CN1123626C - Heavy and residual oil hydrogenating treatment catalyst and its preparing method - Google Patents
Heavy and residual oil hydrogenating treatment catalyst and its preparing method Download PDFInfo
- Publication number
- CN1123626C CN1123626C CN 00123216 CN00123216A CN1123626C CN 1123626 C CN1123626 C CN 1123626C CN 00123216 CN00123216 CN 00123216 CN 00123216 A CN00123216 A CN 00123216A CN 1123626 C CN1123626 C CN 1123626C
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- catalyst
- preparation
- titanium
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention discloses a hydrogenation processing catalyst and a preparation method thereof, particularly a heavy oil hydrogenation processing catalyst and a preparation method thereof. The present invention adopts a low priced titaniferous aluminum hydroxide carrier with friendly environment. In the method of the present invention, the mixing kneading process of titaniferous aluminum hydroxide, metal salt, etc. is used or promoting metal to disperse; all of the materials are mixed and kneaded into plastic bodies and are squeezed into strips, formed and made into the catalyst through high temperature activation. The catalyst prepared by the method of the present invention can be easily formed, has cost obviously reduced than that of the existing methods, has a suitable acid property and simultaneously has good hydrogenation desulphurization activity, good hydrogenation denitrification activity and good hydrogenation carbon residue removing activity.
Description
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly heavy, residuum hydrodesulfurization and residual hydrogenation denitrogenation (HDN) and take off the carbon residue Catalysts and its preparation method.
In heavy, residual hydrocracking process, owing to contain a large amount of heavy metals such as nickel, vanadium in the residual oil, they are accumulated on the catalyzer, make the catalyzer behind the inactivation be difficult to regeneration.And owing to residual oil viscosity height, wherein contain impurity such as a large amount of S, N, thereby the air speed of residual hydrocracking process is very little, so catalyst consumption increases greatly than other oil refining process.So the very big factor of this process technology economic feasibility of decision is how to reduce the cost of catalyzer, makes the cost of whole hydrotreatment process more favourable on Technological Economy.Therefore, guaranteeing to reduce the catalyzer cost under the prerequisite that the every use properties of catalyzer does not descend, be long term studies problem in this area.
The catalyzer cost comprises two aspects, i.e. material cost and production cost.If raw materials variations is little, only on preparation technology, full kneading method has been save carrier roasting, dipping, dipping humectant drying and other steps than pickling process, thereby the former is more more economical, but, often cause the use properties of catalyzer not good because active metal component can not play one's part to the full.Its chief reason is, the catalyst metal degree of scatter of full kneading method preparation is low than catalyst prepared, and metal easily generates the extremely strong inactive substance of interaction with carrier in the full kneading process; For making catalyzer reach certain activity, its terms of settlement is to strengthen the add-on of reactive metal, and this just makes the cost of catalyzer improve greatly.
Usually, the hydrotreating catalyst of hydrocarbon feed is all with γ～Al
2O
3Or contain γ～Al of a small amount of one or more other elements such as Si, P, Ti, B, Mg, F etc.
2O
3Be carrier.In catalyst preparation process, can in system, introduce above-mentioned element in different steps, but the purpose of introducing above-mentioned element is a basically identical, i.e. regulating catalyst acid and/or improve interaction between active ingredient and carrier.But in catalyst preparation process, add certain or more auxiliary agent can make the catalyst preparation process complexity, or cause problem such as shaping of catalyst difficulty; In the support material production process, just add the needed auxiliary agent of preparation catalyzer, can make catalyst preparation process simple, more effectively physico-chemical property such as the acidity of modulation carrier, micropore character and then more effectively regulating catalyst acid and/or improve interaction between active ingredient and carrier simultaneously, impel the homodisperse of active metal component on carrier surface, also can suppress active metal component and Al simultaneously
2O
3Generate nonactive thing phase, also can reduce the problem of environmental pollution in catalyst preparation process.To γ～Al
2O
3In to introduce the method for titanium more, selected to contain titanium species also varied, even can directly add TiO in aluminum oxide
2, rely on the high temperature migration then in the hope of its homodisperse at alumina surface.These class methods are feasible to the preparing carriers process of most catalyzer, because carrier does not contain active ingredient in the process, promptly do not have competition when titanium and aluminum oxide interaction.US5089453 adopts full kneading method to prepare residual oil hydrocatalyst, uses a large amount of TiCl in its preparation process
4Make improvements agent, contain TiO in the catalyzer
2Amount reaches 4～6w%, because TiCl
4Hydrolytic process easily produces harmful fog, makes will use specific equipment in the production process, and the production technique more complicated, the production difficulty is big, and security is low, and cost is higher.CN1070418A adopts the catalyzer of full kneading method preparation, is improving agent with titanium, boron, and its initial activity is better, but because its acidity is stronger, NH
4-TPD acidity reaches 1.449mmol/g, and carbon deposit speed is fast, and catalyst deactivation is fast, the life-span is short; Because it is to adopt aluminium hydrate powder directly to mix with each active ingredient, carry out kneading and compacting, be prepared into catalyzer through the comparatively high temps activation, make active metal component fully not disperse, a part of active metal component and aluminum oxide interact simultaneously, generate nonactive phases such as molybdic acid aluminium and nickel aluminate, disperse insufficient influence in order to offset nonactive phase and metal to catalyst activity, have to increase the content of reactive metal in catalyzer, make the catalyzer cost increase like this, the shaping of catalyst difficulty increases, small grain size abnormity (trifolium or Herba Galii Bungei etc.) strip catalyst can not be prepared with this patented method, the catalyzer of conventional shapes such as cylinder bar shaped can only be prepared.CN96120423.0 adopts the method for dipping to prepare catalyzer, uses a large amount of TiCl in its preparation process
3Make auxiliary agent, contain TiO in the catalyzer
2Amount reaches 3～6w%, for fear of being subjected to TiCl
3Deng the destruction of acidic solution to the aluminum oxide microvoid structure, have to add in advance basic solution such as ammoniacal liquor and mix with aluminum oxide, play the effect of protection aluminum oxide microvoid structure, can cause the carrier difficult forming like this, simultaneously in the carrier roasting process because NH
4 +And Cl
-Existence easily produce harmful fog, etching apparatus, contaminate environment, production technique more complicated simultaneously, the production difficulty is big, cost is higher.CN1098433A adopts and mix-soaks the bonded production technique, can partly solve the dispersity problem of reactive metal like this, but still will advance dipping, step such as drying and activation again after pinching the part reactive metal mixing, Production Flow Chart is long, complicated process of preparation causes Preparation of Catalyst cost height.
The catalyzer of these method preparations all only has hydrodesulfurization activity or hydrodenitrogenationactivity activity, and its activity still can further improve.
One of purpose of the present invention provides that a kind of reactive metal is uniformly dispersed on alumina surface, specific surface area and suitable weight, the catalyst for hydrotreatment of residual oil of big, the acid matter of pore volume.Two of purpose of the present invention be by adopt a kind of novel Ti-contained aluminium hydroxide for carrier provides that a kind of technology is simple, with low cost, shaping of catalyst smoothly, can prepare the preparation method of high performance heavy, the catalyst for hydrotreatment of residual oil of special-shaped catalyst.
Heavy, catalyst for hydrotreatment of residual oil of the present invention contains VIII family metal oxide 3～10% by weight, and group vib metal oxide 10～25% contains titanium dioxide 4～15%, and surplus is an aluminum oxide.The pore volume of catalyzer is 0.40～0.55cm
3/ g, specific surface area is 120～240m
2/ g, infrared acidity (〉=350 ℃) is between 0.070～0.180mmol/g, is preferably 0.080～0.130mmol/g.
Catalyst for hydrotreatment of residual oil of the present invention is a carrier with the titanium-contained aluminum oxide, is active constituent with group vib and VIII family metal, and the reactive metal dispersity is: I
VIB/ I
Al(* 100) are 12.0～24.0, I
VIII/ I
Al(* 100) are 4.0～15.0.Above-mentioned group vib metal is molybdenum or tungsten, is preferably molybdenum, and described VIII metal is nickel or cobalt.Contain the VIII family metal oxide in the catalyzer by weight and be preferably 3～10%, the group vib metal oxide is preferably 15～25%, contains titanium dioxide and is preferably 5～10%.The reactive metal dispersity is preferably: I
Mo/ I
Al(* 100) are 15.0～22.0, I
Ni or Co/ I
Al(* 100) are 6.0～10.0, and the dispersity of auxiliary agent is: I
Ti/ I
Al(* 100) are 10.0～30.0, are preferably I
Ti/ I
Al(* 100) are 15.0～25.0.
Preparation of catalysts method of the present invention may further comprise the steps:
(1) Ti-contained aluminium hydroxide and Powdered group vib compound and Powdered VIII compounds of group mix;
(2) the mixture elder generation adding aqueous solution that (1) is obtained carries out pre-mixing, makes itself and aluminum oxide be able to preferential interaction, and its purpose is to reduce next step and adds peptization acid to the alumina pore structural damage; And then adding the mixed plastic of pinching into of peptization acid solution, plastic extruded moulding and dry, roasting with obtaining promptly make preformed catalyst.
A kind of concrete preparation method of catalyzer of the present invention is: take by weighing Ti-contained aluminium hydroxide powder, Powdered VIII metallic compound preferably basic nickel carbonate or cobaltous dihydroxycarbonate and Powdered VIIIVIB metallic compound preferably molybdic oxide or ammonium molybdate and extrusion aid preferably the sesbania powder mix, add 10～40% of institute's water requirement and mix mixing time 10～60 minutes; Add acetate or dilute hydrochloric acid solution again, the add-on of acid is than reducing 30～60m%, every 100g Al with general aluminium hydroxide
2O
3Add acetate 4～15g, preferably add acetate 6～12g, mix and pinched moulding on banded extruder 0.5～3 hour.The strip of gained 100～150 ℃ dry 2～6 hours down, the catalyzer finished product is promptly made in 550～750 ℃ of following roastings 2～6 hours.
The preparation method of the used Ti-contained aluminium hydroxide of the present invention may further comprise the steps:
(1) preparation sodium aluminate solution, titanium-containing compound slurries;
(2) under agitation condition, sodium aluminate solution, titanium-containing compound slurries and carbon dioxide are reacted into glue, material solution or slurries mix the back and feed carbon dioxide and become glue or wherein one or both to add into glue continuously when feeding carbonic acid gas, stop to feed carbon dioxide after becoming glue to finish;
(3) the liquid-solid mixture of (2) step gained is filtered filter cake washing, drying.
The concentration of above-mentioned sodium aluminate solution is 5～60gAl
2O
3/ l.Above-mentioned titanium-containing compound slurries become granularity less than 65 μ m slurry like material by titanium-containing compounds such as metatitanic acid, titanium dioxide through adding water mill, are preferably the slurry like material of granularity less than 25 μ m, then thin up to 5～40gTiO
2/ l, its pH value is adjusted to 7～11, is preferably 7～8, and carries out under agitation condition, and its pH is suitable to be regulated with ammoniacal liquor, and ammonia concn is preferably 0.2～10%.The add-on of titanium-containing compound slurries is benchmark with the finished product, and wherein containing titanium dioxide is 6～25w%, is preferably 6～20w%.Become the glue temperature to be controlled at 5～30 ℃ according to the porous of needed Ti-contained aluminium hydroxide, concentration of carbon dioxide is controlled at 10～50v% (preferably 20～40v%).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 no more than 2.0 hours at most.The filter cake that obtains behind dope filtration deionized water wash 1～5 time contains Na in the aluminium hydroxide of preparation
+By weight＜0.05%, following dry 2～12 hours at 80～180 ℃ then.
Advantage heavy, catalyst for hydrotreatment of residual oil of the present invention is: (1) catalyzer has good metal dispersity (having reached the metal dispersity of the similar catalyst of immersion process for preparing).(2) has suitable surface acid property, its acidity is than acidity height heavy in the prior art, the residuum hydrodesulfurization catalyzer, therefore has good deep desulfuration activity, the sulphur that some are difficult to remove on common residuum hydrodesulfurization catalyzer, can remove in the presence of catalyzer of the present invention, it directly shows as the raising of desulfurization degree; In addition because catalyzer of the present invention has suitable acidity, compare with common residuum hydrodesulfurization catalyzer and to have higher hydrodenitrification and to take off the carbon residue activity, because hydrodenitrification and removal of ccr by hydrotreating effect, make in the residual oil nitrogen containing polymer structure of matter obtain destroying, thereby sulphur wherein is more prone to remove.Therefore, because hydrodenitrification and the active raising of removal of ccr by hydrotreating have promoted the raising of desulfurization degree again.(3) catalyzer of the present invention has physico-chemical properties such as big pore volume and specific surface area simultaneously, thereby has good result of use, when being used for residual hydrocracking, having higher hydrogenation and take off impurity activity, good hydrogenating desulfurization and hydrodenitrification preferably and removal of ccr by hydrotreating activity are particularly arranged.
The advantage of method for preparing catalyst of the present invention is: (1) Catalyst Production technology is simple, adopts " complete mixing pinched " method, and flow process is short, and productive expense is low significantly.(2) to adopt novel cheap Ti-contained aluminium hydroxide be carrier to catalyzer, has good peptization, only adds a spot of peptization acid and just can mix kneading and be equipped with moulding, makes catalyzer have large pore volume and specific surface area.(3) in kneading process, at first add small amount of deionized water; make the aluminum oxide pre-wetted, make it when next step contacts with acid solution, some part is protected; thereby reduce the destruction of acid, guarantee that finally catalyzer has bigger pore volume the aluminum oxide microvoid structure.
Catalyzer of the present invention can be used for distillate and hydrotreatment heavy, residual oil, especially cooperates with residuum hydrogenating and metal-eliminating catalyst, is used for residuum hydrodesulfurization, take off carbon residue (HDCR) and/or hydrodenitrification (HDN) process.
Following examples further specify the present invention.
Embodiment 1
(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)
With concentration is 30gAl
2O
3The sodium aluminate solution of/l places in the glue jar, 15 ℃ of controlled temperature, and feeding concentration is the carbon dioxide of 40v%, the concentration that adds pulp under continuous whipped state is 20gTiO
2/ l metatitanic acid slurries (the pH value is 8.0, and granularity is less than 40 μ) make carrier contain TiO
2Being 10% by weight, continue feeding carbon dioxide, is to stop logical carbon dioxide at 10 o'clock until slurry pH value, and slurries are aging 1.0hr under whipped state, filters then, uses deionized water wash, contains Na in carrier
+By weight＜0.05% o'clock, dry (110 ℃) 4 hours are crushed to 180 orders again, promptly make to contain TiO
2-Al
2O
370w% Ti-contained aluminium hydroxide powder;
(2) Preparation of catalysts
Take by weighing (1) Ti-contained aluminium hydroxide powder among the 1000g, the Powdered molybdic oxide of 200g (contains MoO
395.2w%), 100.0g Powdered basic nickel carbonate (containing NiO 56.3w%) and sesbania powder 20.0g mix, with the vaporific 150g deionized water that sprays into, premix 30 minutes adds the mixture of 50gHAc and 300g deionized water again in mixing process, mix and pinched 1.5 hours, the strip or the major axis that are extruded into Φ 0.85mm on banded extruder are 1.5mm, and minor axis is the Herba Galii Bungei strip of 1.2mm, and this strip is following dry 4 hours at 110 ℃, 600 ℃ of following roastings 4 hours, promptly make product of the present invention.
Embodiment 2
(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)
Compare with embodiment 1 (1), sodium aluminate solution and metatitanic acid slurries are mixed, sodium aluminate solution concentration is brought up to 50gAl
2O
3/ l, the temperature to 8 when being lowered into glue ℃, feeding concentration is the carbon dioxide of 25v%, until slurry pH value is to stop logical carbon dioxide at 12 o'clock, need not wear out after becoming glue, the unclassified stores consumption is identical with embodiment 1 with operational condition, promptly makes the Ti-contained aluminium hydroxide powder;
(2) Preparation of catalysts
Compare with embodiment 1 (2) method, Powdered molybdic oxide (contains MoO
395.2w%) increase to 240g, correspondingly Powdered basic nickel carbonate (containing NiO 56.3w%) is adjusted into 110g, adds entry 200g in the premix stage, premix 50min, the roasting temperature is 640 ℃, roasting time is 3 hours, other is identical with embodiment 1 (2), i.e. the cost example.
Embodiment 3
(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)
Compare with embodiment 1 (1), sodium aluminate solution and metatitanic acid slurries are mixed, sodium aluminate solution concentration is brought up to 35gAl
2O
3/ l, the temperature to 20 when raising into glue ℃, feeding concentration is the carbon dioxide of 50v%, the unclassified stores consumption is identical with embodiment 1 with operational condition, promptly makes the Ti-contained aluminium hydroxide powder;
(2) Preparation of catalysts
Compare with embodiment 1 (2) method, add entry 100g in the premix stage, premix 20min, the roasting temperature is 540 ℃, and roasting time is 4 hours, and other is identical with embodiment 1 (2), i.e. the cost example.
Embodiment 4
(1) preparation of catalyzer used carrier (Ti-contained aluminium hydroxide powder)
Compare with embodiment 1, make carrier contain TiO
2Be 15.0% by weight, the temperature to 24 when raising into glue ℃, the unclassified stores consumption is identical with embodiment 1 with operational condition, promptly makes the Ti-contained aluminium hydroxide powder;
(2) Preparation of catalysts
Compare with embodiment 1 (2) method, change Powdered basic nickel carbonate into Powdered cobaltous dihydroxycarbonate 80g and add entry 50g in the premix stage, premix 40min, the roasting temperature is 700 ℃, and roasting time is 3 hours, and other is identical with embodiment 1 (2), i.e. the cost example.
Comparative example 1 (press CN1070418A method preparation, main application is attached most importance to, the residual hydrogenation denitrogenation and take off the carbon residue catalyzer)
Take by weighing aluminum hydroxide solid elastomer (containing butt 65%), (contain TiCl with Titanium Trichloride Solution
317%) 45g mixes.Measure 200ml distilled water, add 6gNH
4HCO
3And 7gH
3BO
3, stirring and dissolving is added to this solution and contains in the Ti-Al mixture, mixes.Add 40g1 again: 1 salpeter solution mixes.Add 100gMoO again
3Mix with 36g basic nickel carbonate (containing NiO56.3%) and to pinch into uniform plastic.On banded extruder, be extruded into the cylindrical bar of Φ=0.85mm.Descended dry 4 hours at 100 ℃ then, 550 ℃ of following roastings 3 hours.
Comparative example 2 (press CN96120423.0 method preparation, main application is attached most importance to, slag Hydrobon catalyst)
With pseudo-boehmite dry glue powder (salic 70%) 1000g, add sesbania powder 60g, mix.Is concentration that the ammoniacal liquor 60g of 4w% adds in the material of mixing and mixes, being extruded into diameter on banded extruder is the cylinder bar of 0.82mm, the wet bar of gained is following dry 4 hours at 80～120 ℃, 750 ℃ of following roastings 3 hours, make carrier, respectively through Mo-Ni-P, Mo-Co-P solution impregnation, through 100 ℃ of dryings 4 hours, 450 ℃ of roastings 2 hours make catalyst A 1, A2.
Embodiment 5
This example is the physico-chemical property and the activity rating result of above each routine catalyzer.
The physico-chemical property of each routine catalyzer sees Table 1.Estimate and see Table 2 with stock oil character.Evaluation result sees Table 3.
During evaluate catalysts, from top to bottom by beds, through hydrodemetallation (HDM) (HDM) catalyzer, pass through above each routine catalyzer more earlier after hydrogen and stock oil mix, take One-through design, the HDM catalyzer is with batch Industrial products.The processing condition of estimating each routine catalyzer employing are all identical, are respectively: reaction pressure, 14.6MPa; Temperature of reaction, 400 ℃; Total liquid hourly space velocity, 0.60h
-1Hydrogen-oil ratio (v), 1000.Reactor volume is: φ 25mm * 2000mm.Loaded catalyst is respectively: HDM catalyzer, 80cm
3More than each routine catalyzer, 120cm
3Evaluation result sees Table 3, and evaluating data is sampling analysis data after turning round 200 hours.As can be seen from Table 1, the pore volume specific surface area of each embodiment is all bigger, and metal is scattered, and acid matter is suitable, and the aperture has guaranteed that at pore volume integration rate＞80% of 7～13nm catalyzer has good use properties.Further illustrate each embodiment by table 3 evaluation result and have good activity.
The measuring method of metal dispersity is an X-ray photoelectron spectroscopy among the present invention.The Mo electron binding energy is 233.6ev, and the Ni electron binding energy is 856.6ev, and the Ti electron binding energy is 158.7ev, and the Si electron binding energy is 102.8ev.Dispersity numerical value is big more, illustrates that the dispersion in aluminum oxide of metal or auxiliary agent is even more.Count number as can be seen from table 1, the catalyzer that the metal of catalyzer of the present invention and auxiliary agent dispersity and pickling process are produced is suitable.Above-mentioned meleic acid is that infrared measurement catalyst surface acid process obtains 〉=350 ℃ of meleic acid data.
The physico-chemical property of each catalyzer of table 1
| Physico-chemical property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| A1 | A2 | ||||||
| Particle shape | Four leaves/cylinder | Four leaves/cylinder | Four leaves/cylinder | Four leaves/cylinder | Cylinder | Four leaves/cylinder | |
| Pore volume/cm 3·g -1 | 0.445 | 0.505 | 0.414 | 0.426 | 0.391 | 0.39 | 040 |
| Specific surface area/m 2·g -1 | 176 | 180 | 170 | 130 | 195 | 153 | 166 |
| 7～13nm pore volume integration rate/% | 83 | 81 | 82 | 85 | / | 84 | 85 |
| Meleic acid/mmolg -1(≥ 350℃) | 0.110 | 0.097 | 0.126 | 0.077 | 0.267 | 0.047 | 0.052 |
| Metal dispersity * 100 I Mo/I AlI Ni or Co/I AlI Ti/I Al | 21.5 7.8 25.6 | 20.4 8.1 26.4 | 18.3 7.5 24.1 | 24.3 9.7 28.6 | 11.2 5.5 10.2 | 20.3 6.1 / | 21.0 7.0 / |
| MoO 3/w％ | 20.5 | 22.6 | 19.6 | 20.9 | 18.7 | 18.5 | 18.5 |
| NiO/w％ | 6.21 | 5.93 | 6.60 | 3.50 | 9.15 | 4.65 | 3.45(CoO) |
| TiO 2/w％ | 6.70 | 6.86 | 6.63 | 9.64 | 1.73 | / | / |
Table 2 stock oil property list 3 evaluation results
| Character | Normal slag in the sand |
| Density (20 ℃), g/cm 3 | 0.99 |
| S，w％ | 4.50 |
| N，w％ | 0.24 |
| CCR，w％ | 13.5 |
| Catalyzer | HDS％ | HDCR％ | HDN％ | |
| Embodiment 1 | 76.2 | 45.8 | 42.1 | |
| Embodiment 2 | 78.8 | 44.0 | 41.6 | |
| Embodiment 3 | 74.2 | 46.3 | 42.8 | |
| Embodiment 4 | 76.6 | 43.4 | 40.3 | |
| Comparative example 1 | 70.2 | 53.9 | 49.1 | |
| Comparative example 2 | A1 | 75.3 | 40.5 | 37.4 |
| A2 | 76.2 | 39.2 | 36.1 | |
Claims (17)
1, a kind of heavy, catalyst for hydrotreatment of residual oil is characterized in that containing by weight VIII family metal oxide 2～10%, and group vib metal oxide 10～25% contains titanium dioxide 4～15%, and surplus is an aluminum oxide, and the pore volume of catalyzer is 0.38～0.55cm
3/ g, specific surface area is 120～240m
2/ g, 〉=350 ℃ of infrared acidity are 0.07～0.180mmol/g.
2,, it is characterized in that the activity of such catalysts metal dispersity is: I according to the described catalyzer of claim 1
VIB/ I
Al(* 100) are 12.0～24.0, I
VIII/ I
Al(* 100) are that 4.0～15.0, 〉=350 ℃ of infrared acidity are 0.08～0.130mmol/g.
3, according to the described catalyzer of claim 1, it is characterized in that described group vib metal is molybdenum or tungsten, the VIII metal is nickel or cobalt.
4, according to the described catalyzer of claim 1, it is characterized in that described group vib metal is a molybdenum, the VIII metal is nickel or cobalt.
5, according to the described catalyzer of claim 1, it is characterized in that containing by weight in the catalyzer VIII family metal oxide 3～10%, group vib metal oxide 15～22%, containing titanium dioxide is 5～10%.
6,, it is characterized in that the reactive metal dispersity is: I according to the described catalyzer of claim 4
Mo/ I
Al(* 100) are 15.0～22.0, I
Ni/ I
Al(* 100) are 6.0～10.0 or I
Co/ I
Al(* 100) are 6.0～10.0.
7,, it is characterized in that the dispersity of Ti is: I according to the described catalyzer of claim 1
Ti/ I
Al(* 100) are 10.0～30.0.
8,, it is characterized in that the dispersity of described Ti is: I according to the described catalyzer of claim 1
Ti/ I
Al(* 100) are 15.0～25.0.
9, the described Preparation of catalysts method of a kind of claim 1 is characterized in that may further comprise the steps:
(1) Ti-contained aluminium hydroxide and Powdered group vib compound and Powdered VIII compounds of group mix;
(2) the mixture elder generation adding aqueous solution that (1) is obtained carries out pre-mixing, and then adds the mixed plastic of pinching into of peptization acid solution, and also drying, the roasting of plastic extruded moulding with obtaining promptly makes preformed catalyst;
The add-on that wherein adds the aqueous solution in (2) step is 10～40% of institute's water requirement, and mixing time is 10～60 minutes, and the add-on of acetate is every 100g Al
2O
3Add acetate 4～15g, mix and pinched 0.5～3 hour, the drying and roasting condition is: drying was 2～6 hours under 100～150 ℃, 550～800 ℃ of following roastings 2～6 hours.
10, in accordance with the method for claim 9, it is characterized in that described Powdered VIII metallic compound is basic nickel carbonate or cobaltous dihydroxycarbonate, Powdered VIIIVIB metallic compound is molybdic oxide or ammonium molybdate.
11, in accordance with the method for claim 9, it is characterized in that the preparation method of described Ti-contained aluminium hydroxide, may further comprise the steps:
(1) preparation sodium aluminate solution, titanium-containing compound slurries;
(2) under agitation condition, sodium aluminate solution, titanium-containing compound slurries and carbon dioxide are reacted into glue, material solution or slurries mix the back and feed carbon dioxide and become glue or wherein one or both to add into glue continuously when feeding carbonic acid gas, stop to feed carbon dioxide after becoming glue to finish;
(3) the liquid-solid mixture of (2) step gained is filtered filter cake washing, drying;
Wherein the titanium-containing compound slurries described in (1) step become granularity less than 65 μ m slurry like material, thin up to 5～40gTiO then by metatitanic acid or titanium dioxide through adding water mill
2/ l, its pH value is adjusted to 7～11; One-tenth glue temperature described in (2) step is 5～30 ℃, and the concentration of carbon dioxide of using is 10～50v%, and one-tenth rubber cement liquid pH value to 9～12 o'clock stops to lead to carbonic acid gas; Drying conditions described in (3) step is: drying is 2～12 hours under 80～180 ℃.
12, in accordance with the method for claim 11, it is characterized in that the concentration of sodium aluminate solution is 5～60gAl described in (1) step
2O
3/ l.
13, in accordance with the method for claim 11, the granularity that it is characterized in that described titanium-containing compound slurries is less than 25 μ m, and the pH value is adjusted to 7～8.
14, in accordance with the method for claim 11, it is characterized in that with concentration being that 0.2～10% ammoniacal liquor is regulated the pH value.
15, in accordance with the method for claim 11, it is characterized in that the add-on of titanium-containing compound slurries is a benchmark with final Ti-contained aluminium hydroxide, make that wherein to contain titanium dioxide be 6～25w%.
16, in accordance with the method for claim 11, it is characterized in that described content of titanium dioxide is 6～20w%.
17, in accordance with the method for claim 11, it is characterized in that the filter cake washing described in (3) step is 1～5 time, to the aluminium hydroxide of preparation, contain Na
+By weight＜0.05%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123216 CN1123626C (en) | 2000-11-08 | 2000-11-08 | Heavy and residual oil hydrogenating treatment catalyst and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123216 CN1123626C (en) | 2000-11-08 | 2000-11-08 | Heavy and residual oil hydrogenating treatment catalyst and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1352227A CN1352227A (en) | 2002-06-05 |
| CN1123626C true CN1123626C (en) | 2003-10-08 |
Family
ID=4589680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00123216 Expired - Lifetime CN1123626C (en) | 2000-11-08 | 2000-11-08 | Heavy and residual oil hydrogenating treatment catalyst and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1123626C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100439477C (en) * | 2005-10-19 | 2008-12-03 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and its uses |
| CN103785397B (en) * | 2012-11-01 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of removal of ccr by hydrotreating Catalysts and its preparation method |
| CN104293390B (en) * | 2013-07-18 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of process for hydrogenating residual oil |
| CN106807374A (en) * | 2017-01-20 | 2017-06-09 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina supported ferric catalyst |
| CN106799231A (en) * | 2017-01-20 | 2017-06-06 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina supported nickel catalyst |
| CN106693986A (en) * | 2017-01-20 | 2017-05-24 | 平潭自贸区金瑜环保材料有限公司 | High specific surface area enhanced integrated alumina supported iron-manganese binary catalyst |
| CN106622278A (en) * | 2017-01-20 | 2017-05-10 | 平潭自贸区金瑜环保材料有限公司 | Integral aluminum oxide loaded iron-manganese binary catalyst with high specific surface area |
| CN106732595A (en) * | 2017-01-20 | 2017-05-31 | 平潭自贸区金瑜环保材料有限公司 | High-specific surface area integral alumina copper-loading catalyst |
| CN106732468A (en) * | 2017-01-20 | 2017-05-31 | 平潭自贸区金瑜环保材料有限公司 | A kind of high-specific surface area integral alumina carrier |
| CN110358615B (en) * | 2019-07-24 | 2022-02-22 | 一重集团大连工程建设有限公司 | Device and method for regenerating waste lubricating oil |
-
2000
- 2000-11-08 CN CN 00123216 patent/CN1123626C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1352227A (en) | 2002-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102049265B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN100448532C (en) | A catalyst composition and preparation method thereof | |
| CN103357445A (en) | Heavy-petroleum hydrogenating deasphaltenizing catalyst and preparation and application thereof | |
| CN103055886B (en) | Preparation method of hydrogenation catalyst composition | |
| CN1123626C (en) | Heavy and residual oil hydrogenating treatment catalyst and its preparing method | |
| CN102649069B (en) | With the Hydrogenation active protective agent that is carrier containing IVB race burning aluminium, preparation and application thereof | |
| CN102580758A (en) | NiO-MoO3/ TiO2 catalyst and preparation method thereof | |
| CN104437517A (en) | Heavy-oil hydrotreatment catalyst, and preparation and application thereof | |
| CN103055887A (en) | Preparation method of hydrotreating catalyst composition | |
| CN100537028C (en) | Preparation process of hydroprocessing catalyst | |
| CN1112240C (en) | Macroreticular alumina carrier containing Si and Ti and its preparing process | |
| CN1123627C (en) | Heavy oil hydrogenation conversion catalyst and its preparing method | |
| CN1951558A (en) | Method for preparing catalyst composition | |
| CN1132907C (en) | Catalyst for hydrotreatment of residual oil and its prepn. | |
| CN112657522B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN100340638C (en) | Preparation method of hydrocarbon hydrotreatment catalyst | |
| CN102451703B (en) | Preparation method of hydrogenation catalyst composition | |
| CN1073616C (en) | Preparation method of hydrogenation catalyst | |
| CN1091134C (en) | Hydrotransforming catalyst for residual oil and its preparing process | |
| CN100467570C (en) | Preparation method of hydrogenation catalyst of hydrocarbon | |
| CN1102447C (en) | Preparation method of hydrogenation catlayst | |
| CN1227332C (en) | Heavy, residual oil hydrogenating catalyst and its preparation | |
| CN1072705C (en) | Process for preparing residuum hydrogenation catalyst | |
| CN1147572C (en) | Catalyst for hydrotransforming heavy oil or residual oil and its preparing process | |
| CN1102432C (en) | Ti-contained aluminium hydroxide and its preparing process and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20031008 |