CN103878020A - Preparation method and application method of high-selectivity non-precious-metal long-chain alkane isomerization catalyst - Google Patents
Preparation method and application method of high-selectivity non-precious-metal long-chain alkane isomerization catalyst Download PDFInfo
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Abstract
The invention relates to a high-selectivity non-precious-metal long-chain alkane isomerization catalyst and a preparation method of the high-selectivity non-precious-metal long-chain alkane isomerization catalyst. The catalyst contains SAPO-11/31/41 or modified ZSM-22/23 molecular sieve, a VIBth or VIIIth hydrogenated active metal component, inorganic refractor oxide and the like. The preparation method of the catalyst comprises the following steps of preparing porous CoMoNiW oxide, and synthesizing SAPO-11/31/41 or modifying ZSM-22/23; mixing the molecular sieve and inorganic refractory oxide, adding a peptizing agent, water and an extrusion assistant, and extruding the mixture into cream; mixing the CoMoNiW oxide and the cream, and extruding the mixture into strips; and finally drying and baking the strips to obtain the catalyst. The method can be used for preparing the catalyst with different hydrogenated active component contents and especially with high hydrogenated component content. The prepared catalyst adopts the non-precious metal as a hydrogenated component, the specific surface area and pore volume are large, the catalyst pore canals are smooth, and the catalyst is applicable to the more than C7 long-chain alkane isomerization reaction, good in activity and high in isomerization selectivity.
Description
Technical field
The present invention relates to preparation and the application of isomerization catalyst, specifically a kind of preparation and application process 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 of producing clean gasoline with high octane.Conventional isomerization method for light hydrocarbon is to adopt 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, cracking catalyst activity is too high, the liquid that causes product is incorporated low, process selectively low.Research shows, has the SAPO-11/31/41, ZSM-22/23 molecular sieve of ten-ring pore passage structure due to its unique pore passage structure and gentle acidity, has excellent alkane isomerization selective.Compared with the catalyst that is carrier with SAPO-11/31/41 molecular sieve, the catalyst alkane isomerization taking ZSM-22/23 molecular sieve as carrier is selectively slightly poor, but active high.For improving the selective of isomerization catalyst, people carry out modification to molecular sieve carrier conventionally, regulate its acid strength and sour density, can in the time of synthesis of molecular sieve, regulate silica alumina ratio, and after Zeolite synthesis by its acidity of method modulation such as hydrothermal treatment consists, high-temperature heat treatment, chemical reagent dealuminzation.
It is reported, long chain alkane isomerization is different with the isomerized reaction mechanism of short chain alkanes.It is generally acknowledged, when carbon number exceedes after 8, its isomerization mechanism is all to 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 before use with hydrogen reducing; 2) transient metal sulfide system, catalyst needs presulfurization before use; 3) carbide of transition metal, nitride, phosphide etc.It should be noted that the sulfide of transition metal Co/Mo/Ni/W, when for diesel oil hydrogenation, except reducing condensation point of diesel oil, also have the function of desulfurization, denitrogenation and aromatic saturation.
During taking noble metal as hydrogenation dehydrogenation component, the activity and selectivity of catalyst is high, but catalyst preparation cost is high, and not anti-sulphur, can not be used for diesel oil or lubricating oil isomerization-visbreaking process that sulfur content is higher.
The carrier that contains 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 largely and decline, in the time that in carrier, molecular sieve content is higher, while adopting infusion process dipping, 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 has shown excellent performance in alkane isomerization reaction, and USP5833837, USP5135638 etc. has reported the method for utilizing SAPO-11 to produce lubricating oil for carrier.
CN97116407.x discloses a kind of diesel oil isomerization-visbreaking catalyst, and its hydrogenation activity constituent content is higher.Catalyst adopts infusion process preparation, and because active metallic content in catalyst is high, the content of the oxide that particularly molecule is larger is also higher, causes part active component can stop up the duct of molecular sieve.
CN1352231A discloses a kind of diesel oil isomerization-visbreaking catalyst, adopts method load nickel oxide and/or the oxide of dipping, wherein nickel oxide 1% ~ 6%, tungsten oxide 0 ~ 15%.When oxygen-freeization of catalyst tungsten, during only containing a small amount of nickel oxide, the hydrofinishing performance of catalyst is undesirable, and while adopting in the catalyst prepared of infusion process containing tungsten oxide (raising of hydrogenation component load capacity), the specific surface of catalyst obviously reduces, and pour point depression effect is than only the catalyst effect containing nickel oxide is poor.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of activity preparation method and application process high, selectively good base metal long chain alkane isomerization catalyst, this catalyst has overcome the not shortcoming of anti-sulphur of noble metal, overcome the impact that infusion process significantly reduces for the restriction of catalyst loadings and on specific surface area of catalyst and pore volume simultaneously, so not harsh to the S in raw material, N content requirement, for long chain alkane isomerization reaction, selectively very high.
First, provide the preparation method of long chain alkane isomerization catalyst: taking the weight of catalyst as 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, the 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 selectively 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 has 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), molecular sieve, inorganic refractory oxide or its precursor are mixed, 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, obtains catalyst after dry, roasting; Described baking temperature is 80 ~ 140 DEG C, drying time 2 ~ 12h; Roasting condition is as follows: 200 ~ 400 DEG C of sintering temperatures, roasting time is 2 ~ 8h.Catalyst shape (cross sectional shape) can be circle, quadrangle, triangle, cloverleaf pattern or bunge bedstraw herb shape etc., can be also the distortion of these shapes.
Such scheme can be more preferably:
Peptizing agent is preferably nitric acid or aqueous hydrochloric acid solution, and its addition is to account for 1 ~ 5% of vehicle weight after pure.Peptizing agent is the material that can make mixture peptization, also can in Ludox, basic anhydride or acid compound (such as sulfuric acid, acetic acid, citric acid) etc., select, and carrier is the mixture of molecular sieve, inorganic refractory oxide or its precursor herein.
Inorganic refractory oxide is preferably aluminium oxide, and its precursor is selected from boehmite, boehmite, diaspore, gibbsite and visits one or more in aluminium stone.
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 that adopts 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 respectively cobalt nitrate, basic nickel carbonate/nickel nitrate, ammonium heptamolybdate/ammonium tetramolybdate/molybdenum oxide with, ammonium metatungstate.
In hydro-thermal reaction, can also add starch or sesbania powder, its addition is 1 ~ 5% of metallic compound weight.
For improving the selective of isomerization catalyst, in the time that described molecular sieve is selected ZSM-22/23, 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 that molecular sieve ZSM-22/23 is obtained to modification at 600 ~ 900 DEG C of roasting 2 ~ 8h of temperature; EDTA or NH
4the method of F hydrothermal treatment consists is: molecular sieve ZSM-22/23 adds EDTA or NH
4in the aqueous solution of F, react, 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 control that above-mentioned preparation method obtains is 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, provide the application process of long chain alkane isomerization catalyst prepared by a kind of above-mentioned preparation method, catalyst needs to carry out presulfurization before use, with 1 ~ 5wt%CS
2cyclohexane solution or aviation kerosine be presulfurization oil, presulfurization time 2 ~ 24h, pre-curing temperature is 180 ~ 360 DEG C; Then to C
7above long chain alkane or the oil product that contains a large amount of long chain alkanes carry out hygrogenating isomerization reaction, and reaction condition is: Hydrogen Vapor Pressure 1 ~ 15Mpa, 250 ~ 400 DEG C of temperature, 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 to adopt the mode of dipping to load on carrier, but adopt the method for kneading that molecular sieve is followed to transition metal oxide close contact, the method has plurality of advantages: the catalyst that 1) adopts kneading method to prepare, in catalyst, the content of transition metal oxide can reach higher level, has improved the Hydrogenation of catalyst.2) adopt the catalyst prepared of kneading method, compared with the catalyst of preparing with infusion process, its specific area and pore volume are larger, are conducive to the raising of catalyst activity and selectivity.3) while adopting preparation catalyst, a lot of apertures of molecular sieve will be blocked by metal component, and adopt the method for kneading, make the duct of molecular sieve comparatively unobstructed, and favourable alkane isomerization optionally improves.
Brief description of the drawings
The catalyst based isomerization of Fig. 1: SAPO-11 is selectively with the change curve of conversion ratio;
The catalyst based isomerization of Fig. 2: ZSM-22 is selectively 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 and set forth with regard to method provided by the invention, but invention should not be deemed limited in following embodiment.
Catalyst of the present invention is to adopt 10ml fixed-bed micro-reactor with nC
14for raw material is evaluated, loaded catalyst is 10ml.Before charging, catalyst is carried out to presulfurization, 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) synthetic SAPO-11 molecular sieve, mole proportioning: Al
2o
3: P
2o
5: DPA:0.3SiO
2: 60H
2o.
Mix 250g water and 47.6gSB powder, stir; Mix in the mixed liquor that 77.5g phosphoric acid and 80g water droplet be added to SB powder and water and go, more than dripping stirring 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, stirring reaction is after 5 hours, cooling at 150 DEG C again, filter, 120 DEG C of dry 12h obtain NiW composite oxides.
(3) synthetic 35g SAPO-11 molecular sieve and 15g SB powder are fully mixed, add 3g sesbania powder (5wt% of catalyst gross weight), drip the aqueous solution of nitric acid of 2wt%, be squeezed into paste.
(4) by the NiW composite oxides kneading after paste and 10g pulverizing, extruded moulding, 120 DEG C of dry 8h, 375 DEG C of roasting 4h obtain catalyst, NiW oxide in catalyst, the ratio of molecular sieve and SB powder is 2:7:3.
Reaction result is in table 1, Fig. 1.From table 1, Fig. 1, can find out, the isomerizationization of catalyst 16.7%NiW-Keaded prepared by employing kneading method is selectively high, and the isomerization of the catalyst 20%NiW-Impregnated preparing than equi-volume impregnating is selective high a lot.
Embodiment 2
Basic condition is with embodiment 1, and different is NiW composite oxides in catalyst, and the ratio of molecular sieve and SB powder is 3:7:3, gets 15g NiW composite oxides and participates in kneading.
Reaction result is in table 1, Fig. 1.From table 1, Fig. 1, can find out, the isomerization of catalyst 23.1%NiW-Keaded prepared by employing kneading method is selectively high, and the isomerization of the catalyst 20%NiW-Impregnated preparing than equi-volume impregnating is selective high a lot.
Embodiment 3
Basic condition is with embodiment 1, and different is NiW composite oxides in catalyst, and the ratio of molecular sieve and SB powder is 4:7:3, gets 20g NiW composite oxides and participates in kneading.
Reaction result is in table 1, Fig. 1.From table 1, Fig. 1, can find out, the isomerizationization of catalyst 28.6%NiW-Keaded prepared by employing kneading method is selectively high, and the isomerization of the catalyst 20%NiW-Impregnated preparing than equi-volume impregnating is selective high a lot.
Embodiment 4
The preparation method of catalyst of the present invention is as follows:
(1) the roasting 12h at 550 DEG C of ZSM-22 molecular sieve elder generation 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, filter, washing, dry after 80 DEG C of exchange 4h, roasting 4h repeats 3 times at 550 DEG C.
(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., stirring reaction is after 5 hours, cooling at 150 DEG C again, filter, be dried to obtain NiMoW composite oxides.
(3) get 700 DEG C of 15g ZSM-22 molecular sieve and 20g SB powder after roasting and fully mix, 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 15g NiMoW composite oxides kneading, extruded moulding, 120 DEG C of dry 8h, 375 DEG C of roasting 4h obtain catalyst, NiMoW composite oxides in catalyst, the mass ratio of molecular sieve and SB powder is 3:3:4.
Reaction result is in table 2, Fig. 2.From table 2, Fig. 2, can find out, the isomerizationization of catalyst 30%NiMoW-Keaded prepared by employing kneading method is selectively high, and the isomerization of the catalyst 20%NiMoW-Impregnated preparing than equi-volume impregnating is selective high a lot.
Embodiment 5
Method for preparing catalyst is with embodiment 5, and the mass ratio of different is in catalyst NiMoW composite oxides and molecular sieve and SB powder is 2:3:4, gets 10g NiMoW composite oxides and participates in kneading.
Reaction result is in table 2, Fig. 2.From table 2, Fig. 2, can find out, the isomerizationization of catalyst 22.2%NiMoW-Keaded prepared by employing kneading method is selectively high, and the isomerization of the catalyst 20%NiMoW-Impregnated preparing than equi-volume impregnating is selective high a lot.
Embodiment 6
A kind of preparation method of high selectivity base metal long chain alkane isomerization catalyst is as follows:
(1) the roasting 12h at 550 DEG C of ZSM-22 molecular sieve elder generation 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, filter, washing, dry after 80 DEG C of exchange 4h, roasting 4h repeats 3 times at 550 DEG C.
(2) modification of ZSM-22 molecular sieve: adopt the method for 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., stirring reaction is after 5 hours, cooling at 150 DEG C again, filter, be dried to obtain NiMoW composite oxides.
(4) get 700 DEG C of 15g ZSM-22 molecular sieve and 20g SB powder after roasting and fully mix, 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 15g NiMoW composite oxides kneading, extruded moulding, 120 DEG C of dry 8h, 375 DEG C of roasting 4h obtain catalyst, NiMoW composite oxides in catalyst, the mass ratio of molecular sieve and SB powder is 3:3:4.
Reaction result is in table 2, Fig. 2.From table 2, Fig. 2, can find out, the catalyst 30%NiMoW-Keaded (700*2) that ZSM-22 after 700 DEG C of modification by calcination is carrier, under same conversion, its alkane isomerization selectivity ratios does not have the isomerizationization of the catalyst 30%NiMoW-Keaded that the ZSM-22 of modification is carrier selectively high, and the isomerization of the catalyst 20%NiMoW-Impregnated preparing than equi-volume impregnating is selective high a lot.
Embodiment 7
Method for preparing catalyst is with embodiment 4, and different is the method for modifying difference of ZSM-22.
This example adopts H
4the mode that the EDTA aqueous solution carries out hydrothermal treatment consists to ZSM-22 is carried out modification.Be 0.05mol/L to adding EDTA11.69g(EDTA concentration of aqueous solution in the 800ml aqueous solution, adding 10.88g 25wt% ammoniacal liquor helps EDTA to dissolve), then add 80g ZSM-22 molecular sieve, 80 DEG C of hydro-thermal reaction 4h, filter, washing, dry, 550 DEG C of roasting 4h obtain the ZSM-22 molecular sieve of EDTA modification.
Reaction result is in table 2, Fig. 2.From table 2, Fig. 2, can find out, ZSM-22 after EDTA modification is the catalyst 30%NiMoW-Keaded (EDTA) of carrier, under same conversion, its alkane isomerization selectivity ratios does not have the isomerizationization of the catalyst that the ZSM-22 of modification is carrier selectively high, and the isomerization of the catalyst of preparing than equi-volume impregnating is selective high a lot.
Embodiment 8
Method for preparing catalyst is with example 4, and different is the method for modifying difference of ZSM-22.
This example adopts NH
4the mode that the F aqueous solution carries out hydrothermal treatment consists to ZSM-22 is carried out modification.In 1.2L water, add 6.67gNH
4f(NH
4f concentration of aqueous solution is 0.15 mol/), then add 80g ZSM-22 molecular sieve, 80 DEG C of hydro-thermal reaction 4h, filter, washing, and 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.From table 2, Fig. 2, can find out NH
4zSM-22 after F modification is the catalyst 30%NiMoW-Keaded (NH of carrier
4f), under same conversion, its alkane isomerization selectivity ratios does not have the isomerizationization of catalyst 22.2%/30%NiMoW-Keaded that the ZSM-22 of modification is carrier selectively high, and the isomerization of the catalyst 20%NiMoW-Impregnated preparing than equi-volume impregnating is selective 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) 70g SAPO-11 molecular sieve and the 30g SB powder of synthetic and roasting are fully mixed, 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, the catalyst that adopts infusion process to prepare, compared with carrier, specific surface and the pore volume of dipping rear catalyst decline very large; From table 1, Fig. 1, can find out, 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 methods are 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, making homogeneous phase solution, and then adding 28.57g Nickelous nitrate hexahydrate, with 50ml volumetric flask constant volume.
(2) the roasting 12h at 550 DEG C of ZSM-22 molecular sieve elder generation deviates from template, then carries out ion-exchange.In 1L water, dissolve 80g ammonium nitrate, then add 100g ZSM-22 molecular sieve, 80 DEG C of exchange 4h, have exchanged washing, dry, and then 550 DEG C of roasting 4h, repeat 3 times.
(3) by 30g ZSM-22 molecular sieve and 40g SB powder, do extrusion aid with 3.5g sesbania powder, taking 2wt% aqueous solution of nitric acid as peptizing agent, extruded moulding, 120 DEG C of dry 4h, roasting 4h obtains catalyst carrier at 550 DEG C.
(4) adopt equi-volume impregnating, the catalyst 20g of preparation load capacity 20wt%.From volumetric flask, get 6.1ml NiMoW maceration extract, calculate to such an extent that maceration extract should be diluted with water to 8.0ml according to carrier water absorption rate, then dipping, placements of spending the night, is dried 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, the catalyst that adopts infusion process to prepare, compared with carrier, specific surface and the pore volume of dipping rear catalyst decline very large; From Fig. 2, table 2, can find out, 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 1 NiW/ SAPO-11 Catalyst Conversion and optionally corresponding relation
Table 2 NiMoW-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, taking the weight of catalyst as 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), molecular sieve, inorganic refractory oxide or its precursor are mixed, 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, obtains catalyst after dry, roasting; Described baking temperature is 80 ~ 140 DEG C, drying time 2 ~ 12h; Roasting condition is as follows: 200 ~ 400 DEG C of sintering temperatures, roasting time is 2 ~ 8h.
2. the preparation method of high selectivity base metal long chain alkane isomerization catalyst according to claim 1, is characterized in that, described peptizing agent is nitric acid or aqueous hydrochloric acid solution, and its addition is to account for 1 ~ 5% of vehicle weight after pure.
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, and its precursor is selected from boehmite, boehmite, diaspore, gibbsite and visits one or more in aluminium stone.
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 that adopts 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 with, 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, and its addition is 1 ~ 5% of metallic 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, in the time that described molecular sieve is selected ZSM-22/23, 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 that molecular sieve ZSM-22/23 is obtained to modification at 600 ~ 900 DEG C of roasting 2 ~ 8h of temperature; EDTA or NH
4the method of F hydrothermal treatment consists is: molecular sieve ZSM-22/23 adds EDTA or NH
4in the aqueous solution of F, react, 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 of preparing according to the arbitrary claim of claim 1-9, is characterized in that, described catalyst needs to carry out presulfurization before use, with 1 ~ 5wt%CS
2cyclohexane solution or aviation kerosine be presulfurization oil, presulfurization time 2 ~ 24h, pre-curing temperature is 180 ~ 360 DEG C; Then to C
7above long chain alkane or the oil product that contains a large amount of long chain alkanes carry out hygrogenating isomerization reaction, and reaction condition is: Hydrogen Vapor Pressure 1 ~ 15Mpa, 250 ~ 400 DEG C of temperature, volume space velocity 0.5 ~ 4h
-1, hydrogen to oil volume ratio 200 ~ 1000.
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| CN106799256A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | A kind of alkane isomerization catalyst and preparation method |
| 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 |
| CN112007692A (en) * | 2019-05-31 | 2020-12-01 | 国家能源投资集团有限责任公司 | Catalyst for dewaxing lubricant base oil produced by Fischer-Tropsch wax synthesis and preparation method and application thereof |
| CN112934251A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Bifunctional catalyst for catalyzing n-heptane hydroisomerization and preparation method thereof |
| CN112958147A (en) * | 2021-02-23 | 2021-06-15 | 华南理工大学 | Bifunctional catalyst, preparation method thereof and method for preparing isoparaffin from stearic acid |
| CN112973716A (en) * | 2019-12-16 | 2021-06-18 | 北京中能炜业科技发展有限公司 | Hydrofining catalyst and preparation method thereof |
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| 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 |
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| CN114713209A (en) * | 2021-01-06 | 2022-07-08 | 浙江蓝天环保高科技股份有限公司 | Fluoride modified adsorbent and purification method of hexafluoro-1,3-butadiene crude product |
| 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 |
| CN112958147A (en) * | 2021-02-23 | 2021-06-15 | 华南理工大学 | Bifunctional catalyst, preparation method thereof and method for preparing isoparaffin from stearic acid |
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