CN1179993A - Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method - Google Patents
Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method Download PDFInfo
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- CN1179993A CN1179993A CN 96112685 CN96112685A CN1179993A CN 1179993 A CN1179993 A CN 1179993A CN 96112685 CN96112685 CN 96112685 CN 96112685 A CN96112685 A CN 96112685A CN 1179993 A CN1179993 A CN 1179993A
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- catalyst
- synthetic gas
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- low carbon
- base catalyst
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Abstract
The present invention provides a rhodium-based catalyst in preparation of low-carbon alcohol by using synthetic gas and its preparation method. Said invented catalyst is made up by adopting fractional impregnation and fractional reduction method, and the composition of said catalyst is: M/Rh - Mn -Fe/SiO2, M = Na, Li; Rh capacity is 2.0% (wt): and the atomic ratio of M/Rh, Mn/Rh and Fe/Rh respectively is 3.8-21.8, 0.5-1.5 and 0.2-0.4. For said invented catalyst, under the conditions of 220 deg. C, 0.1 MPa, S. V. =1000h (-1) and CO/H2 = 1/2.2, the total selectivity of oxycompounds of methyl alcohol. ethyl alcohol, acetaldehyde and propyl acohol, etc. is up to above 90%, in which C2 oxycompound selectivity is up to 86%.
Description
The present invention is the method that a kind of preparation is used for the high oxygenate selectivity support type rhodium base catalyst of low carbon alcohol by synthetic gas; The invention belongs to C
1Produce the field of oxygenatedchemicals such as methyl alcohol, ethanol in the chemistry by synthesis gas.
Synthesis gas (CO/H
2) oxygenates such as methyl alcohol, ethanol, acetaldehyde, propyl alcohol are arranged in the converted product on the support type rhodium base catalyst, methane, C are also arranged
2～C
4Hydrocarbon.The growing amount of hydrocarbon such as minimizing methane, improving the oxygenate selectivity is that this catalytic process realizes difficult problem that commercial Application faced.
The support type rhodium base catalyst that traditional multiple-addition agent promotes adopts the co-impregnation preparation more, and promptly carrier carries out disposable dipping with the mixed liquor of catalyst each component solution, then carries out steps such as drying, reduction.The clear 60-32733 of day disclosure special permission communique discloses a kind of catalyst of the low Li content that makes with co-impregnation, and its method for making is: silica gel is with containing RhCl
33H
2O, MnCl
24H
2O, FeCl
24H
2O and LiClH
2The ethanolic solution of O dipping, remove ethanol after, catalyst carries out vacuum drying and H
2Reduction activation.The catalyst that so makes, Li/Rh, Mn/Rh, Fe/Rh atomic ratio are respectively 0.1～0.6,0.1～1.0,0.1～0.2, in 280～300 ℃ of temperature ranges, 50kg/cm
2The CO conversion ratio is 5～9% under the reaction pressure, and the oxygenatedchemicals selectivity is 59～65%, and hydrocarbon content such as methane is up to about 40% in the product.Japan C
1Chemical research association is at " Progress in C
1Chemistry in Japan " in the book, in the low Li content support type rhodium base catalyst of the co-impregnation of announcement with Rh-Mn-Ir-Li/SiO
2(Li/Rh, Mn/Rh, Ir/Rh atomic ratio are respectively 0.1,1,0.3) oxygenate selectivity is the highest, reaches 81.4%, but 20% the hydrocarbon of still having an appointment in the product.
The manufacture craft of single-steeping is difficult to make the catalyst of high Li content.
The purpose of this invention is to provide a kind of high Li or Na content, can improve optionally support type rhodium base catalyst of promoting of multiple-addition agent and preparation method thereof of oxygenate.
Catalyst of the present invention is M//Rh-Mn-Fe/SiO
2, wherein M is Na or Li, and the M/Rh atomic ratio is 3.8～21.8, is preferably 10.9, and the Mn/Rh atomic ratio is 0.5～1.5, is preferably 1.0; The Fe/Rh atomic ratio is 0.2～0.4, is preferably 0.3, and the Rh load capacity is 2% (wt).The used raw materials of component such as Rh, Mn, Fe, Na, Li are respectively in the catalyst: rhodium nitrate, manganese nitrate, iron chloride, sodium chloride, lithium chloride.Catalyst of the present invention adopts step impregnation, step-by-step reduction method to make, and its method for making is: the first step, spherical silica-gel carrier are at first used nitrate and the FeCl of Rh, Mn
3Methanol solution mixed liquor dipping 0.5～3 hour, preferably 1～2 hour, under the room temperature after the vacuum drying, in 200 ℃ of oven dry 3～5 hours down, then at H
2Be warming up to 300～400 ℃ of reduction 8～12 hours in the air-flow.After the reduction, at H
2Reduce to room temperature in the air-flow.In second step, the gained sample is then with the ethanolic solution dipping of NaCl or LiCl 0.5～3 hour, preferably 1～2 hour, continue after carry out with the processing behind the first step dipping.Prepared catalyst is at 220～260 ℃, 0.1～3.0MPa, air speed S.V.=1000～12000h
-1, CO/H
2Under=1/2.2 reaction condition, carry out the synthesis gas conversion reaction, the result: oxygenate overall selectivitys such as methyl alcohol, ethanol reach more than 90%, wherein C
2The oxygenate selectivity is up to～86%.
Advantage of the present invention is: adopt the method for step impregnation, step-by-step reduction, can make the catalyst of high Na or Li content, the catalyst that so makes can significantly improve the selectivity of oxygenate under same reaction conditions.
The following example is done detailed explanation to the present invention.
Embodiment 1
In test tube, add 1.00g spherical silica-gel (30 order), measure the Ph (NO of 0.55ml 0.35mmol/ml respectively
3)
3Mn (the NO of methanol solution, 0.34ml 0.58mmol/ml
3)
2The FeCl of methanol solution, 0.05ml 1.10mmol/ml
3Methanol solution mixes the back injecting tube, and dipping is 1.5 hours under room temperature, and vacuum drying desolventizes methyl alcohol under room temperature again.Then, sample moves into porcelain dish, dries by the fire 4 hours down in 200 ℃, then moves into reactor, at H
2(S.V.=1000h
-1) be warming up to 350 ℃ of reduction 10 hours with 10 ℃/min speed in the air-flow.After the reduction, at H
2Reduce to room temperature in the air-flow.The gained sample reloads test tube, and the NaCl ethanolic solution that injects 1.40ml 1.50mmol/ml flooded 1.5 hours, carries out later on the processing behind the first step dipping.The catalyst of making like this, Na/Ph, Mn/Rh, Fe/Rh atomic ratio are respectively 10.9,1.0,0.3, the catalytic activity of this catalyst under the differential responses condition, selectivity as shown in Table I, by table as seen, methyl alcohol, ethanol etc. the always selectivity of oxygenate reach more than 90%.
The real reaction condition CO converted product selectivity of Table I (iCi/ ∑ iCi * 100%) is executed------------rate (%)------------------routine T (℃) P (MPa) S.V. CO/H
2Methane C
2～C
4Methyl alcohol acetaldehyde ethanol propanol always contains
(h
-1) (V/V) oxygen thing 1 220 0.1 1,000 1/2.2 5.2 6.2 1.8 2.5 7.4 79.1 3.0 92.0 220 3.0 10,000 1/2.2 6.8 4.8 0.6 46.7/46.1 1.8 94.6
Embodiment 2
In the first step dipping, the Mn (NO of 0.58mmol/ml
3)
2The FeCl of methanol solution, 1.10mmol/ml
3The dipping consumption of methanol solution change 0.17ml, 0.04ml respectively into, in the second step dipping, use the NaCl ethanolic solution dipping of 0.60mmol/ml instead, consumption is 1.40ml, all the other operating procedures are with embodiment 1.Like this catalyst of making, Na/Rh, Mn/Rh, Fe/Rh atomic ratio are respectively 3.8,0.5,0.2, and the catalytic activity of this catalyst under the differential responses condition, selectivity are as shown in Table II.The real reaction condition CO converted product selectivity of Table II (iCi/ ∑ iCi * 100%) is executed------------rate (%)---------------------routine T (℃) P (MPa) S.V. CO/H
2Methane C
2～C
4Methyl alcohol acetaldehyde ethanol propanol always contains
(h
-1) (V/V) oxygen thing 2 220 0.1 1,000 1/2.2 4.7 7.6 2.0 2.2 6.7 78.7 2.8 90.4 220 3.0 10,000 1/2.2 5.4 6.8 1.0 46.0/44.2 2.0 92.2
Embodiment 3
In the first step dipping, the Mn (NO of 0.58mmol/ml
3)
2The FeCl of methanol solution, 1.10mmol/ml
3The dipping consumption of methanol solution change 0.50ml, 0.07ml respectively into.In the second step dipping, use the NaCl ethanolic solution dipping of 3.00mmol/ml instead, consumption is 1.40ml, and all the other operating procedures are all with embodiment 1.Like this catalyst of making, Na/Rh, Mn/Rh, Fe/Rh atomic ratio are respectively 21.8,1.5,0.4, and the catalyst activity of this catalyst under the differential responses condition, selectivity are as shown in Table III.
The real reaction condition CO converted product selectivity of Table III (iCi/ ∑ iCi * 100%) is executed------------rate (%)------------------routine T (℃) P (MPa) S.V. CO/H
2Methane C
2～C
4Methyl alcohol acetaldehyde ethanol propanol always contains
(h
-1) (V/V) oxygen thing 3 220 0.1 1,000 1/2.2 4.6 5.8 1.6 2.3 8.1 79.3 2.9 92.6 220 3.0 10,000 1/2.2 5.0 4.7 0.3 46.8/46.0 2.2 95.0
Embodiment 4,5 (catalyst is formed with embodiment 1)
Embodiment 4: first and second step dip time all changes 0.5 hour into, and all the other operating procedures are with embodiment 1.
Embodiment 5: first and second step dip time all changes 3 hours into, and all the other operating procedures are with embodiment 1.
Embodiment 4,5, and catalyst is at 220 ℃, 0.1MPa, S.V.=1000h
-1, CO/H
2Catalytic activity under=1/2.2 the reaction condition, the same Table IV of selectivity.The real CO converted product selectivity of Table IV (iCi/ ∑ iCi * 100%) is executed rate (%)------------------------routine methane C
2～C
4Methyl alcohol acetaldehyde ethanol propanol always contains
Oxygen thing 4 5.3 6.4 1.8 2.6 7.2 79.0 3.0 91.85 4.8 6.0 1.5 2.8 7.3 79.2 3.2 92.5
Embodiment 6
In test tube, add 1.00g spherical silica-gel (30 order), measure the Rh (NO of 0.55ml 0.35mmol/ml respectively
3)
3Mn (the NO of methanol solution, 0.34ml 0.58mmol/ml
3)
2The FeCl of methanol solution, 0.05ml 1.10mmol/ml
3Methanol solution mixes the back injecting tube, and dipping is 1.5 hours under room temperature, and vacuum drying desolventizes methyl alcohol under room temperature again.Then, sample moves into porcelain dish, dries by the fire 4 hours down in 200 ℃, then moves into reactor, at H
2(S.V.=1000h
-1) be warming up to 350 ℃ of reduction 10 hours with 10 ℃/min speed in the air-flow.After the reduction, at H
2Reduce to room temperature in the air-flow.The gained sample reloads test tube, injects the LiCl ethanolic solution of 1.20ml 0.60mmol/ml, floods 1.5 hours, carries out later on the processing behind the first step dipping.The catalyst of making like this, Li/Rh, Mn/Rh, Fe/Rh atomic ratio are respectively 3.8,1.0,0.3, the catalytic activity of this catalyst under the differential responses condition, selectivity as shown in Table V, by table as seen, methyl alcohol, ethanol etc. always the selectivity of oxygenate all more than 90%.
The real reaction condition CO converted product selectivity of Table V (iCi/ ∑ iCi * 100%) is executed------------rate (%)------------------routine T (℃) P (MPa) S.V. CO/H
2Methane C
2～C
4Methyl alcohol acetaldehyde ethanol propanol always contains
(h
-1) (V/V) oxygen thing 220 0.1 1,000 1/2.2 5.6 3.4 1.4 3.2 7.5 79.1 5.3 95.1 220 1.2 10,000 1/2.2 2.8 2.1 1.1 42.9/50.9 3.0 96.86 220 3.0 10,000 1/2.2 7.4 0.3 0.3 66.0/30.8 2.6 99.4 240 0.4 12,000 1/2.2 1.5 3.0 0.6 39.7/54.3 2.5 96.5 240 1.2 10,000 1/2.2 3.5 3.8 0.6 35.5/57.3 2.8 95.6 260 0.4 12,000 1/2.2 2.1 6.4 1.6 30.5/59.1 2.4 92.0
Embodiment 7,8
Mn (the NO of embodiment 7:0.58mmol/ml
3)
2The dipping consumption of the ethanolic solution of the LiCl of methanol solution, 0.60mmol/ml changes 0.50ml, 1.35ml respectively into, and all the other operating procedures are all with embodiment 5.
The dipping consumption of the ethanolic solution of the LiCl of embodiment 8:0.60mmol/ml changes 1.40ml into, and all the other operating procedures are all with embodiment 6.
The composition of embodiment 7,8 catalyst reaches at 220 ℃, 0.1MPa, S.V.=1000h
-1, CO/H
2Catalyst activity under=1/2.2 the reaction condition, selectivity all see Table VI.
The real selectivity of product of Table VI (iCi/ ∑ iCi * 100%) is executed CO and is transformed routine rate catalyst (%) methane C
2～C
4Total oxygenate 7 Li//Rh-Mn-Fe/SiO of methyl alcohol acetaldehyde ethanol propanol
24.8 4.5 1.3 3.6 7.4 80.0 3.2 94.2
4.2∶1.0∶1.5∶0.38 Li//Rh-Mn-Fe/SiO
2 4.5 5.6 1.1 5.2 4.2 82.0 1.9 93.3
4.4∶1.0∶1.0∶0.3
Claims (4)
1. the rhodium base catalyst of a low carbon alcohol by synthetic gas, the catalyst composition is M//Rh-Mn-Fe/SiO
2, it is characterized in that M is Na or Li, M/Rh, Mn/Rh, Fe/Rh atomic ratio are respectively 3.8～21.8,0.5～1.5,0.2～0.4, and the Rh load capacity is 2% (wt).
2. the rhodium base catalyst of low carbon alcohol by synthetic gas as claimed in claim 1 is characterized in that described M/Rh, Mn/Rh, Fe/Rh atomic ratio are respectively 10.9,1.0,0.3.
3. the preparation method of the rhodium base catalyst of a low carbon alcohol by synthetic gas is characterized in that adopting the method for step impregnation, step-by-step reduction to make, and its preparation process is
(1) the spherical silica-gel carrier is at first used nitrate and the FeCl of Rh, Mn
3Methanol solution mixed liquor dipping 0.5～3 hour, under the room temperature after the vacuum drying, in 200 ℃ of bakings 3～5 hours down, then at H
2Be warming up to 300～400 ℃ of reduction 8～12 hours in the air-flow, after the reduction, at H
2Reduce to room temperature in the air-flow;
(2) the gained sample then flooded 0.5～3 hour with the ethanolic solution of NaCl or LiCl, carried out then with the processing behind the first step dipping.
4. the preparation method of the rhodium base catalyst of low carbon alcohol by synthetic gas as claimed in claim 3 is characterized in that nitrate and FeCl with Rh, Mn
3Methanol solution mixed liquor dip time be 1～2 hour; Ethanolic solution dip time with NaCl or LiCl is 1～2 hour.
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|---|---|---|---|
| CN 96112685 CN1179993A (en) | 1996-10-16 | 1996-10-16 | Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method |
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|---|---|---|---|
| CN 96112685 CN1179993A (en) | 1996-10-16 | 1996-10-16 | Rhodium base catalyst for preparation of low carbon alcohol by synthetic gas and its preparing method |
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- 1996-10-16 CN CN 96112685 patent/CN1179993A/en active Pending
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