CN103878020B - A kind of preparations and applicatio method of high selectivity base metal long chain alkane isomerization catalyst - Google Patents
A kind of preparations and applicatio method of high selectivity base metal long chain alkane isomerization catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of high selectivity base metal long chain alkane isomerization catalyst and preparation method thereof.This catalyst contains SAPO-11/31/41 or modified ZSM-5-22/23 molecular sieve, group vib and/or VIII hydrogenation active metals component and inorganic refractory oxide etc.This catalyst preparation process is the oxide of the CoMoNiW first preparing porous, synthesizes SAPO-11/31/41 or carries out modification to ZSM-22/23; Secondly molecular sieve and inorganic refractory oxide are mixed and add peptizing agent, water, extrusion aid etc. and be squeezed into paste; Then by the oxide of CoMoNiW and paste kneading extruded moulding; Namely catalyst is obtained finally by after dry and roasting.The present invention can be used for the catalyst preparing the especially high hydrogenation component content of different hydrogenation active component content.The catalyst adopting the present invention to prepare take base metal as hydrogenation component, and greatly, catalyst duct is unobstructed, is applicable to C for specific area and pore volume
7above long chain alkane isomerization reaction, has activity and very high isomerization selectivity preferably.
Description
Technical field
The present invention relates to preparation and the application of isomerization catalyst, specifically a kind of preparations and applicatio method of high selectivity base metal long chain alkane isomerization catalyst.
Background technology
By C
5/ C
6n-alkane changes into isoparaffin, is the effective ways producing clean gasoline with high octane.Conventional isomerization method for light hydrocarbon adopts molecular screen base bifunctional catalyst to carry out hydroisomerization reaction at 220 ~ 300 DEG C.Conventional molecular sieve has X, Y and modenite etc.
For C
7above n-alkane, if use above-mentioned molecular sieve based catalyst to carry out isomerization reaction, then cracking catalyst activity is too high, low by causing the liquid of product to be incorporated, process selective low.Research shows, has the pore passage structure of SAPO-11/31/41, ZSM-22/23 molecular sieve due to its uniqueness and the acidity of gentleness of ten-ring pore passage structure, has excellent alkane isomerization selective.Compared with the catalyst being carrier with SAPO-11/31/41 molecular sieve, the catalyst alkane isomerization being carrier with ZSM-22/23 molecular sieve is selective slightly poor, but active high.For improving the selective of isomerization catalyst, people carry out modification to molecular sieve carrier usually, regulate its acid strength and sour density, silica alumina ratio can be regulated when synthesis of molecular sieve, and by its acidity of the method modulations such as hydrothermal treatment consists, high-temperature heat treatment, chemical reagent dealuminzation after Zeolite synthesis.
It is reported, long chain alkane isomerization is different with the isomerized reaction mechanism of short chain alkanes.It is generally acknowledged, after carbon number is more than 8, its isomerization mechanism is all carry out according to key mechanism, and isomerization reaction is mainly carried out in molecular sieve aperture and outer surface.
Alkane isomerization catalyst is bifunctional catalyst, by hydrogenation dehydrogenation component and acid carrier two parts component.Hydrogenation dehydrogenation component has a variety of: comprise 1) monometallic or many metal composite system, as Pt, Ni etc., catalyst needs with hydrogen reducing before use; 2) transient metal sulfide system, catalyst needs presulfurization before use; 3) carbide, nitride, phosphide etc. of transition metal.It should be noted that the sulfide of transition metal Co/Mo/Ni/W, when for diesel oil hydrogenation, except reducing except condensation point of diesel oil, also have the function of desulfurization, denitrogenation and aromatic saturation.
When taking noble metal as hydrogenation dehydrogenation component, the activity and selectivity of catalyst is high, but catalyst preparing cost is high, and not sulfur resistive, can not be used in the higher diesel oil of sulfur content or lubricating oil isomerization-visbreaking process.
Carrier containing SAPO-11/31/41, ZSM-22/23 equimolecular sieve, compared with not containing the carrier of molecular sieve, pore volume and specific surface generally have and decline largely, when carrier Middle molecule sieve content is higher, when adopting impregnation, catalyst loadings is very limited, and can cause declining to a great extent of specific surface area of catalyst and pore volume after load, affects the activity and selectivity of catalyst.
SAPO-11 molecular sieve shows excellent performance in alkane isomerization reaction, and USP5833837, USP5135638 etc. report the method utilizing SAPO-11 for carrier production lubricating oil.
CN97116407.x discloses a kind of diesel oil isomerization-visbreaking catalyst, and its hydrogenation active component content is higher.Catalyst adopts infusion process preparation, and because in catalyst, active metallic content is high, particularly the content of the oxide that molecule is larger is also higher, causes amount of activated component can block the duct of molecular sieve.
CN1352231A discloses a kind of diesel oil isomerization-visbreaking catalyst, adopts method load nickel oxide and/or oxide, the wherein nickel oxide 1% ~ 6% of dipping, tungsten oxide 0 ~ 15%.When catalyst oxygen-freeization tungsten, time only containing small amounts nickel, the hydrofinishing performance of catalyst is undesirable, and when containing tungsten oxide (raising of hydrogenation component load capacity) in the catalyst adopting infusion process to prepare, the specific surface of catalyst obviously reduces, and depression effeCt is poorer than the catalyst effect only containing nickel oxide.
Summary of the invention
For the deficiencies in the prior art, the invention provides preparation method and the application process of high, the selective good base metal long chain alkane isomerization catalyst of a kind of activity, this catalyst overcomes the shortcoming of noble metal not sulfur resistive, overcome infusion process for the restriction of catalyst loadings and the impact that significantly reduces specific surface area of catalyst and pore volume simultaneously, require so not harsh to the S in raw material, N content, for long chain alkane isomerization reaction, selective very high.
First, provide the preparation method of long chain alkane isomerization catalyst: with the weight of catalyst for benchmark, it is composed as follows: molecular sieve: 30% ~ 60%, the oxide of hydrogenation active metals: 10% ~ 30%, inorganic refractory oxide: 20% ~ 40%; Described molecular sieve is that one or more in SAPO-11/31/41, ZSM-22/23, ZSM-5, β, mordenite molecular sieve (adopt molecular sieve as the acidic components of isomerization catalyst, especially there is SAPO-11/31/41, ZSM-22/23 molecular sieve of ten-ring one-dimensional channels, due to its special pore passage structure and gentle acidity, this molecular sieve analog selective very good); Described hydrogenation active metals oxide is that (base metal such as Co, Mo, Ni, W does hydrogenation component for the composite oxides of two or three composition in the oxide of Co, Mo, Ni, W, because above-mentioned base metal sulfur resistance is relatively good, and during for diesel oil pour point depression, also have the function of desulfurization, denitrogenation, aromatic saturation); Inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, boron oxide, magnesia, zirconia or clay; Concrete preparation process is as follows:
(1), by molecular sieve, inorganic refractory oxide or its precursor mix, then add peptizing agent, extrusion aid and water, fully kneading is plastic paste together.
(2), by plastic paste and hydrogenation active metals oxide kneading, extruded moulding, namely obtains catalyst after drying, roasting; Described baking temperature is 80 ~ 140 DEG C, drying time 2 ~ 12h; Roasting condition is as follows: sintering temperature 200 ~ 400 DEG C, and roasting time is 2 ~ 8h.Catalyst shape (cross sectional shape) can be circle, quadrangle, triangle, cloverleaf pattern or bunge bedstraw herb shape etc., also can be the distortion of these shapes.
Such scheme can more preferably:
Peptizing agent is preferably nitric acid or aqueous hydrochloric acid solution, its addition be pure after account for 1 ~ 5% of vehicle weight.Peptizing agent is the material that can make mixture peptization, also can select in Ludox, basic anhydride or acid compound (such as sulfuric acid, acetic acid, citric acid) etc., the mixture of carrier and molecular sieve, inorganic refractory oxide or its precursor herein.
Inorganic refractory oxide is preferably aluminium oxide, its precursor be selected from boehmite, boehmite, diaspore, gibbsite and visit in aluminium stone one or more.
Aluminium oxide is preferably the dry glue of macroporous aluminium oxide, and its specific area is 200 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6ml/g.
Hydrogenation active metals oxide is the oxide with meso-hole structure adopting the compound of cobalt, molybdenum, nickel, tungsten to prepare through hydro-thermal reaction, and reaction temperature is 50 ~ 200 DEG C, reaction time 4 ~ 48h; The specific area of the oxide of meso-hole structure is: 50 ~ 200m
2/ g, pore volume: 0.1 ~ 0.3ml/g.
The compound of cobalt, nickel, molybdenum, tungsten is preferably cobalt nitrate, basic nickel carbonate/nickel nitrate, ammonium heptamolybdate/ammonium tetramolybdate/molybdenum oxide respectively with, ammonium metatungstate.
Can also add starch or sesbania powder in hydro-thermal reaction, its addition is 1 ~ 5% of metal compound weight.
For improving the selective of isomerization catalyst, when ZSM-22/23 selected by described molecular sieve, need to carry out modification to it, the method for modification has high-temperature roasting, EDTA or NH
4f hydrothermal treatment consists; Wherein the method for high-temperature roasting is: the molecular sieve ZSM-22/23 namely molecular sieve ZSM-22/23 being obtained modification at temperature 600 ~ 900 DEG C of roasting 2 ~ 8h; EDTA or NH
4the method of F hydrothermal treatment consists is: molecular sieve ZSM-22/23 adds EDTA or NH
4react in the aqueous solution of F, then after filtration, washing, dry and roasting obtain the molecular sieve ZSM-22/23 of modification, wherein EDTA or NH
4the temperature of F hydrothermal treatment consists is 60 ~ 100 DEG C, processing time 2 ~ 12h, EDTA or NH
4f concentration of aqueous solution is 0.02 ~ 0.4mol/L, the solid-to-liquid ratio 1:5 ~ 1:20 of reaction.
The catalyst property that above-mentioned preparation method obtains controls as follows: pore volume: 0.10 ~ 0.30ml/g, specific area is 150 ~ 300m
2/ g, bulk density is 0.65 ~ 1.1g/ml.The isomerization effect of the catalyst of above-mentioned parameter is better.
Then, the application process of the long chain alkane isomerization catalyst providing a kind of above-mentioned preparation method to prepare, catalyst needs to carry out presulfurization, with 1 ~ 5wt%CS before use
2cyclohexane solution or aviation kerosine be presulfurization oil, prevulcanisation time 2 ~ 24h, pre-curing temperature is 180 ~ 360 DEG C; Then to C
7above long chain alkane or the oil product containing a large amount of long chain alkane carry out hygrogenating isomerization reaction, and reaction condition is: Hydrogen Vapor Pressure 1 ~ 15Mpa, temperature 250 ~ 400 DEG C, volume space velocity 0.5 ~ 4h
-1, hydrogen to oil volume ratio 200 ~ 1000.
In the present invention, non-noble metal hydrogenation component is not adopt the mode of dipping to load on carrier, but adopt the method for kneading by molecular sieve with transition metal oxide close contact, the method has plurality of advantages: 1) adopt catalyst prepared by kneading method, in catalyst, the content of transition metal oxide can reach higher level, improves the Hydrogenation of catalyst.2) adopt the catalyst prepared of kneading method, compared with the catalyst prepared with infusion process, its specific area and pore volume larger, be conducive to the raising of catalyst activity and selectivity.3), when adopting preparation catalyst, a lot of apertures of molecular sieve by metal component to blocking, and will adopt the method for kneading, and make the duct of molecular sieve comparatively unobstructed, favourable alkane isomerization optionally improves.
Accompanying drawing explanation
Fig. 1: SAPO-11 catalyst based isomerisation selectivity is with the change curve of conversion ratio;
Fig. 2: ZSM-22 catalyst based isomerisation selectivity is with the change curve of conversion ratio.
Specific embodiments
Below in conjunction with accompanying drawing and example, the present invention is described in further detail: the following examples will be further described with regard to method provided by the invention and set forth, but invention should not be deemed limited in following embodiment.
Catalyst of the present invention adopts 10ml fixed-bed micro-reactor with nC
14for raw material is evaluated, loaded catalyst is 10ml.Before charging, presulfurization is carried out to catalyst, make the metal on catalyst become sulphided state from oxidation state.Presulfurization oil: 3wt%CS
2-cyclohexane, presulfurization condition: 300 DEG C, 4Mpa, presulfurization 8h, volume space velocity 1.5h
-1.Quantitative analysis on gas chromatograph after product condensation.
Embodiment 1
A kind of preparation method of high selectivity base metal long chain alkane isomerization catalyst is as follows:
(1) SAPO-11 molecular sieve is synthesized, mol ratio: Al
2o
3: P
2o
5: DPA:0.3SiO
2: 60H
2o.
Mixing 250g water and 47.6gSB powder, stir; Mixing 77.5g phosphoric acid and 80g water droplet are added in the mixed liquor of SB powder and water and go, and drip and stir more than 4h; Then drip template di-n-propylamine 34.7g, stir more than 2 hours, then drip 23.3g Ludox (SiO
2content 26%), stir more than 2 hours, dress still, 200 DEG C of crystallization 48h, then centrifugal, washing, dried overnight at 120 DEG C, roasting 24h at 550 DEG C.
(2) according to the ratio of Ni/W atomic ratio 1:1, by 44.4g basic nickel carbonate, 76.55g ammonium metatungstate, join in 500ml distilled water, add 10g sesbania powder again, at 150 DEG C, stirring reaction is after 5 hours, cooling, filter, 120 DEG C of dry 12h obtain NiW composite oxides.
(3) the 35gSAPO-11 molecular sieve of synthesis and 15gSB powder are fully mixed, add 3g sesbania powder (5wt% of overall catalyst weight), drip the aqueous solution of nitric acid of 2wt%, be squeezed into paste.
(4) the NiW composite oxides kneading after paste and 10g being pulverized, extruded moulding, 120 DEG C of dry 8h, 375 DEG C of roasting 4h obtain catalyst, NiW oxide in catalyst, and the ratio of molecular sieve and SB powder is 2:7:3.
Reaction result is in table 1, Fig. 1.As can be seen from table 1, Fig. 1, adopt the selective height of isomerizationization of catalyst 16.7%NiW-Keaded prepared by kneading method, the isomerisation selectivity of the catalyst 20%NiW-Impregnated prepared than equi-volume impregnating is high a lot.
Embodiment 2
Basic condition is with embodiment 1, and unlike NiW composite oxides in catalyst, the ratio of molecular sieve and SB powder is 3:7:3, gets 15gNiW composite oxides and participates in kneading.
Reaction result is in table 1, Fig. 1.As can be seen from table 1, Fig. 1, the isomerisation selectivity of catalyst 23.1%NiW-Keaded adopting kneading method to prepare is high, and the isomerisation selectivity of the catalyst 20%NiW-Impregnated prepared than equi-volume impregnating is high a lot.
Embodiment 3
Basic condition is with embodiment 1, and unlike NiW composite oxides in catalyst, the ratio of molecular sieve and SB powder is 4:7:3, gets 20gNiW composite oxides and participates in kneading.
Reaction result is in table 1, Fig. 1.As can be seen from table 1, Fig. 1, adopt the selective height of isomerizationization of catalyst 28.6%NiW-Keaded prepared by kneading method, the isomerisation selectivity of the catalyst 20%NiW-Impregnated prepared than equi-volume impregnating is high a lot.
Embodiment 4
The preparation method of catalyst of the present invention is as follows:
(1) ZSM-22 molecular sieve elder generation roasting 12h at 550 DEG C deviates from template, then carries out ion-exchange.In 1L water, add 80g ammonium nitrate (concentration of ammonium nitrate water solution is 1mol/L), and then add 100gZSM-22 molecular sieve, filtration after 80 DEG C of exchange 4h, washing, drying, at 550 DEG C, roasting 4h repeats 3 times.
(2) according to the ratio of Ni/Mo/W atomic ratio 2:1:1, by 88.7g basic nickel carbonate, 53.1g ammonium metatungstate, 76.6g ammonium molybdate, join in 500ml distilled water, add 15g sesbania powder etc. again, at 150 DEG C, stirring reaction is after 5 hours, cooling, filter, dry NiMoW composite oxides.
(3) get the 15gZSM-22 molecular sieve after 700 DEG C of roastings and 20gSB powder fully mixes, add the sesbania powder of catalyst weight 5wt%, drip the aqueous solution of nitric acid of 2wt%, be squeezed into paste.
(4) by paste and 15gNiMoW composite oxides kneading, extruded moulding, 120 DEG C of dry 8h, 375 DEG C of roasting 4h obtain catalyst, NiMoW composite oxides in catalyst, and the mass ratio of molecular sieve and SB powder is 3:3:4.
Reaction result is in table 2, Fig. 2.As can be seen from table 2, Fig. 2, adopt the selective height of isomerizationization of catalyst 30%NiMoW-Keaded prepared by kneading method, the isomerisation selectivity of the catalyst 20%NiMoW-Impregnated prepared than equi-volume impregnating is high a lot.
Embodiment 5
Method for preparing catalyst, with embodiment 5, is 2:3:4 unlike the mass ratio of NiMoW composite oxides and molecular sieve and SB powder in catalyst, gets 10gNiMoW composite oxides and participates in kneading.
Reaction result is in table 2, Fig. 2.As can be seen from table 2, Fig. 2, adopt the selective height of isomerizationization of catalyst 22.2%NiMoW-Keaded prepared by kneading method, the isomerisation selectivity of the catalyst 20%NiMoW-Impregnated prepared than equi-volume impregnating is high a lot.
Embodiment 6
A kind of preparation method of high selectivity base metal long chain alkane isomerization catalyst is as follows:
(1) ZSM-22 molecular sieve elder generation roasting 12h at 550 DEG C deviates from template, then carries out ion-exchange.In 1L water, add 80g ammonium nitrate (concentration of ammonium nitrate water solution is 1mol/L), and then add 100gZSM-22 molecular sieve, filtration after 80 DEG C of exchange 4h, washing, drying, at 550 DEG C, roasting 4h repeats 3 times.
(2) modification of ZSM-22 molecular sieve: the method adopting high-temperature roasting, 700 DEG C of roasting 2h.
(3) according to the ratio of Ni/Mo/W atomic ratio 2:1:1, by 88.7g basic nickel carbonate, 53.1g ammonium metatungstate, 76.6g ammonium molybdate, join in 500ml distilled water, add 15g sesbania powder etc. again, at 150 DEG C, stirring reaction is after 5 hours, cooling, filter, dry NiMoW composite oxides.
(4) get the 15gZSM-22 molecular sieve after 700 DEG C of roastings and 20gSB powder fully mixes, add the sesbania powder of catalyst weight 5wt%, drip the aqueous solution of nitric acid of 2wt%, be squeezed into paste.
(5) by paste and 15gNiMoW composite oxides kneading, extruded moulding, 120 DEG C of dry 8h, 375 DEG C of roasting 4h obtain catalyst, NiMoW composite oxides in catalyst, and the mass ratio of molecular sieve and SB powder is 3:3:4.
Reaction result is in table 2, Fig. 2.As can be seen from table 2, Fig. 2, ZSM-22 after 700 DEG C of modification by calcination is the catalyst 30%NiMoW-Keaded (700*2) of carrier, under same conversion, its alkane isomerization selectivity ratios does not have the ZSM-22 of modification to be the selective height of isomerizationization of the catalyst 30%NiMoW-Keaded of carrier, and the isomerisation selectivity of the catalyst 20%NiMoW-Impregnated prepared than equi-volume impregnating is high a lot.
Embodiment 7
Method for preparing catalyst is with embodiment 4, and the method for modifying unlike ZSM-22 is different.
This example adopts H
4the EDTA aqueous solution carries out modification to the mode that ZSM-22 carries out hydrothermal treatment consists.In the 800ml aqueous solution, add EDTA11.69g(EDTA concentration of aqueous solution is 0.05mol/L, adds 10.88g25wt% ammoniacal liquor and helps EDTA to dissolve), then add 80gZSM-22 molecular sieve, 80 DEG C of hydro-thermal reaction 4h, filter, washing, drying, 550 DEG C of roasting 4h obtain the ZSM-22 molecular sieve of EDTA modification.
Reaction result is in table 2, Fig. 2.As can be seen from table 2, Fig. 2, the modified ZSM-22 of EDTA is the catalyst 30%NiMoW-Keaded (EDTA) of carrier, under same conversion, its alkane isomerization selectivity ratios does not have the ZSM-22 of modification to be the selective height of isomerizationization of the catalyst of carrier, and the isomerisation selectivity of the catalyst prepared than equi-volume impregnating is high a lot.
Embodiment 8
Method for preparing catalyst is with example 4, and the method for modifying unlike ZSM-22 is different.
This example adopts NH
4the F aqueous solution carries out modification to the mode that ZSM-22 carries out hydrothermal treatment consists.6.67gNH is added in 1.2L water
4f(NH
4f concentration of aqueous solution is 0.15mol/), then add 80gZSM-22 molecular sieve, 80 DEG C of hydro-thermal reaction 4h, filter, washing, dry, 550 DEG C of roasting 4h obtain NH
4the ZSM-22 molecular sieve of F modification.
Reaction result is in table 2, Fig. 2.As can be seen from table 2, Fig. 2, NH
4the modified ZSM-22 of F is the catalyst 30%NiMoW-Keaded (NH of carrier
4f), under same conversion, its alkane isomerization selectivity ratios does not have the ZSM-22 of modification to be the selective height of isomerizationization of the catalyst 22.2%/30%NiMoW-Keaded of carrier, and the isomerisation selectivity of the catalyst 20%NiMoW-Impregnated prepared than equi-volume impregnating is high a lot.
Comparative example 1
Comparative catalyst 1 preparation method is as follows:
(1) SAPO-11 Zeolite synthesis method is with embodiment 1
(2) 70gSAPO-11 molecular sieve and the 30gSB powder that will synthesize also roasting fully mix, and add 5g sesbania powder, drip the aqueous solution of nitric acid of 2wt%, extrusion, 120 DEG C of dry 4h, 550 DEG C of roasting 4h obtain catalyst carrier.
(3) prepare 20g catalyst, add appropriate distilled water with 1.56g nickel nitrate and 3.03g ammonium metatungstate (NiW atomic ratio 1:1) and dissolve, join maceration extract, adopt equi-volume impregnating, get 18g carrier and flood, then ambient temperature overnight, 120 DEG C of dry 4h, 375 DEG C of roasting 4h obtain catalyst.
Catalyst Pore Structure Parameters is in table 3, and reaction result is in table 1, Fig. 1.As can be seen from Table 3, adopt catalyst prepared by infusion process, compared with carrier, specific surface and the pore volume of dipping rear catalyst decline very large; As can be seen from table 1, Fig. 1, catalyst 20%NiW-SAPO-11-Impregnated prepared by equi-volume impregnating, under same conversion, catalyst 16.7%NiW-SAPOP-11-Keaded, 23.1%NiW-SAPO-11-Keaded prepared by its alkane isomerization selectivity ratios kneading method are much lower.
Comparative example 2
Comparative catalyst 2 preparation method is as follows:
(1) join NiMoW maceration extract: by 9g molybdenum oxide, 16.93g, 3.96g basic nickel carbonate, add suitable quantity of water and 2.11g SPA and add thermal agitation, obtained homogeneous phase solution, and then add 28.57g Nickelous nitrate hexahydrate, with 50ml volumetric flask constant volume.
(2) ZSM-22 molecular sieve elder generation roasting 12h at 550 DEG C deviates from template, then carries out ion-exchange.Dissolve 80g ammonium nitrate in 1L water, then add 100gZSM-22 molecular sieve, 80 DEG C exchange 4h, have exchanged washing, drying, and then 550 DEG C of roasting 4h, repeat 3 times.
(3) by 30gZSM-22 molecular sieve and 40gSB powder, do extrusion aid with 3.5g sesbania powder, with 2wt% aqueous solution of nitric acid for peptizing agent, extruded moulding, 120 DEG C of dry 4h, at 550 DEG C, roasting 4h obtains catalyst carrier.
(4) equi-volume impregnating is adopted, the catalyst 20g of preparation load capacity 20wt%.From volumetric flask, get 6.1mlNiMoW maceration extract, calculate maceration extract should be diluted with water to 8.0ml according to carrier water absorption rate, then flood, placement of spending the night, dry 4h at 120 DEG C, roasting 4h at 375 DEG C.
Catalyst Pore Structure Parameters is in table 3, and reaction result is in table 2, Fig. 2.As can be seen from Table 3, adopt catalyst prepared by infusion process, compared with carrier, specific surface and the pore volume of dipping rear catalyst decline very large; As can be seen from Fig. 2, table 2, catalyst 20%NiMoW-Impregnated prepared by equi-volume impregnating, under same conversion, catalyst 20%NiMoW-Keaded, 30%NiMoW-Keaded prepared by its alkane isomerization selectivity ratios kneading method are much lower.
Table 1NiW/SAPO-11 Catalyst Conversion and optionally corresponding relation
Table 2NiMoW-ZSM-22 Catalyst Conversion and optionally corresponding relation
The pore structure parameter of the various catalyst of table 3, molecular sieve and oxide
Claims (10)
1. the preparation method of a high selectivity base metal long chain alkane isomerization catalyst, it is characterized in that, with the weight of catalyst for benchmark, it is composed as follows: molecular sieve: 30% ~ 60%, the oxide of hydrogenation active metals: 10% ~ 30%, inorganic refractory oxide: 20% ~ 40%; Described molecular sieve is one or more in SAPO-11/31/41, ZSM-22/23, ZSM-5, β, mordenite molecular sieve; Described hydrogenation active metals oxide is the composite oxides of two kinds or three kinds compositions in the oxide of Co, Mo, Ni, W; Inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, boron oxide, magnesia, zirconia or clay; Concrete preparation process is as follows:
(1), by molecular sieve, inorganic refractory oxide or its precursor mix, then add peptizing agent, extrusion aid and water, fully kneading is plastic paste together;
(2), by plastic paste and hydrogenation active metals oxide kneading, extruded moulding, namely obtains catalyst after drying, roasting; Described baking temperature is 80 ~ 140 DEG C, drying time 2 ~ 12h; Roasting condition is as follows: sintering temperature 200 ~ 400 DEG C, and roasting time is 2 ~ 8h.
2. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 1, it is characterized in that, described peptizing agent is nitric acid or aqueous hydrochloric acid solution, its addition be pure after account for 1 ~ 5% of vehicle weight.
3. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 1, it is characterized in that, described inorganic refractory oxide is preferably aluminium oxide, its precursor be selected from boehmite, boehmite, diaspore, gibbsite and visit in aluminium stone one or more.
4. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 3, is characterized in that, described aluminium oxide is the dry glue of macroporous aluminium oxide, and its specific area is 200 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6ml/g.
5. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 1, it is characterized in that, described hydrogenation active metals oxide is the oxide with meso-hole structure adopting the compound of cobalt, molybdenum, nickel, tungsten to prepare through hydro-thermal reaction, reaction temperature is 50 ~ 200 DEG C, reaction time 4 ~ 48h; The specific area of the oxide of described meso-hole structure is: 50 ~ 200m
2/ g, pore volume: 0.1 ~ 0.3ml/g.
6. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 5, it is characterized in that, the compound of described cobalt, nickel, molybdenum, tungsten is respectively cobalt nitrate, basic nickel carbonate/nickel nitrate, ammonium heptamolybdate/ammonium tetramolybdate/molybdenum oxide, ammonium metatungstate.
7. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 5, is characterized in that, can also add starch or sesbania powder in described hydro-thermal reaction, its addition is 1 ~ 5% of metal compound weight.
8. according to the preparation method of the arbitrary described high selectivity base metal long chain alkane isomerization catalyst of claim 1-7, it is characterized in that, when ZSM-22/23 selected by described molecular sieve, need to carry out modification to it, the method for modification has high-temperature roasting, EDTA or NH
4f hydrothermal treatment consists; Wherein the method for high-temperature roasting is: the molecular sieve ZSM-22/23 namely molecular sieve ZSM-22/23 being obtained modification at temperature 600 ~ 900 DEG C of roasting 2 ~ 8h; EDTA or NH
4the method of F hydrothermal treatment consists is: molecular sieve ZSM-22/23 adds EDTA or NH
4react in the aqueous solution of F, then after filtration, washing, dry and roasting obtain the molecular sieve ZSM-22/23 of modification, wherein EDTA or NH
4the temperature of F hydrothermal treatment consists is 60 ~ 100 DEG C, processing time 2 ~ 12h, EDTA or NH
4f concentration of aqueous solution is 0.02 ~ 0.4mol/L, the solid-to-liquid ratio 1:5 ~ 1:20 of reaction.
9. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 8, is characterized in that, described in the catalyst property that obtains as follows: pore volume: 0.10 ~ 0.30ml/g, specific area is 150 ~ 300m
2/ g, bulk density is 0.65 ~ 1.1g/ml.
10. the application process of the high selectivity base metal long chain alkane isomerization catalyst prepared according to the arbitrary claim of claim 1-9, it is characterized in that, described catalyst needs to carry out presulfurization, with 1 ~ 5wt%CS before use
2cyclohexane solution or aviation kerosine be presulfurization oil, prevulcanisation time 2 ~ 24h, pre-curing temperature is 180 ~ 360 DEG C; Then to C
7above long chain alkane or the oil product containing a large amount of long chain alkane carry out hygrogenating isomerization reaction, and reaction condition is: Hydrogen Vapor Pressure 1 ~ 15Mpa, temperature 250 ~ 400 DEG C, volume space velocity 0.5 ~ 4h
-1, hydrogen to oil volume ratio 200 ~ 1000.
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| CN106799256B (en) * | 2015-11-26 | 2019-12-13 | 中国科学院大连化学物理研究所 | alkane isomerization catalyst and preparation method thereof |
| CN108745411A (en) * | 2018-05-23 | 2018-11-06 | 中国中化股份有限公司 | A kind of long-chain normal paraffin catalyst for hydroisomerizing and preparation method thereof |
| CN112007692B (en) * | 2019-05-31 | 2024-03-29 | 国家能源投资集团有限责任公司 | Catalyst for dewaxing lubricating oil base oil for Fischer-Tropsch wax production and preparation method and application thereof |
| CN112934251B (en) * | 2019-12-11 | 2023-06-06 | 中国科学院大连化学物理研究所 | Double-function catalyst for catalyzing hydroisomerization of n-heptane and preparation method thereof |
| CN112973716B (en) * | 2019-12-16 | 2023-08-18 | 山西腾茂科技股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN114713209B (en) * | 2021-01-06 | 2024-04-05 | 浙江蓝天环保高科技股份有限公司 | Fluoride modified adsorbent and method for purifying crude hexafluoro-1,3-butadiene |
| CN112958147B (en) * | 2021-02-23 | 2022-11-18 | 华南理工大学 | Bifunctional catalyst, preparation method thereof and method for preparing isoparaffin from stearic acid |
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