CN101396665A - Fixed bed Raney catalyst, preparation method and modification method thereof - Google Patents
Fixed bed Raney catalyst, preparation method and modification method thereof Download PDFInfo
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- CN101396665A CN101396665A CNA2007102018654A CN200710201865A CN101396665A CN 101396665 A CN101396665 A CN 101396665A CN A2007102018654 A CNA2007102018654 A CN A2007102018654A CN 200710201865 A CN200710201865 A CN 200710201865A CN 101396665 A CN101396665 A CN 101396665A
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Abstract
The invention discloses a fixed bed Raney catalyst, a preparation method thereof and a modification method thereof. The fixed bed Raney catalyst is prepared by processing foam metal, aluminum powder, an inorganic binder, an organic binder, water and an alloy element. The foam metal is foam Ni, form Co, foam Pt or foam Pd. The alloy element is 0-1wt percent of the foam meal and can be one or the mixture of a plurality of Mg, Ca, Sr, Ba, Cr, Mn, Fe, Cu, Zn, Si, Zr, La, Ce, Mo and W. The fixed bed Raney catalyst has the advantages of high catalytic activity, strong mechanical strength and long service life and can be applied to the borohydride hydrolysis hydrogen preparation field.
Description
Technical field
The present invention relates to a kind of catalyst, be specifically related to a kind of fixed bed raney catalyst.The invention still further relates to the preparation method of said fixing bed Reni catalyst and utilize precious metal element to its modification to improve its active method.
Background technology
Binhong Liu etc. reported catalysis sodium borohydride hydrolysis generation hydrogen such as adopting Raney's nickel, thunder Buddhist nun cobalt and Raney's nickel cobalt method (Journal of Alloys and Compounds, 415,2006,288-293).Reaction equation is as follows:
NaBH
4+2H
2O→4H
2+NaBO
2
In this report, utilize catalysis sodium borohydride decomposing hydrogen-productions such as powder Raney's nickel, powder thunder Buddhist nun cobalt.Powdered Reni catalyst runs off in actual applications easily, has increased to generate the difficulty of hydrogen and catalyst separation, thereby has made its application be restricted.In being the patent application of CN 1774390A, publication number utilizes the raney ni catalysis producing hydrogen by decomposing sodium borohydride, it adopts two kinds of methods to solve the losing issue of powder Raney's nickel, first method is that Raney's nickel is attached on the magnet of catalyst fixed cell, is immersed in the water; Second method is with polyurethane foam Raney's nickel to be fixed on the nickel screen, is stored in the distilled water then.Above-mentioned two kinds of methods all make reaction unit more complicated, when reactant liquor flows through Raney's nickel catalyst of fixed bed with big flow velocity, the easy fragmentation of catalyst comes off, and be reduced to 2wt% or when following when the concentration of boron hydride, the generating rate of hydrogen reduces very fast, thereby its application is restricted.
Publication number be CN1283359C patent disclosure the skeleton metallic catalyst used of a kind of fixed bed hydrogenation and preparation method thereof, this catalyst is the alloy powder by one or more metallic elements in al and ni, cobalt, copper, the iron, the jelly of inorganic matter preparations such as employing boehmite is as adhesive, natural or synthetic organic substance such as sesbania powder, carboxymethyl cellulose is as duct template agent, directly kneading, moulding, roasting, and make through the caustic solution activation.Alloy powder in the embodiment all is nickel alumin(i)um alloy powder, and the catalyst behind the roast only contains a kind of composition of nickel, so there is the low defective of mechanical strength.
Summary of the invention
The purpose of this invention is to provide a kind of advantages of high catalytic activity that has, the stronger mechanical strength and the fixed bed raney catalyst in long service life.
A further object of the present invention provides the preparation method of said fixing bed Reni catalyst.
Another object of the present invention provide utilize precious metal element to the modification of said fixing bed Reni catalyst to improve its active method.
For achieving the above object, the present inventor has carried out a large amount of research and performing creative labour on the basis of existing technology, developed and had advantages of high catalytic activity, the stronger mechanical strength and the fixed bed raney catalyst in long service life, its preparation method and further its active method that improves have obtained unexpected effect.Described fixed bed raney catalyst is to be formed by the following components by part by weight processing and preparing:
Foam metal 20-80, aluminium powder 20-80, inorganic binder 0-25, organic binder bond 0-5.0, water 20-50 and alloying element; Be preferably: foam metal 20-80, aluminium powder 20-80, inorganic binder 525, organic binder bond 0.4-5.0, water 20-50 and alloying element; Described foam metal is nickel foam, foam cobalt, foam platinum or foam palladium;
Described alloying element is the 0-1wt% of foam metal, and it can be a kind of or wherein several mixture among Mg, Ca, Sr, Ba, Cr, Mn, Fe, Cu, Zn, Si, Zr, La, Ce, Mo, the W; The granularity of described aluminium powder is 40-400 orders.
Described inorganic binder is boehmite and/or alumina gel; Described organic binder bond is a kind of or wherein several mixture in sesbania powder, polyethylene, starch, methylcellulose, carboxymethyl cellulose, polyacrylamide, the cyclodextrin.
A kind of preparation method of described fixed bed raney catalyst comprises the steps:
1. step prepares mixed slurry
In inorganic binder, add glue and mix, regulate its pH value to 25, add aluminium powder, organic binder bond, water and alloying element again, mix, get mixed slurry;
2. step prepares fixed bed raney catalyst
Step mixed slurry 1. is coated in vacuum coating installation on the foam metal, destarch, drying, roasting, activation is fixed a Reni catalyst.
Described glue is salpeter solution, hydrochloric acid solution or sulfuric acid solution,
Described foam metal pre-treating method is: foam metal is flooded 524h in 5-15wt% dilute acid soln, take out, water flushing back moves in the absolute ethyl alcohol soaks, take out, and be the empty dry 5-12h of vacuum drying under the 40-80 ℃ of condition in temperature.
Described destarch is destarch 0.5-1h in centrifuge, and the destarch rotating speed of described centrifuge is 200-1800 rev/min.
Described drying is dry 8-15h under the vacuum 50-90 ℃ condition.
Described roasting is under protective atmosphere, is roasting 1-5h under the 600-1700 ℃ of condition in temperature, and temperature is preferably 600-800 ℃.
Described protective atmosphere is nitrogen or inert gas.
Described activation is to be under the 70-90 ℃ of condition in temperature, leaches 1-48h in alkaline solution; Described alkaline solution is NaOH or the potassium hydroxide solution of 5-40wt%.
A kind of method that increases the fixed bed raney catalyst activity, described method are to immersion the aqueous solution that adds noble metal acid or noble metal hydrochlorate in the alkaline solution of fixed bed raney catalyst to be arranged, after mixing, again to wherein adding reducing agent; Wherein the content of the precious metal element in noble metal acid or the noble metal hydrochlorate is the 0.05-0.1wt% of fixed bed raney catalyst, and the consumption of reducing agent is noble metal acid or noble metal hydrochlorate weight 2-20 a times.
Described noble metal acid or noble metal hydrochlorate are a kind of or wherein several mixture in Pt acid or its salt, Ru salt, Rh acid, Pd salt or the Au acid.Described Pt acid or its salt are chloroplatinic acid, platinic sodium chloride or potassium chloroplatinate; Ru salt is ruthenium trichloride; Rh acid is the acid of chlorine rhodium; Pd salt is palladium bichloride; Au acid is gold chloride.Described reducing agent is that hydrazine or percentage by weight are the sodium borohydride solution of 2-10%.
Fixed bed raney catalyst of the present invention is that mixed slurry is coated in vacuum coating installation on the foam metal, again through destarch, drying, roasting, activation and get.Described mixed slurry is that aluminium powder water is mixed, and preferred mixed slurry also comprises a kind of in inorganic binder, organic binder bond and the alloying element or two kinds or three's mixture wherein.Utilize this mixed slurry that foam metal is applied in the process of back preparation fixed bed raney catalyst, comprise destarch, roasting and activation step.
Described destarch step is destarch in centrifuge, and the destarch rotating speed of centrifuge is 200-1800 rev/min, can remove the mixed slurry in the foam metal micropore like this; And roasting process can be burnt organic binder bond, thereby generates macroporous structure in fixed bed raney catalyst; The part inorganic binder is converted into inert substance a-Al2O3 in the roasting process simultaneously, and it can make thunder damping alloy sintering together, plays the effect of further curing, thereby has improved the mechanical strength of catalyst greatly.Activation step is to be under the 70-90 ℃ of condition with moulding thunder damping alloy in temperature, leaches 1-48h again in alkaline solution, can with unconverted in the moulding thunder damping alloy be a-Al
2O
3The Al element remove, and in moulding thunder damping alloy, form a large amount of holes, increased the specific area of catalyst, improved activity of such catalysts.Because nickel foam, foam cobalt, foam platinum or foam palladium had both served as the nickel in the catalyst alloy, cobalt, platinum or palladium source, had played the effect of carrier simultaneously, so the fixed bed raney catalyst that is prepared into has higher mechanical strength and high reaction activity and high.Simultaneously, can before coating, foam metal be prepared into shape required in the actual needs and size according to actual needs, omit the step of shaping of catalyst, make that the preparation technology of Raney's nickel catalyst of fixed bed is simpler, reduce cost.Alloying element in the mixed slurry has played the effect of non-spontaneous core, make grain refinement, the particle activity and the intensity of catalyst obtain balance preferably, thereby have both effectively improved the activity of fixed bed raney catalyst, the life-span of having improved fixed bed raney catalyst again.
In order further to improve activity of such catalysts, the present inventor has also carried out study on the modification to the fixed bed raney catalyst of preparation.Find through great deal of experimental, to immersion the aqueous solution that adds noble metal acid or salt in the alkaline solution of fixed bed raney catalyst is arranged, after mixing, again to wherein adding reducing agent, noble metal acid or salt can be reduced to superfine metal particle, load on the surface of fixed bed raney catalyst.Be deposited on the metal particle on Raney's nickel catalyst surface and the hydrolysis of Raney's nickel concerted catalysis boron hydride, accelerated the reaction rate of boron hydride, especially make the decomposition rate of boron hydride solution of low concentration (0-5wt%) obviously accelerate.
Therefore, fixed bed raney catalyst provided by the invention has compared with prior art been obtained unexpected effect, has obvious improvement.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Mixed slurry comprises following component: water 30g, granularity are 40-100 purpose aluminium powder 70g, organic binder bond sesbania powder 20g, inorganic binder boehmite 5g, alloying element Mg0.02g, Ca0.05g, Sr0.06g, Ba0.07g, Cr0.08g, Mn0.12g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Adding glue nitric acid in the inorganic binder boehmite, to make the pH value be 3, mixes, and makes gluey inorganic binder; Water, aluminium powder, organic binder bond, gluey inorganic binder, alloying element are mixed, promptly get mixed slurry;
2. step prepares fixed bed raney catalyst
The 40g nickel foam is put into the 10wt% dilute hydrochloric acid solution fully stir, dipping 10h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 50 ℃ of conditions vacuum drying 10h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned nickel foam is carried out pasting, and the nickel foam after the pasting is placed centrifuge destarch 0.8h, and the destarch rotating speed of centrifuge is 1000 rev/mins; With the vacuum drying 12h under 80 ℃ of conditions of the nickel foam after the destarch, again under nitrogen protection, be roasting 5 hours under 680 ℃ of conditions in temperature, moulding thunder damping alloy;
Is under 75 ℃ of conditions with moulding thunder damping alloy in temperature, leaches 40h in the sodium hydroxide solution of 30wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds chloroplatinic acid in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, again to wherein adding hydrazine reducing agent; Wherein the platinum constituent content of chloroplatinic acid is the 0.08wt% of fixed bed raney catalyst, and the consumption of hydrazine reducing agent is 10 times of chloroplatinic acid weight.
Embodiment 2
Mixed slurry comprises following component: water 20g, granularity are 80-200 purpose aluminium powder 50g, organic binder bond starch 5.0g, inorganic binder alumina gel 22g, alloying element Sr0.02g, Ba0.05g, Cu0.04g, Zr0.08g, La0.12g, Ce0.03g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Adding glue sulfuric acid in the inorganic binder alumina gel, to make the pH value be 2, mixes, and makes gluey inorganic binder; Water, aluminium powder, alloying element, organic binder bond, gluey inorganic binder are mixed, promptly get mixed slurry;
2. step prepares fixed bed raney catalyst
80g foam cobalt is put into the 5wt% dilute hydrochloric acid solution fully stir, dipping 24h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 70 ℃ of conditions vacuum drying 8h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned foam cobalt is carried out pasting, and the foam cobalt after the pasting is placed centrifuge destarch 0.9h, and the destarch rotating speed of centrifuge is 500 rev/mins; With the vacuum drying 15h under 70 ℃ of conditions of the foam cobalt after the destarch, under the helium protective atmosphere, be that roasting got moulding thunder damping alloy after 3 hours under 900 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 80 ℃ of conditions in temperature, leaches 20h in the sodium hydroxide solution of 5wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds platinic sodium chloride in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, again to wherein adding reducing agent, be weight percentage 5% sodium borohydride solution of described reducing agent; Wherein the platinum constituent content of platinic sodium chloride is the 0.05wt% of fixed bed raney catalyst, and the consumption of borane reducing agent sodium hydride is 15 times of platinic sodium chloride weight.
Embodiment 3
Mixed slurry comprises following component: water 40g, granularity are 200-400 purpose aluminium powder 40g, organic binder bond methylcellulose 1g, inorganic binder boehmite 15g, alloying element Mg0.01g, Ba0.02g, Cr0.05g, Mn0.03g, Si0.01g, Zr0.02g, Mo0.03g, W0.02g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Adding glue hydrochloric acid in the inorganic binder boehmite, to make the pH value be 4, mixes, and makes gluey inorganic binder; Water, aluminium powder, alloying element, organic binder bond, gluey inorganic binder are mixed, promptly get mixed slurry;
2. step prepares fixed bed raney catalyst
30g foam platinum is put into the 15wt% dilution heat of sulfuric acid fully stir, dipping 5h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 40 ℃ of conditions vacuum drying 12h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned foam platinum is carried out pasting, and the foam platinum after the pasting is placed centrifuge destarch 1h, and the destarch rotating speed of centrifuge is 200 rev/mins; With the vacuum drying 10h under 85 ℃ of conditions of the foam platinum after the destarch, under the neon protective atmosphere, be that roasting got moulding thunder damping alloy after 4 hours under 600 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 70 ℃ of conditions in temperature, leaches 1h in the sodium hydroxide solution of 40wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds potassium chloroplatinate in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, again to wherein adding reducing agent, be weight percentage 2% sodium borohydride solution of described reducing agent; Wherein the platinum constituent content of potassium chloroplatinate is the 0.1wt% of fixed bed raney catalyst, and the consumption of borane reducing agent sodium hydride is 20 times of potassium chloroplatinate weight.
Embodiment 4
Mixed slurry comprises following component: water 24g, granularity are 300-350 purpose aluminium powder 80g, organic binder bond polyethylene 0.4g, inorganic binder boehmite 10g and alumina gel 10g, alloying element Mg0.06g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Adding glue nitric acid in inorganic binder boehmite and the alumina gel, to make the pH value be 2.5, mixes, and makes gluey inorganic binder; Water, aluminium powder, alloying element, organic binder bond, gluey inorganic binder are mixed, promptly get mixed slurry;
2. step prepares fixed bed raney catalyst
60g foam palladium is put into the 10wt% dilute nitric acid solution fully stir, dipping 15h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 80 ℃ of conditions vacuum drying 5h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned foam palladium is carried out pasting, and the foam palladium after the pasting is placed centrifuge destarch 0.5h, and the destarch rotating speed of centrifuge is 1800 rev/mins; With the vacuum drying 16h under 60 ℃ of conditions of the foam palladium after the destarch, under argon shield atmosphere, be that roasting got moulding thunder damping alloy after 0.1 hour under 1000 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 90 ℃ of conditions in temperature, leaches 10h in the potassium hydroxide solution of 20wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds ruthenium trichloride in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, again to wherein adding reducing agent, be weight percentage 10% sodium borohydride solution of described reducing agent; Wherein the ruthenium element content of ruthenium trichloride is the 0.06wt% of fixed bed raney catalyst, and the consumption of borane reducing agent sodium hydride is 2 times of ruthenium trichloride weight.
Embodiment 5
Mixed slurry comprises following component: water 38g, granularity are 80-120 purpose aluminium powder 20g, organic binder bond carboxymethyl cellulose 3.5g, inorganic binder boehmite 18g, alloying element Sr0.3g, Ba0.26g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Adding glue hydrochloric acid in the inorganic binder boehmite, to make the pH value be 3.5, mixes, and makes gluey inorganic binder; Water, aluminium powder, alloying element, organic binder bond, gluey inorganic binder are mixed, promptly get mixed slurry.
2. step prepares fixed bed raney catalyst
The 70g nickel foam is put into the 8wt% dilution heat of sulfuric acid fully stir, dipping 20h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 60 ℃ of conditions vacuum drying 8h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned nickel foam is carried out pasting, and the nickel foam after the pasting is placed centrifuge destarch 0.7h, and the destarch rotating speed of centrifuge is 1500 rev/mins; With the vacuum drying 10h under 65 ℃ of conditions of the nickel foam after the destarch, under the helium protective atmosphere, be that roasting got moulding thunder damping alloy after 2 hours under 1700 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 85 ℃ of conditions in temperature, leaches 15h in the potassium hydroxide solution of 10wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds ruthenium trichloride in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, again to wherein adding reducing agent, be weight percentage 8% sodium borohydride solution of described reducing agent; Wherein the ruthenium element content of ruthenium trichloride is the 0.07wt% of fixed bed raney catalyst, and the consumption of borane reducing agent sodium hydride is 5 times of ruthenium trichloride weight.
Embodiment 6
Mixed slurry comprises following component: water 26g, granularity are 120-200 purpose aluminium powder 30g, organic binder bond polyacrylamide 3.0g, inorganic binder alumina gel 25g, alloying element Ba 0.02g, Cr 0.03g, Mn 0.01g, Fe 0.02g, Cu0.04g, W 0.06g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Adding glue hydrochloric acid in the inorganic binder alumina gel, to make the pH value be 4.5, mixes, and makes gluey inorganic binder; Water, aluminium powder, alloying element, organic binder bond, gluey inorganic binder are mixed, promptly get mixed slurry.
2. step prepares fixed bed raney catalyst
The 20g nickel foam is put into the 12wt% dilute nitric acid solution fully stir, dipping 18h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 75 ℃ of conditions vacuum drying 6h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned nickel foam is carried out pasting, and the nickel foam after the pasting is placed centrifuge destarch 0.8h, and the destarch rotating speed of centrifuge is 1200 rev/mins; With the vacuum drying 13h under 70 ℃ of conditions of the nickel foam after the destarch, under nitrogen protection atmosphere, be that roasting got moulding thunder damping alloy after 1 hour under 800 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 80 ℃ of conditions in temperature, leaches 25h in the potassium hydroxide solution of 15wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
Have to immersion to add chlorine rhodium aqueous acid in the alkaline solution of said fixing bed Reni catalyst, after mixing, again to wherein adding reducing agent, be weight percentage 3% sodium borohydride solution of described reducing agent; Wherein the rhodium element content of chlorine rhodium acid is the 0.09wt% of fixed bed raney catalyst, and the consumption of borane reducing agent sodium hydride is 8 times of chlorine rhodium acid weight.
Embodiment 7
Mixed slurry comprises following component: water 22g, granularity are 60-100 purpose aluminium powder 60g
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Water and aluminium powder are mixed, promptly get mixed slurry.
2. step prepares fixed bed raney catalyst
The mixed slurry that 1. step is prepared places vacuum coating installation that the 65g nickel foam is carried out pasting, and the nickel foam after the pasting is placed centrifuge destarch 0.9h, and the destarch rotating speed of centrifuge is 800 rev/mins; With the vacuum drying 10h under 65 ℃ of conditions of the nickel foam after the destarch, under the neon protective atmosphere, be that roasting got moulding thunder damping alloy after 1.5 hours under 1500 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 70 ℃ of conditions in temperature, leaches 48h in the sodium hydroxide solution of 25wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds palladium bichloride in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, again to wherein adding reducing agent, be weight percentage 7% sodium borohydride solution of described reducing agent; Wherein the palladium constituent content of palladium bichloride is the 0.06wt% of fixed bed raney catalyst, and the consumption of borane reducing agent sodium hydride is 12 times of palladium bichloride weight.
Embodiment 8
Mixed slurry comprises following component: water 34g, granularity are 200-250 purpose aluminium powder 35g, organic binder bond cyclodextrin 1.5g, alloying element Mn 0.02g, Fe 0.03g, Cu 0.01g, Ce 0.01g, Mo 0.02g, W 0.01g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Water, aluminium powder, alloying element, organic binder bond are mixed, promptly get mixed slurry.
2. step prepares fixed bed raney catalyst
The 35g nickel foam is put into the 7wt% dilution heat of sulfuric acid fully stir, dipping 16h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 75 ℃ of conditions vacuum drying 7h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned nickel foam is carried out pasting, and the nickel foam after the pasting is placed centrifuge destarch 0.7h, and the destarch rotating speed of centrifuge is 1100 rev/mins; With the vacuum drying 8h under 85 ℃ of conditions of the nickel foam after the destarch, under nitrogen protection atmosphere, be that roasting got moulding thunder damping alloy after 2.5 hours under 1200 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 75 ℃ of conditions in temperature, leaches 35h in the potassium hydroxide solution of 35wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds palladium bichloride in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, to wherein adding hydrazine reducing agent, wherein the palladium constituent content of palladium bichloride is the 0.07wt% of fixed bed raney catalyst again, and the consumption of hydrazine reducing agent is 18 times of chloroplatinic acid weight.
Embodiment 9
Mixed slurry comprises following component: water 28, granularity are 60-150 purpose aluminium powder 65g, inorganic binder boehmite 4g and alumina gel 6g, alloy element Zn 0.03g, Si 0.02g, Zr 0.01g, La 0.05g, Ce 0.01g, Mo 0.08g, W0.05g;
The preparation method of fixed bed raney catalyst:
1. step prepares mixed slurry
Adding glue hydrochloric acid in inorganic binder boehmite and alumina gel, to make the pH value be 4.5, mixes, and makes gluey inorganic binder; Water, aluminium powder, alloying element, gluey inorganic binder are mixed, promptly get mixed slurry.
2. step prepares fixed bed raney catalyst
The 50g nickel foam is put into the 6wt% dilution heat of sulfuric acid fully stir, dipping 22h takes out with moving in the absolute ethyl alcohol behind the distilled water flushing and soaks, take out, temperature be under 45 ℃ of conditions vacuum drying 10h to remove the remaining water in foam metal surface;
The mixed slurry that 1. step is prepared places vacuum coating installation that above-mentioned nickel foam is carried out pasting, and the nickel foam after the pasting is placed centrifuge destarch 0.6h, and the destarch rotating speed of centrifuge is 1600 rev/mins; With the vacuum drying 7h under 90 ℃ of conditions of the nickel foam after the destarch, under argon shield atmosphere, be that roasting got moulding thunder damping alloy after 3.5 hours under 660 ℃ of conditions again in temperature;
Moulding thunder damping alloy is under 80 ℃ of conditions in temperature, leaches 30h in the sodium hydroxide solution of 28wt%, promptly gets fixed bed raney catalyst.
Increase the method for said fixing bed Reni catalyst activity:
To immersion the aqueous solution that adds gold chloride in the alkaline solution of said fixing bed Reni catalyst is arranged, after mixing, again to wherein adding reducing agent, be weight percentage 6% sodium borohydride solution of described reducing agent; Wherein the gold element of chloroplatinic acid is the 0.08wt% of fixed bed raney catalyst, and the consumption of borane reducing agent sodium hydride is 15 times of gold chloride weight.
Claims (16)
- [claim 1] a kind of fixed bed raney catalyst is characterized in that described fixed bed raney catalyst is to be formed by the following components by part by weight processing and preparing:Foam metal 20-80, aluminium powder 20-80, inorganic binder 0-25, organic binder bond 0-5.0, water 20-50 and alloying element;Described foam metal is nickel foam, foam cobalt, foam platinum or foam palladium;Described alloying element is the 0-1wt% of foam metal, and it can be a kind of or wherein several mixture among Mg, Ca, Sr, Ba, Cr, Mn, Fe, Cu, Zn, Si, Zr, La, Ce, Mo, the w.
- [claim 2] is characterized in that according to the described fixed bed raney catalyst of claim 1 described fixed bed raney catalyst is to be formed by the following components by part by weight processing and preparing:Foam metal 20-80, aluminium powder 20-80, inorganic binder 525, organic binder bond 0.4-5.0, water 20-50 and alloying element.
- [claim 3] is characterized in that according to the described fixed bed raney catalyst of claim 1 described inorganic binder is boehmite and/or alumina gel; Described organic binder bond is a kind of or wherein several mixture in sesbania powder, polyethylene, starch, methylcellulose, carboxymethyl cellulose, polyacrylamide, the cyclodextrin.
- The preparation method of the described fixed bed raney catalyst of [claim 4] a kind of claim 1 is characterized in that described method comprises the steps:1. step prepares mixed slurryIn inorganic binder, add glue and mix, add aluminium powder, organic binder bond, water and alloying element again, mix, get mixed slurry;2. step prepares fixed bed raney catalystStep mixed slurry 1. is coated in vacuum coating installation on the foam metal, destarch, drying, roasting, activation is fixed a Reni catalyst.
- [claim 5] is characterized in that according to the preparation method of the described fixed bed raney catalyst of claim 4 described glue is salpeter solution, hydrochloric acid solution or sulfuric acid solution.
- [claim 6] is according to the preparation method of the described fixed bed raney catalyst of claim 4, it is characterized in that described foam metal pre-treating method is: foam metal is flooded 524h in 5-15wt% dilute acid soln, take out, water flushing back moves in the absolute ethyl alcohol soaks, taking out, is vacuum drying 5-12h under the 40-80 ℃ of condition in temperature.
- [claim 7] is characterized in that according to the preparation method of the described fixed bed raney catalyst of claim 4 described destarch is destarch 0.5-1h in centrifuge, and the destarch rotating speed of described centrifuge is 200-1800 rev/min.
- [claim 8] is characterized in that according to the preparation method of the described fixed bed raney catalyst of claim 4 described roasting is under protective atmosphere, is roasting 1-5h under the 600-1700 ℃ of condition in temperature.
- [claim 9] be the preparation method of described fixed bed raney catalyst according to Claim 8, it is characterized in that described protective atmosphere is nitrogen or inert gas.
- [claim 10] be the preparation method of described fixed bed raney catalyst according to Claim 8, it is characterized in that described temperature is 600-800 ℃.
- [claim 11] according to the preparation method of the described fixed bed raney catalyst of claim 4, it is characterized in that described activation is is under the 70-90 ℃ of condition in temperature, leaches 1-48h in alkaline solution.
- [claim 12] is characterized in that according to the preparation method of the described fixed bed raney catalyst of claim 11 described alkaline solution is NaOH or the potassium hydroxide solution of 5-40wt%.
- [claim 13] a kind of method that increases the fixed bed raney catalyst activity, it is characterized in that described method is to immersion the aqueous solution that adds noble metal acid or noble metal hydrochlorate in the alkaline solution of fixed bed raney catalyst to be arranged, after mixing, again to wherein adding reducing agent; Wherein the content of the precious metal element in noble metal acid or the noble metal hydrochlorate is the 0.05-0.1wt% of fixed bed raney catalyst, and the consumption of reducing agent is noble metal acid or noble metal hydrochlorate weight 2-20 a times.
- [claim 14] is characterized in that according to the method for the described increase fixed bed raney catalyst of claim 13 activity described noble metal acid or noble metal hydrochlorate are a kind of or wherein several mixture in Pt acid or its salt, Ru salt, Rh acid, Pd salt or the Au acid.
- [claim 15] is characterized in that according to the method for the described increase fixed bed raney catalyst of claim 14 activity described Pt acid or its salt are chloroplatinic acid, platinic sodium chloride or potassium chloroplatinate; Ru salt is ruthenium trichloride; Rh acid is the acid of chlorine rhodium; Pd salt is palladium bichloride; Au acid is gold chloride.
- [claim 16] is characterized in that according to the method for the described increase fixed bed raney catalyst of claim 13 activity described reducing agent is that hydrazine or percentage by weight are the sodium borohydride solution of 2-10%.
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| CNA2007102018654A CN101396665A (en) | 2007-09-26 | 2007-09-26 | Fixed bed Raney catalyst, preparation method and modification method thereof |
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