CN104258869B - The preparation method of the catalyst of neopentyl glycol is prepared in the special valeral liquid-phase hydrogenatin of a kind of hydroxyl - Google Patents
The preparation method of the catalyst of neopentyl glycol is prepared in the special valeral liquid-phase hydrogenatin of a kind of hydroxyl Download PDFInfo
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Abstract
The present invention relates to the special valeral liquid-phase hydrogenatin of a kind of hydroxyl and prepare the preparation method of the catalyst of neopentyl glycol. Press the total restatement of catalyst, catalyst composition comprises cupric oxide 20-65wt%, aluminium oxide 15-50wt%, zinc oxide 2-25wt%, tin oxide 0.1-5wt%, alkaline earth oxide 0.5-25wt%, titanium oxide and/or zirconia 0-20wt%. Cupric, aluminium, zinc, tin, alkaline earth metal compound are configured to that mixture aqueous solution and alkaline precipitating agent adopt and stream joins in the dispersion liquid that contains nano-oxide in proportion, through precipitation reaction, aging, filter, the step such as washing, dry, roasting, compressing tablet obtains preformed catalyst. Catalyst prepared by employing this method is not only active high, selectively good while preparing neopentyl glycol for the special valeral liquid-phase hydrogenatin of hydroxyl, promotes 1115 esters to transform, and has effectively improved the liquid-repellency of catalyst, and catalyst strength is high, good stability.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to the special valeral liquid-phase hydrogenatin of a kind of hydroxyl and prepare new penta 2The preparation method of the catalyst of alcohol.
Background technology
Neopentyl glycol (NPG) is a kind of important chemical intermediate, mainly for the production of powdery paints, poly-Ester resin, plasticizer, lube oil additive, water soluble alkyd resin etc., be widely used in automobile, weaving,The fields such as medicine, coating and oil; Also the selection that can be used for aromatic hydrocarbons and cycloalkane separates, and market prospects are wideWealthy.
The method of current industrial production neopentyl glycol has two kinds: sodium formate method and catalytic hydrogenation method. Sodium formateMethod is that the special valeral of hydroxyl (HPA) of formaldehyde and isobutylaldehyde generation with formaldehyde, health is occurred to intersect under base catalysisNi Zhaluo reaction, generates neopentyl glycol and a large amount of accessory substance sodium formate, aftertreatment technology complexity, and cost is high;Catalytic hydrogenation method is that the special valeral of hydroxyl of formaldehyde and isobutylaldehyde generation is carried out to catalytic hydrogenation, has product yieldHigh, accessory substance is few, technological process is short, product purity is high, low cost and other advantages, has significant advantage.
Because of the special valeral poor heat stability of hydroxyl, its Hydrogenation generally enters for neopentyl glycol process under liquid-phase conditionOK, in order to avoid the special valeral of hydroxyl resolves into isobutylaldehyde and formaldehyde in a large number and cause reaction selectivity poor. Liquid-phase hydrogenatinReaction requires high to catalyst liquid-repellency and working strength. That the special valeral hydrogenation catalyst of hydroxyl mainly contains is Ni-based,The noble metal catalysts such as copper base and palladium, compared with Ni-based, noble metal catalyst, copper-based catalysts is for HPAHydrogenation reaction has the advantages such as activity and selectivity is high, cost is low. The special valeral hydrogenation of hydroxyl of open report is urgedThe copper-based catalysts that agent is prepared mainly with the precipitation method is main, and catalyst needs to reduce before use.
Disclosed copper-chromium-the Mn catalyst of US4855515 need carry out while being used for HPA hydrogenation at 160-170 DEG C,The easy thermal decomposition of HPA causes NPG selectively low. The disclosed catalyst copper of CN102513107A source adopts sulfuric acidCopper, carrier adopts diatomite, and catalyst is the fine catalyst through pneumatic conveying drying, does not carry out compressing tablet before useOr extruded moulding, this catalyst can be in 150-170 DEG C of temperature range Hydrogenation for neopentyl glycol.The disclosed catalyst of CN102728370A consists of copper zinc-aluminium-titanium zirconium-hafnium-rhenium, and this catalyst has higherConversion ratio and selective, but in patent and intensity and the mechanical stability of not mentioned catalyst.CN102302937A disclose a kind of copper zinc-aluminium Mn catalyst for catalysis HPA Hydrogenation for NPG, this is urgedAgent activity is high, and good stability also has good hydrogenation ability to hydroxypivalyl hydroxypivalate simultaneously,Can tolerate the aldolisation catalyst such as a small amount of triethylamine, in this patent the intensity of not mentioned post catalyst reaction andFilling. The Cu-series catalyst of above-mentioned open report all adopts precipitation method preparation, but all not mentioned moulding in reportIntensity after mechanical stability when catalyst uses and use.
In prior art, for the Cu-series catalyst of hydrogenation reaction, need go through storage from being prepared into come into operationDeposit, the process such as filling, heating reduction, reaction, be subject to the effect of various inside or external force, it is for liquidWhen phase reaction, the actual working strength that also can make catalyst due to soaked with liquid, the reason such as swelling significantly underFall, cause catalyst in easily broken, the efflorescence of liquid-phase hydrogenatin system, cause reactor plugs, threaten industryDevice stable operation, affects catalyst life.
In prior art, adopt the anti-liquid ability of conventional Cu-series catalyst prepared of the precipitation method, catalyst is insteadAnswer easily broken, efflorescence in running in device, will greatly affect device stable operation. Therefore improve liquid phaseThe working strength of aldehyde hydrogenation copper series catalysts and stability are for ensureing that commercial plant stable operation is most important.
Summary of the invention
The invention provides the special valeral liquid-phase hydrogenatin of a kind of hydroxyl and prepare the preparation method of the catalyst of neopentyl glycol,Adopt the catalyst prepared of the method not only active high, selectively good, can promote 3-hydroxypivalic acid new penta 2Alcohol ester (1115 ester) transforms, and has excellent anti-liquid ability, and catalyst is gone through reduction, liquid-phase hydrogenatinPost reaction strength is high.
For achieving the above object, the technical solution used in the present invention is:
The special valeral Hydrogenation of hydroxyl, for a preparation method for the catalyst of neopentyl glycol, comprises the following steps:
(1) in reactor, add deionized water, then add nano-oxide, and stir, be made intoThe dispersion liquid of nano-oxide, described nano-oxide is selected from nano aluminium oxide, nano-titanium oxide and nanometer oxygenChange the one or two or more in zirconium;
(2) by copper-containing compound, aluminum contained compound, zinc compound, sn-containing compound and alkaline including earth metalCompound is dissolved in the water, and is configured to mixture aqueous solution, by mixture aqueous solution and alkaline precipitating agent whileSplash in the dispersion liquid of nano-oxide and react, control reaction system pH in course of reaction and be5.0-8.0, reaction finishes rear use alkaline precipitating agent regulation system pH to 7.0-9.0, then aging, is starchedMaterial;
(3) slurry filtered, wash, be dried, obtain filter cake;
(4) filter cake is carried out to roasting, fragmentation, compression molding, obtain catalyst.
The temperature of the dispersion liquid of step of the present invention (1) is 60-90 DEG C.
The temperature of the course of reaction of step of the present invention (2) is 60-90 DEG C, controls reaction system pH to be5.5-7.0, the time is 1-3h; Reaction finishes rear use alkaline precipitating agent system pH is adjusted to 7.5-8.5; AlwaysChange temperature is 60-90 DEG C, and ageing time is 1-3h.
The baking temperature of step of the present invention (3) is 100 DEG C, and be 12-24h drying time.
The sintering temperature of step of the present invention (4) is 350-900 DEG C, and roasting time is 2-8h.
Copper-containing compound of the present invention be copper nitrate, copper chloride and copper acetate one or both or manyKind; Aluminum contained compound is the one or two or more of aluminum nitrate, aluminium chloride and aluminium acetate; Zinc compoundFor the one or two or more of zinc nitrate, zinc chloride and zinc acetate; Sn-containing compound be selected from stannous acetate and/Or stannous chloride; Described alkaline earth metal compound is selected from nitrate, chloride and the acetate of magnesium, calcium and bariumOne or two or more.
The particle diameter < 100nm of nano-oxide of the present invention, preferably 1-50nm, more preferably 20-40nm.
Nano-oxide particle diameter needs within the specific limits, and particle diameter is too large, and nano-oxide is difficult in catalystBe evenly distributed, preformed catalyst stress in reduction process is concentrated and easily produces fine crack, soaks through liquidBubble rear catalyst is easily broken, causes catalyst strength to decline; Particle diameter is too little, nano-oxide be difficult for disperse andCost is high, can not further improve catalyst strength and liquid-repellency energy.
In dispersion liquid of the present invention, the solid content of nano-oxide is 0.1-5wt%, preferably 0.5-2wt%, withThe total restatement of dispersion liquid.
Alkaline precipitating agent of the present invention is sodium carbonate, potash, sodium acid carbonate, saleratus, hydroxideOne or two or more in sodium, potassium hydroxide, ammonium carbonate, carbonic hydroammonium and ammoniacal liquor.
The consumption of nano-oxide of the present invention accounts for 0.5～20wt% of catalyst gross weight, preferably1-10wt%, more preferably 2-5wt%.
When nano-oxide addition is too low, do not have enough nano-oxide induced precipitations to be accumulated into tight knotStructure, can not play structural re-enforcement, cannot improve catalyst liquid-repellency energy; Nano-oxide addition tooWhen many, nano-oxide can not fully be disperseed, and can affect on the contrary catalyst strength, causes catalyst anti-Liquid poor-performing.
Adopt catalyst composition prepared by method of the present invention to comprise: cupric oxide 20-65wt%, aluminium oxide15-50wt%, zinc oxide 2-25wt%, tin oxide 0.1-5wt%, in magnesia, calcium oxide and barium monoxideOne or two or more 0.5-25wt%, titanium oxide and/or zirconia 0-20wt%, by catalyst gross weightMeter.
Preferably, catalyst composition of the present invention comprises: cupric oxide 40-63wt%, aluminium oxide20-45wt%, zinc oxide 5-20wt%, tin oxide 0.2-3wt%, in magnesia, calcium oxide and barium monoxideOne or two or more 1-10wt%, one or both 0-10wt% in titanium oxide and zirconia, by urgingThe total restatement of agent.
More preferably, catalyst composition of the present invention comprises: cupric oxide 42-60wt%, aluminium oxide22-40wt%, zinc oxide 10-18wt%, tin oxide 0.5-2wt%, in magnesia, calcium oxide and barium monoxideOne or two or more 2-5wt%, one or both 0-5wt% in titanium oxide and zirconia, by urgingThe total restatement of agent.
Adding of tin improved decentralization and the stability of copper in catalyst, can promote turning of 1115 esters in raw materialChange.
Catalyst prepared by the method for the invention adds nano-oxide, induced precipitation in preparation processParticle forms closely, stable structure, and particle Interaction Force is strong, and nano-oxide plays structure increasingThe effect of strong agent, makes catalyst have high cohesive force, has reduced catalyst small splitting in reduction processThe generation of line, make catalyst through soaked with liquid, wash away and react after can broken, efflorescence, still have goodGood intensity.
Catalyst of the present invention need to carry out just possessing corresponding catalytic activity after reduction activation, for addingHydrogen is prepared NPG.
The method of the reduction activation of catalyst of the present invention comprises: the mist that keeps hydrogen and nitrogenVolume space velocity 300-1000h-1, first temperature of reactor being risen to 160-180 DEG C, constant temperature 1-2h removes catalysisThe mechanical water of agent absorption, then passes into containing volume fraction 5v%H2Hydrogen and the gaseous mixture of nitrogen also carry out in advanceFormer 1h, the ratio that progressively improves afterwards hydrogen in hydrogen and nitrogen mixture to 10v%, 20v%, 50v%,100%, control this process beds hot(test)-spot temperature and be no more than 220 DEG C, be finally warming up to 220 DEG C pureReductase 12-5h under nitrogen atmosphere, obtains the catalyst of reduction-state.
The catalyst of reduction-state of the present invention is used for HPA Hydrogenation for NPG, reaction pressure 3-5MPa,Reaction temperature is 120-140 DEG C, H2/ HPA mol ratio 2-20:1, catalyst treatment amount is 0.2-0.5gHPA/gcat/h。
Pressure of the present invention is relative pressure.
Catalyst of the present invention is prepared the process of neopentyl glycol for the special valeral liquid-phase hydrogenatin of hydroxyl, urgeAgent is not only active high, selectively good, and has good anti-liquid ability, and icp analysis shows hydrogenation liquidMiddle without copper loss, post catalyst reaction profile is complete, breakage rate is low, side pressure strength is high, can promote 1115Ester transforms.
Detailed description of the invention
Below in conjunction with embodiment, the inventive method is described in detail, but be not limited to embodiment.
The side pressure strength of catalyst adopts granule strength tester to measure, catalyst hydrogenation liquid(20wt%NPG+40wt% methyl alcohol+40wt% water) soaks protection, in case catalyst is oxidized, measures 40Grain post catalyst reaction side pressure strength, gets its mean value.
In hydrogenation liquid, content of copper ion adopts inductively coupled plasma emission spectrometer (ICP) to measure.
Embodiment 1
In reactor, add 3kg water, and add the nano-titanium oxide of 19.5g particle diameter at 20-40nm, stir allEven. By 384.1g copper nitrate, 619.3g aluminum nitrate, 90.8g zinc nitrate, 2.92g stannous chloride, 51.4gCalcium nitrate is dissolved in 2.7kg water and is made into mixed-salt aqueous solution, by the carbon that is made into 20wt% soluble in water sodium carbonateAcid sodium solution, is heated to 60 DEG C by two kinds of solution respectively. Adopt the method for co-precipitation, by two kinds of solution simultaneouslySplash in reactor, control 60 DEG C of precipitation process temperature in the kettle, system pH and be 6.0, the reaction time is 1h.After saline solution to be mixed adds, adopt sodium carbonate liquor that system pH is adjusted to 7.5, and aging at 70 DEG C3h, then filter, wash and by filter cake at 110 DEG C of dry 12h, and in 350 DEG C of roasting 3h, carry out fragmentationAfter be pressed into 5*5mm cylinder (diameter 5mm, height 5mm) catalyst, obtain catalyst A.
Catalyst reduction: catalyst A is loaded in fixed bed hydrogenation reactor to loaded catalyst200ml. Catalyst reduces before using under nitrogen and hydrogen mixed gas, keeps mixing in reduction processGas volume air speed 300h-1, first temperature of reactor is risen to 160 DEG C of constant temperature 2h Removal of catalysts absorptionMechanical water, then passes into containing volume fraction 5v%H2Hydrogen and the gaseous mixture of nitrogen carry out prereduction 1h, itAfter progressively improve hydrogen in hydrogen and nitrogen mixture ratio to 10v%, 20v%, 50v%, 100%,Control this process beds hot(test)-spot temperature and be no more than 220 DEG C, be finally warming up to 220 DEG C under pure hydrogen atmosphereReduction 3h.
Hydrogenating materials consist of 20wt%HPA, 0.7wt%1115 ester, 38.5wt% methyl alcohol, 40wt% water andOther component (formaldehyde, isobutylaldehyde etc.) of 0.8wt%, at pressure 4Mpa, 140 DEG C of temperature, H2/HPAMol ratio 20:1, catalyst treatment amount is 0.4gHPA/gcatUnder the condition of/h, react. Get and add at interval of 24hHydrogen liquid is also measured content of copper ion in hydrogenation liquid. After reaction 500h, catalyst is removed and uses hole from reactorThe stainless steel sub-sieve of footpath 4mm sieves catalyst, and calculates the catalyst granules of particle diameter < 4mmQuality accounts for the ratio of catalyst gross mass, using this as catalyst breakage rate. Adopt granule strength tester to surveyDetermine post catalyst reaction side pressure strength. In hydrogenation reaction result and hydrogenation liquid, average copper ion concentration is in table 1.Before and after reaction, catalyst contrasts in table 2.
Embodiment 2
In reactor, add 3kg water, and add the nano-titanium oxide of 11.7g particle diameter at 20-30nm, stir allEven. By 530.4g copper nitrate, 358.6g aluminum nitrate, 90.8g zinc nitrate, 71.8g magnesium nitrate, 11.7g chlorinationYa Xi is dissolved in 2.5kg water and is made into mixed-salt aqueous solution, by the carbonic acid that is made into 20wt% soluble in water sodium carbonateSodium solution, is heated to 80 DEG C by two kinds of solution respectively. Adopt the method for co-precipitation, two kinds of solution are dripped simultaneouslyEnter in reactor, control 80 DEG C of precipitation process temperature in the kettle, system pH and be 5.5, the reaction time is 1.5h.After saline solution to be mixed adds, adopt sodium carbonate liquor that system pH is adjusted to 7.0, and continue at 70 DEG CAging 3h, then filter, wash and by filter cake at 110 DEG C of dry 12h, and in 500 DEG C of roasting 3h, will roastAfter catalyst breakage after burning, be pressed into 5*5mm cylinder (diameter 5mm, height 5mm) catalyst,Obtain catalyst B.
All the other conditions are with reference to embodiment 1.
Embodiment 3
In reactor, add 3kg water, and add the nano zircite of 15.6g particle diameter at 20-30nm, stir allEven. By 439.0g copper nitrate, 358.6g aluminum nitrate, 181.6g zinc nitrate, 33.2g barium nitrate, 5.84g chlorineChange sub-tin and be dissolved in 2.5kg water and configure mixed-salt aqueous solution, by the carbon that is made into 20wt% soluble in water sodium carbonateAcid sodium solution, is heated to 60 DEG C by two kinds of solution respectively. Adopt the method for co-precipitation, by two kinds of solution simultaneouslySplash in reactor, control 60 DEG C of precipitation process temperature in the kettle, system pH and be 5.5, the reaction time is 2h.After saline solution to be mixed adds, adopt sodium carbonate liquor that system pH is adjusted to 7.7, and continue at 80 DEG CAging 3h, then filter, wash and by filter cake at 110 DEG C of dry 12h, and in 650 DEG C of roasting 3h, will roastAfter catalyst breakage after burning, be pressed into 5*5mm cylinder (diameter 5mm, height 5mm) catalyst,Obtain catalyst C.
All the other conditions are with reference to embodiment 1.
Embodiment 4
In reactor, add 3kg water, and add the nano-titanium oxide of 9.75g particle diameter at 20-40nm, stir allEven. By 457.3g copper nitrate, 488.9g aluminum nitrate, 136.2g zinc nitrate, 32.8g calcium nitrate, 2.92g chlorineChange sub-tin and be dissolved in 2.7kg water and be made into mixed-salt aqueous solution, by the carbon that is made into 20wt% soluble in water sodium carbonateAcid sodium solution, is heated to 85 DEG C by two kinds of solution respectively. Adopt the method for co-precipitation, by two kinds of solution simultaneouslySplash in reactor, control 85 DEG C of precipitation process temperature in the kettle, system pH and be 6.7, the reaction time is 1h.After saline solution to be mixed adds, adopt sodium carbonate liquor that system pH is adjusted to 8.0, and continue at 85 DEG CAging 3h, then filter, wash and by filter cake at 110 DEG C of dry 12h, and in 600 DEG C of roasting 3h, will roastAfter catalyst breakage after burning, be pressed into 5*5mm cylinder (diameter 5mm, height 5mm) catalyst,Obtain catalyst D.
All the other conditions are with reference to embodiment 1.
Embodiment 5
In reactor, add 3kg water, and add 9.75g particle diameter to exist at 20-30nm nano-titanium oxide, particle diameterThe 9.75g nano zircite of 20-40nm, stirs. By 439.0g copper nitrate, 358.6g aluminum nitrate,195.2g zinc nitrate, 28.5g calcium nitrate, 5.84g stannous chloride are made into mixed-salt aqueous solution in 2.5kg water,By the sodium carbonate liquor that is made into 20wt% soluble in water sodium carbonate, respectively two kinds of solution are heated to 70 DEG C. AdoptBy the method for co-precipitation, two kinds of solution are splashed in reactor simultaneously, control precipitation process temperature in the kettle70 DEG C, system pH are 6.5, the reaction time is 2.5h. After saline solution to be mixed adds, adopt sodium carbonateSolution is adjusted to 8.5 by system pH, and continues aging 3h at 90 DEG C, then filters, washs and filter cake is existed110 DEG C of dry 12h, and in 700 DEG C of roasting 3h, will after the catalyst breakage after roasting, be pressed into 5*5mm cylinderBody (diameter 5mm, height 5mm) catalyst, obtains catalyst E.
All the other conditions are with reference to embodiment 1.
Embodiment 6
In reactor, add 3kg water, and add the nano aluminium oxide of 19.5g particle diameter at 20-30nm, stir allEven. By 647.8g copper nitrate, 350.4g aluminum nitrate, 136.2g zinc nitrate, 16.6g barium nitrate, 5.84g chlorineChange sub-tin and be dissolved in 2.8kg water and be made into mixed-salt aqueous solution, by the carbon that is made into 20wt% soluble in water sodium carbonateAcid sodium solution, is heated to 60 DEG C by two kinds of solution respectively. Adopt the method for co-precipitation, by two kinds of solution simultaneouslySplash in reactor, control 60 DEG C of precipitation process temperature in the kettle, system pH and be 6.5, the reaction time is 2h.After saline solution to be mixed adds, adopt sodium carbonate liquor that system pH is adjusted to 7.5, and continue at 70 DEG CAging 3h, then filter, wash and by filter cake at 110 DEG C of dry 12h, and in 550 DEG C of roasting 3h, will roastAfter catalyst breakage after burning, be pressed into 5*5mm cylinder (diameter 5mm, height 5mm) catalyst,Obtain catalyst F.
All the other conditions are with reference in embodiment 1.
Comparative example 1
548.7g copper nitrate, 488.9g aluminum nitrate, 90.8g zinc nitrate are dissolved in 2.6kg water and are made into salt-mixtureThe aqueous solution, by the sodium carbonate liquor that is made into 20wt% soluble in water sodium carbonate, is heated to two kinds of solution respectively70 DEG C. In stillpot, add 3000g water. The method that adopts co-precipitation splashes into reaction by two kinds of solution simultaneouslyIn still, control 70 DEG C of precipitation process temperature in the kettle, system pH and be 6.0, the reaction time is 1h. Adopt carbonic acidSodium solution is adjusted to 8.5 by system pH, and at 80 DEG C aging 2h, then filter, wash and filter cake is existed110 DEG C of dry 12h, and in 500 DEG C of roasting 3h, will after the catalyst breakage after roasting, be pressed into 5*5mm cylinderBody (diameter 5mm, height 5mm) catalyst, obtains catalyst G.
All the other conditions are with reference to embodiment 1.
Comparative example 2
In reactor, add 3kg water, by 439.0g copper nitrate, 358.6g aluminum nitrate, 181.6g zinc nitrate,33.2g barium nitrate, 5.84g stannous chloride are dissolved in 2.5kg water and are made into mixed-salt aqueous solution, and sodium carbonate is dissolved inIn water, be made into the sodium carbonate liquor of 20wt%, respectively two kinds of solution be heated to 80 DEG C. Adopt the side of co-precipitationMethod splashes into two kinds of solution in reactor simultaneously, and 80 DEG C of control precipitation process temperature in the kettle, system pH are6.5, the reaction time is 1h. After saline solution to be mixed adds, adopt sodium carbonate liquor that system pH is adjusted to7.5, and at 80 DEG C, continue to add the nano zircite of 20g particle diameter at 20-40nm after aging 3h, thenFilter, washing and by filter cake at 110 DEG C of dry 12h, and in 700 DEG C of roasting 3h, by the catalyst after roastingAfter fragmentation, be pressed into 5*5mm cylinder (diameter 5mm, height 5mm) catalyst, obtain catalyst H.
All the other conditions are with reference to embodiment 1.
Comparative example 3
In reactor, add 3kg water, and add the nano-titanium oxide of 91.6g particle diameter at 100-300nm, stirEvenly. By 384.1g copper nitrate, 358.6g aluminum nitrate, 90.8g zinc nitrate, 28.5g calcium nitrate, 2.92g chlorineChange sub-tin and be dissolved in 2.4kg water and be made into mixed-salt aqueous solution, by the carbon that is made into 20wt% soluble in water sodium carbonateAcid sodium solution, is heated to 80 DEG C by two kinds of solution respectively. Adopt the method for co-precipitation, by two kinds of solution simultaneouslySplash in reactor, control 80 DEG C of precipitation process temperature in the kettle, system pH and be 5.5, the reaction time is1h. After saline solution to be mixed adds, adopt sodium carbonate liquor that system pH is adjusted to 7.0, and at 70 DEG CContinue aging 3h, then filter, wash and by filter cake at 110 DEG C of dry 12h, and in 500 DEG C of roasting 3h,To after the catalyst breakage after roasting, be pressed into 5*5mm cylinder (diameter 5mm, height 5mm) catalyst,Obtain catalyst I.
All the other conditions are with reference to embodiment 1.
Average copper ion concentration in table 1 hydrogenation reaction result and hydrogenation liquid
Note: " not detecting " represents average copper ion concentration < 0.1 μ g/ml in hydrogenation liquid
Catalyst contrast before and after table 2 reaction
Even * 1 catalyst breakage applied force of N/ Ke Shi catalyst strength unit
From table 1, table 2, while using catalyst A to catalyst F, copper in hydrogenation liquid, do not detected,Complete and the side pressure strength of post catalyst reaction is more than 45N/ grain; And comparative example 1 is to catalysis described in comparative example 3Agent, post catalyst reaction is broken seriously, side pressure strength is low, and there is efflorescence so that cannot survey in catalyst G and IIts side pressure strength, icp analysis shows that in hydrogenation liquid, copper content is higher, illustrates that catalyst has obvious loss. AndAnd, catalyst A to catalyst F can effectively promote 1115 esters transform.
Claims (16)
1. the special valeral Hydrogenation of hydroxyl, for a preparation method for the catalyst of neopentyl glycol, comprises the following steps:
(1) in reactor, add deionized water, then add nano-oxide, and stir, be made intoThe dispersion liquid of nano-oxide, described nano-oxide is selected from nano aluminium oxide, nano-titanium oxide and nanometer oxygenChange the one or two or more in zirconium;
(2) by copper-containing compound, aluminum contained compound, zinc compound, sn-containing compound and alkaline including earth metalCompound is dissolved in the water, and is configured to mixture aqueous solution, by mixture aqueous solution and alkaline precipitating agent whileSplash in the dispersion liquid of nano-oxide and react, controlling reaction system pH in course of reaction is 5.0-8.0,Reaction finishes rear use alkaline precipitating agent regulation system pH to 7.0-9.0, then aging, obtains slurry;
(3) slurry filtered, wash, be dried, obtain filter cake;
(4) filter cake is carried out to roasting, fragmentation, compression molding, obtain catalyst;
The particle diameter < 100nm of described nano-oxide, the consumption of described nano-oxide accounts for catalyst gross weight0.5～20wt％。
2. method according to claim 1, is characterized in that, the dispersion liquid of described step (1)Temperature is 60-90 DEG C.
3. method according to claim 1, is characterized in that, the course of reaction of described step (2)Temperature be 60-90 DEG C, controlling reaction system pH is 5.5-7.0, the time is 1-3h; Reaction finishes rear useSystem pH is adjusted to 7.5-8.5 by alkaline precipitating agent; Aging temperature is 60-90 DEG C, and ageing time is 1-3h.
4. method according to claim 1, is characterized in that, the baking temperature of described step (3)Be 100 DEG C, be 12-24h drying time.
5. method according to claim 1, is characterized in that, the sintering temperature of described step (4)For 350-900 DEG C, roasting time is 2-8h.
6. method according to claim 1, is characterized in that, described copper-containing compound be copper nitrate,The one or two or more of copper chloride and copper acetate; Aluminum contained compound is aluminum nitrate, aluminium chloride and aluminium acetateOne or two or more; Zinc compound be zinc nitrate, zinc chloride and zinc acetate one or both orMultiple; Sn-containing compound is selected from stannous acetate and/or stannous chloride; Described alkaline earth metal compound be selected from magnesium,The one or two or more of nitrate, chloride and the acetate of calcium and barium.
7. method according to claim 1, is characterized in that, the particle diameter of described nano-oxide is1-50nm。
8. method according to claim 7, is characterized in that, the particle diameter of described nano-oxide is20-40nm。
9. method according to claim 1, is characterized in that, nano-oxide in described dispersion liquidSolid content is 0.1-5wt%, with the total restatement of dispersion liquid.
10. method according to claim 9, is characterized in that, nano-oxide in described dispersion liquidSolid content be 0.5-2wt%, with the total restatement of dispersion liquid.
11. methods according to claim 1, is characterized in that, described alkaline precipitating agent be sodium carbonate,Potash, sodium acid carbonate, saleratus, NaOH, potassium hydroxide, ammonium carbonate, carbonic hydroammonium and ammoniaOne or two or more in water.
12. methods according to claim 1, is characterized in that, the consumption of described nano-oxide accounts forThe 1-10wt% of catalyst gross weight.
13. methods according to claim 12, is characterized in that, the consumption of described nano-oxide accounts forThe 2-5wt% of catalyst gross weight.
14. catalyst that make according to the method described in claim 1-13 any one, is characterized in that, pressThe total restatement of catalyst, catalyst composition comprises: cupric oxide 20-65wt%, aluminium oxide 15-50wt%, oxidationZinc 2-25wt%, tin oxide 0.1-5wt%, one or both in magnesia, calcium oxide and barium monoxide or manyPlant 0.5-25wt%, titanium oxide and/or zirconia 0-20wt%.
15. catalyst according to claim 14, is characterized in that, by the total restatement of catalyst, catalysisAgent composition comprises: cupric oxide 40-63wt%, aluminium oxide 20-45wt%, zinc oxide 5-20wt%, tin oxide0.2-3wt%, the one or two or more 1-10wt% in magnesia, calcium oxide and barium monoxide, titanium oxideWith one or both 0-10wt% in zirconia.
16. catalyst according to claim 15, is characterized in that, by the total restatement of catalyst, catalysisAgent composition comprises: cupric oxide 42-60wt%, aluminium oxide 22-40wt%, zinc oxide 10-18wt%, tin oxide0.5-2wt%, the one or two or more 2-5wt% in magnesia, calcium oxide and barium monoxide, titanium oxide andOne or both 0-5wt% in zirconia.
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| CN106582660B (en) * | 2016-12-05 | 2019-04-23 | 万华化学集团股份有限公司 | A kind of aldehyde add hydrogen prepare alcohol catalyst preparation method |
| CN108187689B (en) * | 2016-12-08 | 2021-01-15 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method thereof and method for preparing 1,2-pentanediol |
| CN109482192B (en) * | 2018-11-30 | 2021-09-07 | 万华化学集团股份有限公司 | Preparation method and application of catalyst for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation |
| CN111874940B (en) * | 2020-07-13 | 2022-12-06 | 滁州学院 | Preparation method and application of tubular tin dioxide and carbon-coated tubular tin dioxide nanocomposite |
| CN113926460B (en) * | 2021-11-23 | 2022-05-27 | 鲁西催化剂有限公司 | Hydroxypivalaldehyde hydrogenation catalyst, and preparation method and application thereof |
| CN115894169B (en) * | 2022-07-28 | 2024-01-30 | 沾化瑜凯新材料科技有限公司 | Production process of high-purity neopentyl glycol |
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