 40g process, adopt the extrusion mode in embodiment 1 and above-mentioned aluminium oxide kneading, extruded moulding.Adopt the method for preparing catalyst in above-described embodiment 1 to obtain catalyst, be denoted as HDN-9.
Respectively to 9 catalyst obtained by above embodiment 1 ~ 9, with the wax tailings of the low-sulfur high-nitrogen of poor quality for raw material (sulfur content 2400 μ g/g, nitrogen content 4400 μ g/g), at reaction condition: temperature 380 DEG C, pressure 8MPa, hydrogen to oil volume ratio 800, volume space velocity is 1h
-1under condition, loaded catalyst 10mL, the hydrodenitrogeneration ability of evaluate catalysts.Wherein, before carrying out hydrodenitrogeneration to poor oil, carry out presulfurization to catalyst, this process adopts " hypo-hyperthermia " classification sulfuration, and conditions of vulcanization is: volume space velocity 4h
-1, pressure 4MPa, low temperature 200 DEG C of sulfuration 4.8h, temperature is increased to 400 DEG C of sulfuration 6.4h, hydrogen-oil ratio 400.
Embodiment 10
For raw material, above-mentioned " hypo-hyperthermia " vulcanization is adopted with the deasphalted oil of poor quality (sulfur content 32900 μ g/g, nitrogen content 4400 μ g/g); At reaction condition: temperature 390 DEG C, pressure 9MPa, hydrogen to oil volume ratio 1000, volume space velocity is 1h
-1the hydrodenitrogeneration ability of lower evaluate catalysts HDN-1.
Embodiment 11
To implement above-mentioned wax tailings inferior for raw material, adopt conventional thermostatic sulfuration method, conditions of vulcanization is: volume space velocity 4h
-1, pressure 4MPa, curing temperature 320 DEG C of sulfuration 11h.At reaction condition: temperature 380 DEG C, pressure 6MPa, hydrogen to oil volume ratio 800, volume space velocity is 1h
-1, evaluate the hydrodenitrogeneration ability of HDN-1 catalyst.
Comparative example 1
The catalyst preparation technology of equal-volume step impregnation conveniently, preparation Ref-1 catalyst as a comparison.Concrete preparation method: get the aluminium oxide extruded moulding in 200g embodiment 1, screen size is for subsequent use at 20 ~ 40 object alumina particles (water absorption rate 1.25) 70g, take 30.6g ammonium molybdate, be dissolved in 87.5mL deionized water, adding ammoniacal liquor adjust ph is 9.5, is stirred to ammonium molybdate particle and all dissolves, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, 550 DEG C of roasting 3h, first make MoO
3/ Al
2o
3sample; Then take 19.5g nickel nitrate, be dissolved in 87.5g deionized water, by this solution incipient impregnation at above-mentioned MoO
3/ Al
2o
3on sample, normal temperature leaves standstill 6h, 120 DEG C of dry 4h, and it is 5%, MoO that 550 DEG C of roasting 3h obtain NiO content
3content is the catalyst of 25%, is denoted as Ref-1.With above-mentioned wax tailings inferior (sulfur content 2400 μ g/g, nitrogen content 4400 μ g/g) for raw material, at reaction condition: temperature 380 DEG C, pressure 8MPa, hydrogen to oil volume ratio 800, volume space velocity is 1h
-1the hydrodenitrogeneration ability of lower evaluate catalysts.Vulcanization is " hypo-hyperthermia " sulfuration, and conditions of vulcanization is: volume space velocity 4h
-1, pressure 4MPa, low temperature 200 DEG C of sulfuration 2.4h, temperature is increased to 400 DEG C of sulfuration 3.2h, hydrogen-oil ratio 400.
Comparative example 2
With above-mentioned wax tailings inferior (sulfur content 2400 μ g/g, nitrogen content 4400 μ g/g) for raw material, adopt the reaction condition in embodiment 11 and constant temperature vulcanization, evaluate the hydrodenitrogeneration ability of the catalyst Ref-1 in comparative example 1.
Comparative example 3
Adopt above-mentioned deasphalted oil inferior (sulfur content 32900 μ g/g, nitrogen content 4400 μ g/g) to be raw material, adopt the vulcanization in reaction condition and embodiment 11 in embodiment 10, evaluate the hydrodenitrogeneration ability of Ref-1.
The hydrogenation evaluation result of above embodiment 1 ~ 11 and comparative example 1 ~ 3 is as follows:
Can find out, the present invention is by carrying out character and the acidity of the effective modulation carrier surface of pretreatment to aluminium oxide and Y molecular sieve, and organic complexing agent is added in maceration extract, dispersion and the curability of metal component can be improved, and the method for calcined catalyst is exempted from further combined with high-low temperature classification sulfuration, make prepared catalyst have higher hydrodenitrogenationactivity activity in heavy distillate hydroprocessing processes, have higher hydrodesulfurization performance simultaneously concurrently.
Claims (8)
1. the preparation method of a heavy distillate hydrodenitrogenation catalyst, the method comprises: carry out surface acid etching to aluminium oxide and HY molecular sieve respectively, then using the aluminium oxide after acid treatment and the HY molecular sieve after acid treatment machinery compound as carrier, by flooding the maceration extract and catalyst-loaded active component that contain catalyst activity component, drying again, obtained heavy distillate hydrodenitrogenation catalyst; Wherein:
The process of aluminium oxide being carried out to surface acid etching comprises: organic acid soln organic acid being mixed with concentration range 0.002 ~ 0.5mol/L, under temperature 25 ~ 80 DEG C of conditions, be alumina powder and the organic acid soln mix and blend 20 ~ 120min of 1:10 ~ 1:100 by solid-liquid mass ratio, form suspension, filter afterwards, be 7 ~ 9 by washing of precipitate to filtrate pH value, be deposited in 100 ~ 140 DEG C of drying 2 ~ 6h, roasting 2 ~ 6h at 400 ~ 800 DEG C, obtains the alumina powder after acid treatment; Described organic acid be selected from citric acid, oxalic acid or tartaric acid one or more;
The process of HY molecular sieve being carried out to surface acid etching comprises: in the isothermal reactor of 30 ~ 80 DEG C, add citric acid, oxalic acid or tartaric acid solution that concentration is 0.005 ~ 0.5mol/L, drop into HY molecular sieve, wherein solid-liquid mass ratio controls within the scope of 1:10 ~ 1:120, stir process 30 ~ 100min, after filtration, washing, by the molecular sieve after process at 100 ~ 140 DEG C of drying 2 ~ 6h, roasting 2 ~ 8h at 400 ~ 800 DEG C, obtains the HY molecular sieve after acid treatment;
With the gross weight of described carrier for benchmark, the HY molecular sieve content 5wt% ~ 20wt% in carrier after acid treatment;
Described catalyst activity component comprises: main metal M o and/or W and promoter metal Co and/or Ni; Further, also complexing agent is contained in described maceration extract; Described complexing agent be selected from citric acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ethylenediamine one or more, promoter metal and complexing agent mol ratio are 0.1 ~ 5.0:1;
With the gross weight of gained catalyst for benchmark, with the oxide basis of activity component metal, in catalyst, the content of Mo and/or W oxide is the content of 10wt% ~ 30wt%, Co and/or Ni oxide is 1wt% ~ 10wt%.
2. the preparation method of heavy distillate hydrodenitrogenation catalyst according to claim 1, wherein, comprises the process of the aluminium oxide after acid treatment and the machinery of the HY molecular sieve after acid treatment compound:
Mixed with the HY molecular sieve after acid treatment by alumina powder after acid treatment, through compressing tablet, spin or extruded moulding after kneading, 100 ~ 140 DEG C of drying 12 ~ 20h, roasting 4 ~ 12h at 400 ~ 800 DEG C, obtains the complexes carrier of aluminium oxide and Y molecular sieve.
3. the preparation method of heavy distillate hydrodenitrogenation catalyst according to claim 1, be wherein adopt step impregnation method catalyst-loaded active component on carrier, described step impregnation method comprises:
Prepare the solution of the soluble-salt of main metal as main metal impregnation liquid, adopt the main metal of method load of incipient impregnation on carrier, after placing 4 ~ 14h under the sample normal temperature flooded, dry 2 ~ 6h at 80 ~ 140 DEG C, roasting 2 ~ 6h at 400 ~ 800 DEG C, obtains the catalyst preparation sample containing main metal;
The soluble-salt of the promoter metal of preparation desired concn and the mixed solution of described complexing agent are as promoter metal maceration extract, wherein promoter metal and complexing agent mol ratio are 0.1 ~ 5.0:1, the promoter metal maceration extract equal-volume prepared is supported on aforementioned containing on the catalyst preparation sample of main metal, obtains the catalyst supporting main metal and promoter metal;
After afterwards the catalyst supporting main metal and promoter metal being placed 4 ~ 14h under normal temperature, at 80 ~ 140 DEG C, drying 10 ~ 30 hours, obtains described heavy distillate hydrodenitrogenation catalyst.
4. a heavy distillate hydrodenitrogenation catalyst, it prepares according to method described in any one in claims 1 to 3.
5. the heavy distillate hydrodenitrogenation catalyst according to right 4, the specific area of this catalyst is 160 ~ 350m
2/ g, average pore size 5.0 ~ 12.0nm, pore volume is 0.3 ~ 0.8ml/g.
6. an application process for heavy distillate hydrodenitrogenation catalyst, the method comprises the process using the catalyst described in claim 4 or 5 as heavy distillate hydrodenitrogenation catalyst.
7. application process according to claim 6, the method comprises the process of described catalyst being carried out to presulfurization, described presulfurization adopts hypo-hyperthermia classification vulcanization, conditions of vulcanization is: cryogenic vulcanization temperature is 150 ~ 300 DEG C, high temperature vulcanized temperature is 300 ~ 450 DEG C, the cryogenic vulcanization time is 0.2 ~ 1:1 with the ratio of high temperature vulcanized time, pressure 4 ~ 6MPa, liquid hourly space velocity (LHSV) 2.0 ~ 10.0h
-1, sulfuration 4 ~ 20h, hydrogen-oil ratio 300 ~ 600.
8. the application process according to claim 6 or 7, wherein, described heavy distillate is the mixture of one or more in vacuum distillate, wax tailings, deasphalted oil, de-residue oil.
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| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
| CN105833879B (en) * | 2016-05-03 | 2018-06-26 | 中国石油天然气股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN107983400B (en) * | 2017-12-08 | 2021-04-13 | 西安近代化学研究所 | Reductive amination catalyst and preparation method thereof |
| CN111921535A (en) * | 2019-05-13 | 2020-11-13 | 中海石油炼化有限责任公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN111569938A (en) * | 2020-06-04 | 2020-08-25 | 深圳市汇德丰控股集团有限公司 | Hydrofining catalyst and preparation method and application thereof |
| CN113385220A (en) * | 2021-07-21 | 2021-09-14 | 西南化工研究设计院有限公司 | Preparation method of catalyst for preparing pyridine and picoline by methanol and ammonia water in one step |
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