CN108014786A - A kind of high metal dispersion degree catalyst and preparation method and application - Google Patents
A kind of high metal dispersion degree catalyst and preparation method and application Download PDFInfo
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- CN108014786A CN108014786A CN201711296358.3A CN201711296358A CN108014786A CN 108014786 A CN108014786 A CN 108014786A CN 201711296358 A CN201711296358 A CN 201711296358A CN 108014786 A CN108014786 A CN 108014786A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The present invention provides a kind of high metal dispersion degree catalyst and preparation method and application, which is included Al2O3It is dispersed in water, adjusts pH to 3.0~7.0；Anion surfactant is added, adjusts pH to 3.0~7.0；Addition source metal, after stirring evenly, constant temperature, high metal dispersion degree catalyst is obtained after filtering, washing, dry, roasting；The present invention can also impregnate the second metal component, and bimetallic component catalyst is obtained after dry, roasting.The catalyst has the characteristics that high metal dispersion degree, has high removal of mercaptans/alkene conversion selectivity, is reacted available for demercaptaning for gasoline.
Description
Technical field
The present invention relates to a kind of high metal dispersion degree catalyst and preparation method and application, belong to catalyst field.
Background technology
Increasingly stringent with environmental regulation, limitation of the countries in the world to sulfur content in gasoline is more and more stringenter.Mercaptan is
A kind of sulfur-containing compound in gasoline, it not only has foul odour, but also has faintly acid, meeting etching apparatus, its reactivity
It is relatively strong, easily cause the catalyst inactivation in downstream process and make the active hydro carbons in gasoline that oxidation reaction generation colloid occur,
Therefore the mercaptan in removing gasoline is imperative.Wherein Merox deodorization techniques are most typical technologies in gasoline deodorization technique, though
So improved fixed bed mercaptan removal technique caustic is reduced, but still suffers from the emission problem of spent lye.Using conventional hydro
Process for purification removing mercaptan can bring a large amount of saturations of alkene in gasoline, cause octane number to be greatly reduced.Mercaptan-alkene hydrocarbyl ether
Change reaction since its reaction temperature is relatively low, only need to can be by itself existing small molecule mercaptan and two in gasoline under hydro condition
Alkene or olefine reaction generate high boiling sulfide compound, are then cut full distillation gasoline, and gained light petrol is low
Sulfur oil, it is not necessary to further hydrodesulfurization processing can directly carry out oil product reconciliation, therefore can while removal of mercaptans,
The octane number caused by olefins hydrogenation is reduced to lose.
Existing document report solid acid catalyst and transition-metal catalyst can be applied to thioetherification reaction.Solid acid
Catalyst, such as sulfonate resin, solid phosphoric acid and intercalation compound, are the effective catalysts of mercaptan thioetherification reaction, but due to micro-
The presence in the oil of the basic nitrogen compound of amount and easily inactivate.Transition metal Ni, Pt, Pd and Ag etc. possess preferable sulphur
Etherification reaction performance, especially Ni bases catalyst are facing hydrogen thioether because having good resistant to sulfur poisoning performance and cheap price
Change and be widely adopted in sweetening reaction.For support type Ni/Al2O3Catalyst, since nickel active component is in the work of carrier surface
Property bit class and quantity and the activity and selectivity of its catalyst it is closely related, therefore improve nickel by optimizing preparation condition and deposit
It is always the hot spot of such catalyst research in the dispersion degree and sulphidity of form and raising nickel.
In general, infusion process, coprecipitation and sol-gel process are to prepare Ni/Al2O3The main method of catalyst, they are right
Active component dispersion degree influences very notable.Catalyst activity component obtained by traditional infusion process, which often exists easily to reunite, burns
The deficiencies of knot, dispersion degree are low, and nickel component utilization rate is not high.Coprecipitation and sol-gel process help to improve nickel in the carrier
Dispersion degree, but stronger Metal-Support interaction reduction/vulcanization difficulty of nickel species can be caused to be significantly increased.
Guohui Li et al. people (Guohui Li, Linjie Hu, Josephine M.Hill, Appl.Catal.A Gen.301 (2006)
16-24.) Ni/Al prepared by infusion process, coprecipitation, sol-gel process has been investigated2O3Catalyst, finds coprecipitation, molten
Glue-gel method strengthens the interaction of nickel species and carrier, generates the surface nickel species of a large amount of difficult reduction, this is to follow-up living
The formation of property phase is totally unfavorable.
Xinli Zhu et al. (Xinli Zhu, Peipei Huo, Yueping Zhang, Dangguo Cheng,
Changjun Liu,Appl.Catal.B:Environ.81 (2008) 132-140.) discovery is studied, plasma sputtering method helps
In nickel species being uniformly distributed in carrier surface, and the raising of nickel active phase dispersion degree, but active component is equally existed with carrying
The problem of Interaction enhanced between body.
Jeong Gil Seo et al. (Jeong Gil Seo, Min HyeYoun, Ji ChulJung, In KyuSong,
Int.J.Hydrogen Energ.35 (2010) 6738-6746.) propose with CO2The colloidal sol that supercritical drying coordinates-solidifying
Glue method, this method are suitable for preparing the finely dispersed Ni/Al of finely dispersed nickel nano particle2O3Catalyst, but this side
Method carries out under high pressure, it is necessary to the device of high cost.
In conclusion the catalyst for preparing high metal dispersion degree is still a very big challenge.
The content of the invention
In view of the deficiencies of the prior art, it is an object of the invention to provide a kind of preparation side of high metal dispersion degree catalyst
Method, the catalyst prepared by the preparation method have the characteristics that metal dispersity is high.
Another object of the present invention is to provide the catalyst obtained by above-mentioned preparation method, which is a kind of high de-
The mercaptan-eliminating catalyst of mercaptan/alkene conversion selectivity.
It is still another object of the present invention to provide the application of above-mentioned catalyst.
To reach above-mentioned purpose, on the one hand, the present invention provides a kind of preparation method of catalyst, it mainly includes following
Step：
(1) by Al2O3It is dispersed in water, adjusts pH value to 3.0~7.0, obtain mixed liquor A；
(2) anion surfactant is added in mixed liquor A, adjusts pH value to 3.0~7.0, obtain mixed liquid B；
(3) source metal is dissolved in mixed liquid B, obtains mixed liquor C；
(4) mixed liquor C is placed in closed container, constant temperature obtains mixed liquor D；
(5) by after mixed liquor D filterings, washing, dry, roasting, the catalyst is obtained.
In the above-mentioned preparation method of the present invention, step (1) changes Al by adjusting pH2O3Surface charging property and meanwhile in step
(2) anion surfactant is added in, the water-wet side of anion surfactant is negatively charged, the Al with positively charged2O3Effect,
Its surface is adsorbed in, makes Al2O3There is one layer of water-wet side on surface towards Al2O3The anion surfactant on surface；Due to polarity phase
The molten principle of patibhaga-nimitta, separately there is an anion surfactant layer, its hydrophobic side and Al2O3The anion surfactant on surface is dredged
Water end (W.E.) interacts, and forms water-wet side towards the anion surfactant layer in outside；The metal ion of positively charged and the water-wet side
Water-wet side towards the anion surfactant layer in outside is adsorbed in its surface by electrostatic interaction, high dispersive；Due to the moon from
The effect of sub- surfactant, metal component and Al2O3Between strong interaction is not present, metal component is still in high score after roasting
Bulk state.The catalyst being prepared by the present invention has high metal dispersion degree selectivity.
In above-mentioned preparation method, it is preferable that further include step (6)：Impregnated on the catalyst that step (5) obtains
Two metal component of load regulation, then obtains bimetallic component catalyst after drying, roasting.
The above-mentioned preparation method the step of in (2), it is preferable that the anion surfactant includes dodecyl sulphate
Sodium, neopelex, fatty alcohol-ether sodium sulfate, sodium alkyl sulfate, ammonium alkyl sulfate, fatty alcohol ether ammonium sulfate,
α-sodium olefin sulfonate, fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, alcohol ether carboxylate, sulfosuccinic
One or more in hydrochlorate, amino-acid salt etc..
The above-mentioned preparation method the step of in (2), it is preferable that the anion surfactant is added to the mixed liquor
After A, its concentration is 0.01~1mol/L.
The above-mentioned preparation method the step of in (3), it is preferable that the source metal include the inorganic salts of nickel, platinum inorganic salts,
One or more in the inorganic salts of palladium and the inorganic salts of silver.
The above-mentioned preparation method the step of in (3), it is preferable that the source metal and anionic surface described in step (2)
The molar ratio of activating agent is 1:1~5.
The above-mentioned preparation method the step of in (1), it is preferable that the Al2O3Mass ratio with water is 1:30~100.
The above-mentioned preparation method the step of in (1) and step (2), it is preferable that adjust pH, institute using inorganic acid or its solution
Stating inorganic acid or its solution includes the one or more in hydrochloric acid, sulfuric acid, nitric acid.
The above-mentioned preparation method the step of in (2), it is preferable that the stirring is 1~10h of stirring at 10~50 DEG C.
The above-mentioned preparation method the step of in (4), it is preferable that the closed container be with polytetrafluoroethyllining lining not
Become rusty steel reaction kettle.
The above-mentioned preparation method the step of in (4), it is preferable that the constant temperature is in a dynamic condition；Preferably, it is described dynamic
State condition is to be placed in closed container to rotate in constant temperature oven.
The above-mentioned preparation method the step of in (4), it is preferable that the temperature of the constant temperature is 80~200 DEG C, and constant temperature time is
10~48h.
The above-mentioned preparation method the step of in (5), it is preferable that in step (5), the washing is washing to neutrality.
The above-mentioned preparation method the step of in (5), it is preferable that the drying is dry 10~48h at 80~150 DEG C.
The above-mentioned preparation method the step of in (5), it is preferable that the roasting is 3~10h of roasting at 450~600 DEG C.
The above-mentioned preparation method the step of in (6), it is preferable that second metal component is the inorganic salts of molybdenum and the nothing of iron
One or more in machine salt.
The above-mentioned preparation method the step of in (6), it is preferable that in step (6), (such as with MoO, Fe in terms of oxide2O3
Meter), the load capacity of second metal component is 3~10wt.%.
The above-mentioned preparation method the step of in (6), it is preferable that the drying is in 80~150 DEG C of dry 10~48h.
The above-mentioned preparation method the step of in (6), it is preferable that the roasting is to roast 3~10h in 450~600 DEG C.
It should be noted that the technical characteristic of the present invention can be mutually combined to realize superior technique effect, the present invention exists
Additional technical feature afterwards is suitable for preceding and in rear any technical solution.
On the other hand, the present invention provides a kind of catalyst, it is prepared by aforementioned preparation process.The catalyst is
A kind of mercaptan-eliminating catalyst of high removal of mercaptans/alkene conversion selectivity.
Another further aspect, the excellent performance of the catalyst obtained based on the present invention, the present invention provide the catalyst de-
Application in thiol reaction.Preferably, the sweetening reaction is that the mercaptan in oil product exists with alkene therein and/or alkadienes
There are the thioetherification reaction of mercaptan under conditions of the catalyst and alkene and/or alkadienes.It is highly preferred that the oil product is vapour
Oil.
In conclusion invention broadly provides a kind of preparation method of high metal dispersion degree catalyst and by party's legal system
The mercaptan-eliminating catalyst of the high removal of mercaptans obtained/alkene conversion selectivity.The preparation method changes Al by adjusting pH2O3Surface
Charging property while anion surfactant is added, make metal component high dispersive is carried on Al2O3Surface, due to anion table
The effect of face activating agent, metal component and Al2O3Between strong interaction is not present, metal component is still in high score bulk after roasting
State.After the second metal component is added, the Mercaptan removal rate of the catalyst can be further improved.
Brief description of the drawings
Fig. 1 is the catalyst and Al that the embodiment of the present invention 1 and comparative example 1 are prepared2O3XRD diagram.
Fig. 2 is the XRD diagram for the catalyst that the embodiment of the present invention 2, comparative example 2 and comparative example 3 are prepared.
Fig. 3 is that the catalyst that the embodiment of the present invention 1 and comparative example 1 are prepared is passed through through vulcanizing nickel species grain in rear catalyst
Distribution.
Fig. 4 is the evaluation result for the catalyst that the embodiment of the present invention 1 and comparative example 1 are prepared.
The evaluation result for the catalyst that Fig. 5 positions embodiment of the present invention 2, comparative example 2 and comparative example 3 are prepared.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, in conjunction with specific implementation
Example carries out technical scheme described further below, it should be understood that these examples are merely to illustrate the present invention rather than limit
The scope of the present invention processed.In embodiment, each Starting reagents material is commercially available, and the experimental method that actual conditions is not specified is
Conventional method known to fields and normal condition, or according to the condition proposed by apparatus manufacturer.
Embodiment 1
By 1.0g Al2O3It is scattered in 70mL deionized waters, the hydrochloric acid solution that 38wt.% is added dropwise adjusts pH to 5.0；
4.68g dodecylbenzene sodium sulfonates are added in above-mentioned mixed liquor, stirs to being completely dissolved, is added dropwise 38wt.%'s
Hydrochloric acid solution adjusts pH to 5.0；
Then the Nickelous nitrate hexahydrate of 1.30g is added in above-mentioned mixed solution, 4h is stirred in 25 DEG C；
Finally, above-mentioned mixed solution is transferred in closed reactor, reaction kettle is placed in 120 DEG C and rotated in baking oven and is reacted
24h, takes out cooling, filtering, washs to pH=7, the dry 12h of 120 DEG C of gained sample after the completion of reaction, then is transferred in Muffle furnace
500 DEG C of roasting 4h, obtain catalyst, are denoted by Ni-SDEA.
Embodiment 2
Will be dissolved with 1.52g Fe (NO3)3·9H2The Ni-SDEA that the aqueous solution of O is impregnated into 20~40 mesh 5g embodiments 1 is urged
In agent, it is dried overnight through 120 DEG C, 500 DEG C of roasting 4h, obtain ferronickel bimetallic catalyst, be denoted by NiFe-SDEA.
Comparative example 1
By dissolved with the aqueous solution of 2.72g Nickelous nitrate hexahydrates, incipient impregnation is in the Al of 20~40 mesh of 5.0g2O3In, 120
DEG C dry 12h, 500 DEG C of roasting 4h, Ni-IM is denoted as by catalyst.
Comparative example 2
Will be dissolved with 1.52g Fe (NO3)3·9H2The aqueous solution of O is impregnated into the Ni-IM in 20~40 mesh comparative examples 1 of 5.0g
In catalyst, it is dried overnight through 120 DEG C, 500 DEG C of roasting 4h, obtain ferronickel bimetallic catalyst, be denoted as NiFe-IM.
Comparative example 3
Will be dissolved with 1.52g Fe (NO3)3·9H2The aqueous solution of O is impregnated into the Al of 20~40 mesh of 5.0g2O3In, 120 DEG C are dry
Dry 12h, 500 DEG C of roasting 4h, Fe-IM is denoted as by catalyst.
The composition of catalyst passes through inductively coupled plasma method by PerkinElmer OPTIMA 7000DV spectrometers
Measure.Before measuring, dissolve a sample in chloroazotic acid.Each catalyst metal content is as shown in table 1.
Metal component content in 1 different catalysts of table
Note：Tenor is in terms of oxide, i.e. Ni contents are in terms of the mass fraction of NiO, and Fe contents are with Fe2O3Quality point
Number meter.
The catalyst of acquisition is analyzed using XRD, Fig. 1 is the Ni-SDEA catalyst that is prepared of embodiment 1 and right
The Ni-IM catalyst and Al that ratio 1 is prepared2O3XRD diagram.
Fig. 2 is the NiFe-IM catalyst that the NiFe-SDEA catalyst that is prepared of embodiment 2, comparative example 2 are prepared
The XRD diagram for the Fe-IM catalyst being prepared with comparative example 3.
As shown in Figure 1, in Ni-SDEA, Ni-IM and Al2O3XRD spectra in, 2 θ angles is at 39.4 °, 46.0 ° and 66.8 °
Diffraction maximum belong to carrier Al2O3Characteristic peak.There is ownership at 2 θ angles is 43.4 ° and 62.8 ° in Ni-IM catalyst
In the characteristic peak of NiO, show that the NiO particle sizes in Ni-IM are big, dispersion degree is low；And do not go out in the XRD spectra of Ni-SDEA
The characteristic peak of existing body phase NiO, illustrates that NiO therein exists with high dispersive, little particle state.To sum up analysis is understood, with conventional leaching
Stain method is compared, and anion surfactant is modified, the active component Ni in catalyst carrier have smaller particle size and
Preferably dispersiveness.
As shown in Figure 2, do not occur Fe in the XRD spectra of Fe-IM2O3The characteristic diffraction peak of crystalline phase, shows content of metal
Relatively low, Fe species are in Al2O3Upper is in high dispersion state.Also do not occur NiO and Fe in the XRD spectra of NiFe-SDEA2O3Crystalline phase
Characteristic diffraction peak, show into Ni-SDEA introduce 5.9wt.% Fe2O3Shi Wei causes metal component to disperse in carrier surface
The change of state, exists by the active component in surfactant-modified catalyst with high dispersion state, active metal ruler
It is very little smaller.In the XRD spectra of NiFe-IM, the diffraction maximum near 2 θ=37.3 °, 43.4 ° and 62.8 ° belongs to NiO phases,
Show NiO in Al2O3Assembled on surface；Observed at 2 θ=35.7 ° and 54.0 ° and significantly belong to NiFe2O4Phase
Diffraction maximum, it is the compound phase for being reacted and being formed by Ni the and Fe oxides being in close contact, and illustrates to use conventional impregnation method
The NiFe-IM catalyst activity metal particle sizes of preparation are big, and dispersion degree is low.
Use 1- propanethiols (200 μ g/g S), 1- octenes (23.0wt.%), isoprene (0.4wt.%), octane
The mixture of (46.6wt.%) and toluene (30.0wt.%) carries out reactivity worth evaluation as mould oil to above-mentioned catalyst.
Before catalyst reaction performance evaluation is carried out, catalyst need to be vulcanized, specific vulcanisation step is：Will catalysis
N in agent bed2By H2Displacement is complete, and keeps H2Air speed is 500~3000h-1, adjustment reaction bed temperature to 120~180
DEG C, to catalyst bed with 1~5h-1Volume space velocity injection straight-run naphtha, adjustment hydrogen to oil volume ratio is to 200~500:1；Will
Catalyst bed is warming up to 150~200 DEG C with 10~30 DEG C/h, starts to inject vulcanizing agent (such as dimethyl disulfide), adjustment
Its injection rate to straight-run naphtha 1~5wt.%；Then proceed to be warming up to 210~250 DEG C with the speed of 10~30 DEG C/h,
6~10h of constant temperature；270~290 DEG C are warming up to the speed of 10~30 DEG C/h, 6~10h of constant temperature；It is warming up to 10~30 DEG C/h
310~350 DEG C, 6~10h of constant temperature；With each catalyst bed reaction temperature of 10~30 DEG C/h coolings；Finally, with reaction oil product
Sulfurized oil in exchange system, vulcanization terminate.
In order to accurately analyze the dispersiveness of metal component after Ni-SDEA and Ni-IM presulfidings of catalyst, pass through scanning electron
20 photos that microscope shoots each catalyst, then count 500~600 nickel species therein, are obtained
The particle size distribution information of two kinds of catalyst, the results are shown in Figure 3.From the figure 3, it may be seen that surfactant-modified Ni-
Ni-IM catalyst ns iS prepared by SDEA catalyst and equi-volume impregnatingxThe mean size of particle size be respectively 2.8nm and
It is also substantially fewer than Ni-IM to occupy ratio for large-size metallic particles in 7.9nm, Ni-SDEA catalyst.Ni-SDEA catalyst tables
Metal particle size on face is obviously reduced, and dispersiveness improves, and illustrates the surface that metal and carrier are connected in catalyst preparation
Activating agent can polymerize to avoid active component under the conditions of high-temperature roasting and presulfurization, improve Ni species in carrier surface
Dispersiveness.
XPS characterizations are carried out to sulphided state Ni-SDEA, Ni-IM catalyst, is then fitted by peak, can be calculated each metal
The relative amount of component and various forms S, the results are shown in table 2.There was only 15.6% Ni in sulphided state Ni-IM as shown in Table 2
Species cure, and the NiS in sulphided state Ni-SDEAxThe relative amount of phase brings up to 34.6%, is 2.22 times of Ni-IM.With
S2 2-The removal of mercaptans activity of the Ni of bonding is better than and S2-And Sn 2-The Ni of bonding, from table 2 it can be seen that the method for the present invention preparation is urged
In agent, S2 2-Ratio be far above conventional impregnation prepare catalyst.Catalyst prepared by preparation method of the present invention has more
High high removal of mercaptans active sites ratio.
The XPS fitting results of 2 sulphided state Ni-SDEA, Ni-IM catalyst of table
XPS characterizations are carried out to oxidation state NiFe-SDEA, NiFe-IM and Fe-IM catalyst, is then fitted, calculated by peak
The relative amount of each metal component can be obtained, the results are shown in table 3.
The XPS fitting results of 3 oxidation state NiFe-SDEA, NiFe-IM and Fe-IM catalyst of table
As shown in Table 3, after Fe is added into monometallic Ni base catalyst, divide in NiFe-SDEA and NiFe-IM catalyst
Do not occur 33.6% and 22.7% and belong to NiFe2O4The Ni of phase2+Species, meanwhile, in NiFe-SDEA catalyst NiO and
NiFe2O4Ni in phase2+Species relative amount is higher than NiFe-IM catalyst, and 50.5% during by NiFe-IM is brought up to
76.7% during NiFe-SDEA, and the Ni of both types2+Species are NiSxWith NiS (FeS) active sites precursor；NiFe-SDEA
NiAl in catalyst2O4Ni in phase2+Species relative amount is lower than NiFe-IM catalyst.Added in catalyst preparation process
After surfactant SDBS, Fe in Fe-O-Al phases3+33.3% when species relative amount is by NiFe-IM is reduced to NiFe-SDEA
When 18.4%.Show that the method for the present invention can weaken Al2O3Carrier and the interaction of metal object inter-species, suppress difficult vulcanization
NiAl2O4Species are formed, so as to form the NiO and NiFe that can more vulcanize2O4Species.
XPS characterizations are carried out to sulphided state NiFe-SDEA, NiFe-IM and Fe-IM catalyst, is then fitted, calculated by peak
The relative amount of each metal component and various forms S can be obtained, the results are shown in table 4.
The XPS fitting results of 4 sulphided state NiFe-SDEA, NiFe-IM and Fe-IM catalyst of table
As shown in Table 4, sulphided state NiS in NiFe-SDEA catalystxWith the Ni in NiFeS phases2+Species relative amount compares
The height of NiFe-IM catalyst, NiSxMiddle Ni2+16.6% when species relative amount is by Ni-IM when bringing up to NiFe-SDEA
Ni in 29.9%, NiS (FeS)2+11.0% when species relative amount is by Ni-IM brings up to 17.0% during NiFe-SDEA, table
Bright the method for the present invention has high nickel species state of cure (vulcanization), is conducive to the increase of chain carrier number.Compared to the body such as conventional
NiFe-IM catalyst prepared by product infusion process, NiFe-SDEA catalyst prepared by the method for the present invention have more and S2 2-Key
(removal of mercaptans activity is higher than and S for the Ni active sites of conjunction2-And Sn 2-The Ni active sites of bonding).
After vulcanization, react in 1.0MPa, 135 DEG C, 6h-1Liquid hourly space velocity (LHSV) (LHSV) and 30 (v/v) H2Under/oil ratio
Carry out.Product is collected after stable state is reached, the Mercaptan removal rate and olefin conversion of Ni-SDEA and Ni-IM catalyst are such as
Shown in Fig. 4, the Mercaptan removal rate and olefin conversion of NiFe-SDEA, NiFe-IM and Fe-IM catalyst are as shown in Figure 5.
As shown in Figure 4, Ni-SDEA catalyst has excellent thioetherification activity, and thiol conversion 90.2% is identical anti-
The activity of Ni-IM catalyst is 74.9% under the conditions of answering.The olefin conversion of Ni-SDEA and Ni-IM is respectively 1.1% He
0.7%, show that the olefin conversion of both catalyst is very low.The above results show that Ni-SDEA has excellent desulfurization
Alcohol/alkene converts selective and high Mercaptan removal rate.
As shown in Figure 5, the mercaptan removal rate of Fe-IM shows that the thioether activity of the catalyst is poor down to 43.6%.Three
In kind catalyst, the thioether activity highest of NiFe-SDEA, Mercaptan removal rate is 99.5%, significantly larger than NiFe-IM.NiFe-
The olefin conversion of SDEA is 1.3%, slightly above NiFe-IM and Fe-IM.The above results show that NiFe-SDEA has excellent
Removal of mercaptans/alkene conversion selectivity.
Claims (10)
1. a kind of preparation method of catalyst, it comprises the following steps：
(1) by Al2O3It is dispersed in water, adjusts pH value to 3.0~7.0, obtain mixed liquor A；
(2) anion surfactant is added in mixed liquor A, adjusts pH value to 3.0~7.0, obtain mixed liquid B；
(3) source metal is dissolved in mixed liquid B, obtains mixed liquor C；
(4) mixed liquor C is placed in closed container, constant temperature obtains mixed liquor D；
(5) by after mixed liquor D filterings, washing, dry, roasting, the catalyst is obtained.
2. preparation method according to claim 1, it further includes step (6)：On the catalyst that step (5) obtains
The second metal component of dip loading, then obtains bimetallic component catalyst after drying, roasting.
3. preparation method according to claim 1 or 2, wherein：
Preferably, in step (2), the anion surfactant includes lauryl sodium sulfate, dodecyl benzene sulfonic acid
Sodium, fatty alcohol-ether sodium sulfate, sodium alkyl sulfate, ammonium alkyl sulfate, fatty alcohol ether ammonium sulfate, α-sodium olefin sulfonate, fat
In sour methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, alcohol ether carboxylate, sulfosuccinate, amino-acid salt etc.
One or more；
Preferably, in step (2), the anion surfactant is added to the mixed liquor A, its concentration for 0.01~
1mol/L。
4. preparation method according to claim 1 or 2, wherein：
Preferably, in step (3), the source metal includes the nothing of the inorganic salts of nickel, the inorganic salts of platinum, the inorganic salts of palladium and silver
One or more in machine salt；
Preferably, in step (3), the molar ratio of the source metal and anion surfactant described in step (2) is 1:1
~5.
5. preparation method according to claim 1 or 2, wherein：
Preferably, in step (1), the Al2O3Mass ratio with water is 1:30~100；
Preferably, pH, the inorganic acid or its solution bag are adjusted using inorganic acid or its solution in step (1) and step (2)
Include the one or more in hydrochloric acid, sulfuric acid, nitric acid；
Preferably, stirring described in step (2) is 1~10h of stirring at 10~50 DEG C.
6. preparation method according to claim 1 or 2, wherein：
Preferably, in step (4), the closed container is the stainless steel cauldron with polytetrafluoroethyllining lining；
Preferably, in step (4), the constant temperature is in a dynamic condition；Preferably, the dynamic condition is by closed container
It is placed in and rotates in constant temperature oven；
Preferably, in step (4), the temperature of the constant temperature is 80~200 DEG C, and constant temperature time is 10~48h.
7. preparation method according to claim 1 or 2, wherein：
Preferably, in step (5), the washing is washed to neutrality；
Preferably, in step (5), the drying is dry 10~48h at 80~150 DEG C；
Preferably, in step (5), the roasting is 3~10h of roasting at 450~600 DEG C.
8. the preparation method according to any one of claim 2~7, wherein：
Preferably, in step (6), second metal component is one kind or more in the inorganic salts of molybdenum and the inorganic salts of iron
Kind；
Preferably, in step (6), in terms of oxide, the load capacity of second metal component is 3~10wt.%；
Preferably, in step (6), the drying is in 80~150 DEG C of dry 10~48h；
Preferably, in step (6), the roasting is to roast 3~10h in 450~600 DEG C.
9. a kind of catalyst, preparation method is prepared as any one of claim 1~8.
10. application of the catalyst described in claim 9 in sweetening reaction, it is preferable that the sweetening reaction is oil product
In mercaptan and alkene therein and/or alkadienes mercaptan and alkene and/or alkadienes under conditions of there are the catalyst
Thioetherification reaction；It is highly preferred that the oil product is gasoline.
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| CN101298047A (en) * | 2007-04-30 | 2008-11-05 | 中国石油天然气集团公司 | Preparation of hydrogenation catalyst |
| CN101474574A (en) * | 2008-10-24 | 2009-07-08 | 长春工业大学 | Solid catalyst for petroleum liquid component sweetening and preparation method |
| CN102125846A (en) * | 2010-12-24 | 2011-07-20 | 中国石油大学(北京) | Mercaptan etherification catalyst |
| WO2016029387A1 (en) * | 2014-08-27 | 2016-03-03 | 中国石油天然气集团公司 | Bimetallic mercaptan transfer catalyst used in low-temperature mercaptan removal of liquefied petroleum gas |
| CN106390989A (en) * | 2015-08-03 | 2017-02-15 | 中国石油天然气集团公司 | Hydrodesulfurization catalyst for gasoline, and controlled preparation method and application thereof |
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- 2017-12-08 CN CN201711296358.3A patent/CN108014786A/en active Pending
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|---|---|---|---|---|
| CN101298047A (en) * | 2007-04-30 | 2008-11-05 | 中国石油天然气集团公司 | Preparation of hydrogenation catalyst |
| CN101474574A (en) * | 2008-10-24 | 2009-07-08 | 长春工业大学 | Solid catalyst for petroleum liquid component sweetening and preparation method |
| CN102125846A (en) * | 2010-12-24 | 2011-07-20 | 中国石油大学(北京) | Mercaptan etherification catalyst |
| WO2016029387A1 (en) * | 2014-08-27 | 2016-03-03 | 中国石油天然气集团公司 | Bimetallic mercaptan transfer catalyst used in low-temperature mercaptan removal of liquefied petroleum gas |
| CN106390989A (en) * | 2015-08-03 | 2017-02-15 | 中国石油天然气集团公司 | Hydrodesulfurization catalyst for gasoline, and controlled preparation method and application thereof |
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