CN1345632A - Hydrogenation catalyst carrier preparation method and use thereof - Google Patents
Hydrogenation catalyst carrier preparation method and use thereof Download PDFInfo
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- CN1345632A CN1345632A CN 00124995 CN00124995A CN1345632A CN 1345632 A CN1345632 A CN 1345632A CN 00124995 CN00124995 CN 00124995 CN 00124995 A CN00124995 A CN 00124995A CN 1345632 A CN1345632 A CN 1345632A
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Abstract
The present invention relates to a hydrogenation catalyst carrier and its preparation method. It is characterized by using blended mixture of silicon dioxide with wider pore size distribution or diatomite with different pore size distribution and/or white carbon black as mother substance, adding various adjuvants of pore-forming agent, etc. and adopting the processes of extrusion forming and roasting at 900-1200 deg.c so as to can obtain the silicon dioxide carrier with with high-strength, large pore volume, low specific surface area, multi-stage pore size distribution and adjustable acidity. Said carrier is specially applicable to preparation of hydrogenation reaction catalyst of macromolecular hydrocarbons of above C6, for example, hydrogenation catalyst of 2-hexyl hexene aldehyde and complete distillate gasoline, and said obtained catalyst possesses high activity and selectivity.
Description
The present invention relates to a kind of catalyst carrier for hydrgenating and its production and use, more particularly, the present invention relates to a kind of C of being particularly useful for making
6Carrier of above macromolecule hydrocarbon catalyst for hydrogenation and its production and use.
Silicon-dioxide is one of most widely used carrier of petrochemical industry.As everyone knows, as support of the catalyst, intensity, pore volume, specific surface area, pore size distribution and surface acidity are the indexs of most critical.Because the carrier that adopts existing carrier moulding and treatment process to make can not make these indexs harmonious, usually attends to one thing and lose sight of another, and therefore, how to make the carrier that various indexs can both meet the demands, and is the problem that those skilled in the art thirst for solving always.
In the prior art, some have been arranged about the moulding of silicon-dioxide and preparation method's report.(on May 19th, 1975 is open for the clear 50-13261 of Japanese Patent, be incorporated herein by reference in full) a kind of method that adopts diatomite to prepare silica supports is provided, the ratio of the shaping raw material that it adopts is: diatomite: water: tackiness agent (starch or Mierocrystalline cellulose)=1: 0.8～1.5: 0.05～0.2.Aperture according to the carrier of this patented method preparation concentrates in the aperture scope (less than 20000 dusts) fully, causes catalyzer to be subjected to the influence of serious interior outdiffusion effect.The calcination temperature of carrier is low in addition, makes that more B acid and the sour structure of L is not destroyed in the carrier, causes the total surface acidity of carrier higher, thereby has reduced the selectivity of some reactions.Intensity is another important indicator of carrier, and adding the clay auxiliary agent is present the most frequently used method to improve support strength, but has also introduced foreign ions such as Al, Fe simultaneously; We also studied and use silicon sol as tackiness agent, though can improve intensity, silicon sol has also stopped up the diatomaceous micropore of part, caused that pore volume descends.In addition, Chinese patent CN1030365 (on January 18th, 1989 is open) discloses a kind of method for steam treatment of diatomite support, though adopt this method can improve intensity, cost is too high.So, need that exploitation is a kind of to have suitable pore size distribution range and intensity height, pore volume is big, surface acidity is an adjustable novel silica supports.
Therefore, an object of the present invention is to provide the adjustable silica supports of a kind of large pore volume, high strength, pore size distribution and surface acidity.Carrier of the present invention is the intensity height not only, and aperture and pore volume are big, and interior external diffusion is easy, can make by its catalyzer that makes and obtain good activity and selectivity simultaneously.
Another object of the present invention provides a kind of method for preparing silica supports of the present invention.Adopt moulding process of the present invention,, can prepare the ideal silica supports in conjunction with traditional calcination treatment process.
A further object of the present invention is that carrier of the present invention is used to prepare C
6Above macromolecule hydrocarbon catalyst for hydrogenation.Carrier of the present invention especially is fit to the hydrogenation catalyst of full distillation gasoline hydrogenation catalyst of preparation and the basic hexenoic aldehyde of 2-.
Catalyst carrier for hydrgenating of the present invention can comprise following component:
(1) 100 weight part is selected between different types of diatomite, between different types of white carbon black or the silicon-dioxide of the mixture between diatomite and the white carbon black; Preferred silicon-dioxide comprises the diatomite of (a) most probable aperture 800～15000 dusts; (b) the white carbon black of most probable aperture 100～150 dusts; Wherein (a) and weight ratio (b) are 1: (0.1～1);
(2) 2～55 weight parts are selected from one or more the tackiness agent in starch or its sex change product, Mierocrystalline cellulose or its sex change product, ethylene glycol, glycol ether and the polyvinyl alcohol, and the described various tackiness agents that are used alone or in combination are that the consumption of 100 weight parts can be starch or its sex change product 15～55 weight parts, Mierocrystalline cellulose or its sex change product 5～20 weight parts, ethylene glycol 40～50 weight parts, glycol ether 40～50 weight parts, polyvinyl alcohol 2～7 weight parts in silicon-dioxide.Preferred polyvinyl alcohol is that the polymerization degree is the polyvinyl alcohol of 1500-2000.
Carrier of the present invention can have following rerum natura: intensity 4～13kgf/ grain (Ф 4 * 5, side pressure), pore volume 0.4～1.5ml/g, specific surface area 10～220m
2/ g, total acidity 0.0000～0.13mmol n-Butyl Amine 99/g has broad peak, bimodal or multimodal pore size distribution.
Carrier of the present invention can prepare by following method: with described silicon-dioxide (a) and tackiness agent (b), for example place kneader, mixing, add quantitative water, mediate aftershaping (for example using forcing machine), after 100-150 ℃ of oven dry, in 800～1200 ℃ the carrier calcination was decomposed 2～5 hours again.Diatomite and/or the proportioning of the white carbon black mean pore size of regulating carrier of the present invention by adjusting different pore size distributions distributes, and by adjusting calcination temperature, changes the most probable aperture and the total acidity of carrier.
The invention also discloses carrier of the present invention at preparation C
6Application in the catalysts of above macromolecule hydrocarbon, the particularly application in the hydrogenation catalyst of full distillation gasoline hydrogenation catalyst of preparation or the basic hexenoic aldehyde of 2-.
Below the present invention is carried out more detailed description.Before disclosure and description hydrogenation reaction carrier of the present invention and its production and use, need point out that the present invention is not limited to the restriction of special construction described herein, method steps and material, these structures, method steps and material can change to some extent.
The present invention carries out blend by having two kinds of different most probables aperture or two or more diatomite, two kinds or two or more white carbon black or diatomite and white carbon black, tentatively regulate the pore size distribution that the ratio at different pore size distributions peak can easily be regulated carrier by regulating proportioning, make carrier have suitable pore size distribution.In other words, by simple blend, just can make and both contain bigger hole in the carrier of the present invention (greater than 10
5Dust), contain less hole (less than 4000 dusts) again.Add the tackiness agent that starch and denatured products, Mierocrystalline cellulose and denatured products thereof, ethylene glycol, glycol ether or polyvinyl alcohol etc. can calcination decompose, can further improve the pore volume of carrier.The size that also can further regulate pore volume by the add-on of regulating auxiliary agent.In addition, can also regulate the intensity of carrier, surface acidity and final pore size distribution (comprising unimodal or the multimodal distribution, most probable aperture location, the ratio in the hole of several types etc.) by regulating calcination temperature.Say that briefly the present invention forms and these two means of control calcination process by adjusting raw material, can prepare the adjustable silica supports of a kind of large pore volume, high strength, pore size distribution and surface acidity.
The diatomite in the different places of production, contained diatomaceous kind difference, thereby have different pore size distributions, as shown in table 1.Above listed diatomaceous pore size distribution range broad, but the most probable aperture is generally between 500～15000 dusts, the percentage ratio that the hole of other scope accounts for total pore volume is lower.From then on table it can also be seen that indexs such as pore volume, specific surface, the heap of listed raw material compare also differ bigger, so we should select the diatomite material in a certain place of production or several places of production as the case may be.
Be raw material with one or more diatomite separately, the carrier of preparing after 1000 ℃ of calcinations is general only 10
5The dust place has single most probable pore size distribution, and this scope pore volume accounts for more than 95% of total pore volume, and all the other are aperture.
Be that the carrier (less than 900 ℃) under lower calcination temperature that feedstock production goes out only generates the single aperture distribution with white carbon black separately, the most probable aperture increases with the rising of temperature.800～1000 ℃ of calcinations, 100 ℃ of the every risings of temperature, the most probable aperture rises to original 3 times.More than 1000 ℃ during calcination, the aperture of the white carbon black of part is melted, and forms the part macropore.Can prepare this moment and have the carrier that diplopore distributes.1000 ℃ of calcinations are handled, and the hole of carrier 1000 dusts of preparing accounts for 80%, 10
4The hole of dust only accounts for 20%, but has only 10 for macropore
4The carrier of dust, the speed of mass transfer and heat transfer can not satisfy the requirement of high loading reaction, continue to improve calcination temperature to 1150 ℃, and then to the drift of wide aperture direction, ratio also changes simultaneously in this hole of two types, and 10
5The hole of dust accounts for 80%, 5 * 10 of total pore volume
4The hole of dust accounts for 20%, and calcination temperature is increased to 1150 ℃ from 1000 ℃, and the aperture increases 50-100 doubly suddenly.Macropore diameter and the natural diatomaceous earth that form this moment are close, but the pore volume of carrier is very low, has only 0.4ml/g, has limited its should have in some field.
But do carrier with white carbon black separately, only generate carrier, and the most probable aperture of carrier is lower than 1000 dusts with unimodal distribution in calcination below 1000 ℃.Desire to make carrier under lower calcination temperature, just to have bimodal pore size distribution, just need be with diatomite and white carbon black blend.The most probable aperture of the general white carbon black of synthetic be tens dusts to the hundreds of dust, our preferred aperture is the white carbon black of 100-150 dust.In sum, diatomite support and white carbon black support will have the white carbon black of aperture and have the diatomite mixing moulding of macropore, the carrier of preparing will have two types hole simultaneously, has bimodal distribution, make this carrier have good mass transfer, heat transfer and kinetics catalytic performance, be fit to do the catalyzed reaction carrier of high loading.Promptly form in calcination below 1000 ℃ with the carrier of this method preparation and to have bimodal distribution (10
5Dust and＜4000 dusts) carrier.
Calcination temperature and carrier acidity are closely related in addition.Natural diatomaceous earth and white carbon black chemical ingredients all are silicon-dioxide, thereby surface acidity also shows similar rule.Just, contain more aluminum ion, so acidity is higher than white carbon black because the white carbon black of natural diatomaceous earth purity is low.Be that the carrier total acidity that the carrier of feedstock production forms after 800 ℃ of calcinations reaches 0.13mmol n-Butyl Amine 99/g with white carbon black, 900 ℃ of calcinations then fall sharply and are 0.005mmol n-Butyl Amine 99/g, and are close with the acidity value of natural diatomaceous earth carrier of calcination more than 1000 ℃.White carbon black support is almost neutral through 1000 ℃ of calcination rear surfaces.
Surprisingly, the pore size distribution of the broad that obtains by the inventive method makes carrier of the present invention be especially suitable for use as the carrier of high activated catalyst.The inventor thinks, adopt hole less in the catalyzer of preparing carriers of the present invention (less than the hole of 4000 dusts) to provide enough kinetic activity centers for reaction, and bigger hole is (greater than 10
5Dust) again for mass transfer provides enough ducts, make catalyzer have bigger spread coefficient, effectively eliminated general catalyzer common interior outdiffusion effect, improved activity of such catalysts.For example, the inventor is by discovering, the most probable aperture is 10
5The carrier of dust than most probable aperture 10
4The catalyst of the preparing carriers of dust is active high 5 times.In addition, bigger hole (10
5Dust) rate of mass transfer can be improved, but the side reaction of selecting the type type can not be caused.Owing to this essential reason, adopt the catalyzer of preparing carriers of the present invention, can reduce temperature of reaction on the one hand greatly and/or reduce the active ingredient consumption, can replace noble metal component with general active ingredient on the other hand, reduce the catalyzer cost.For example, from respective embodiments of the present invention, can find out, in the basic hexenoic aldehyde liquid-phase hydrogenatin of 2-reaction, adopt activity of such catalysts that preparing carriers of the present invention goes out and selective data all to be higher than open catalyzer (changing into the catalyzer of company as the Mitsubishi of BASF AG's catalyzer of DE3228881 and JP53-54188).Wherein, BASF catalyst activity component concentration is 22% of a catalyst weight, be to adopt 2 times of catalyzer (from controlling catalyst) that preparing carriers of the present invention goes out, but under 130 ℃, it is 37% unconverted that raw material has, have only just to reach the activity of homemade catalyzer under 130 ℃ when temperature of reaction brought up to 180 ℃, and adopt the activity of such catalysts components contents of preparing carriers of the present invention also to have only 1/2nd of BASF catalyzer.As seen, adopt preparing carriers catalyzer of the present invention, temperature of reaction is reduced greatly, therefore can reduce production energy consumption.And for example, be that the effect of full distillation gasoline one-stage hydrogenation catalyzer can compare favourably with 8601 Pd series catalysts of commercially available Lan Hua company with the nickel of preparing carriers of the present invention, can be used to substitute noble metal catalyst.In full distillation gasoline hydrogenation experiment, suitable with 8601 activity, selectivity is higher than 8601 catalyzer far away, and concrete data see also the embodiment of the invention.Therefore, carrier of the present invention is with a wide range of applications at petrochemical industry.
Catalyst carrier for hydrgenating of the present invention can comprise following component:
(a) 100 weight parts be selected between different types of diatomite, between different types of white carbon black or the silicon-dioxide of the mixture between diatomite and the white carbon black; White carbon black and diatomaceous weight ratio that the diatomite of preferred most probable aperture 800～15000 dusts removes most probable aperture 100～150 dusts are 1: (0.1～1) mixture;
(b) 2～55 weight parts are selected from one or more the tackiness agent in starch or its sex change product, Mierocrystalline cellulose or its sex change product, ethylene glycol, glycol ether and the polyvinyl alcohol, and the described various adhesive consumption that are used alone or in combination can be starch or its sex change product 15～55 weight parts, Mierocrystalline cellulose or its sex change product 5～20 weight parts, ethylene glycol 40～50 weight parts, glycol ether 40～50 weight parts, polyvinyl alcohol 2～7 weight parts.
Diatomite be frustule (skeleton or the bone) form with diatom exist be rich in bio-silicon dioxide (i.e. the silicon-dioxide that generates or produce by active organism) settling.Diatom belongs to the single celled Chrysophyceae of micro-inequality family of Diatomacae class, and they have change and magnificent diatom bone complex construction (being frustule).Although the size of most of frustule drops in the scope of 10-150 micron, the size of typical frustule is in the scope of 0.75-1000 micron.The basic chemical constitution of the frustule of diatom and complicated and vesicular structure make diatomite have other natural forms silicon-dioxide fabulous industrial value and the versatility that can't compare.The fine-grained structure of diatom bone has been given low density and high surface area and high porosity and perviousness.Diatomaceous earth products can prepare with the whole bag of tricks that produces physics and chemical property difference and multiple resource.
All types of diatomite may be used to prepare carrier of the present invention.Preferred diatomaceous most probable aperture is 500～15000 dusts, more preferably 800～10000 dusts,
In fact, between the diatomite of different most probable pore size distributions, can mix mutually with arbitrary proportion between the white carbon black of different most probable pore size distributions and between the diatomite of different most probable pore size distributions and the white carbon black, also can adopt a kind of diatomite or white carbon black separately with broad pore size distribution.Theoretically, the every raw material that the pore size distribution of broad is provided can for carrier of the present invention, no matter be mixture or one matter, all be applicable to of the present invention.Being specially adapted to silica material of the present invention and being the diatomite of most probable aperture 800～15000 dusts or the white carbon black of most probable aperture 100～150 dusts or white carbon black and diatomaceous weight ratio is 1: (0.1～1) mixture;
Preferred adhesive of the present invention is one or more in starch or its sex change product, Mierocrystalline cellulose or its sex change product, ethylene glycol, glycol ether, acrylic resin, urethane, Resins, epoxy and the polyvinyl alcohol etc., more preferably one or more in 2～55 weight part starch or its sex change product, Mierocrystalline cellulose or its sex change product, ethylene glycol, glycol ether and the polyvinyl alcohol (polymerization degree 1500～2000), special preferred starch or its sex change product, Mierocrystalline cellulose or its sex change product, most preferably modified starch and/or modified cellulose.Whether the described various adhesive consumption that is used alone or in combination can and be easy to dispersing and mixing according to its bonding strength is determined.In addition, adhesive consumption also depends on the rerum natura of silicon-dioxide, if the bulk density of silicon-dioxide is big, then adhesive consumption is relatively just few, otherwise adhesive consumption is relatively just many.Those skilled in the art can easily select to be applicable to tackiness agent of the present invention and consumption thereof according to practical situation.Preferred adhesive of the present invention and consumption thereof be for being 100 parts of weight in silicon-dioxide, starch or its sex change product 15～55 weight parts, Mierocrystalline cellulose or its sex change product 5～20 weight parts, ethylene glycol 40～50 weight parts, glycol ether 40～50 weight parts, polyvinyl alcohol 2～7 weight parts.When being used in combination, can adjust the ratio of various tackiness agents according to practical situation.Adhesive consumption can not be too many, otherwise can cause generation difficulty when moulding, cracks when perhaps decomposing; Otherwise, if the pore volume of the carrier that consumption very little, is prepared is on the low side.
Carrier of the present invention can prepare by following method: described silicon-dioxide (a) and tackiness agent (b) are placed the kneader mixing, add quantitative water, mediate back extruded moulding on forcing machine, in 800～1200 ℃ the carrier calcination was decomposed 2～5 hours then.Diatomite and/or the proportioning of the white carbon black pore size distribution of regulating carrier of the present invention by adjusting different pore size distributions by adjusting calcination temperature, changes the most probable aperture and the total acidity of carrier.
In one embodiment of the invention, silicon-dioxide (a) and tackiness agent (b) were mediated 5-30 minute in kneader, taken out kneaded material then, place the banded extruder extrusion moulding, be cut into the carrier granule of Ф 5 * 5 then.This carrier decomposes 2～5 hours treatment times, best 3～4 hours then prior to 100-150 ℃ of baking 6～10 hours in 800～1200 ℃ of calcinations.Higher calcination temperature is sintered to inert substance with small amount of impurities, can not influence selectivity of catalyst, and gives the surface acidity of the enough intensity of carrier, reduction carrier.Shown in subordinate list, improve the calcination temperature of silica supports, the most probable aperture that can improve catalyzer can make carrier change into bimodal or the multimodal distribution from unimodal on the other hand, and carrier surface acidity can be reduced to 0.0007mmol/g by 0.13 on the one hand.
Prior art adopts lower calcination temperature, as JP-50-13261, adopts 500-850 ℃ of temperature calcination, and the carrier most probable aperture of preparing is below 20000 dusts, and carrier surface acidity also can be higher.Most probable aperture meeting on the low side causing catalyzer mass transfer difficulty makes reaction be subjected to the influence of serious internal diffusion, has limited the performance of catalyst activity.High surface acidity can cause some dehydration reactions, makes reactant generation esterification and etherification reaction.
Adopt 800-1200 ℃ calcination temperature, the shortcoming above having overcome.At first make carrier have high strength, moreover low surface acidity can make selectivity of catalyst be improved.Obtained simultaneously big most probable aperture (greater than 100000 dusts) again, improved mass transfer and heat transfer efficiency, advantageously eliminated the common internal diffusion influence of catalyzer, made catalyst activity be able to the performance of ceiling ground.But the most probable aperture raises, and the surface-area of carrier is descended, in order to remedy this defective, we dose the white carbon black that part has aperture, to improve the specific surface area of carrier,, have enough mass transfer macropores simultaneously again for catalyzer provides enough catalytic active centers.The add-on visual response type of white carbon black and deciding is if be used for C
5The hydrogenation reaction of following unsaturated compound, then the add-on of white carbon black should be more, are used for C
5The hydrogenation reaction of above unsaturated compound, then white carbon black should add less.
Calcination temperature is lower than 800 ℃, and then support strength is low, and surface acidity is higher, and the aperture is less than normal, and resistance to mass transfer is bigger, and catalyst activity is low.Be higher than 1200 ℃ of calcinations, then carrier can be sintered, and pore structure disappears, and can't use.
The carrier that makes according to the inventive method has following rerum natura: intensity 4～13kgf/ grain (4 * 5, side pressure), pore volume 0.4～1.5ml/g, specific surface area 10～220m
2/ g, total acidity 0.0000～0.13mmol n-Butyl Amine 99/g has broad peak, bimodal or multimodal pore size distribution.
The ZQJ-II type intelligence particle experimental machine that support strength adopts big connection intelligent experimental machine factory to make is measured.Get 50 cylindrical samples, grind to form 5mm length, measure side pressure strength, average.
The Auto Pore III 9420 type mercury injection apparatuses that pore volume and specific surface area adopt Micromeritics company to make are measured.
Total surface acidity adopts traditional n-butylamine titration method to measure.Concrete steps are:
1. the preparation of solution
1. the preparation of 1: 1 hydrochloric acid soln
2. the preparation of 1.0M sodium hydroxide solution
3. the preparation of standard zinc solution: zinc granule with 1: 1 salt acid elution, wash the acid of desalting with water again, with acetone or nothing
The water-ethanol flushing in 110 ℃ of bakings several minutes, accurately takes by weighing the zinc granule of handling well 0.62～0.63 then
Restrain in the 250ML flask, add 1: 1 hydrochloric acid of 5ML, the heating for dissolving zinc granule moves into 500ML in case of necessity
In the volumetric flask, be diluted with water to scale, shake up.
Zinc concentration=W/500 (gram/ml)
4. the preparation of 0.05M EDTA solution
Take by weighing 20 gram EDTA, be dissolved in the 1000ML distilled water
Demarcate: pipette zinc standardized solution 25.00ML, adding distil water 20ML adds 3 xylenol orange
Indicator, hexamethyl tetramine to the solution of dropping 20% is stable red-violet colour, and is many again
Add 3ML, to glassy yellow, promptly reach terminal point with the titration of above-mentioned EDTA solution.
M
EDTA=M
The zinc standardized solution* V
The zinc standardized solution/ (65.38 * V
EDTA)
5. the preparation of 0.1M zinc chloride standardized solution
Take by weighing 14 gram zinc chloride, be dissolved in the 1000ML distilled water, add the 0.5ML concentrated hydrochloric acid, shake up.
Demarcate: pipette EDTA standardized solution 20.00ML, adding distil water 20ML, dropping 20%
The hexamethyl tetramine adds 4 xylenol orange indicator to solution 15ML, uses above-mentioned chlorination
The zinc solution titration promptly reaches terminal point to red-violet colour.
M
Zinc chloride=M
EDTA* V
EDTA/ V
Zinc chloride
2 sample preparation
1. with the catalyzer grind into powder
2. accurately take by weighing about powdered sample 0.5 gram, add 1: 1 hydrochloric acid 5ML, add water 40ML after 1 hour,
Filter, collect filtrate.
3. filtrate being neutralized to pH value with sodium hydroxide solution is 5～6
4. in above-mentioned solution, add 0.05M EDTA solution 25ML, firmly shake.
3 demarcate
The hexamethyl tetramine solution 15ML of adding 20% in above-mentioned solution adds 4 xylenol orange indications
Agent changes rose into zinc chloride standard solution titration to the bright green of 0.1M, promptly reaches end
The point.
Ni(mol/g)＝(V
0-V)×0.1/W
In the formula: V
0The zinc chloride standardized solution ML that blank test consumes
V adds the zinc chloride standardized solution ML of sample post consumption
The weight of the catalyzer of W weighing
The invention also discloses carrier of the present invention at C
6Application in the reaction of above macromolecule hydrocarbon, the particularly application in the hydrogenation of full distillation gasoline hydrogenation or the basic hexenoic aldehyde of 2-.Adopt ordinary method well known by persons skilled in the art just can use preparing carriers of the present invention to be applicable to the catalyzer of above-mentioned hydrogenation reaction easily, for example JP53-54188 (on May 17th, 1978) has promptly introduced the company that changes into of Mitsubishi and has prepared the butyraldehyde hydrogenation catalyst with examples of such carriers.The using method of these catalyzer obtains detailed disclosing, for example JP61-172838 in the prior art.
As mentioned above, compared with prior art, carrier of the present invention has intensity height, characteristics that pore volume is big, and total surface acidity and pore size distribution are adjustable, and concrete data see also embodiments of the invention.Carrier of the present invention can have bimodal or the multimodal pore distribution.Wherein, hole (less than the hole of 4000 dusts) less in the carrier provides enough kinetic activity centers for reaction, and bigger hole is (greater than 10
5Dust) for mass transfer provides enough ducts, make catalyzer have bigger spread coefficient, effectively eliminated general catalyzer common interior outdiffusion effect, improved activity of such catalysts, thereby can reduce catalyst production cost.Therefore, carrier of the present invention is with a wide range of applications at petrochemical industry.
Fig. 1 is the pore size distribution curve of carrier 1.Wherein X is a pore radius, unit: nanometer; Y is accumulative total percentage pore volume (%), with+represent; Z is pore size distribution differential curve (%), represents with zero.
The following examples have been done further description to technical scheme of the present invention, and these embodiment are used to illustrate the present invention but not the present invention is limited.
The rerum natura of used silica material is among the embodiment: diatomite 1: area, Yongkang, Zhejiang, place of production content (Wt%) SiO
292.61, Al
2O
34.69, TiO
20.27, K
2O 0.64 most probable aperture 800～8000 dust diatomite 2: place of production Changbai mountain, Jilin area content (Wt%) SiO
290.87, Al
2O
35.15, TiO
20.70 K2O 0.86, Fe
2O
31.76 the white carbon black of most probable aperture 10000-12000 dust: Tai County, Jiangsu, place of production content (Wt%) SiO
298.50, Al
2O
30.15, Na
2O 0.87, Fe
2O
30.46 most probable aperture 100-150 dust
Embodiment 1
Place kneader to mix 200 gram diatomite 1 and 200 white carbon blacks of gram and 75 gram starch, add 380 gram distilled water, mediates extrusion moulding after 10 minutes, after 110 ℃ of oven dry, it is interior in 1000 ℃ of calcinations decomposition 3 hours to transfer to retort furnace, obtains carrier 1.
Embodiment 2
Place kneader to mix 200 gram diatomite 1 and 200 white carbon blacks of gram and 200 gram starch, add 450 gram distilled water, mediates extrusion moulding after 10 minutes, after 110 ℃ of oven dry, it is interior in 1000 ℃ of calcinations decomposition 3 hours to transfer to retort furnace, obtains carrier 2.
Embodiment 3
Restraining diatomite 1 and the 200 white carbon blacks of gram and 75 gram methylcellulose gum with 200 places kneader to mix, add 450 gram distilled water, mediate extrusion moulding after 10 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 3 in 1000 ℃ of calcinations.
Embodiment 4
Restraining diatomite 1 and the 200 white carbon blacks of gram and 75 gram methylcellulose gum with 200 places kneader to mix, add 450 gram distilled water, mediate extrusion moulding after 10 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 4 in 800 ℃ of calcinations.Embodiment 5
Place kneader to mix with 75 gram methylcellulose gum the white carbon black of 400 grams, add 450 gram distilled water, mediate extrusion moulding after 15 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 5 in 800 ℃ of calcinations.
Embodiment 6
Place kneader to mix with 75 gram methylcellulose gum the white carbon black of 400 grams, add 450 gram distilled water, mediate extrusion moulding after 15 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 6 in 900 ℃ of calcinations.
Embodiment 7
Place kneader to mix with 75 gram methylcellulose gum the white carbon black of 400 grams, add 450 gram distilled water, mediate extrusion moulding after 15 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 7 in 1000 ℃ of calcinations.
Embodiment 8
Place kneader to mix with 75 gram methylcellulose gum the white carbon black of 400 grams, add 450 gram distilled water, mediate extrusion moulding after 15 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 8 in 1150 ℃ of calcinations.
Embodiment 9
Restraining diatomite 1 and the 200 white carbon blacks of gram and 75 gram starch with 200 places kneader to mix, add the solution that contains 5% polyvinyl alcohol (polymerization degree 1500-2000) 400 grams that prepare in advance, mediate extrusion moulding after 10 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 9 in 1000 ℃ of calcinations.
Embodiment 10
Place kneader to mix with 75 gram starch in 400 gram diatomite 1, adding concentration is the aqueous solution 400 grams of 50% glycol ether, mediates extrusion moulding after 15 minutes, after 110 ℃ of oven dry, transfers in the retort furnace and decomposes 3 hours in 1000 ℃ of calcinations, obtains carrier 10.
Embodiment 11
Restraining diatomite 1 and 200 gram diatomite 2 and 40 gram starch with 200 places kneader to mix, adding concentration is 50% aqueous glycol solution 400 grams, mediates extrusion moulding after 15 minutes, after 110 ℃ of oven dry, transfer in the retort furnace and decomposed 3 hours, obtain carrier 11 in 1150 ℃ of calcinations.Table 1
Application example 1
| Project | The Linqu County, Shandong Province | The white county of Jilin governor | Sea otter county, Jilin Province | The Huadian, Jilin | The Shengxian County, Zhejiang Province | New people village, Miyi County, Sichuan Province | Chinese ditch is returned Miyi County in Sichuan Province | Hubei Suixuan County |
| Bulk density g/ml | ??0.29 | ??0.34 | ??0.54 | ??0.45 | ??0.50 | ??0.52 | ||
| Pore volume ml/g | ??1.40 | ??1.00 | ??0.98 | ??1.35 | ??0.97 | ??0.76 | ??0.66 | |
| Specific surface area m 2/g | ??65.1 | ??21.8 | ??46.0 | ??58.0 | ??57.2 | ??43.4 | ??57.5 | ??32.2 |
| Main pore radius A | ??500～ ??8000 | ??500～ ??7000 | ??500～ ??5000 | ?500～ ?7000 | ?500～ ?8000 | ?500～ ?5500 | ?500～ ?5000 | ?＜3000 |
Dissolving 50 gram Ni (NO
3)
2.6H
2O and 10 gram Cr (NO
3)
3.9H
2O is in 11 ml waters, then with on this solution impregnation to 75 gram carrier 1, the carrier 1 that dipping is good was handled 5 hours in 105 ℃, decomposed 5 hours in 450 ℃ then, in 700 ℃ of reduction 3 hours, be prepared into the catalyzer that contains 10-15%Ni at last, load 40 milliliters of these catalyzer and in internal diameter is the single tube reactor of 20 millimeters of Ф, carry out hydrogenation reaction, the condition of evaluate catalysts is: raw material is formed the basic hexenoic aldehyde of 2-: the basic hexanol of 2-=1: 4, the liquid air speed of the basic hexenoic aldehyde of 2-is 0.2hr
-1, 130 ℃ of hot(test)-spot temperatures.Comparative example 1
Prepare the basic hexenoic aldehyde liquid phase hydrogenating catalyst of 2-by the JP53-54188 disclosed method, containing 12%Ni is carrier with diatomite, is called catalyst A.Load 40 milliliters, appreciation condition is with application example 1.
The comparative evaluation the results are shown in subordinate list 3, the catalyzer of carrier 1 preparation can make raw material 100% transform, and by product in the hydrogenation crude product (high boiling material) content is 0.00%, and catalyst A promptly occurs the basic hexenoic aldehyde of unconverted raw material 2-in reaction after 200 hours, the carrier that utilizes the present invention prepared is described, owing to have rational pore size distribution and acidity character, make the catalyzer of making at α, have high activity and selectivity in the hydrogenation reaction of beta-unsaturated aldehyde.
Table 3 from controlling catalyst and catalyst A activity, selectivity ratios
The rerum natura of table 2 carrier 1～9
Comparative example 2
| Catalyzer | Accumulative total reaction times hour | Stablize back end hydrogenation crude product analytical results % | Transformation efficiency % | Selectivity % | |||
| Octenal | Intermediate | 2-Ethylhexyl Alcohol | High boiling material | ||||
| From controlling catalyst | ??100 | ????0.00 | ??0.45 | ??99.23 | ??0.00 | ??100 | ??96.15 |
| ??200 | ????0.00 | ??0.40 | ??99.34 | ??0.01 | ??100 | ??96.70 | |
| Catalyst A | ??100 | ????0.00 | ??1.60 | ??97.30 | ??0.20 | ??100 | ??86.50 |
| ??200 | ????0.03 | ??1.50 | ??97.60 | ??0.22 | ??99.85 | ??88.00 | |
| Bearer number | Material is formed (g) | Calcination temperature ℃ | The carrier rerum natura | |||||||||||||||
| Diatomite 1 | Diatomite 2 | White carbon | Starch | Mierocrystalline cellulose | Water | Glycol ether | Ethylene glycol | Polyvinyl alcohol | Intensity kgf/ grain | Pore volume ml/g | Specific surface area m 2/g | Total acidity mmol n-Butyl Amine 99/g | Pore size distribution | |||||
| Peak 1 position dust | Peak 1 proportion | Peak 2 position dusts | Peak 2 proportions | |||||||||||||||
| ??1 | ?200 | ?- | ??200 | ??75 | ??- | ?380 | ???- | ???- | ????- | ?1000 | ?6.0 | ??0.7 | ??30.2 | ????0.0007 | ??＜4000 | ??40％ | ??＞105 | ??50％ |
| ??2 | ?200 | ?- | ??200 | ??200 | ??- | ?450 | ???- | ???- | ????- | ?1000 | ?6.0 | ??1.5 | ??27.8 | ????0.0006 | ??＜4000 | ??38％ | ??＞105 | ??50％ |
| ??3 | ?200 | ?- | ??200 | ??- | ??75 | ?450 | ???- | ???- | ????- | ?1000 | ?5.8 | ??0.75 | ??26.0 | ????0.0000 | ??＜4000 | ??36％ | ??＞105 | ??55％ |
| ??4 | ?200 | ?- | ??200 | ??- | ??75 | ?450 | ???- | ???- | ????- | ??800 | ??5.0 | ??0.8 | ?106.0 | ????0.09 | ??100～ ????200 | ??25％ | ??＞105 | ??70％ |
| ??5 | ?- | ?- | ??400 | ??- | ??75 | ?450 | ???- | ???- | ????- | ??800 | ??4.5 | ??1.0 | ?220.0 | ????0.13 | ??100～ ????200 | ??100％ | ||
| ??6 | ?- | ?- | ??400 | ??- | ??75 | ?450 | ???- | ???- | ????- | ??900 | ??5.5 | ??0.80 | ?120.0 | ????0.0005 | ??400～ ????500 | ??100％ | ||
| ??7 | ?- | ?- | ??400 | ??- | ??75 | ?450 | ???- | ???- | ????- | ?1000 | ??8.0 | ??0.45 | ??40.2 | ????0.0000 | ??1000 | ??70％ | ??＞104 | ??20％ |
| ??8 | ?- | ?- | ??400 | ??- | ??75 | ?450 | ???- | ???- | ????- | ?1150 | ?12.0 | ??0.40 | ??10.0 | ????0.0000 | ??5×104 | ??20％ | ??＞105 | ??70％ |
| ??9 | ?200 | ?- | ??200 | ??75 | ??- | ?380 | ???- | ???- | ????20 | ??1000 | ??7.0 | ??0.75 | ??21.3 | ????0.0000 | ??＜4000 | ??30％ | ??＞105 | ??65％ |
| ??10 | ?400 | ?- | ???- | ??75 | ??- | ?200 | ??200 | ???- | ????- | ??1000 | ??5.8 | ??0.75 | ??13.0 | ????0.0004 | ??＜4000 | ??5％ | ??＞105 | ??90％ |
| ??11 | ?200 | ?200 | ???- | ??40 | ??- | ?200 | ???- | ??200 | ????- | ??1150 | ??7.0 | ??0.64 | ??14.0 | ????0.0007 | ????104 | ??40％ | ??＞105 | ??55％ |
Press the catalyzer of DE3228881 disclosed method preparation, be called catalyst B, load 40 milliliters and compare experiment, except that the temperature of reaction difference, all the other appreciation conditions are with application example 1.
Evaluation result shows, because liquid phase aldehyde hydrogenating catalyst B's is unreasonable, make catalyzed reaction be subjected to the influence of significantly interior outdiffusion effect, limited the performance of catalyst activity greatly, though the active component content of catalyst B is 2 times from controlling catalyst, under 130 ℃ temperature of reaction, activity is very low, have only when temperature of reaction is increased to 180 ℃, just near the self-control activity of such catalysts.This example proves absolutely, makes the reasonableness of support of the catalyst pore size distribution by oneself, can reduce the consumption of active ingredient greatly, reduces the catalyzer cost, and operational condition is relented, and cuts down the consumption of energy.
Table 4 catalyst B is active, selectivity under the different evaluation temperature
Application example 2
| Catalyzer | Temperature of reaction ℃ | Stablize back end hydrogenation crude product analytical results % | Transformation efficiency % | Selectivity % | |||
| Octenal | Intermediate | 2-Ethylhexyl Alcohol | High boiling material | ||||
| Catalyst B | ?120 | ?3.12 | ?7.24 | ?89.37 | ?0.00 | ?63.80 | ?72.86 |
| ?140 | ?2.87 | ?3.65 | ?92.99 | ?0.106 | ?81.75 | ?79.44 | |
| ?170 | ?0.81 | ?0.18 | ?98.56 | ?0.00 | ?99.10 | ?93.64 | |
| ?180 | ?0.23 | ?0.03 | ?98.95 | ?0.00 | ?99.85 | ?94.75 | |
Adopt with application example 1 identical way and be prepared into the catalyzer that contains 10-15%Ni with carrier 1, loading 40 milliliters of these catalyzer is in the single tube reactor of 20 millimeters of Ф in internal diameter, carry out one section gasoline hydrogenation reaction, the raw material of evaluate catalysts consists of full distillation gasoline, and (rerum natura is: bromine number 95%, the diene value is 18%), the liquid air speed of charging is 6.0hr
-1, 160 ℃ of hot(test)-spot temperatures.The bromine number of product is 70.96% behind the hydrogenation, and the diene value is 3.84%.Comparative example 3
Loading 40 milliliters of commercially available orchidization 8601 palladiums is that full distillation gasoline hydrogenation catalyst (rerum natura sees attached list 1) compares experiment (commercial catalyst contains 3%Pd equally, is carrier with the aluminum oxide), and appreciation condition is with application example 2.The hydrogenation result is a bromine number 49%, diene value 3.32%.
By relatively making nickel by oneself is that full distillation gasoline hydrogenation catalyst and commercially available palladium are full distillation gasoline hydrogenation catalyst, though homemade nickel catalyst active (being embodied by the diene value) is low slightly, it is high slightly to show as the diene value, but selectivity is higher than the commercial catalyst far away, bromine number reaches 70%, this result proves absolutely that this can reduce the production cost of gasoline hydrogenation catalyst significantly because the superiority of carrier makes nickel catalyst can compare favourably with palladium series catalyst fully.
Claims (8)
1. catalyst carrier for hydrgenating, this carrier comprises the silicon-dioxide of 100 weight parts and the tackiness agent of 2～55 weight parts, wherein: silicon-dioxide be selected between different types of diatomite, between different types of white carbon black or the mixture between diatomite and the white carbon black; Tackiness agent is selected from one or more in starch or its sex change product, Mierocrystalline cellulose or its sex change product, ethylene glycol, glycol ether and the polyvinyl alcohol.
2. according to the catalyst carrier for hydrgenating of claim 1, it is characterized in that: described silicon-dioxide comprises
(a) diatomite of most probable aperture 500～15000 dusts;
(b) the white carbon black of most probable aperture 100～150 dusts;
(a) and weight ratio (b) be 1: (0.1～1).
3. according to the catalyst carrier for hydrgenating of claim 1, it is characterized in that: the described various tackiness agents that are used alone or in combination are that the consumption of 100 weight parts is: starch or its sex change product 15～55 weight parts, Mierocrystalline cellulose or its sex change product 5～20 weight parts, ethylene glycol 40～50 weight parts, glycol ether 40～50 weight parts, polyvinyl alcohol 2～7 weight parts in the silicon-dioxide consumption.
4. according to the catalyst carrier for hydrgenating of claim 1, it is characterized in that: described carrier has following rerum natura: side pressure strength 4～13kgf/ grain, pore volume 0.4～1.5ml/g, specific surface area 10～220m
2/ g, total acidity 0.0000～0.13mmol n-Butyl Amine 99/g has broad peak, bimodal or multimodal pore size distribution.
5. as the preparation method of carrier as described among the claim 1-4 any, comprise the steps: described silicon-dioxide (a) and tackiness agent (b) mixing, the water that adds significant quantity, mediate aftershaping, then in 100-150 ℃ of oven dry, and in 800～1200 ℃ the carrier calcination was decomposed 2～5 hours.
6. preparing carriers method as claimed in claim 5 is characterized in that: by adjusting the blend ratio and the calcination temperature of diatomite and white carbon black, change the most probable aperture and the total acidity of carrier.
As carrier as described in one of claim 1～4 at preparation C
6Application in the catalyst for hydrogenation of above macromolecule hydrocarbon.
8. the application of carrier as claimed in claim 7 is characterized in that: described carrier is used for the hydrogenation of full distillation gasoline hydrogenation or the basic hexenoic aldehyde of 2-.
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|---|---|---|---|
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|---|---|---|---|
| CNB001249959A CN1150996C (en) | 2000-09-29 | 2000-09-29 | Hydrogenation catalyst carrier preparation method and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105330767A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
| US10225398B2 (en) | 2014-12-19 | 2019-03-05 | Unify Gmbh & Co. Kg | Telecommunication system and method for flexible control of the telecommunication system using a switching command issued by an application to a platform |
| US10525448B2 (en) | 2015-07-22 | 2020-01-07 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
-
2000
- 2000-09-29 CN CNB001249959A patent/CN1150996C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105330767A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
| CN105330768A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
| CN105330768B (en) * | 2014-06-13 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application |
| US10225398B2 (en) | 2014-12-19 | 2019-03-05 | Unify Gmbh & Co. Kg | Telecommunication system and method for flexible control of the telecommunication system using a switching command issued by an application to a platform |
| US10432787B2 (en) | 2014-12-19 | 2019-10-01 | Unify Gmbh & Co. Kg | Telecommunication system and method for flexible control of the telecommunication system using a switching command issued by an application to a platform |
| US10582048B2 (en) | 2014-12-19 | 2020-03-03 | Unify Gmbh & Co. Kg | Telecommunication system and method for flexible control of the telecommunication system using a switching command issued by an application to a platform |
| US10525448B2 (en) | 2015-07-22 | 2020-01-07 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
| US10864500B2 (en) | 2015-07-22 | 2020-12-15 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
| US12064749B2 (en) | 2015-07-22 | 2024-08-20 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
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|---|---|
| CN1150996C (en) | 2004-05-26 |
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