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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- 239000010948 rhodium Substances 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000007598 dipping method Methods 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- -1 minimizing methane Chemical class 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000011017 operating method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- 101001031591 Mus musculus Heart- and neural crest derivatives-expressed protein 2 Proteins 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN1179993A true CN1179993A (en) | 1998-04-29 |
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