CN103785432A - Distillate oil hydrogenation catalyst and preparation method thereof - Google Patents
Distillate oil hydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a distillate oil hydrogenation catalyst. In terms of the weight of the oxide of an active metal component, the catalyst contains 9 to 30% of the active metal MoO3 and 2 to 10% of a group-VIII metal oxide, wherein group-VIII metal is Ni and/or Co. The hydrogenation catalyst is prepared by dipping an active component-loaded alumina carrier in a solution containing a hydrazine derivative and then carrying out hydrogen activation. A preparation method for the distillate oil hydrogenation catalyst comprises the following steps: (1) dipping the alumina carrier or alumina carrier containing an auxiliary agent by using a conventional active metal dipping solution and then carrying out drying and roasting; (2) preparing the solution containing the hydrazine derivative, dipping the material obtained in the step (1) and carrying out drying; and (3) subjecting the material obtained in the step (2) to hydrogen activation so as to obtain the finished hydrotreatment catalyst. The catalyst is easy to prepare, does not need sulfuration before usage, is applicable to hydrotreatment of heavy distillate oil and has high denitrification and desulphurization activity.
Description
Technical field
The present invention relates to a kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof, particularly relate to a kind of heavy distillate hydrotreating catalyst and preparation method thereof.
Background technology
Most infusion process preparation, for example various hydrogenation catalysts of adopting of loaded catalyst.While preparing hydrogenation catalyst by infusion process, the structure of dipping solution pH value to active metal on catalyst surface (as Mo), decentralization and with carrier (as Al
2o
3) interaction have a significant impact.The raising of pH value can reduce the loss of carrier specific area in dipping process, and specific surface area of catalyst is increased to some extent.
In general, hydrogenation catalyst maceration extract used has two types: an alkaline solution for VI B family and VIII family element; Two is the acid solution of VI B family and VIII family element.Chinese patent CN93109141.1 points out to contain when solution used the ammonia spirit of molybdenum and cobalt (nickel) simultaneously, this dipping solution is alkalescence, if single-steeping is made catalyst, need to be made into dense molybdenum-cobalt (nickel)-ammonia solution, this solution is unstable, brings difficulty to dip operation.This maceration extract can not carry out saturated spray, in spray process, along with the volatilization of ammonia, is easy to separate out precipitation.Therefore while carrying out Kaolinite Preparation of Catalyst with alkaline solution, be difficult to complete by a step infusion process.And adopt two steps or multistep infusion process, not only make preparation process complexity, and some physico-chemical property of catalyst is brought to adverse effect.
The acid solution of VI B family and VIII family element can be made into higher concentration.In Chinese patent CN98114346.6, mention the preparation of high concentration Mo-Ni-P solution: phosphate aqueous solution is joined in the molybdenum oxide of aequum, be warming up to micro-boiling, and be heated to, after most of molybdenum oxide dissolving, system temperature is down to 60～70 ℃, add the basic nickel carbonate of aequum.Again being heated to micro-boiling all dissolves basic nickel carbonate.Last slowly heating evaporation, removes unnecessary moisture and makes solution concentrated, makes the Mo-Ni-P solution of high concentration, high stability.Therefrom can find out the process for preparation complexity of this solution, and P/MoO in solution
3weight ratio is 0.08～0.18, and solution acidic is stronger.US4444905 has introduced the preparation method of a kind of Mo, Ni, P solution.Main points are by MoO
3, H
2o and H
3pO
4(75%) make pulpous state.After 15 minutes, add a certain amount of nickelous carbonate, be warmed up to 93 ℃ and at this temperature, heat 2 hours, make bright green solution.The maceration extract that above-mentioned technology is mentioned has all added more phosphoric acid, and its pH value is lower.
Hydrotreating catalyst is greatly mainly with γ-Al
2o
3for carrier, its isoelectric point is 7～9, and conventional Mo, Ni(Co), the most <2 of pH value of P maceration extract, much smaller than the isoelectric point of carrier, this makes active component and carrier in maceration extract interact too strong, the activity of catalyst is had to obvious impact, moreover the too small carrier specific area that also can cause of pH value is lost in dipping process.If but acid maceration extract pH value is too high, can cause metal to deposit at carrier surface when dipping, in catalyst, active component does not can be uniformly dispersed, and affects the serviceability of catalyst.
At present, adopt hydrotreating catalyst prepared by distinct methods well not solve above shortcoming, the performance of hydrotreating catalyst still needs further raising.Above-mentioned hydrogenation catalyst needs to carry out normal vulcanizing treatment before using, and active metal is converted into sulphided state, and sulfidation not only increases cost, and easily pollutes.
Summary of the invention
For problems of the prior art, the invention provides a kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof.This catalyst preparation process is simple, before using, without vulcanizing, is applicable to the hydrotreatment of heavy distillate, denitrogenation, desulphurizing activated height.
A kind of catalyst used for hydrogenation of distilled oil fraction, with the weighing scale of active metal component oxide, in catalyst, active metallic content is MoO
39%～30%, VIII family metal oxide 2%～10%, VIII family metal is Ni and/or Co, first described hydrogenation catalyst adopts containing the alumina support after hydrazine derivative solution impregnation load active component, then carries out hydrogen activation and makes.
In catalyst of the present invention, described hydrazine derivative can use any hydrazine derivative, preferably uses dialkyl group hydrazine, particularly dimethyl hydrazine NH
2n (CH
3)
2.The mass concentration of hydrazine derivative is 20%-70%.
In the preparation method of hydrotreating catalyst of the present invention, described hydrogen activation condition is: with the programming rate of 5 ℃/min ~ 10 ℃/min, rise to 250 ℃ ~ 450 ℃ from room temperature, then with 1 ℃ of heating rate/min ~ 3 ℃/min, be warming up to 500 ~ 700 ℃, and under maximum temperature constant temperature 2 ~ 8 hours.Be preferably the programming rate with 5 ℃/min ~ 10 ℃/min, rise to 400 ℃ ~ 450 ℃ from room temperature, then with 2 ℃ of heating rates/min ~ 3 ℃/min, be warming up to 500 ~ 650 ℃, and under maximum temperature constant temperature 2 ~ 6 hours.
A preparation method for catalyst used for hydrogenation of distilled oil fraction, comprises following content:
(1) adopt conventional active metal dipping solution oxide impregnation alumina supporter or the alumina support containing auxiliary agent, then dry, roasting;
(2) preparation contains hydrazine derivative solution, and the material of impregnation steps (1), and then dry;
(3) step (2) material carries out hydrogen activation, obtains final hydrotreating catalyst after activation.
Conventional active metal dipping solution described in the inventive method can be the known any maceration extract that contains active metal component of technical staff, maceration extract be acidity or alkalescence all can, be preferably acidity.Active metal is selected from periodic table ⅧZu JiⅥ B family metal.Suitable VI B family non-noble metal components comprises molybdenum, tungsten, chromium or its mixture, preferably molybdenum, tungsten or its mixture.The base metal of suitable VIII family is as cobalt, nickel, iron or its mixture, preferably cobalt, nickel or its mixture.
Aluminium oxide described in the inventive method or containing the stereoscopic different various shapes that require can be made into of the carrying alumina of auxiliary agent, for example spherical, tablet or bar shaped.Preferably bar shaped (clover, bunge bedstraw herb etc.).Carrier preparation method is: at aluminum hydroxide solid elastomer powder or containing adding peptizing agent and extrusion aid in the aluminum hydroxide solid elastomer powder of auxiliary agent, through kneading, roll, make after moulding, dry, calcination steps.Dry and roasting in carrier preparation process adopts prior art condition, and if baking temperature is 70 ℃～250 ℃, be 0.5h～20h drying time; Sintering temperature is 400 ℃～750 ℃, and roasting time is 0.5h～20h.Aluminum hydroxide solid elastomer powder and the aluminum hydroxide solid elastomer powder that contains adjuvant component can or adopt any one prior art preparation for commercial goods.After dry glue powder activation, (500 ℃ roasting 3 hours) specific surface is 200～450m
2/ g, is preferably 250～350 m
2/ g, pore volume is 0.5～1.0mL/g, is preferably 0.5～0.8mL/g.Auxiliary agent in dry glue powder is selected from one or more in silicon, phosphorus, fluorine, boron, titanium and zirconium.Auxiliary agent (in element) 0.2%～10% by weight.
In the inventive method, dipping adopts the known method of technical staff to carry out, and can be incipient impregnation, also excessive dipping, preferably equal-volume total immersion stain.Dry, roasting after dipping adopt prior art condition, and baking temperature is 70 ℃～200 ℃, is preferably 100 ℃～160 ℃, and be 0.5h～20h drying time, is preferably 1h～6h; Sintering temperature is 300 ℃～600 ℃, is preferably 300 ℃～500 ℃, and roasting time is 0.5h～20h, is preferably 1h～6h.
In the inventive method, described hydrazine derivative can use any hydrazine derivative, preferably uses dialkyl group hydrazine, particularly dimethyl hydrazine NH
2n (CH
3)
2.The mass concentration of hydrazine derivative is 20%-70%.
In the preparation method of hydrotreating catalyst of the present invention, described hydrogen reducing condition is: with the programming rate of 5 ℃/min ~ 10 ℃/min, rise to 250 ℃ ~ 450 ℃ from room temperature, then with 1 ℃ of heating rate/min ~ 3 ℃/min, be warming up to 500 ~ 700 ℃, and under maximum temperature constant temperature 2 ~ 8 hours.
Be preferably the programming rate with 5 ℃/min ~ 10 ℃/min, rise to 400 ℃ ~ 450 ℃ from room temperature, then with 2 ℃ of heating rates/min ~ 3 ℃/min, be warming up to 500 ~ 650 ℃, and under maximum temperature constant temperature 2 ~ 6 hours.
Compared with prior art, Catalysts and its preparation method tool of the present invention has the following advantages:
(1) hydrotreating catalyst of the present invention floods hydrazine derivative after impregnating metal solution, in the hydrogen activation process of catalyst, be conducive to the generation of more polygon, angle, rib position, and the intrinsic activity that increases activated centre, obviously increases hydrodesulfurization and denitrification activity;
(2) hydrogenation catalyst that prepared by the inventive method can directly use after over hydrogenation, just can obtain high performance catalyst, the pollution of having avoided sulfidation to cause without vulcanizing;
(3) the inventive method preparation process is simple, just can realize production on existing catalyst preparation facilities, is suitable for commercial Application.
The specific embodiment
The detailed process that the invention is further illustrated by the following examples, but invention should not be deemed limited in this embodiment, the percentage composition relating to is weight percentage.
Comparative example 1
Take dry glue powder (specific surface 350m siliceous, boron
2/ g, pore volume is 0.90mL/g, siliceous 1.32%, boracic 1.58%) 400g, add citric acid and the each 6g of sesbania powder, after being mixed evenly, add acid solution 345g, HNO in acid solution
3concentration be 1.74%, all the other are distilled water.Roll after 20min, by the clover orifice plate extrusion of diameter 1.7mm.500 ℃ of roasting 3h after 120 ℃ of dry 4h.Carrier after roasting is designated as Z1.
Get Z1 carrier 100g, with 75mL active metal maceration extract 1(MoO
3for 89.2g/100mL, NiO is 15.0g/100mL, and P is 2.5g/100mL) incipient impregnation Z1, through 120 ℃ of dry 4h, after 500 ℃ of roasting 2h, the catalyst of acquisition is designated as BC1.
Comparative example 2
(specific area is 370m to take dry glue powder
2/ g, pore volume is 0.90mL/g) 300g, add SB powder 100g, add citric acid and the each 6g of sesbania powder, after being mixed evenly, add acid solution 345g, HNO in acid solution
3concentration be 1.74%, all the other are distilled water.Roll after 20min, by the clover orifice plate extrusion of diameter 1.7mm.500 ℃ of roasting 3h after 120 ℃ of dry 4h, the alumina support bar making is designated as Z2.
Get Z2 carrier 100g, with 75mL active metal maceration extract 2(MoO
3for 83.1g/100mL, NiO is 15.6g/100mL, and P is 1.94g/100mL) incipient impregnation Z2, through 120 ℃ of dry 4h, after 500 ℃ of roasting 2h, the catalyst of acquisition is designated as BC2.
Comparative example 3
(specific surface is 320m to get dry glue powder
2/ g, pore volume is 0.8mL/g, SiO
2content 4.5%) 150g, add SB powder 50g, add citric acid and the each 8g of sesbania powder, after being mixed evenly, add the made adhesive of SB powder of 200g nitric acid peptization, kneading 20min, rolls 20min, by the clover orifice plate extrusion of diameter 1.7mm.500 ℃ of roasting 4h after 120 ℃ of dry 4h.Carrier after roasting is designated as Z3.
Get Z3 carrier 100g, with 75mL active metal maceration extract 3(MoO
3for 39.0g/100mL, NiO is 6.5g/100mL, and P is 1.1g/100mL) incipient impregnation Z1, through 120 ℃ of dry 4h, after 500 ℃ of roasting 2h, the catalyst of acquisition is designated as BC3.
Embodiment 1
Prepare weight concentration and be 30% dimethyl hydrazine NH
2n (CH
3)
2solution; get catalyst B C1 in comparative example; with the solution incipient impregnation for preparing 2 hours; 100 ℃ dry 4 hours, then reduction activation under hydrogen atmosphere, reduction activation program is for to rise to 450 ℃ with 5 ℃/min from room temperature; take heating rate as 2 ℃/min; rise to 500 ℃ from 450 ℃, and 500 ℃ of constant temperature 2 hours, is prepared into catalyst C-1 of the present invention.
Embodiment 2
Prepare weight concentration and be 60% dimethyl hydrazine NH
2n (CH
3)
2solution; get catalyst B C2 in comparative example; with the solution incipient impregnation for preparing 2 hours, 100 ℃ dry 4 hours, then under hydrogen atmosphere; carry out hydrogen activation; first rise to 350 ℃ with 10 ℃/min from room temperature, take heating rate as 1 ℃/min, rise to 500 ℃ from 350 ℃; and 500 ℃ of constant temperature 4 hours, prepare nitrogenize transition-metal catalyst C-2.
Embodiment 3
Prepare weight concentration and be 40% dimethyl hydrazine NH
2n (CH
3)
2solution; get catalyst B C3 in comparative example; with the solution incipient impregnation for preparing 2 hours; 100 ℃ dry 4 hours, then under hydrogen atmosphere, carry out activation processing, first rise to 450 ℃ with 8 ℃/min from room temperature; take heating rate as 1 ℃/min; rise to 650 ℃ from 450 ℃, and 650 ℃ of constant temperature 4 hours, prepare nitrogenize transition-metal catalyst C-3.
The main character of catalyst prepared by above-mentioned comparative example and embodiment is in table 1
Table 1
| Catalyst | C1 | C2 | C3 | BC1 | BC2 | BC3 |
| Specific area, m 2/g | 228 | 200 | 202 | 196 | 184 | 180 |
| Total pore volume, mL/g | 0.39 | 0.40 | 0.41 | 0.39 | 0.37 | 0.36 |
| Average pore size, nm | 8.0 | 8.0 | 8.1 | 8.0 | 8.0 | 8.0 |
| Mo,% | 13.95 | 13.97 | 13.87 | 12.86 | 13.47 | 13.37 |
| Ni,% | 2.76 | 2.78 | 2.70 | 2.61 | 2.62 | 2.68 |
| Si,% | 1.01 | 1.04 | 1.05 | 0.98 | 1.02 | 1.06 |
| B,% | 1.21 | 1.18 | 1.17 | 1.18 | 1.20 | 1.24 |
| P,% | 0.57 | 0.56 | 0.55 | 0.55 | 0.56 | 0.57 |
Embodiment 4
The present embodiment is the active appraisal experiment of catalyst.Catalyst activity evaluation experimental carries out on 50mL small hydrogenation device, need hydrotreating catalyst prepared by comparative example to carry out presulfurization, and the catalyst that embodiment obtains directly reacts before activity rating.Evaluating catalyst condition is at reaction stagnation pressure 9.0MPa, volume space velocity 1.0 h
-1, hydrogen-oil ratio 700:1, reaction temperature is 380 ℃.Active appraisal experiment is by feedstock oil character in table 2, and activity rating the results are shown in Table 3.
Table 2
| Feedstock oil | Iran VGO |
| Density (20 ℃), gcm -3 | 0.9168 |
| Boiling range, ℃ | ? |
| IBP | 336 |
| EBP | 542 |
| S，% | 1.59 |
| N，μg·g -1 | 1681 |
Table 3
| Catalyst | C1 | C2 | C3 | BC1 | BC2 | BC3 |
| Denitrification activity relatively, % | 157 | 150 | 159 | 102 | 100 | 92 |
| Relatively desulphurizing activated, % | 150 | 145 | 148 | 103 | 100 | 90 |
Claims (10)
1. a catalyst used for hydrogenation of distilled oil fraction, with the weighing scale of active metal component oxide, in catalyst, active metallic content is MoO
39%～30%, VIII family metal oxide 2%～10%, VIII family metal is Ni and/or Co, it is characterized in that: first described hydrogenation catalyst adopts containing the alumina support after hydrazine derivative solution impregnation load active component, then carries out hydrogen activation and makes.
2. catalyst according to claim 1, is characterized in that: described hydrazine derivative is dialkyl group hydrazine, and the mass concentration of hydrazine derivative is 20%-70%.
3. catalyst according to claim 1, is characterized in that: described hydrazine derivative is for being dimethyl hydrazine NH
2n (CH
3)
2.
4. catalyst according to claim 1, it is characterized in that: described hydrogen activation condition is: with the programming rate of 5 ℃/min ~ 10 ℃/min, rise to 250 ℃ ~ 450 ℃ from room temperature, again with 1 ℃ of heating rate/min ~ 3 ℃/min, be warming up to 500 ~ 700 ℃, and under maximum temperature constant temperature 2 ~ 8 hours.
5. according to the catalyst described in claim 1 or 4, it is characterized in that: with the programming rate of 5 ℃/min ~ 10 ℃/min, rise to 400 ℃ ~ 450 ℃ from room temperature, then with 2 ℃ of heating rates/min ~ 3 ℃/min, be warming up to 500 ~ 650 ℃, and under maximum temperature constant temperature 2 ~ 6 hours.
6. the preparation method of catalyst used for hydrogenation of distilled oil fraction described in claim 1, is characterized in that: comprise following content:
(1) adopt conventional active metal dipping solution oxide impregnation alumina supporter or the alumina support containing auxiliary agent, then dry, roasting;
(2) preparation contains hydrazine derivative solution, and the material of impregnation steps (1), and then dry;
(3) step (2) material carries out hydrogen activation, obtains final hydrotreating catalyst after activation.
7. method according to claim 6, is characterized in that: active metal is selected from periodic table ⅧZu JiⅥ B family metal.
8. according to the method described in claim 6 or 7, it is characterized in that: VI B family non-noble metal components comprises molybdenum, tungsten, chromium or its mixture, the base metal of VIII family comprises cobalt, nickel, iron or its mixture.
9. method according to claim 6, it is characterized in that: described aluminium oxide or be spherical, tablet or bar shaped containing the alumina support of auxiliary agent, carrier preparation method is: at aluminum hydroxide solid elastomer powder or containing adding peptizing agent and extrusion aid in the aluminum hydroxide solid elastomer powder of auxiliary agent, through kneading, roll, make after moulding, dry, calcination steps.
10. method according to claim 6, it is characterized in that: dipping adopts incipient impregnation or excessive dipping, dry, roasting after dipping adopt prior art condition, baking temperature is 70 ℃～200 ℃, be 0.5h～20h drying time, sintering temperature is 300 ℃～600 ℃, and roasting time is 0.5h～20h.
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Cited By (3)
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| CN112717965A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrogenation pretreatment catalyst, and preparation method and application thereof |
| CN113019406A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst |
| CN116408098A (en) * | 2021-12-30 | 2023-07-11 | 中国石油天然气股份有限公司 | Residual oil hydrogenation catalyst and preparation method and application thereof |
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