CN101837299B - Catalyst used in hydrogenation modification of catalytic gasoline and preparation method thereof - Google Patents
Catalyst used in hydrogenation modification of catalytic gasoline and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst used in hydrogenation modification of catalytic gasoline and a preparation method and application thereof. The method comprises the following steps of: putting HZSM-5 molecular sieve or HZSM-5 molecular sieve subjected to hydro-thermal treatment into alkali solution in a liquid-solid ratio of 5-15ml/g, regulating the pH to between 9 and 14 and stirring the mixture for 2 to 6 hours at the temperature of between 60 and 90 DEG C, performing ammonium exchange after washing and drying, drying and roasting the product, performing hydro-thermal treatment at the temperature of between 400 and 600 DEG C to obtain modified HZSM-5 molecular sieve; performing band extrusion on the modified HZSM-5 molecular sieve and a binder, and drying and roasting the product to obtain a catalyst carrier; and loading metal active ingredients on the catalyst carrier, and drying and roasting the product to obtain the target catalyst. The modified HZSM-5 molecular sieve of the invention shows high activity and stability when used in the hydrogenation modification of the catalytic gasoline.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for catalytic gasoline hydrogenation modifying.
Background technology
Be the atmosphere pollution that the control motor vehicle exhaust emission causes, has all formulated with low-sulfur, low olefin-content countries in the world is the clean gasoline standard of sign.From China's oil processing industry existing processes flow process and development trend thereof; In the quite a long time from now on, China's motor petrol blend component is that master, antiknock component (reformation gasoline and gasoline alkylate) present situation seldom are difficult to obtain the change of essence with the catalytically cracked gasoline.Therefore; For satisfying the clean gasoline standard-required of increasingly stringent; The upgrading of catalytically cracked gasoline just becomes one of key technology that China clean fuel for vehicle produces, and the loss that how to reduce the saturated octane number that causes of alkene is catalytic gasoline hydrogenation desulfurization and the difficult point that reduces the olefin(e) centent problem.
USP 5,362, and 376 have introduced a kind of gasoline hydrodesulfurizationmethod and octane value recovering two-stage catalytic agent group technology.The heavy distillat of catalytically cracked gasoline is at first through a kind of conventional Hydrobon catalyst Ni-Mo/Al
2O
3Or Co-Mo/Al
2O
3Carry out desulfurization; Desulfurization product is handled through the NiO/HZSM-5 molecular sieve catalyst more then; Low-octane alkane shape slective cracking or isomery are turned to high-octane alkane; Thereby recover the loss of octane number that causes because of alkene is saturated in first section hydrodesulfurization, and then be in harmonious proportion together with the light fractions of FCC naphtha of prefractionation.This patent is pointed out the too weak cracking activity that reduces catalyst of the acidity of molecular sieve, influences the recovery effects of octane number; And acidic zeolite can cause the generation of excessive fragmentation reaction too by force, influences the liquid yield of final gasoline products; Desirable acidic zeolite should guarantee that appropriate cracking and molecular rearrangement etc. recover the generation of reactions such as octane number.
USP 5,413, and 698 have introduced two sections assembly catalyze desulfurization process of gasoline of another kind of hydrodesulfurization/octane value recovering.Catalytic gasoline heavy distillat is at first carried out desulfurization through a kind of conventional hydrodesulfurization Mo-Co or Mo-Ni catalyst; Desulfurization product is again through containing the mesopore HZSM-5 molecular sieve/macropore HBeta molecular sieve catalyst selective cracking of nickel oxide then; Low-octane big molecule alkane cracking is high-octane little molecule alkane, is high-octane highly-branched chain isomerous alkane with low-octane normal alkane isomerization, thereby recover because of the saturated loss of octane number that causes of hydrogenation of olefins in the hydrodesulfurization.
Because the olefin(e) centent of China's catalytically cracked gasoline (40～55v%) far above foreign level (20～30v%), external existing catalytic gasoline hydrogenation modifying technology is applied to be difficult to realize satisfactory results in China's catalytic gasoline hydrogenation reaction.
CN93102129.4 discloses a kind of catalytic modification of poor quality gasoline-aromatization method.Thick catalytically cracked gasoline is catalytic reforming under conditions of non-hydrogen at first, and then on Zn-Al or Zn-Al-rare earth HZSM-5, carries out aromatisation, and the temperature of aromatisation is 480～650 ℃, and pressure is 0.05～1.5MPa.Final yield of gasoline is 55～75wt%.Because the aromatized catalyst coking deactivation is very fast, general aromatized catalyst will be regenerated once in 15 days.
It is the catalyst of carrier loaded Mo that CN99108827.1, CN200410028083.1 etc. disclose with the HZSM-5 molecular sieve, and it is the method for other active components such as carrier loaded Mo and Fe, Cu as catalyst that CN200410024877.0, CN02135601.7, CN02115329.9, CN200610035278.8 etc. disclose with the HZSM-5 molecular sieve.
CN00122963.X discloses a kind of aromatization of low carbon hydrocarbon catalyst, is carrier with HZSM-5 molecular sieve and aluminium oxide, is active component with nickel and zinc; It is matrix with the HZSM-5 molecular sieve that CN85100324 discloses a kind of, is adhesive with clay or aluminium oxide, is the Hydrodewaxing catalyst of active component with nickel; CN200410080227.8 discloses a kind of method of producing diesel oil from tetracarbon olefin polymerization, and its polymerization catalyst comprises the NiO of 1～20wt%, the HZSM-5 molecular sieve of 40～80wt% and the aluminium oxide of 1～50wt%.The common preparation method of such catalyst is with HZSM-5 and alumina powder, dry, the roasting of inorganic acid kneading and compacting, the further hydrothermal treatment consists again that has, and that dipping is active is dry again after forming, roasting or hydrothermal treatment consists.CN96108703.X discloses a kind of catalyst of direct synthesis of arene with methane, it is characterized in that using MoO
3Be first modified material, ZnO, WO
3, CuO, Cr
2O
3, the wherein a kind of of NiO be second modified material, modified HZSM-5 zeolite, component Mo
6+Content is 3～6%, second component and the first component M
N+/ Mo
6+Mol ratio is 0.01～0.11, and surplus is HZSM-5.This catalyst adopts infusion process or the preparation of solid-state polishing, and preparation technology is simple, compares with single component catalyst, has improved methane conversion, and it does not contain alumina component.
Summary of the invention
The object of the present invention is to provide a kind of high activity of catalytic gasoline hydrogenation modifying and catalyst of high stability of being applied to.
For realizing above-mentioned purpose, catalytic gasoline hydrogenation modifying catalyst provided by the invention is characterized in that: in catalyst weight; The HZSM-5 molecular sieve that contains 20～80wt% modification in the catalyst; 10～80wt% binding agent, 3～10wt% molybdenum oxide, 1～5wt% nickel oxide; Wherein the modified HZSM-5 molecular sieve obtains through following method: the HZSM-5 molecular sieve is carried out alkali treatment, ammonium exchange and hydrothermal treatment consists, process the modified HZSM-5 molecular sieve; Alkali treatment is that the HZSM-5 molecular sieve is perhaps placed aqueous slkali through the HZSM-5 molecular sieve of hydrothermal treatment consists by liquid-solid ratio 5～15ml/g; PH is adjusted to 9～14; Stirred 2～6 hours down at 60～90 ℃; Then product is filtered, washs, 110～130 ℃ of dryings, 450～520 ℃ of roastings 2～6 hours.The alkali that adopts is selected from NaOH, KOH, Na
2CO
3Or K
2CO
3, preferred NaOH.
Hydrothermal treatment consists, ammonium give-and-take conditions are all identical with prior art among the present invention, and the present invention does not have specific (special) requirements.
Ammonium exchange described in the present invention preferably will place ammonium salt solution through the HZSM-5 of alkali treatment molecular sieve; Molecular sieve wherein: ammonium salt: water weight ratio is 1: 0.2～1.8: 5～15; And under 60～98 ℃, stirred 2～6 hours; Then product is filtered, washs, 110～130 ℃ of dryings, 450～520 ℃ of roastings 2～6 hours, the ammonium of employing was selected from NH
4NO
3Or NH
4Cl, preferred NH
4NO
3
Hydrothermal treatment consists described in the present invention preferably perhaps fed steam treatment 2～6 hours through the HZSM-5 molecular sieve of alkali treatment and ammonium exchange down at 400～600 ℃ with the HZSM-5 molecular sieve; HZSM-5 molecular sieve silica alumina ratio is 25～80.
Binding agent is meant boehmite, Al among the present invention
2O
3, SiO
2, in the diatomite one or more.
In the prior art, the acquisition of catalyst more is directly to adopt the HZSM-5 molecular sieve to mix with binding agent, adds HNO
3The aqueous solution is pinched through mixing, after extruded moulding, drying and the roasting, to process catalyst carrier; Carried metal active component on catalyst carrier; After drying, roasting; Process the method for catalyst, what difference of the present invention was to use is that all the other all can adopt general operating condition of the prior art through the HZSM-5 molecular sieve of modification rather than common HZSM-5 molecular sieve.
In the present invention, the exchange of the alkali treatment when the HZSM-5 molecular sieve is carried out modification and ammonium is very necessary, if only be the acidity that hydrothermal treatment consists just can only the modulation molecular sieve and can not optimize the pore structure of molecular sieve; If only there is alkali treatment not have ammonium exchange, molecular sieve is the Na type, acidity a little less than; If only there is the exchange of alkali treatment and ammonium not have a hydrothermal treatment consists, pore structure that then can only the modulation molecular sieve and the acidity of molecular sieve can not optimized.The exchange of alkali treatment and ammonium can be that before hydrothermal treatment consists, to carry out also can be after hydrothermal treatment consists, to carry out; Preferably before hydrothermal treatment consists, carry out; Can more effectively optimize the acidity and the pore structure of molecular sieve like this, thereby improve the reactivity worth of corresponding catalyst.
Obtain owing to carry out the exchange of alkali treatment and ammonium again after using the HZSM-5 molecular sieve of modification that the HZSM-5 molecular sieve is carried out earlier carrying out hydrothermal treatment consists again or carrying out hydrothermal treatment consists earlier after alkali treatment and ammonium exchange, therefore have the acidity and the pore structure of complex optimum.
The present invention also provides a kind of best preparation method of this catalyst, comprises the modified HZSM-5 molecular sieve is mixed with binding agent, pinches through mixing, moulding, drying, 480～650 ℃ of roastings be after 3～7 hours, processes catalyst carrier; Adopt the method load molybdenum oxide and the nickel oxide of dipping, process catalyst after 3～5 hours through dry, 450～520 ℃ of roastings.
Mix the HNO pinch, preferably to add 2～6wt% sesbania powder and 3～10wt% in the forming process among the present invention at carrier
3The aqueous solution helps extruding and having a higher mechanical strength of carrier like this.
Among the present invention; The predecessor aqueous solution maceration extract that preferably adopts metal active constituent during the carried metal active component is 0.8～1.2 with the ratio of the pore volume of carrier; Adopt step impregnation substep calcination activation then, also can the activation of step impregnation bakes to burn the article, the present invention is special demands not.
The best preparation method that the present invention recommends is: elder generation's load molybdenum back loading nickel during the carried metal active component, divide one-step baking, specifically can be:
Catalyst carrier impregnated in the ammonium molybdate solution 6～12 hours, through catalyst intermediate dry, 450～520 ℃ of roastings must contain molybdenum oxide after 2～6 hours; This catalyst intermediate impregnated in the nickel nitrate solution, get catalyst after 2～6 hours through dry, 450～520 ℃ of roastings.
Catalyst provided by the present invention can be used in the catalytic gasoline hydrogenation modifying, has hydrodesulfurization, the alkene ability falls in isomerization/aromatisation, compares with unmodified catalyst, and the catalyst of this invention shows higher reaction stability.
The specific embodiment
Raw material sources and analytical method standard:
HZSM-5 molecular sieve (SiO
2/ Al
2O
3Mol ratio=51.2): the prosperous chemical plant of Shanghai China;
Boehmite (the Al that contains 76wt%
2O
3The crystallization water with 24wt%): German Sasol company;
Diatomite: upright chemical industry Co., Ltd of Tianjin unit;
Aluminium oxide: γ-Al
2O
3
SiO
2: upright chemical industry Co., Ltd of Tianjin unit;
Sesbania powder: China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute;
Research octane number (RON) (RON): GB/T5487;
Liquid yield: product liquid quality/charging quality * 100%;
Catalyst agent active component content assay method: XRF;
SiO
2/ Al
2O
3Mol ratio assay method: XRF.
Further specify the present invention through embodiment below, but the present invention is not limited to this.
Evaluating catalyst carries out on the isothermal fixed bed, and the composition of used catalytic cracking full distillate gasoline is (v%) as follows: n-alkane: 5.94; Isoparaffin: 31.76; Alkene: 35.66; Cycloalkane: 7.42; Aromatic hydrocarbons: 19.22.The sulfur content of this catalytic cracking full distillate gasoline is 76 μ g/g, and RON is 91.6.
Embodiment 1
The HZSM-5 molecular sieve is placed the aqueous solution of NaOH by the liquid-solid ratio of 10ml/g, pH is adjusted to 13, stirred 4 hours down in 75 ℃.Filter, wash to neutral, 3 hours, 480 ℃ roastings of 120 ℃ of dryings 4 hours; The HZSM-5 molecular sieve that to handle through NaOH is by molecular sieve: ammonium salt: water weight ratio is in 80 ℃ to stir 4 hour at 1: 0.8: 10, then product is filtered, washs, and in 120 ℃ of dryings, 480 ℃ of roastings 4 hours; Gained HZSM-5 molecular sieve is broken into the particle of 20～40 order numbers, puts into the hydrothermal treatment consists stove, after in 520 ℃, 100% steam, handling 4 hours the HZSM-5 molecular sieve of comprehensively modifying.
Take by weighing HZSM-5 molecular sieve, 26 gram boehmite binding agents and the 2.4 gram sesbania powder of 50 gram comprehensively modifyings; And it is its ground and mixed is even; Adding 33ml concentration is the salpeter solution of 4.6 gram/100ml, on banded extruder, is extruded into the bar that diameter is 1.5mm after fully mixed the pinching.After 120 ℃ of dryings, in 520 ℃ of roastings 6 hours, be cut into the bar of 2～3mm, process catalyst carrier.
30 gram said catalyst carrier impregnated in 22ml contain 2.1 gram MoO
3Ammonium molybdate solution in, in leaving standstill 3 hours, 480 ℃ roastings of 9 hours, 120 ℃ dryings under the room temperature after 4 hours, process catalyst intermediate.
With above-mentioned catalyst intermediate impregnated in 22ml contain 0.9 the gram NiO nickel nitrate solution in, in leaving standstill 3 hours, 480 ℃ roastings of 9 hours, 120 ℃ dryings under the room temperature after 4 hours, make catalyst 1.Wherein molecular sieve 64.85%, MoO
36.36%, NiO 2.73%.
Embodiment 2
The preparation method is identical with embodiment 1, and the binding agent that different is in the preparing carriers process is 20 gram Al
2O
3Obtain catalyst 2 at last.Wherein molecular sieve 64.94%, MoO
36.36%, NiO2.73%.
Embodiment 3
The preparation method is identical with embodiment 1, and different is that binding agent is 15 gram Al in the preparing carriers process
2O
3With 4 gram SiO
2Obtain catalyst 3 at last.Wherein molecular sieve 65.87%, MoO
36.36%, NiO 2.73%.
Embodiment 4
The preparation method is identical with embodiment 1, and different is that binding agent is 15 gram γ-Al in the preparing carriers process
2O
3With 4.5 gram diatomite.Obtain catalyst 4 at last.Wherein molecular sieve 65.82%, MoO
36.36%, NiO 2.73%.
Embodiment 5
The preparation method is identical with embodiment 1, and different is that binding agent is 15 gram boehmites and 9.2 gram Al in the preparing carriers process
2O
3Obtain catalyst 5 at last.Wherein molecular sieve 64.38%, MoO
36.36%, NiO 2.73%.
Embodiment 6
The preparation method is identical with embodiment 1, and different is that the HZSM-5 molecular sieve is carried out hydrothermal treatment consists earlier, and then it is carried out NaOH handle and NH
4NO
3Ion-exchange.Obtain catalyst 6 at last.Wherein molecular sieve 64.85%, MoO
36.36%, NiO 2.73%.
Embodiment 7
The preparation method is identical with embodiment 6, and different is that binding agent is 15 gram Al in the preparing carriers process
2O
3, 2.0 the gram diatomite and 3.5 the gram SiO
2Obtain catalyst 7 at last.Wherein molecular sieve 64.65%, MoO
36.36%, NiO 2.73%.
Embodiment 8
The preparation method is identical with embodiment 6, and different is that binding agent is 15 gram boehmites, 5 gram Al in the preparing carriers process
2O
3, 2.0 the gram diatomite and 3.5 the gram SiO
2Obtain catalyst 8 at last.Wherein molecular sieve 63.39%, MoO
36.36%, NiO 2.73%.
Embodiment 9
The preparation method is identical with embodiment 1, and different is that the HZSM-5 molecular sieve is carried out hydrothermal treatment consists+NaOH processing+NH
4NO
3After the ion-exchange; Take by weighing HZSM-5 molecular sieve, 43.8 gram boehmites and the 3.3 gram sesbania powder of 50 gram modifications; And its ground and mixed is even, adding 46ml concentration is the salpeter solution of 4.6 gram/100ml, on banded extruder, is extruded into the bar that diameter is 1.5mm after fully mixed the pinching.After 120 ℃ of dryings, in 480 ℃ of roastings 6 hours, be cut into the bar of 2～3mm, process catalyst carrier.
30 gram said catalyst carrier impregnated in 20ml contain 0.9 gram MoO
3Ammonium molybdate solution in, in leaving standstill 3 hours, 500 ℃ roastings of 9 hours, 120 ℃ dryings under the room temperature after 4 hours, process catalyst intermediate.
With above-mentioned catalyst intermediate impregnated in 20ml contain 0.3 the gram NiO nickel nitrate solution in, in leaving standstill 3 hours, 500 ℃ roastings of 9 hours, 120 ℃ dryings under the room temperature after 4 hours, obtain catalyst 9 at last.Wherein molecular sieve 57.72%, MoO
32.88%, NiO 0.96%.
Embodiment 10
The preparation method is identical with embodiment 9, and different is that binding agent is 25 gram Al in the preparing carriers process
2O
3, 5 the gram diatomite.Obtain catalyst 10 at last.Wherein molecular sieve 60.47%, MoO
32.88%, NiO 0.96%.
Embodiment 11
The preparation method is identical with embodiment 9, and different is that binding agent is 15 gram boehmites, 15 gram Al in the preparing carriers process
2O
3, 5 the gram diatomite.Obtain catalyst 11 at last.Wherein molecular sieve 59.42%, MoO
32.88%, NiO 0.96%.
Embodiment 12
The HZSM-5 molecular sieve is placed the aqueous solution of NaOH by the liquid-solid ratio of 15ml/g, pH is adjusted to 9, stirred 2 hours down in 90 ℃.Filter, wash to neutral, 3 hours, 480 ℃ roastings of 120 ℃ of dryings 4 hours; The HZSM-5 molecular sieve that to handle through NaOH is by molecular sieve: ammonium salt: water weight ratio is in 98 ℃ to stir 2 hour at 1: 0.2: 15, then product is filtered, washs, and in 120 ℃ of dryings, 480 ℃ of roastings 4 hours; Gained HZSM-5 molecular sieve is broken into the particle of 20～40 order numbers, puts into the hydrothermal treatment consists stove, feed 100% steam treatment down after 6 hours, through HZSM-5 molecular sieve dry, that get comprehensively modifying after grinding at 400 ℃.
Take by weighing HZSM-5 molecular sieve, the 35 gram Al of 30 gram comprehensively modifyings
2O
3With 4.00 gram sesbania powder, and its ground and mixed is even, and adding 15ml concentration is the salpeter solution of 5.6 gram/100ml, on banded extruder, is extruded into the bar that diameter is 1.5mm after fully mixed the pinching.After 120 ℃ of dryings, in 500 ℃ of roastings 6 hours, be cut into the bar of 2～3mm, process catalyst carrier.
20 gram said catalyst carrier impregnated in 16ml contain 2.5 gram MoO
3Ammonium molybdate solution in, in leaving standstill 3 hours, 480 ℃ roastings of 9 hours, 120 ℃ dryings under the room temperature after 4 hours, process catalyst intermediate.
With above-mentioned catalyst intermediate impregnated in 16ml contain 1.5 the gram NiO nickel nitrate solution in, in leaving standstill 3 hours, 480 ℃ roastings of 9 hours, 120 ℃ dryings under the room temperature after 4 hours, obtain catalyst 12 at last.Wherein molecular sieve 38.46%, MoO
310.41%, NiO 6.25%.
Embodiment 13
The preparation method is identical with embodiment 12, and different is that binding agent is 20.0 gram boehmites, 10 gram Al in the preparing carriers process
2O
3With 5.0 gram diatomite, obtain catalyst 13 at last.Wherein molecular sieve 41.87%, MoO
310.41%, NiO 6.25%.
Embodiment 14
The preparation method is identical with embodiment 9, and different is places the aqueous solution of NaOH with the HZSM-5 molecular sieve by the liquid-solid ratio of 5ml/g, and pH is adjusted to 11, stirs 6 hours down in 60 ℃.Filter, washing is to neutral, 3 hours, 500 ℃ roastings of 120 ℃ of dryings are after 4 hours, by molecular sieve: ammonium salt: water weight ratio be 1: 1.8: 5 in 60 ℃ of stirrings 6 hours, then product is filtered, washs, and in 120 ℃ of dryings, 500 ℃ of roastings 4 hours; Gained HZSM-5 molecular sieve is broken into the particle of 20～40 order numbers, puts into the hydrothermal treatment consists stove, fed 100% steam treatment 2 hours, after drying, obtain the HZSM-5 molecular sieve of comprehensively modifying at 600 ℃.
Take by weighing HZSM-5 molecular sieve, the 10 gram Al of 50 gram comprehensively modifyings
2O
3With 2.4 gram sesbania powder, and its ground and mixed is even, and adding 30ml concentration is the salpeter solution of 4.6 gram/100ml, on banded extruder, is extruded into the bar that diameter is 1.5mm after fully mixed the pinching.After 120 ℃ of dryings, in 520 ℃ of roastings 6 hours, be cut into the bar of 2～3mm, process catalyst carrier.All the other preparation methods are identical with embodiment 9.Obtain catalyst 14 at last.Wherein molecular sieve 80.12%, MoO
32.88%, NiO 0.96%.
Embodiment 15
The HZSM-5 molecular sieve is placed NaOH solution by the liquid-solid ratio of 10ml/g, pH is adjusted to 14, stirred 3 hours down in 80 ℃.Filter, washing is to neutral, 3 hours, 450 ℃ roastings of 120 ℃ of dryings are after 4 hours, by molecular sieve: ammonium salt: water weight ratio be 1: 1: 10 in 70 ℃ of stirrings 6 hours, then product is filtered, washs, and in 120 ℃ of dryings, 480 ℃ of roastings 4 hours; Gained HZSM-5 molecular sieve is broken for the particle of 20～40 order numbers, puts into the hydrothermal treatment consists stove, feed in the steam at 550 ℃ and handled 2 hours, after drying, obtain the HZSM-5 molecular sieve of comprehensively modifying.
Take by weighing HZSM-5 molecular sieve, the 50 gram boehmites 5 gram sesbania powder of 10 gram comprehensively modifyings, and its ground and mixed is even, adding 45ml concentration is the salpeter solution of 4.6 gram/100ml, fully mixes on banded extruder, to be extruded into the bar that diameter is 1.5mm after pinching.After 120 ℃ of dryings, in 520 ℃ of roastings 6 hours, be cut into the bar of 2～3mm, process catalyst carrier.All the other preparation methods are identical with embodiment 1.Obtain catalyst 15 at last.Wherein molecular sieve 18.93%, MoO
36.36%, NiO 2.73%.
Embodiment 16
The preparation method is identical with embodiment 15, and different is that binding agent is 20.0 gram boehmites, 15 gram Al in the preparing carriers process
2O
3With 5.0 gram diatomite, obtain catalyst 16 at last.Wherein molecular sieve 20.33%, MoO
36.36%, NiO 2.73%.
Comparative Examples 1
The preparation method is identical with embodiment 9, and different is the HZSM-5 molecular sieve not to be carried out any processing.Obtain catalyst 17 at last.Wherein molecular sieve 57.72%, MoO
32.88%, NiO 0.96%.
Comparative Examples 2
The preparation method is identical with embodiment 1, and different is that the HZSM-5 molecular sieve is only carried out hydrothermal treatment consists.Obtain catalyst 18 at last.Wherein molecular sieve 64.85%, MoO
36.36%, NiO 2.73%.
Comparative Examples 3
The preparation method is identical with embodiment 1, and different is the HZSM-5 molecular sieve only to be carried out NaOH handle and NH
4NO
3Ion-exchange.Obtain catalyst 19 at last.Wherein molecular sieve 64.85%, MoO
36.36%, NiO 2.73%.
Embodiment 17
The catalyst and the application of Comparative Examples catalyst in catalytic gasoline hydrogenation modifying of the present invention's preparation adopted in the present embodiment explanation.
Catalyst 1～19 is respectively charged in the continuous fixed bed reactors loaded catalyst 4 grams (about 6ml).At first use N
2After purging 1h catalyst is carried out presulfurization, sulfuration liquid is for containing 3wt%CS
2Direct steaming gasoline, sulfide stress 2.8MPa, hydrogen to oil volume ratio 300, weight (hourly) space velocity (WHSV) 2.0h
-1, 150 ℃ were vulcanized 2 hours, and 230 ℃, 260 ℃, 290 ℃ and 320 ℃ were vulcanized respectively 4 hours.The evaluating catalyst condition is 390 ℃ of temperature, pressure 1.8MPa, and hydrogen to oil volume ratio 200, weight (hourly) space velocity (WHSV) is 2.0h
-1Evaluation result is as shown in table 1.
Can find out by table 1; Catalyst 1～19 all has hydrodesulfurization ability preferably; But hydroisomerization is different with aromatization activity, shows method of modifying, modified condition, the composition of catalyst carrier and the reactivity worth that content of metal influences catalyst of molecular sieve.
Reactivity worth through comparing catalyst 1～8 and 17～19 can find out that the method for modifying of HZSM-5 molecular sieve influences the reactivity worth of catalyst.React after 72 hours, the HZSM-5 molecular sieve is without any modification processing with only through NaOH+NH
3NO
4Although it is active that the catalyst for preparing after the ion-exchange treatment also has certain hydroisomerization, aromatization activity is very low.This mainly is because catalyst 17 and 18 acidity are stronger, makes the catalyst carbon deposit inactivation very fast.The HZSM-5 molecular sieve is carried out the acidity that hydrothermal treatment consists can reduce catalyst, and prepared catalyst 19 still has hydrogenation of olefins isomerization activity preferably in reaction after 72 hours, but aromatization activity is lower.Can find out through the reactivity worth of catalyst 1～8 relatively, compare that the acidity that hydrothermal treatment consists can more effective modulation molecular sieve after the first alkali treatment, form more mesopore, catalyst deactivation rate reduces with alkali treatment after the first hydrothermal treatment consists.
Reactivity worth through comparing catalyst 1～16 can find out that the modified condition of HZSM-5 molecular sieve, the composition of catalyst carrier and content of metal influence the reactivity worth of catalyst.Content of metal higher on the catalyst can improve the desulphurizing activated of catalyst, and can improve the aromatisation shape selectivity and the octane number hold facility of catalyst when containing more HZSM-5 molecular sieve in the catalyst carrier.React after 72 hours, catalyst 1 still has higher hydrodesulfurization, hydroisomerization and aromatization activity, shows best combined reaction performance.
Catalytic gasoline hydrogenation modifying reaction result (72h) on table 1 catalyst
Can be known that by above-mentioned analysis catalyst 1 has catalytic gasoline hydrogenation modifying effect preferably, therefore, selecting catalyst 1 is made the catalytic gasoline hydrogenation modifying stability study, and the result is as shown in table 2.Can find out that this catalyst has the higher alkene ability of falling, hydroisomerization and aromatization activity and stability preferably, product research method octane number and feedstock oil are suitable basically, and have higher liquid yield, show certain prospects for commercial application.
The stability experiment result of table 2 catalyst 1
Claims (12)
1. a catalytic gasoline hydrogenation modifying catalyst is characterized in that: in catalyst weight, contain the HZSM-5 molecular sieve of 20～80wt% modification in the catalyst, 10～70.58wt% binding agent, 3～10wt% molybdenum oxide, 1～5wt% nickel oxide; Wherein the modified HZSM-5 molecular sieve obtains through following method: the HZSM-5 molecular sieve is carried out alkali treatment, ammonium exchange and hydrothermal treatment consists, process the modified HZSM-5 molecular sieve; Alkali treatment is that the HZSM-5 molecular sieve is perhaps placed aqueous slkali through the HZSM-5 molecular sieve of hydrothermal treatment consists by liquid-solid ratio 5～15ml/g; PH is adjusted to 9～14; Stirred 2～6 hours down at 60～90 ℃; Then product is filtered, washs, 110～130 ℃ of dryings, 450～520 ℃ of roastings 2～6 hours.
2. catalyst according to claim 1 is characterized in that: alkali is selected from NaOH, KOH, Na
2CO
3Or K
2CO
3
3. catalyst according to claim 1; It is characterized in that: the ammonium exchange is with placing ammonium salt solution through the HZSM-5 of alkali treatment molecular sieve; Molecular sieve wherein: ammonium salt: water weight ratio is 1: 0.2～1.8: 5～15; And stirred 2～6 hours down at 60～98 ℃, then product is filtered, washs, 110～130 ℃ of dryings, 450～520 ℃ of roastings 2～6 hours.
4. catalyst according to claim 3, it is characterized in that: ammonium is selected from NH
4NO
3Or NH
4Cl.
5. catalyst according to claim 1 is characterized in that: hydrothermal treatment consists is that the HZSM-5 molecular sieve was perhaps fed steam treatment 2～6 hours through the HZSM-5 molecular sieve of alkali treatment and ammonium exchange down at 400～600 ℃.
6. catalyst according to claim 1 is characterized in that: HZSM-5 molecular sieve silica alumina ratio is 25～80.
7. catalyst according to claim 1 is characterized in that: binding agent is meant boehmite, γ-Al
2O
3, SiO
2, in the diatomite one or more.
8. the said Preparation of catalysts method of claim 1 is characterized in that the modified HZSM-5 molecular sieve is mixed with binding agent, pinches through mixing, extruded moulding, drying, 480～650 ℃ of roastings be after 3～7 hours, processes catalyst carrier; Adopt the method load molybdenum oxide and the nickel oxide of dipping, process catalyst after 3～5 hours through dry, 450～520 ℃ of roastings.
9. Preparation of catalysts method according to claim 8 is characterized in that: carrier mixes and to pinch, add the HNO of 2～6wt% sesbania powder and 3～10wt% in the extruded moulding process
3The aqueous solution.
10. Preparation of catalysts method according to claim 8; It is characterized in that: when the method load molybdenum oxide of employing dipping and nickel oxide; Ratio by maceration extract and the pore volume of carrier is 0.8～1.2, and the predecessor aqueous solution of preparation molybdenum oxide and nickel oxide metal is as maceration extract.
11. Preparation of catalysts method according to claim 8 is characterized in that: elder generation's load molybdenum back loading nickel when the method load molybdenum oxide of employing dipping and nickel oxide, divide one-step baking.
12. Preparation of catalysts method according to claim 8 is characterized in that: catalyst carrier impregnated in the ammonium molybdate solution 6～12 hours, through catalyst intermediate dry, 450～520 ℃ of roastings must contain molybdenum oxide after 2～6 hours; This catalyst intermediate impregnated in the nickel nitrate solution, get catalyst after 2～6 hours through dry, 450～520 ℃ of roastings.
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| CN103769202A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Gasoline selective hydro-desulfurization catalyst, preparation method and applications thereof |
| CN104399518B (en) * | 2014-11-11 | 2018-02-16 | 沈阳工业大学 | A kind of light FCC gasoline aromatized catalyst preparation method |
| CN106669802B (en) * | 2015-11-09 | 2019-04-12 | 中国石油化工股份有限公司 | Produce the catalyst and preparation method thereof of high quality hydrocracking tail oil |
| CN107583659B (en) * | 2016-07-07 | 2020-07-14 | 中国石油天然气股份有限公司 | Catalyst for selective hydrodesulfurization and preparation method thereof |
| CN109847793B (en) * | 2019-01-11 | 2021-12-10 | 中国石油大学(华东) | Method for synthesizing ZSM-5 molecular sieve based non-supported hydrogenation catalyst by eutectic method |
| CN112295596B (en) * | 2019-07-30 | 2023-07-25 | 中国石油天然气股份有限公司 | Catalyst for catalyzing gasoline hydrogenation modification containing mesoporous-macroporous ZSM-5 molecular sieve and preparation method thereof |
| CN112973660B (en) * | 2019-12-14 | 2022-04-22 | 中国科学院大连化学物理研究所 | High-dispersion non-noble metal catalyst and preparation method and application thereof |
| CN113171793A (en) * | 2021-04-06 | 2021-07-27 | 广东石油化工学院 | Hydrodealkylation catalyst and preparation method thereof |
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| CN1628904A (en) * | 2003-12-16 | 2005-06-22 | 广东工业大学 | Highly effective catalyst for purifying automobile exhaust and its preparing process |
| CN1785519A (en) * | 2004-12-08 | 2006-06-14 | 中国科学院广州能源研究所 | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method |
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| CN1628904A (en) * | 2003-12-16 | 2005-06-22 | 广东工业大学 | Highly effective catalyst for purifying automobile exhaust and its preparing process |
| CN1785519A (en) * | 2004-12-08 | 2006-06-14 | 中国科学院广州能源研究所 | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method |
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