CN103316710A - Hydroisomerization/cracking catalyst, and preparation method and application thereof - Google Patents
Hydroisomerization/cracking catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hydroisomerization/cracking catalyst and a preparation method thereof. The catalyst is composed of an acidic isocraking carrier and a metal active component loaded on the acidic isocraking carrier; the acidic isocraking carrier is composed of a ZSM-22 molecular sieve and an amorphous oxide; and the mass ratio of the acidic isocraking carrier to the metal active component (by metal oxide and/or metal element) is 70-99.9:0.1-30. The preparation method of the catalyst comprises the following steps: 1, mixing the amorphous oxide with the ZSM-22 molecular sieve, carrying out adjusting and kneading molding by using an acid solution, and drying and roasting to obtain the acidic isocraking carrier; and 2, dipping the acidic isocraking carrier in an aqueous solution of a soluble salt of the active metal component, and drying and roasting to obtain the catalyst. The catalyst can crack high-melting-point long-chain normal paraffins into lightweight diesel oil during hydroisomerization, generates a small amount of gases and naphtha, and effectively reduces the condensation points of products.
Description
Technical field
The present invention relates to a kind of hysomer/Cracking catalyst and preparation method thereof and application.
Background technology
F-T synthetic heavy diesel oil mainly is comprised of straight-chain hydrocarbons, and generally at 16～25 ° of C, its low-temperature characteristics and greasy property are relatively poor for condensation point, are not suitable for using at cold district.The diesel oil distillate of identical boiling range is because the difference that wherein forms, the condensation point difference is very large, for example boiling range is 325 ° of C～350 ° C, condensation point is 13 ° of C when the isomers mass content is 18%, and condensation point is-36 ° of C when the isomers mass content is 80%, so the straight-chain hydrocarbons hysomer is highly effective means that reduce its condensation point in the diesel oil distillate.
The heavy diesel hysomer is to adopt the bifunctional catalyst with special pore structure to make that the high-melting-point long-chain normal paraffin is converted into the lower one-sided chain isomerism alkane of fusing point in the heavy diesel.Provide isomerized acidic site by acid carrier, the metal position provides the hydrogenation/dehydrogenation function.But the alkane fusing point that isomerisation degree is high is higher on the contrary, so isomerisation degree that just must control long-chain normal paraffin molecule, this has just proposed strict requirement to the Acidity of acidic components and pore structure and hydrogenation component.Acidic components will have the acid centre of moderate strength and have the pore structure of spatial limitation in general, and hydrogenation component has fast hydrogenation dehydrogenation activity, prevent further isomery and even the cracking of uncle's carbonium ion.
The ZSM-22 molecular sieve is artificial synthetic new-type high silicon aluminium zeolite molecular sieve.The ZSM-22 molecular sieve belongs to the TON topological structure, has the one-dimensional channels of ten-ring, port size
Have benefited from having the most suitable pore passage structure and stronger surface acid characteristic, strong acidproof and carbon accumulation resisting ability, the ZSM-22 molecular sieve shows very high catalytic activity with selective in alkene and isomerization of paraffins reaction, have the unrivaled superiority of other molecular sieve, good application prospect is arranged.US4556477, US4902406, US5707600, US5783168 have announced preparation method and the application in the normal alkane isomerization reaction thereof of ZSM-22 molecular sieve.
For the n-alkane in the synthetic heavy bavin cut of F-T, because its condensation point is higher, cause low temperature flow poor, if only by isomerization reaction, often can not make its condensation point drop to desirable effect, and may cause viscosity index (VI) to reduce, therefore isomerized simultaneously some high-melting-point normal paraffin components that are difficult for occuring isomerization reactions to be carried out suitable cracking be light diesel occuring, and so also can reach the purpose of reduction oil product condensation point.So just wish that a catalyst has shape slective cracking and isomerized multi-functional simultaneously, if adopt single molecular sieve then do not reach good effect.
Summary of the invention
The purpose of this invention is to provide a kind of hysomer/Cracking catalyst and preparation method thereof and application, catalyst provided by the invention is specially adapted to the hydro-isomerization of Fischer-Tropsch synthetic heavy diesel oil/cracking pour point depression.
A kind of hysomer/Cracking catalyst provided by the present invention is comprised of heterogeneous acidic cracking carrier and the metal active constituent that is carried on the described heterogeneous acidic cracking carrier;
Described heterogeneous acidic cracking carrier is comprised of ZSM-22 molecular sieve and amorphous oxide;
The mass ratio of described heterogeneous acidic cracking carrier and described metal active constituent is 70～99.9:0.1～30, and wherein, the quality of described metal active constituent is in the quality of its oxide and/or element.
In above-mentioned hysomer/Cracking catalyst, the mass ratio of described heterogeneous acidic cracking carrier and described metal active constituent specifically can be 72:28,74:26,76:24,92:8 or 96:4.
In above-mentioned hysomer/Cracking catalyst, in the described heterogeneous acidic cracking carrier, the mass ratio of described ZSM-22 molecular sieve and described amorphous oxide can be 4～35:60～96, specifically can be 4～35:40～88,4.6:87.4,10.8:61.2,18.5:55.5,33.6:62.4 or 34.2:41.8;
Described amorphous oxide can be amorphous aluminum silicide or amorphous silicon magnesium.
In above-mentioned hysomer/Cracking catalyst, described amorphous oxide can be the amorphous aluminum silicide with following physicochemical property: SiO
2Mass content be 20%～75%, specifically can be 25%, 35%, 50%, 65% or 72%, pore volume is 0.3～1.8ml/g, specifically can be 0.58ml/g, 0.76ml/g, 0.98ml/g, 1.2ml/g or 1.38ml/g, specific area is 200～600m
2/ g specifically can be 330～550m
2/ g, 335.9m
2/ g, 384.5m
2/ g, 490.3m
2/ g, 510.3m
2/ g or 535.6m
2/ g, the pore volume in the hole between 3～15nm accounts for 60～85% of total pore volume, specifically can be 64%, 66%, 69%, 75% or 82%, infrared acidity can be 0.05～0.8mmol/g, specifically can be 0.4mmol/g, 0.46mmol/g, 0.5mmol/g, 0.57mmol/g or 0.68mmol/g.
In above-mentioned hysomer/Cracking catalyst, described ZSM-22 molecular sieve has following physicochemical property: SiO
2/ Al
2O
3Mol ratio can be 20～200, specifically can be 80～160,80,92,111,120 or 160, specific area can be 220～550m
2/ g specifically can be 350～550m
2/ g, 368.5m
2/ g, 396.8m
2/ g, 403.6m
2/ g, 486.9m
2/ g or 535.6m
2/ g; Infrared acidity can be 0.05～0.7mmol/g, specifically can be 0.098mmol/g, 0.11mmol/g, 0.13mmol/g, 0.18/mmol/g or 0.26mmol/g, Na
2O content≤0.1% specifically can be 0.01%, 0.02% or 0.03%, and pore volume can be 0.15～0.40mL/g, specifically can be 0.19mL/g, 0.22mL/g, 0.26mL/g, 0.29mL/g or 0.35mL/g.
In above-mentioned hysomer/Cracking catalyst, described metal active constituent is selected from the periodic table of elements in VIII family and/or the VI B metal at least a;
Described metal active constituent is selected from molybdenum, tungsten, cobalt, nickel, palladium and the platinum at least a.
The present invention also further provides the preparation method of above-mentioned catalyst, comprises the steps:
(1) described amorphous oxide and described ZSM-22 molecular sieve are mixed, then with acid solution modulate, kneading and compacting, drying and roasting namely get described heterogeneous acidic cracking carrier again;
(2) with described heterogeneous acidic cracking carrier impregnation in the aqueous solution of the soluble-salt of described active metal component, then drying and roasting namely get described catalyst.
Among the above-mentioned preparation method, described acid solution can be aqueous solution of nitric acid and/or acetic acid aqueous solution;
The mass percentage concentration of described acid solution can be 3%～8%, specifically can be 3%, 5%, 7% or 8%;
Described amorphous oxide is crossed 200 mesh sieves.
Among the above-mentioned preparation method, described metal active constituent is nickel, and the soluble-salt of described metal active constituent is at least a in nickelous carbonate, nickel nitrate or the nickel acetate;
Described metal active constituent is molybdenum, and the soluble-salt of described metal active constituent is at least a in ammonium molybdate, molybdic acid and the molybdenum oxide;
Described metal active constituent is tungsten, and the soluble-salt of described metal active constituent is at least a in ammonium metatungstate, ethyl ammonium metatungstate and the wolframic acid;
Described metal active constituent is cobalt, and the soluble-salt of described metal active constituent is at least a in basic cobaltous carbonate, cobalt nitrate and the cobalt oxide;
Described metal active constituent is palladium, and the soluble-salt of described metal active constituent is at least a in palladium nitrate and the ammonium nitrate palladium;
Described metal active constituent is platinum, and the soluble-salt of described metal active constituent is at least a in tetramino dinitro platinum and the chloroplatinic acid.
Among the above-mentioned preparation method, in step (1) and the step (2), the temperature of described drying all can be 100～150 ° of C, specifically can be 100 ° of C, 110 ° of C, 120 ° of C, 130 ° of C or 150 ° of C, and the time all can be 4～6h, specifically can be 4h, 5h or 6h; The temperature of described roasting all can be 500～650 ° of C, specifically can be 500 ° of C, 550 ° of C, 600 ° of C or 650 ° of C, and the time all can be 4～6h, specifically can be 4h, 5h or 6h.
Catalyst provided by the invention can be used for catalysis Fischer-Tropsch synthetic heavy diesel oil hydro-isomerization/cracking pour point depression reaction, and its reaction condition can be: reaction pressure is 3.0～15.0Mpa, and hydrogen to oil volume ratio is 400～1500, and volume space velocity is 0.5～10.0h
-1, reaction temperature is 320～400 ° of C.
Heavier cut in the diesel product that described Fischer-Tropsch synthetic heavy diesel oil refers to obtain in the F-T building-up process is generally C
16 +Hydrocarbon molecules, this heavy diesel have without sulphur, without the characteristics of nitrogen, low aromatic hydrocarbons, and its organic hydrocarbon is take straight-chain hydrocarbons as main.
The present invention compared with prior art has the following advantages:
(1) catalyst provided by the invention has good isomerization performance, can significantly reduce the condensation point of raw material.
(2) catalyst provided by the invention can be light diesel with the cracking of high-melting-point long-chain normal paraffin, and produce a small amount of gas and naphtha in hydroisomerization, effectively reduces the product condensation point.
(3) catalyst provided by the invention is the effective isomerization-visbreaking catalyst of the high pour point depression of a kind of diesel yield.
The specific embodiment
Employed experimental technique is conventional method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
The preparation of embodiment 1, hysomer/Cracking catalyst Cat-1
(1) takes by weighing the ZSM-22 molecular sieve (SiO of porphyrize
2/ Al
2O
3Mol ratio is 80, and specific area is 535.6m
2/ g, infrared acidity is 0.26mmol/g, Na
2O content is 0.02%, and pore volume is 0.35mL/g) the 4.6g(butt) and amorphous aluminum silicide (SiO
2Mass content be 25%, pore volume is 1.38ml/g, specific area is 535.6m
2/ g, the pore volume in the hole between 3～15nm accounts for 75% of total pore volume, infrared acidity is 0.68mmol/g) the 87.4g(butt) mix, place kneading machine mixing 30min, dilute nitric acid solution modulation with 3%, kneading are to paste, and extrusion becomes column type, catalyst diameter 1.4mm.With it dry 4h under 120 ° of C in baking oven, be cooled to room temperature behind 600 ° of C roasting 4h, just available heterogeneous acidic cracking carrier.
(2) 17.55g cobalt nitrate and 5.26g ammonium nitrate palladium maceration extract are sprayed on the carrier of above-mentioned preparation, dry 6h under 100 ° of C in baking oven is cooled to room temperature behind 500 ° of C roasting 6h again, just can obtain catalyst Cat-1.
Wherein the mass percent of each component consists of: ZSM-22 type molecular sieve: amorphous aluminum silicide: cobalt oxide: Pd=4.6:87.4:5.0:3.0.
The catalyst Cat-1 of the present embodiment preparation is used for the hydro-isomerization of catalysis F-T synthetic heavy diesel oil/cracking pour point depression, and reaction condition is: reaction pressure is 4.0Mpa, and hydrogen to oil volume ratio is 500, and air speed is 2.0h
-1, reaction temperature is 320 ° of C.
The character of F-T synthetic heavy diesel oil is as shown in table 1, and catalytic result is as shown in table 2.
The preparation of embodiment 2, hydroisomerization/Cracking catalyst Cat-2
(1) takes by weighing the ZSM-22 molecular sieve (SiO of porphyrize
2/ Al
2O
3Mol ratio is 92, and specific area is 486.9m
2/ g, infrared acidity is 0.18mmol/g, Na
2O content is 0.01%, and pore volume is 0.29mL/g) the 10.8g(butt) and amorphous aluminum silicide (SiO
2Mass content be 35%, pore volume is 0.98ml/g, specific area is 490.3m
2/ g, the pore volume in the hole between 3～15nm accounts for 69% of total pore volume, infrared acidity is 0.57mmol/g) the 61.2g(butt) mix, place kneading machine mixing 15min.To paste, extrusion becomes trifolium-shaped, catalyst diameter 1.5mm with the modulation of the acetic acid solution of 3wt%, kneading.With it dry 4h under 130 ° of C in baking oven, be cooled to room temperature behind 550 ° of C roasting 4h, just can obtain heterogeneous acidic cracking carrier.
(2) aqueous solution with 80.43g nickel nitrate and 8.85g ammonium metatungstate is sprayed on the carrier of above-mentioned preparation, with it dry 5h under 120 ° of C in baking oven, is cooled to room temperature behind 550 ° of C roasting 4h, just can obtain catalyst Cat-2.
Wherein the mass percent of each component consists of: ZSM-22 type molecular sieve: amorphous aluminum silicide: nickel oxide: tungsten oxide=10.8:61.2:20.0:8.0.
The catalyst Cat-2 of the present embodiment preparation is used for the hydro-isomerization of catalysis F-T synthetic heavy diesel oil/cracking pour point depression, and reaction condition is: reaction pressure is 6.0Mpa, and hydrogen to oil volume ratio is 1000, and air speed is 4.0h
-1, reaction temperature is 336 ° of C.
The character of F-T synthetic heavy diesel oil is as shown in table 1, and catalytic result is as shown in table 2.
The preparation of embodiment 3, hydroisomerization/Cracking catalyst Cat-3
(1) takes by weighing the ZSM-22 molecular sieve (SiO of porphyrize
2/ Al
2O
3Mol ratio is 111, and specific area is 396.8m
2/ g, infrared acidity is 0.13mmol/g, Na
2O content is 0.03%, and pore volume is 0.26mL/g) the 18.5g(butt) and amorphous aluminum silicide (SiO
2Mass content be 50%, pore volume is 0.58ml/g, specific area is 384.5m
2/ g, the pore volume in the hole between 3～15nm accounts for 64% of total pore volume, infrared acidity is 0.50mmol/g) the 55.5g(butt) mix, place kneading machine mixing 40min, the diluted nitric acid aqueous solution modulation kneading of 5wt% is to paste, and extrusion becomes the bunge bedstraw herb type, catalyst diameter 1.7mm.With it dry 5h under 120 ° of C in baking oven, be cooled to room temperature behind 550 ° of C roasting 6h, just can obtain heterogeneous acidic cracking carrier.
(2) 16.09g nickel nitrate, 19.91g ammonium metatungstate and 4.91g ammonium molybdate are dissolved in the water, are sprayed on the carrier of above-mentioned preparation.With it dry 4h under 150 ° of C in baking oven, be cooled to room temperature behind 650 ° of C roasting 3h, just can obtain catalyst Cat-3.
Wherein the mass percent of each component consists of: ZSM-22 type molecular sieve: amorphous aluminum silicide: nickel oxide: tungsten oxide: molybdenum oxide=18.5:55.5:4.0:18.0:4.0.
The catalyst Cat-3 of the present embodiment preparation is used for the hydro-isomerization of catalysis F-T synthetic heavy diesel oil/cracking pour point depression, and reaction condition is: reaction pressure is 8.0Mpa, and hydrogen to oil volume ratio is 1200, and air speed is 10.0h
-1, reaction temperature is 390 ° of C.
The character of F-T synthetic heavy diesel oil is as shown in table 1, and catalytic result is as shown in table 2.
The preparation of embodiment 4, hydroisomerization/Cracking catalyst Cat-4
(1) takes by weighing the ZSM-22 molecular sieve (SiO of porphyrize
2/ Al
2O
3Mol ratio is 120, and specific area is 403.6m
2/ g, infrared acidity is 0.11mmol/g, Na
2O content is 0.02%, and pore volume is 0.22mL/g) the 33.6g(butt) and amorphous aluminum silicide (SiO
2Mass content be 65%, pore volume is 1.2ml/g, specific area is 510.3m
2/ g, the pore volume in the hole between 3～15nm accounts for 82% of total pore volume, infrared acidity is 0.46mmol/g) the 62.4g(butt) mix, placing kneading machine mixing 40min, the acetic acid aqueous solution modulation kneading of 7wt% is to paste, and extrusion becomes the butterfly type, catalyst diameter 2.0mm.With it dry 6h under 120 ° of C in baking oven, be cooled to room temperature behind 500 ° of C roasting 6h, just can obtain heterogeneous acidic cracking carrier.
(2) 2.65g chloroplatinic acid and 5.26g ammonium nitrate palladium are dissolved in the water obtain on the carrier that maceration extract is sprayed on above-mentioned preparation, with it dry 4h under 130 ° of C in baking oven, be cooled to room temperature behind 600 ° of C roasting 5h, just can obtain catalyst Cat-4.
Wherein the mass percent of each component consists of: ZSM-22 type molecular sieve: amorphous aluminum silicide: platinum: palladium=33.6:62.4:1.0:3.0.
The catalyst Cat-4 of the present embodiment preparation is used for the hydro-isomerization of catalysis F-T synthetic heavy diesel oil/cracking pour point depression, and reaction condition is: reaction pressure is 15.0Mpa, and hydrogen to oil volume ratio is 1500, and air speed is 7.0h
-1, reaction temperature is 360 ° of C.
The character of F-T synthetic heavy diesel oil is as shown in table 1, and catalytic result is as shown in table 2.
The preparation of embodiment 5, hydroisomerization/Cracking catalyst Cat-5
(1) takes by weighing the ZSM-22 molecular sieve (SiO of porphyrize
2/ Al
2O
3Mol ratio is 160, and specific area is 368.5m
2/ g, infrared acidity is 0.098mmol/g, Na
2O content is 0.02%, and pore volume is 0.19mL/g) the 41.8g(butt) and amorphous aluminum silicide (SiO
2Mass content be 72%, pore volume is 0.76ml/g, specific area is 335.9m
2/ g, the pore volume in the hole between 3～15nm accounts for 66% of total pore volume, infrared acidity is 0.40mmol/g) the 34.2g(butt) mix, place kneading machine mixing 40min, the diluted nitric acid aqueous solution modulation kneading of 8wt% is to paste, and extrusion becomes clover, catalyst diameter 2.0mm.With it dry 6h under 100 ° of C in baking oven, be cooled to room temperature behind 650 ° of C roasting 3h, just can obtain heterogeneous acidic cracking carrier.
(2) the 96.52g nickel nitrate aqueous solution is sprayed on the carrier of above-mentioned preparation, with it dry 5h under 110 ° of C in baking oven, is cooled to room temperature behind 650 ° of C roasting 4h, just can obtain catalyst Cat-5.
Wherein the mass percent of each component consists of: ZSM-22 type molecular sieve: amorphous aluminum silicide: nickel oxide=34.2:41.8:24.0.
The catalyst Cat-4 of the present embodiment preparation is used for the hydro-isomerization of catalysis F-T synthetic heavy diesel oil/cracking pour point depression, and reaction condition is: reaction pressure is 12.0Mpa, and hydrogen to oil volume ratio is 800, and air speed is 6.0h
-1, reaction temperature is 350 ° of C.
The character of F-T synthetic heavy diesel oil is as shown in table 1, and catalytic result is as shown in table 2.
Can be found out by the data in the table 2, when adopting catalyst of the present invention to be used for F-T diesel oil hydrogenation pour point depression production low-coagulation diesel oil, the linear paraffin isomerization is selectively high, and heavy bavin to a certain degree cracking is light bavin, has very high diesel oil distillate yield and good pour point depression effect.In addition, catalyst activity and selectivity behind running 3168h is not found to reduce, and illustrates that catalyst of the present invention has good stability.
Table 1 feedstock oil character
Table 2 experimental result
Claims (10)
1. hysomer/Cracking catalyst is characterized in that:
Described catalyst is comprised of heterogeneous acidic cracking carrier and the metal active constituent that is carried on the described heterogeneous acidic cracking carrier;
Described heterogeneous acidic cracking carrier is comprised of ZSM-22 molecular sieve and amorphous oxide;
The mass ratio of described heterogeneous acidic cracking carrier and described metal active constituent is 70～99.9:0.1～30, and wherein, the quality of described metal active constituent is in the quality of its oxide and/or element.
2. hysomer/Cracking catalyst according to claim 1, it is characterized in that: in the described heterogeneous acidic cracking carrier, the mass ratio of described ZSM-22 molecular sieve and described amorphous oxide is 4～35:60～96;
Described amorphous oxide is amorphous aluminum silicide or amorphous silicon magnesium.
3. hysomer/Cracking catalyst according to claim 2, it is characterized in that: described amorphous oxide is the amorphous aluminum silicide with following physicochemical property: SiO
2Mass content be 20%～75%, pore volume is 0.3～1.8ml/g, specific area is 200～600m
2/ g, the pore volume in the hole between 3～15nm accounts for 60～85% of total pore volume, and infrared acidity is 0.05～0.8mmol/g.
4. each described hysomer/Cracking catalyst according to claim 1-3 is characterized in that: described ZSM-22 molecular sieve has following physicochemical property: SiO
2/ Al
2O
3Mol ratio be 20～200, specific area is 420～750m
2/ g, infrared acidity is 0.05～0.7mmol/g, Na
2O content≤0.1%, pore volume are 0.25～0.40mL/g.
5. each described hysomer/Cracking catalyst according to claim 1-4 is characterized in that: described metal active constituent is selected from the periodic table of elements in VIII family and/or the VI B metal at least a.
6. the preparation method of each described catalyst among the claim 1-5 comprises the steps:
(1) described amorphous oxide and described ZSM-22 molecular sieve are mixed, then with acid solution modulate, kneading and compacting, drying and roasting namely get described heterogeneous acidic cracking carrier again;
(2) with described heterogeneous acidic cracking carrier impregnation in the aqueous solution of the soluble-salt of described active metal component, then drying and roasting namely get described catalyst.
7. preparation method according to claim 6, it is characterized in that: described acid solution is aqueous solution of nitric acid and/or acetic acid aqueous solution;
The mass percentage concentration of described acid solution is 3%～8%;
Described amorphous oxide is crossed 200 mesh sieves.
8. according to claim 6 or 7 described preparation methods, it is characterized in that: described metal active constituent is nickel, and the soluble-salt of described metal active constituent is at least a in nickelous carbonate, nickel nitrate or the nickel acetate;
Described metal active constituent is molybdenum, and the soluble-salt of described metal active constituent is at least a in ammonium molybdate, molybdic acid and the molybdenum oxide;
Described metal active constituent is tungsten, and the soluble-salt of described metal active constituent is at least a in ammonium metatungstate, ethyl ammonium metatungstate and the wolframic acid;
Described metal active constituent is cobalt, and the soluble-salt of described metal active constituent is at least a in basic cobaltous carbonate, cobalt nitrate and the cobalt oxide;
Described metal active constituent is palladium, and the soluble-salt of described metal active constituent is at least a in palladium nitrate and the ammonium nitrate palladium;
Described metal active constituent is platinum, and the soluble-salt of described metal active constituent is at least a in tetramino dinitro platinum and the chloroplatinic acid.
9. each described preparation method according to claim 6-8 is characterized in that:
In step (1) and the step (2), the temperature of described drying is 100～150 ° of C, and the time is 4～6h; The temperature of described roasting is 500～650 ° of C, and the time is 4～6h.
10. the application of each described catalyst in the hysomer/cracking reaction of Fischer-Tropsch synthetic heavy diesel oil among the claim 1-5.
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