CN101940957A - Method for preparing carbon-containing catalyst - Google Patents
Method for preparing carbon-containing catalyst Download PDFInfo
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- CN101940957A CN101940957A CN2009100124484A CN200910012448A CN101940957A CN 101940957 A CN101940957 A CN 101940957A CN 2009100124484 A CN2009100124484 A CN 2009100124484A CN 200910012448 A CN200910012448 A CN 200910012448A CN 101940957 A CN101940957 A CN 101940957A
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Abstract
The invention discloses a method for preparing a carbon-containing catalyst, which comprises the following steps of: (1) preparing a porous inorganic refractory oxide carrier; (2) soaking a carbon precursor in the inorganic refractory oxide carrier; (3) introducing a metal aid into the step (1) or the step (2); (4) performing thermal treatment, namely thermally treating the porous inorganic refractory oxide carrier carrying the carbon precursor and the metal aid, and decomposing the carbon precursor into carbon so as to obtain a carbon-containing catalyst carrier; and (5) loading an active metal component to obtain the catalyst. The carbon-containing carrier is prepared by pre-soaking the carbon precursor, and then the active metal is loaded to prepare the carbon-containing catalyst so as to simplify the preparation process of the carbon-containing catalyst carrier and improve the physical and chemical properties and the use property of the carbon-containing catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of carbon-contained catalyst, particularly the carbon containing hydrogenization catalyst preparation method.
Background technology
Traditional hydrotreating catalyst uses Al mostly
2O
3As carrier, but active A l
2O
3(as γ-Al
2O
3) more Lewis acid site is arranged, easily cause the catalyst coking, and γ-Al
2O
3Stronger interaction is arranged between carrier and the metal component, make metal component be difficult for being converted into highly active active phase.
Research is thought and the active phase full cure of II type is accumulation (lamination) MoS
2Structure for the active phase of the Co-Mo-S of high-sulfur coordination, is piled up (lamination) together by bigger sheet usually, does not link to each other with carrier, and active each activated centre mutually of II type is dived active high, thiophene hydrodesulfurization (HDS) and pyridine hydrodenitrogeneration (HDN) specific activity I type height.Prepare the active phase catalyst of II type, the following measure of general at present employing: high temperature vulcanized, use special carrier such as active carbon etc.
The shortcoming of absorbent charcoal carrier is bad mechanical strength, cost height.Aluminium oxide covers the carrier mechanical strength height that charcoal obtains through the surface, the substitute that can be used as absorbent charcoal carrier is used.In the prior art, often adopt following method to prepare carbon covered carrier: a kind of method is in stainless steel reactor, is carrier gas with nitrogen, and anthracene is that the charcoal precursor is at γ-Al
2O
3Last pyrolytic covers charcoal; A kind of method is to adopt semiconductor carbon membrane material technology, with γ-Al
2O
3Be placed in the vertical quartz tube reactor Deng refractory oxides, feed organic matter such as hydrocarbons such as benzene, ethene from top.Above method preparation process complexity, the cost height.
CN200410000952.X proposes a kind of preparation method of carbon containing catalyst for hydrorefining distillate oil, and the carbon in the catalyst adds carbon powder when the carrier moulding or the carbon precursor obtains, and the weight mixing ratio of carbon and aluminium oxide is 1: 99-20: 80.Owing to add these carbon precursor, the sintering temperature of carrier just can not be too high in oxygen-containing atmosphere, otherwise carbon loses oxidized, therefore for the catalyst that some carriers need high-temperature process, this method is infeasible, and the affiliation that adds of too much carbon powder has influence on the intensity of catalyst, is unfavorable for large-scale application.
Active carbon is except that the deficiency with bad mechanical strength, it is big also to have specific surface, pore volume and aperture features of smaller, and less aperture certainly will be caused obstruction to the diffusion of the macromolecular S of containing, N compound, reduce the effective rate of utilization on surface, thereby reduce activity of such catalysts.Therefore utilize the carrier of forming, covering charcoal on its surface is a desirable way, as required, can prepare the catalyst of Different Pore Structures.But existing charcoal method preparation process complexity, the cost height of covering is difficult to heavy industrialization.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of preparation method of carbon-contained catalyst, prepare carbon-containing carrier by pre-preg carbon precursor, reactive metal makes carbon-contained catalyst in the load then, simplify the preparation technology of carbon-contained catalyst carrier, improve the physical and chemical performance and the serviceability of carbon-contained catalyst.
The preparation process of carbon-contained catalyst of the present invention comprises: (1) preparation porous, inorganic refractory oxide carrier; (2) impregnated carbon precursor on the inorganic refractory oxide carrier; (3) in step (1) and/or step (2), introduce metal promoter; (4) heat treatment, with the porous, inorganic refractory oxide carrier heat treatment of load carbon precursor and metal promoter, the carbon precursor is decomposed into carbon, promptly makes carbon-contained catalyst carrier; (5) the supported active metal component makes catalyst.
In the carbon-contained catalyst carrier preparation process of the present invention, porous, inorganic refractory oxide carrier is that aluminium oxide, silica, silica-alumina, silica-alumina are scattered in one or more in wherein aluminium oxide, aluminium oxide that silica is covered with paint, lacquer, colour wash, etc., magnesia, zirconia, boron oxide, titanium dioxide, the molecular sieve etc., can specifically select according to the requirement of catalyst application.The auxiliary agent that can contain the catalyst needs in the porous, inorganic refractory oxide carrier, the type of auxiliary agent and content can specifically be selected by this area instructions for use.
In the carbon-contained catalyst carrier preparation process of the present invention, the amount of carbon containing is 0.1%～10% of a vehicle weight in the carrier.The carbon precursor is the organic matter of carbon containing, and organic boiling point is higher than 100 ℃, is preferably in organic compounds containing nitrogen, organic compounds containing sulfur and the oxygen-containing organic compound one or more, preferably contains the organic compound of 2～20 carbon.In the methods of the invention, under the suitable condition and under the effect of catalyst activity metal, complex reactions such as above-mentioned carbon precursor generation dehydrogenation, decomposition, charing generate nonvolatile similar carbon or burnt product, on surface, catalyst duct, the initial feed of use claims the carbon precursor.
In the carbon-contained catalyst carrier preparation process of the present invention, the metal promoter of introducing is VIII and/or group vib metal component, and content accounts for catalyst carrier 0.1%～8% in metal oxide weight.Metal promoter is specially one or more among W, Mo, Ni and the Co, and metal promoter plays in the catalyst carrier preparation process and promotes the carbon precursor to decompose the effect of charing.
In the carbon-contained catalyst carrier preparation process of the present invention, flood the porous refractory oxide carrier of forming with the carbon precursor, need through heat treatment step after the introducing carbon precursor in the carrier, condition is anaerobic or oxygen-containing atmosphere; Heat treatment temperature is 150～500 ℃, and heat treatment time is 0.5～8 hour; Under the facilitation of heat-treat condition and metal component, the carbon precursor is decomposed charing.Under the situation that the carbon precursor may run off, the dip loading amount of general carbon precursor generally wants excessive about 10%～100% more than theoretical requirement.
In the inventive method, heat treatment method can be a heat treated under the condition of oxygen-containing atmosphere (as air), and heat treatment temperature is 150～450 ℃, heat treatment time 0.5～6 hour; Described heat treatment also can be carried out under inert gas atmosphere, and described inert gas is selected from one or more in nitrogen, argon gas, helium, carbon dioxide and the water vapour, 150～500 ℃ of heat treatment temperatures, heat treatment time 0.5～8 hour.Also can preferably carry out drying before the heat treatment and handle, dry treatment temperature is 50～140 ℃, 0.5～6 hour time.Described heat treated temperature-rise period adopts and is rapidly heated, and the heating-up time that promptly reaches heat treatment temperature is no more than 30 minutes, and the heating-up time that preferably reaches heat treatment temperature is no more than 15 minutes.Studies show that, be rapidly heated and help organic decomposition charing, the more important thing is, because heat treatment temperature generally is higher than organic boiling temperature, if the heating-up time is longer, organic matter volatilization loss is more, the employing method that is rapidly heated, under the catalytic action of metal promoter on the carrier, catalytic dehydrogenating reaction took place in organic matter before desorption, and products of dehydrogenation reactions and catalyst carrier have stronger interaction, can not break away from carrier, help carbonization reaction further takes place to decompose, and therefore reduced organic volatilization loss, improved organic utilization rate.
Among the carbon containing hydrotreating catalyst preparation method of the present invention, dipping solution prepares by the compound with group vib and VIII family metal, contain two or more components in molybdenum, tungsten, nickel, the cobalt, its solution concentration can be regulated by the dosage of each compound, thereby the catalyst of preparation specified activity constituent content, the compound method of solution is conventionally known to one of skill in the art.According to the catalyst that common application requires, active metal component is 5%～50% in the content of oxide weight in the catalyst.The method of supported active metal component comprises solution impregnation and dry run etc.
In the reactive metal maceration extract, also can introduce organic additive, organic additive is 0.01: 1～10: 1 (in a final catalyst content) with group vib atomic molar ratio.Organic additive is one or more in organic compounds containing nitrogen, organic compounds containing sulfur and the oxygen-containing organic compound.The kind of organic additive and preparation in the carbon-containing carrier used carbon precursor identical.
In the catalyst carrier preparation process of the present invention,, the carbon precursor is decomposed by the facilitation of little metal auxiliary agent, harsh treatment conditions have been avoided, form covering on the catalyst carrier surface, regulate the catalyst carrier surface nature, reach the purpose that improves the catalyst serviceability.Carbon in the catalyst carrier of the present invention adds by dipping after the moulding of porous refractory oxide carrier, and this adding method is compared with preparation carbon covered carrier method commonly used, has the technology characteristic of simple; Compare with in the carrier forming process, adding the carbon precursor, have the utilization rate advantage that improves support strength and improve carbon in the carrier, increase substantially the hydrotreatment activity of heavy distillate.
The specific embodiment
In the catalyst carrier preparation process of the present invention, before carbon precursor dipping porous refractory oxide carrier and/or in the impregnated carbon precursor, introduce VIII, group vib metallic salt simultaneously, decompose charing to promote the carbon precursor.Described carrier is looked the different different shapes that require can be made into, for example spherical, tablet or bar shaped.Preferably bar shaped (clover, bunge bedstraw herb).The carrier moulding can be carried out according to a conventional method, as methods such as compressing tablet, spin, extrusions.When for example being equipped with alumina support, aluminum oxide dry glue powder is mixed with suitable quantity of water, add peptizing agent and extrusion aid, through mixedly pinching, roll, obtaining after the moulding, drying, calcination steps with the extrusion legal system.
Described dry glue powder can be commercially available commodity or adopt any one prior art for preparing.Its specific surface is preferably 200～450m
2/ g, more preferably 250～400m
2/ g, pore volume is preferably 0.5～1.2ml/g, more preferably 0.6～1.0ml/g.
Described organic compounds containing nitrogen is for comprising the organic matter of a covalent bond nitrogen-atoms at least, carbon number is 2～20 in the organic compounds containing nitrogen, concrete as ethylenediamine, hexamethylene diamine etc., be preferably except that the nitrogen-atoms that comprises at least one covalent bond, the organic compound that also comprises a hydroxyl or carboxy moiety at least, as: monoethanolamine, diethanol amine, triethanolamine, ethylenediamine tetra-acetic acid (EDTA), nitrilotriacetic acid (NTA) and ring ethylenediamine tetra-acetic acid etc.
Described organic compounds containing sulfur is for comprising the organic matter of a covalent bond sulphur atom at least, and carbon number is generally 2～20 in the organic compounds containing sulfur.((general formula R-S-R), (general formula R-S-S-R), the R in these sulfur-containing compounds is the alkyl that contains 1～10 carbon atom to disulphide, as dodecyl mercaptan carbon, allyl sulfide, DMDS etc. for general formula R-SH), thioether as mercaptan.The group that can contain one or more carboxyls, carbonyl, ester, ether, hydroxyl, sulfydryl in the organic compounds containing sulfur replaces, as TGA, mercaptopropionic acid, dimercaprol dimercaptopropanol etc.Except that above-mentioned sulfur-containing compound, can comprise sulfone and sulfoxide compound, as dimethyl sulfoxide (DMSO), dimethyl sulfone etc.
Described oxygen-containing organic compound is for containing the organic matter of a carbon atom and an oxygen atom at least.Preferably comprise the organic compound of at least two oxygen atoms and two carbon atoms, the oxygen-containing organic compound carbon number is preferably 2～20.Contain oxygen and partly can be carboxyl, carbonyl, hydroxylic moiety or their combination.These materials can be acids, as acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, citric acid etc., can be alcohols, as ethylene glycol, propane diols, butanediol, glycerine etc., can be ethers,, can be carbohydrate as diethylene glycol (DEG), DPG, triethylene glycol, three butanediols, tetraethylene glycol, polyethylene glycol etc., as glucose, fructose, lactose, maltose, sucrose etc., also can be ketone, phenols, aldehydes and lipid.
The prior art condition is adopted in drying in the porous, inorganic refractory oxide preparing carriers process and roasting, is 40 ℃～250 ℃ as baking temperature, and be 0.5h～20h drying time; Sintering temperature is 300 ℃～1000 ℃, and roasting time is 0.5h～20h.
Utilize the process of porous, inorganic refractory oxide preparing carriers carbon-containing carrier to be: not have carbon carrier with organic matter or organic solution impregnation, can adopt incipient impregnation or supersaturation dipping, also can unsaturatedly spray, after Overheating Treatment, obtain carbon-contained catalyst carrier.
Group VIII and/or group vib metal component can add in the carbon-free porous refractory oxide carrier simultaneously with the carbon precursor, with water miscible group VIII and/or group vib metal component and carbon precursor wiring solution-forming, impregnated carrier, can adopt incipient impregnation or supersaturation dipping, after Overheating Treatment, obtain carbon-containing carrier.Heat treatment method is identical with the process of utilizing carbon-free preparing carriers carbon-containing carrier.
After the further load hydrogenation activity of the carbon-contained catalyst carrier that the present invention the makes component, can obtain hydrogenation catalyst.
The technical characterictic that the invention is further illustrated by the following examples, but invention should not be deemed limited among this embodiment.
Required group vib and VIII family metal are from the compound of types such as salt, oxide or acid in the method for preparing catalyst of the present invention, as molybdenum from molybdenum oxide, ammonium molybdate, the ammonium paramolybdate one or more, tungsten is generally from ammonium metatungstate, nickel is from nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel chloride, the nickel oxalate one or more, and cobalt is from cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobalt chloride, the cobalt oxalate one or more.
Required group vib and/or group VIII metal component has two kinds of adding methods in the carbon-containing carrier preparation, promptly adds before the impregnated carbon precursor or adds simultaneously in the impregnated carbon precursor, and two kinds of methods also can be used simultaneously.Wherein adding group vib and/or group VIII metal component are divided into three kinds of modes again before the impregnated carbon precursor: adding in the dry glue powder preparation process, kneading method add and infusion process adds, method can adopt known systems, is that example describes with aluminium oxide as carrier components:
One, when the carrier moulding, adds to mix the form of pinching.Aluminum oxide dry glue powder and group vib and/or group VIII compound water solution are mixed, add acid solution and mix and pinches, until becoming plastic, extruded moulding on banded extruder carries out drying, carbon-free alumina support is made in roasting then.
Two, in the preparation process of aluminum oxide dry glue powder, add, as introducing with co-precipitation, fractional precipitation mode.Make carbon-free alumina support after utilizing this aluminum oxide dry glue powder extruded moulding drying, roasting then.
Three, acid solution is added aluminum oxide dry glue powder, mix and pinch, until becoming plastic, extruded moulding on banded extruder carries out drying, carrier is made in roasting then.With the solution impregnation of alumina carrier bar that contains group vib and/or group VIII metal component, carbon-free alumina support is made in drying, roasting afterwards.
Can add in other required auxiliary agent of extrusion aid, bonding agent, peptizing agent and catalyst etc. one or more in above-mentioned aluminum oxide dry glue powder, addition can be determined by this area knowledge according to the preparation catalyst property.Wherein used aluminum oxide dry glue powder is aluminium chloride-ammoniacal liquor method, carbonizatin method or the boehmite of aluminum sulfate method production and the SB alumina powder of Zlegler synthetic reaction accessory substance etc.
Carrier is looked different demands and be can be made into different shape, for example spherical, tablet or bar shaped etc.Preferably bar shaped (clover, bunge bedstraw herb, cylinder bar etc.).Can make different sizes as required.
The prior art condition is adopted in drying in the carbon-free porous refractory oxide preparing carriers process and roasting, is 40 ℃～250 ℃ as baking temperature, and be 0.5h～20h drying time; Sintering temperature is 300 ℃～1000 ℃, and roasting time is 0.5h～20h.
Required group VIII and/or group vib metal component can add in the no carbon carrier simultaneously with the carbon precursor in the carbon-containing carrier preparation, water miscible group VIII and/or group vib metal component and carbon precursor are made into the aqueous solution, impregnated carrier, can adopt incipient impregnation or supersaturation dipping, after Overheating Treatment, obtain carbon-containing carrier.
The solution of group vib and group VIII metal component is to support on the carbon-containing carrier by infusion process in the step (5), can be incipient impregnation, and also excessive dipping can be a step impregnation, also floods altogether, and preferably equal-volume floods altogether.Dipping method is that the technical staff is known.In described dipping solution, except that active metal component, can also contain phosphorus-containing compound, as be in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and the ammonium phosphate etc. one or more.
Flood above-mentioned carbon-containing carrier with the aqueous solution that contains active metal component, also will make final catalyst through drying steps behind the dipping, baking temperature is 70 ℃～290 ℃, is preferably 100 ℃～280 ℃, and be 0.5h～20h drying time, is preferably 1h～6h; Dry atmospheric condition can be air atmosphere, inert atmosphere (as nitrogen), reducing atmosphere (as hydrogen), steam atmosphere, vacuum atmosphere etc.
The detailed process that the invention is further illustrated by the following examples, but invention should not be deemed limited among this embodiment, the percentage composition that relates to is a weight percentage.
Embodiment 1
The present embodiment introduction prepares carbon-free alumina support with the boehmite dry glue powder.The dry glue powder specific area is 370m
2/ g, pore volume are 0.90ml/g.
Take by weighing dry glue powder 300g, add SB powder 100g, add citric acid and each 6g of sesbania powder, mixed evenly after, add acid solution 345g, HNO in the acid solution
3Concentration be 1.74%, all the other are distilled water.After rolling 20min, with the clover orifice plate extrusion of diameter 1.7mm.500 ℃ of roasting 3h behind 120 ℃ of dry 4h, the alumina support bar that makes is designated as A.
Embodiment 2
The present embodiment introduction prepares no carbon carrier with boehmite dry glue powder and nickel nitrate.The dry glue powder specific area is 370m
2/ g, pore volume are 0.90ml/g.
Take by weighing dry glue powder 300g, add SB powder 100g, add citric acid and each 6g of sesbania powder, mixed evenly after, add acid solution 345g, HNO in the acid solution
3Concentration be 1.74%, nickel nitrate content 3.9% is for all the other are distilled water.After rolling 20min, with the clover orifice plate extrusion of diameter 1.7mm.500 ℃ of roasting 3h behind 120 ℃ of dry 4h, the carrier strip that makes is designated as B.
Embodiment 3
The present embodiment introduction prepares no carbon carrier with the boehmite dry glue powder of tungstenic.The dry glue powder specific area is 360m
2/ g, pore volume are 0.90ml/g, WO
3Content is 2.7%.
Take by weighing dry glue powder 300g, add SB powder 100g, add citric acid and each 6g of sesbania powder, mixed evenly after, add acid solution 345g, HNO in the acid solution
3Concentration be 1.74%, all the other are distilled water.After rolling 20min, with the clover orifice plate extrusion of diameter 1.7mm.500 ℃ of roasting 3h behind 120 ℃ of dry 4h, the carrier strip that makes is designated as C.
Embodiment 4
Present embodiment is introduced the preparation method of carbon-containing carrier.
Be made into the aqueous solution with 10g glycerine and 5g mercaptopropionic acid, incipient impregnation 50g support C was placed after 2 hours, under nitrogen atmosphere, was warmed up to 300 ℃ from room temperature with 20 fens clock times, constant temperature 3 hours, the carbon-containing carrier called after S1 that obtains.
Be made into the aqueous solution with the 15g glycerine, incipient impregnation 50g carrier B was placed after 2 hours, in air atmosphere, was warmed up to 200 ℃ from room temperature with 10 fens clock times, constant temperature 2 hours, the carbon-containing carrier called after S2 that obtains.
Be made into the aqueous solution with 10g polyvinyl alcohol and 1.5g ammonium metatungstate, incipient impregnation 50g carrier A, place after 2 hours, under nitrogen atmosphere, be warmed up to 80 ℃ from room temperature with 5 fens clock times, constant temperature was warmed up to 300 ℃ with 10 fens clock times from 80 ℃ after 2 hours, constant temperature 1.5 hours, the carbon-containing carrier called after S3 that obtains.
Be made into the aqueous solution with 10g polyvinyl alcohol and 1.5g ammonium metatungstate, incipient impregnation 50g carrier B, place after 2 hours, in air atmosphere, be warmed up to 80 ℃ from room temperature with 5 fens clock times, constant temperature was warmed up to 200 ℃ with 10 fens clock times from 80 ℃ after 2 hours, constant temperature 1 hour, the carbon-containing carrier called after S4 that obtains.
Be made into the aqueous solution with the 1.5g ammonium metatungstate, incipient impregnation 50g carrier A, place after 2 hours, 120 ℃ of dryings are after 2 hours in air atmosphere, 500 ℃ of roastings make the no carbon carrier that contains the group vib metal after 2 hours, this carrier of aqueous solution incipient impregnation that is made into the 10g glycerine then, place after 2 hours, in air atmosphere, be warmed up to 80 ℃ from room temperature with 5 fens clock times, constant temperature was warmed up to 250 ℃ with 10 fens clock times from 80 ℃ after 2 hours, constant temperature 1 hour, the carbon-containing carrier called after S5 that obtains.
The character of carbon-containing carrier sees Table 1.
The physico-chemical property of table 1 carbon-containing carrier
| Carrier | S1 | S2 | S3 | S4 | S5 | Z1 |
| Specific area, m 2/g | 301 | 295 | 290 | 294 | 300 | 303 |
| Total pore volume, ml/g | 0.61 | 0.59 | 0.59 | 0.58 | 0.58 | 0.62 |
| Average pore size, nm | 8.1 | 8.0 | 8.1 | 7.9 | 7.7 | 8.2 |
| Carbon content, % | 4.2 | 5.3 | 6.0 | 7.7 | 4.6 | 10.4 |
| NiO，％ | - | 0.9 | - | 0.9 | - | - |
| WO 3，％ | 1.9 | - | 2.2 | 2.0 | 2.1 | - |
| Intensity, N/cm | 208 | 197 | 210 | 199 | 205 | 169 |
The carbon content analytical method: X-ray diffraction result shows that carbonization reaction has taken place the organic matter on the catalyst carrier, adopts high-temperature combustion method to measure the carbon content of sample, and carbon burns in high purity oxygen atmosphere and generates CO
2, CO
2Send into chromatogram by carrier gas,, calculate the carbon content of sample through the conductance cell check and analysis.
Embodiment 5
The present embodiment introduction prepares the method for catalyst with carbon-containing carrier of the present invention.
With the maceration extract difference incipient impregnation carrier S 1, S4 and the S5 that contain Mo, Ni, P, 150 ℃ of air atmospheres are after dry 2 hours, and the catalyst that obtains is designated as CS1, CS4 and CS5.The composition of catalyst sees Table 2
Table 2 catalyst is formed
| Catalyst | CS1 | CS4 | CS5 | CZ1 |
| MoO 3，％ | 23.95 | 23.53 | 23.71 | 23.88 |
| WO 3，％ | 1.5 | 1.5 | 1.6 | - |
| NiO，％ | 3.14 | 4.08 | 3.18 | 3.20 |
| P，％ | 1.12 | 1.25 | 1.16 | 1.19 |
Comparative Examples 1
The introduction of this Comparative Examples prepares carbon-containing carrier by the method that patent CN1648214A provides.
Take by weighing dry glue powder 300g, add SB powder 100g, add citric acid and each 6g of sesbania powder, 40g high wear-resistant carbon black powder, mixed evenly after, add acid solution 350g, HNO in the acid solution
3Concentration be 1.94%, all the other are distilled water.After rolling 20min, with the clover orifice plate extrusion of diameter 1.7mm.Behind 120 ℃ of dry 4h, roasting 3h under 500 ℃ of nitrogen atmospheres, the carrier strip that makes is designated as Z1.Carrier character sees Table 1.
By table 1 as seen, the intensity of carbon-containing carrier provided by the invention with high strength preparing carriers catalyst, helps reducing the fragmentation of catalyst in transportation and use far above the carbon-containing carrier intensity of Comparative Examples, improves the impact resistance of catalyst.
Comparative Examples 2
The introduction of this Comparative Examples prepares catalyst with the carbon-containing carrier of Comparative Examples 1 preparation.
With the maceration extract incipient impregnation carrier Z1 that contains Mo, Ni, P, 150 ℃ of air atmospheres are after dry 2 hours, and the catalyst that obtains is designated as CZ1.The composition of catalyst sees Table 2.
Embodiment 6
The activity of such catalysts evaluation experimental of present embodiment for making with carbon-containing carrier of the present invention.
The catalyst activity evaluation experimental carries out on the 50ml small hydrogenation device, before the activity rating catalyst is carried out presulfurization.The evaluating catalyst condition is at reaction stagnation pressure 9.0MPa, volume space velocity 1.0h
-1, hydrogen-oil ratio 700: 1, reaction temperature is 380 ℃.Active appraisal experiment sees Table 3 with feedstock oil character.
Activity rating the results are shown in Table 4.
Table 3 feedstock oil character
| Feedstock oil | Iran VGO |
| Density (20 ℃), gcm -3 | 0.9168 |
| Boiling range, ℃ | |
| IBP | 336 |
| EBP | 542 |
| S，％ | 1.59 |
| N，μg·g -1 | 1681 |
Comparative Examples 3
The hydrogenation performance of this Comparative Examples explanation Comparative Examples 2 catalyst.Adopt the method evaluation CZ1 identical with embodiment 6, activity rating the results are shown in Table 4.
Table 4 catalyst activity evaluation result
| Catalyst | CS1 | CS4 | CS5 | CZ1 |
| Relative denitrification activity, % | 127 | 129 | 125 | 100 |
| Desulphurizing activated relatively, % | 129 | 131 | 128 | 100 |
By data in the table 4 as seen, adopt the carbon-containing carrier of the inventive method preparation to prepare catalyst, the hydrogenation activity of catalyst is apparently higher than the Comparative Examples catalyst, and the carbon content of used carbon-containing carrier is lower than the carbon content of Comparative Examples carbon-containing carrier, illustrate that method provided by the invention can improve the utilization rate of carbon in the carrier, and can increase substantially hydrodenitrogeneration and hydrodesulfurization activity with such preparing carriers catalyst.
Claims (10)
1. the preparation method of a carbon-contained catalyst, process comprises: (1) preparation porous, inorganic refractory oxide carrier; (2) impregnated carbon precursor on the inorganic refractory oxide carrier; (3) in step (1) and/or step (2), introduce metal promoter; (4) heat treatment, with the porous, inorganic refractory oxide carrier heat treatment of load carbon precursor and metal promoter, the carbon precursor is decomposed into carbon, promptly makes carbon-contained catalyst carrier; (5) the supported active metal component makes catalyst.
2. it is characterized in that in accordance with the method for claim 1: phosphorus content is 0.1%～10% of a carbon-contained catalyst carrier weight in the described carbon containing catalytic carrier.
3. in accordance with the method for claim 1, it is characterized in that: the carbon precursor is the organic matter of carbon containing, and organic boiling point is higher than 100 ℃, is in organic compounds containing nitrogen, organic compounds containing sulfur and the oxygen-containing organic compound one or more.
4. in accordance with the method for claim 1, it is characterized in that: in the carbon-contained catalyst carrier preparation process, the metal promoter of introducing is VIII and/or group vib metal component, content accounts for catalyst carrier 0.1%～8% in metal oxide weight, and metal promoter is specially one or more among W, Mo, Ni and the Co.
5. it is characterized in that in accordance with the method for claim 1: heat-treat condition is anaerobic or oxygen-containing atmosphere; Heat treatment temperature is 150～500 ℃, and heat treatment time is 0.5～8 hour.
6. in accordance with the method for claim 1, it is characterized in that: heat treated temperature-rise period adopts and is rapidly heated, and the heating-up time that reaches heat treatment temperature is no more than 30 minutes.
7. it is characterized in that in accordance with the method for claim 1: the heating-up time that reaches heat treatment temperature is no more than 15 minutes.
8. it is characterized in that in accordance with the method for claim 1: the method for the described supported active metal component of step (5) comprises solution impregnation and dry run.
9. in accordance with the method for claim 3, it is characterized in that: described organic compounds containing nitrogen is for comprising the organic matter of a covalent bond nitrogen-atoms at least, and carbon number is 2～20 in the organic compounds containing nitrogen; Organic compounds containing sulfur is for comprising the organic matter of a covalent bond sulphur atom at least, and carbon number is generally 2～20 in the organic compounds containing sulfur; Oxygen-containing organic compound is for containing the organic matter of a carbon atom and an oxygen atom at least, and the oxygen-containing organic compound carbon number is 2～20.
10. in accordance with the method for claim 3, it is characterized in that: described nitrogen-containing compound is selected from ethylenediamine, hexamethylene diamine, monoethanolamine, diethanol amine, triethanolamine, one or more in ethylenediamine tetra-acetic acid, nitrilotriacetic acid and the ring ethylenediamine tetra-acetic acid; Described organic compounds containing sulfur is selected from one or more in dodecyl mercaptan carbon, allyl sulfide, DMDS, TGA, mercaptopropionic acid, dimercaprol dimercaptopropanol, dimethyl sulfoxide (DMSO), the dimethyl sulfone; Described oxygen-containing organic compound is selected from one or more in acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, citric acid, ethylene glycol, propane diols, butanediol, glycerine, diethylene glycol (DEG), DPG, triethylene glycol, three butanediols, tetraethylene glycol, polyethylene glycol, glucose, fructose, lactose, maltose, the sucrose.
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