CN1073465C - Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst - Google Patents

Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst Download PDF

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CN1073465C
CN1073465C CN97102713A CN97102713A CN1073465C CN 1073465 C CN1073465 C CN 1073465C CN 97102713 A CN97102713 A CN 97102713A CN 97102713 A CN97102713 A CN 97102713A CN 1073465 C CN1073465 C CN 1073465C
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acid
heteropolyacid salt
catalyst
pmo
nickel
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CN1173394A (en
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蔡天锡
刘百军
吕连海
岩谷胜能
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Dalian University of Technology
Nikko Rica Corp
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Dalian University of Technology
Nikko Rica Corp
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Abstract

The present invention relates to heteropoly acid salt which is composed of alkali metal or alkaline earth metal or transition-metal cations and various heteropoly acid anions and has the following general formula: (M')80-12m-n<+L>/L (X<n+>M12<m+>O40)<-(80-12m-n)>, wherein the X stands for hetero atoms; the M' stands for counterbalance cations; the M stands for polyatoms; the L stands for the valence state of the M'; the m stands for the valence state of the M; the n stands for the valence state of the X. Framework nickel catalysts modified in an immersion method can be used for furfuryl alcohol liquid phase hydrogenation to prepare furfuryl alcohol. The framework nickel catalysts modified by the heteropoly acid salt does not generate poison and environmental pollution reactive conditions are gental, and framework nickel catalysts have high activity and high selectivity. Compared with effects using pure framework nickel, the effects are obviously improved.

Description

The preparation of heteropolyacid salt modified skeletal nickel catalyst and application thereof
Heteropolyacid salt modified skeletal nickel catalyst of the present invention belongs to the liquid-phase hydrogenatin skeleton metallic catalyst that a class has high activity and high selectivity.
Usually adopt copper-chromium catalyst to carry out preparing furancarbinol from liquid-phase furol hydrogenation, require under high-temperature and high-pressure conditions, to carry out 170～220 ℃ of reaction temperatures, reaction pressure 2.45～10.0MPa (" modern chemical industry ", 24 pages of the 2nd phases of nineteen ninety).The shortcoming of using the copper-chromium catalyst maximum is the big and pollution on the environment of its toxicity.Sokol skil etc. add 20～30% Gd in Ni-Al alloy preparation process, this alloy is soaked the molten skeletal nickel catalyst that contains Gd that makes, and have improved the activity and the selectivity (SU481302 (1975)) of furfural hydrogenation significantly.In the Co-Al alloy, add 0.5～15% transition metal, wherein with the selectivity of the skeleton cobalt that adds 15%Re best (Chinese patent, CN1066610A).
U.S. Pat 4,153,578 have reported with ammonium molybdate (NH 4) 6Mo 7O 24The skeletal nickel catalyst of dipping modification, reaction condition are just relatively gentleer, at 60 ℃, carry out furfural hydrogenation system furfuryl alcohol under the 2.0MPa condition, and yield is very high.Chinese patent CN 1066610A has also reported and will contain cobalt 35.1～46.5%, aluminium 40.2～60.7%, and the alloy of chromium 4.2～13.2% soaks the molten skeletal Co catalysts that obtains with alkali, 120 ℃ of hydrogenation reaction temperature, Hydrogen Vapor Pressure 1.0MPa, conversion ratio 〉=99%.S.Hamar-Thibault has studied and has used chromium chloride CrCl 3Flood modified raney ni, and be used for the hydrogenation of acetophenone, find that the selectivity of generation 1-benzyl carbinol is very high, yield reaches 94% (Applied Catalysis A:General 99 (1993) 147-159).People such as Zhang Wenzhong have studied and have used antimony chloride SbCl 3Modified skeletal nickel catalyst is used for catalysis ethanol and is converted into ethyl acetate and n-butanol, but SbCl in the catalyst 3Be easy to split away off, thereby lose catalytic activity (" Journal of Molecular Catalysis ", 219 pages of the 3rd phases of nineteen ninety) from the surface of skeleton nickel.
For improving reaction condition by aldehyde hydrogenation system alcohol, utilize the peculiar property exploitation reaction condition gentleness of heteropolyacid salt, the heteropolyacid salt modified skeletal nickel catalyst that has high catalytic activity and high selectivity has simultaneously again become purpose of the present invention.
Heteropoly acid is a kind of in the polyacid that is formed by two or more oxyacid condensation, and its heteropolyanion is made up of hetero atom (X), polyatom (M) and oxygen atom, has multiple ad hoc structure, the H in the heteropoly acid +Can replace by various counter cations and form heteropolyacid salt.Only relate to the heteropolyacid salt with ke-qqin type structure among the present invention, its general formula is:
M ′l+ (80-12m-n)/ l[X n+M 12 m+O 40] (80-12-n]-
X representative in the formula: P, Si, As, Ge, B, Ti, Ga, Co, Fe, Al, Cr, Ca, elements such as Te;
M representative: Mo, W, elements such as V;
In the M ' representative element periodic table:
I family: Li, Na, K, Rb, Cs, Cu, Ag, Au, etc.;
II family: Mg, Ca, Sr, Ba, Zn, Ca, Hg etc.;
III family: Sc, La, Ce, Al, Ga, In etc.;
IV family: Fe, Co, Ni, Ru, Pd, Pt etc.;
Other: Sn, Pb, Mn, Bi, Cr, NH 4 +Deng.
L represents the valence state of M '; M represents the valence state of M; N represents the valence state of X;
By above-mentioned alkali metal or alkaline-earth metal or transition-metal cation and various heteropoly acid (as: phosphomolybdic acid, phosphotungstic acid, P-Mo-Wo acid, molybdovanaphosphoric acid, P-Mo-Wo-V acid, tungstovanadophosphoric acid, molybdovanaphosphoric acid; Silico-tungstic acid, silicomolybdic acid, silicon molybdenum wolframic acid, silicon molybdenum tungsten vanadic acid; Germanotungstic acid; Borotungstic acid, boron molybdic acid, boron molybdenum wolframic acid, boron molybdenum vanadic acid, boron molybdenum tungsten vanadic acid; The cobalt molybdic acid, the cobalt wolframic acid; The arsenic molybdic acid, arsenowolframic acid; Titanium molybdic acid, cerium molybdic acid etc.) heteropolyacid salt that heteropolyanion is formed.For example:
Li 3PW 12O 40,Na 3PW 12O 40；
Mg 1.5PW 12O 40,Ca 1.5PW 12O 40,Zn 1.5PW 12O 40；
Ag 4SiW 12O 40,Mg 2SiW 12O 40；
Li 3PMo 12O 40,Na 3PMo 12O 40,Mg 1.5PMo 12O 40,Ca 1.5PMo 12O 40,
Cu 1.5PMo 12O 40
Zn 1.5PMo 12O 40,CrPMo 12O 40,FePMo 12O 40,Co 1.5PMo 12O 40,Ni 1.5PMo 12O 40；
Na 4SiMo 12O 40, Cu 2SiMo 12O 40, Co 2SiMo 12O 40, Fe 4/3SiMo 12O 40Deng.
The preparation method of heteropolyacid salt modified skeletal nickel catalyst, at first with commercial Ni-Al alloyed powder (Ni/Al=50/50m/m), granularity 200～300 orders, about 50 ℃, the Ni-Al alloyed powder is added in the 20%NaOH aqueous solution, water temperature is elevated to 90 ℃ then, kept 1～2 hour, and be washed till neutrality repeatedly with deionized water, standby.
Secondly, the preparation heteropolyacid salt (is pressed the Tsigdinos method, referring to Ind.Eng.Chem.Prod.Res.Develop 13, (4) 267 (1974) is that various cationic nitrate, carbonate or acetate etc. with needs join in the corresponding heteropoly acid aqueous solution, 120 ℃ of oven dry down, 300 ℃ of calcinations 6 hours, promptly get corresponding heteropolyacid salt then.Again this heteropolyacid salt is made into the aqueous solution or alcoholic solution, standby.
At last, the skeleton nickel that takes by weighing requirement places conical flask, adds deionized water, at N 2Under the gas shiled, stir, skeleton nickel is suspended in the water, add heteropolyacid salt solution,, behind the dipping, promptly get heteropolyacid salt modified skeletal nickel catalyst 0～100 ℃ of continuous stirring 0.5～48 hour.Static, treat solution clarification after, get the content of supernatant liquor with each element of Shimadzu AA-64b type atomic absorption spectrometry, again it is converted into the adhesion amount of macerate.
The liquid-phase hydrogenatin reaction of furfural is to carry out in stainless steel autoclave, earlier the skeletal nickel catalyst of heteropolyacid salt modified (or unmodified) is transferred in the autoclave, wash five times with absolute ethyl alcohol, each with 15 milliliters, add absolute ethyl alcohol then and make solvent, add the distilled furfural of decompression again, the logical hydrogen exchange in airtight back 10 times, the autoclave that displacement is good places water-bath or oil bath, water-bath or oil bath temperature are adjusted to reaction temperature, Hydrogen Vapor Pressure is transferred to 0.1～5.0MPa, and the hydrogenation reaction temperature is 50～150 ℃, 0.5～20 hour reaction time, the skeletal nickel catalyst consumption is 1: 10～1: 100 to the furfural mass ratio, reactant is analyzed the conversion ratio of furfural＞98%, the selectivity of furfuryl alcohol＞98% with ShimadzuGC-8A type gas chromatograph.
Heteropolyacid salt for the adhesive force of skeleton nickel, dipping adhesion amount and to conversion ratio and optionally influence can see the following form:
On table 1 skeleton nickel dipping adhesion amount of heteropolyacid salt and to conversion ratio and optionally the influence
No Heteropolyacid salt Addition heteropolyacid salt: skeleton nickel Dipping adhesion amount (g/100g skeleton nickel) Furfural hydrogenation
Conversion ratio (mol%) Selectivity (mol%)
1 2 3 4 5 6 7 Cu 1.5PMo 12O 40 ″ ″ ″ ″ ″ ″ 1.1∶100 2.0∶100 4.0∶100 5.0∶100 6.0∶100 7.0∶100 8.3∶100 1.0 1.9 3.8 4.7 5.6 6.7 7.7 65.5 75.6 83.0 94.8 96.8 97.3 98.1 90.0 92.1 93.6 96.5 96.5 97.0 98.5
Reaction condition: P Hz=2.0MPa, T=353K, t=60 minute, furfural/ethanol=10ml/10ml, catalyst 0.5 gram.
As can be seen from Table 1, the present invention is with Cu 1.5PMo 12O 40Investigated the active and optionally influence of heteropolyacid salt dipping adhesion amount for example, found along with Cu to furfural hydrogenation 1.5PMo 12O 40The increase of dipping adhesion amount, furfural conversion ratio and furfuryl alcohol selectivity significantly increase, when the dipping adhesion amount is 7.7 (g/100g skeleton nickel), conversion ratio and selectivity reach 98.1% and 98.5% respectively, with unmodified skeleton nickel contrast, under same reaction condition, the conversion ratio of furfural has only 24.5%, the selectivity of furfuryl alcohol only is 75%, find out that thus heteropolyacid salt modified skeletal nickel catalyst is than unmodified skeletal nickel catalyst, no matter be the catalytic activity or the selectivity of furfuryl alcohol, all obtain to improve very significantly.
The present invention has also investigated the PMo that different counter cations replace 12The skeletal nickel catalyst of salt modification is active and optionally influence to furfural hydrogenation.
The different counter cations of table 2 are active and optionally influence to furfural hydrogenation
No Heteropolyacid salt Heteropolyacid salt: skeleton nickel Dipping adhesion amount (g/100g skeleton nickel) Furfural hydrogenation
Conversion ratio (mol%) Selectivity (mol%)
1 2 3 4 5 6 7 Cu 1.5PMo 12O 40 Cu 1.5PMo 12O 40 Zn 1.5PMo 12O 40 Co 1.5PMo 12O 40 FePMo 12O 40 Ca 1.5PMo 12O 40 Na 3PMo 12O 40 8.3∶100 5.0∶100 5.0∶100 5.0∶100 5.0∶100 5.0∶100 5.0∶100 7.7 4.7 4.7 4.7 4.7 4.5 4.5 98.1 94.8 94.6 94.4 92.2 91.4 93.8 98.5 96.5 97.8 95.6 95.5 92.8 92.2
Reaction condition is with table 1.
Table 2 shows, the PMo that various cations replace 12Salt all has goodish modified effect, active and selectivity has all obtained improving greatly, conversion ratio and selectivity are all more than 90%, and the effect of mantoquita is best, also can find out on the heteropolyacid salt modified skeletal nickel catalyst of different counter cations slightly difference, the transition metal salt improves the furfuryl alcohol selectivity and is better than alkali metal and alkaline-earth metal salt.
The present invention has also investigated the active and optionally influence to the skeletal nickel catalyst of modification of different heteropolyanions, is that counter cation has been investigated the active and optionally influence to furfural hydrogenation of several heteropolyanions with the copper ion, and the result is as shown in table 3:
The skeleton nickel of the different heteropolyanion modifications of table 3 is active and optionally influence to furfural hydrogenation
No Heteropolyacid salt Addition heteropolyacid salt: skeleton nickel Dipping adhesion amount (g/100g skeleton nickel) Furfural hydrogenation
Conversion ratio (mol%) Selectivity (mol%)
1 2 3 4 Cu 1.5PW 12O 40 Cu 2SiMo 12O 40 Cu 2SiW 12O 40 Cu 1.5PMo 12O 40 5.0∶100 5.0∶100 5.0∶100 5.0∶100 4.7 3.2 3.3 4.7 51.4 72.6 70.0 94.8 84.6 73.5 87.3 96.5
Reaction condition is with table 1.
Find relatively that by table 3 these four kinds of heteropolyacid salts have all improved furfural hydrogenation activity and selectivity significantly, and are especially best with the catalyst effect of phosphomolybdate modification.
The result of comparison sheet 2 and table 3 can think why heteropolyacid salt has so good modified effect, is mainly determined by heteropolyanion.The good modified effect of phosphomolybdic acid at first should belong to the contribution of Mo element, can be from (NH 4) 6M 7O 24Also having similar modified effect is confirmed.The modifying function of tungstenic heteropolyanion also is significant, but does not have molybdenum (Mo) good.Heteroatomic influence in the heteropolyanion, P is better than Si as seen from Table 3.
To report (NH such as De Thomas 4) 6Mo 7O 24The skeletal nickel catalyst of modification, did comparative studies among the present invention under the same conditions, find that selectivity reaches 98% with the result of report is consistent really when conversion ratio is 80% left and right sides, drop to below 90% that modified effect is obviously not as Cu but conversion ratio reaches the selectivity of 98% o'clock furfuryl alcohol 1.5PMo 12O 40The skeletal nickel catalyst of modification.
The present invention is also to Cu 1.5PMo 12O 40Modified skeletal nickel catalyst with do not carried out the reaction time to furfural conversion ratio and optionally comparative study of furfuryl alcohol with heteropolyacid salt modified skeleton nickel, the result shows that heteropolyacid salt modified skeletal nickel was at the 1st hour, the conversion ratio of furfural sharply is increased to 98.1%, the selectivity of furfuryl alcohol remains on about 98% always, only descended 1.2% through 3 hours, but unmodified skeleton nickel is with the prolongation in reaction time, though it is very slow that the furfural conversion ratio increases, but the selectivity of furfuryl alcohol obviously descends, after 20 hours, conversion ratio just reaches 97.4%, and the selectivity of this moment has dropped to 62.2%.
Owing to there is the competition that generates furfuryl alcohol and tetrahydrofurfural parallel reaction in the furfural hydrogenation course of reaction, reaction temperature is directly changing the selectivity of reaction to the influence of these two reactions, studies show that, rising along with reaction temperature, the conversion ratio of furfural sharply increases, and the selectivity of furfuryl alcohol is keeping constant more than 98% below the 353K, just slightly descends during to 363K.Thereby can think reaction temperature only to improve reaction speed and little to the selectivity influence, heteropolyacid salt modified effect has mainly increased the activity to carbonyl, the carbonyl hydrogen reaction is become be more prone to, so reaction temperature is to optionally influence is just very little.
Preparation, performance and application study by above-mentioned heteropolyacid salt modified skeletal nickel catalyst, be not difficult to find out when catalyst of the present invention not only has aldehyde hydrogenation system alcohol reaction condition gentleness, high activity, the usefulness of high selectivity, but also characteristics such as tool is nontoxic, non-environmental-pollution.
Embodiment 1
Take by weighing 0.5 gram skeleton nickel and transfer in 100 milliliters the conical flask, add 30 ml waters and stir, skeleton nickel is suspended in water, add 5 milliliters of (5mg/ml) phosphomolybdic acid cobalt (Co 1.5PMo 12O 40) solution, at room temperature stir 24 hours, static, make the solution clarification, get supernatant liquor, analyze each constituent content, the adhesion amount that records the dipping heteropolyacid salt is the 4.7g/100g skeleton nickel.
The skeletal nickel catalyst of this modification is transferred in the autoclave, be washed till anhydrous with absolute ethyl alcohol, add 10 milliliters of absolute ethyl alcohols and 10 milliliters of furfurals, after airtight, autoclave is connected with hydrogen, fills hydrogen pressure and reach 1.0MPa, for a moment static, gas slowly in the autoclave is emitted, and filling hydrogen pressure again, to reach 1.0MPa static, emits 10 times repeatedly, at last Hydrogen Vapor Pressure is transferred to 2.0Mpa, autoclave is placed water-bath, and water temperature rises to 353K (80 ℃), reacts 1 hour, assay products is formed, calculating the furfural conversion ratio is 98.1%, and the selectivity of furfuryl alcohol is 98.5%, and the productive rate of furfuryl alcohol is 96.6%.
Embodiment 2
Use heteropolyacid salt instead phosphomolybdic acid zinc (Zn by embodiment 1 1.5PMo 12O 40), under same immersion condition and reaction condition, the conversion ratio of furfural as a result of reaction is 92.2%, and the furfuryl alcohol selectivity is 95.5%, and the productive rate of furfuryl alcohol is 88.0%.
Embodiment 3
Use heteropolyacid salt instead phosphomolybdic acid copper (Cu by embodiment 1 1.5PMo 12O 40), except that 0.5g skeleton nickel addition is changed into the 41.5mg, other is identical with embodiment 1, and reaction result is a furfural conversion ratio 98.1%, and the furfuryl alcohol selectivity is 98.5%.
Embodiment 4～9
Use heteropolyacid salt instead silicomolybdic acid copper, phosphotungstic acid copper, silico-tungstic acid copper, phosphomolybdic acid iron, phosphomolybdic acid calcium by embodiment 1, sodium phosphomolybdate, under same immersion condition and reaction condition, furfural conversion ratio and furfuryl alcohol selectivity the results are shown in Table 4:
The different heteropolyacid salt modified skeletal nickel of table 4 are to the result of furfural hydrogenation system furfuryl alcohol
Embodiment Heteropolyacid salt Furfural conversion ratio (mol%) Furfuryl alcohol selectivity (mol%)
4 Cu 2SiMo 12O 40 72.6 73.5
5 Cu 1.5PW 12O 40 51.4 84.6
6 Cu 2SiW 12O 40 70.0 87.3
7 FePMo 12O 40 92.2 95.5
8 Ca 1.5PMo 12O 40 91.4 92.8
9 Na 3PMo 12O 40 93.8 92.2
Embodiment 10
Taking by weighing the unmodified skeleton nickel of 0.5 gram transfers in the autoclave, be washed till anhydrously with absolute ethyl alcohol, add 10 milliliters of absolute ethyl alcohols and 10 milliliters of furfurals again, airtight after, fill hydrogen pressure 1.0MPa, replace repeatedly 10 times, transferring hydrogen pressure at last is 2.0MPa, 80 ℃ of warming-in-water, reacted 1 hour, get furfural conversion ratio 24.5%, the furfuryl alcohol selectivity is 75.0%, and the furfuryl alcohol productive rate is 18.3%.
Embodiment 11
Press consumption and the reaction condition of embodiment 10, reacted 20 hours, the sample analysis result is: the furfural conversion ratio is 97.4%, and the furfuryl alcohol selectivity is 62.2%, and the furfuryl alcohol productive rate is 60.6%.

Claims (3)

1. a skeletal nickel catalyst made from nickel-Al alloy powder is characterized in that this catalyst except that skeleton nickel is made major catalyst, also has heteropolyacid salt to make co-catalyst, and heteropolyacid salt can be represented with following general formula:
M ' l+ (80-12m-n)/ l[X N+M 12 M+O 40] (80-12m-n)Among-the Shi: X representative: P, Si, Co, Fe, Ca, As, Ge, B, Ti, Ga, Al, Cr, Te hetero atom;
M representative: Mo, W, V, and by the combination of one or two or more kinds element in the three elements;
M ' representative: I family: Li in the periodic table of elements, Na, K, Rb, Cs, Cu, Ag, Au;
II family: Mg, Ca, Sr, Ba, Zn, Cd, Hg;
III family: Sc, La, Ce, Al, Ga, In;
VIII family: Fe, Co, Ni, Ru, Pd, Pt;
Also has other element: Sn, Pb, Mn, Bi, Cr, NH 4 +
L represents the valence state of M '; M represents the valence state of M; N represents the valence state of X;
Any by in any and following heteropoly acid in above-mentioned alkali metal or alkaline-earth metal or the transition-metal cation: phosphomolybdic acid, phosphotungstic acid, P-Mo-Wo acid, molybdovanaphosphoric acid, P-Mo-Wo-V acid, tungstovanadophosphoric acid; Silico-tungstic acid, silicomolybdic acid, silicon molybdenum wolframic acid, silicon molybdenum tungsten vanadic acid; Borotungstic acid, boron molybdic acid, boron molybdenum wolframic acid, boron molybdenum vanadic acid, boron molybdenum tungsten vanadic acid; The cobalt molybdic acid, the cobalt wolframic acid; The arsenic molybdic acid, arsenowolframic acid, the titanium molybdic acid, the heteropolyacid salt that the heteropolyanion of cerium molybdic acid is formed:
Li 3PW 12O 40,Na 3PW 12O 40；
Mg 1.5PW 12O 40,Ca 1.5PW 12O 40,Zn 1.5PW 12O 40；
Ag 4SiW 12O 40,Mg 2SiW 12O 40；
Li 3PMo 12O 40,Na 3PMo 12O 40,Mg 1.5PMo 12O 40,Ca 1.5PMo 12O 40；
Cu 1.5PMo 12O 40；
Zn 1.5PMo 12O 40,CrPMo 12O 40,FePMo 12O 40,Co 1.5PMo 12O 40,Ni 1.5PMo 12O 40；
Na 4SiMo 12O 40,Cu 2SiMo 12O 40,Co 2SiMo 12O 40,Fe 4/3SiMo 12O 40；
Any in the above-mentioned heteropolyacid salt, through the heteropolyacid salt modified skeletal nickel catalyst that dipping obtains on attached to skeleton nickel, the dipping adhesion amount of its co-catalyst heteropolyacid salt on the major catalyst skeleton nickel is 1.0～15.0%.
2. Preparation of catalysts method made from claim 1, it is characterized in that heteropolyacid salt modified skeletal nickel catalyst is earlier with commercial nickel-Al alloy powder, make skeleton nickel according to a conventional method, add water then, under agitation add heteropolyacid salt, the mass ratio of heteropolyacid salt and skeleton nickel addition is 0.1～0.5: 100,0～100 ℃ of dipping temperature, dip time 0.5～48 hour.
3. the purposes of the catalyst made from claim 1, it is characterized in that heteropolyacid salt modified skeletal nickel catalyst can make furfural hydrogenation system furfuryl alcohol, modified catalyst/furfural=1: 10～100, its reaction temperature is 50～150 ℃, reaction pressure is 0.1～5.0MPa, and the reaction time is 0.5～20.0 hour.
CN97102713A 1997-02-27 1997-02-27 Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst Expired - Fee Related CN1073465C (en)

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