CN1060409C - Catalyst for synthetizing carbinol from and CO and hydrogen and its prodn. method - Google Patents
Catalyst for synthetizing carbinol from and CO and hydrogen and its prodn. method Download PDFInfo
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- CN1060409C CN1060409C CN97101425A CN97101425A CN1060409C CN 1060409 C CN1060409 C CN 1060409C CN 97101425 A CN97101425 A CN 97101425A CN 97101425 A CN97101425 A CN 97101425A CN 1060409 C CN1060409 C CN 1060409C
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- catalyst
- synthesizing methanol
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Abstract
The present invention relates to a catalyst for synthesizing methanol with CO and H2. The present invention is an oxide with the coexistence of Cu, Zn, Al, M' and M', wherein M' stands for the oxide of a metal in the IIIB group, and M' stands for the oxide of a metal in the IVB group or the VIB group; the present invention is prepared from the five metals of the proportion by an atomic ratio: 20 to 80 of Cu, 20 to 70 of Zn, 6 to 15 of Al, 0.1 to 10 of M' and 0.1 to 5 of M'. The present invention is prepared by a coprecipitation mixing method; compared with Cu/Zn/Al products, the catalyst provided by the present invention has good low-temperature activity, high initial activity, good thermal stability and high methanol selectivity, the activity is increased by 30% to 45% after heat resistance, and the service life can be prolonged by 1 to 3 months; the present invention is particularly suitable for the production technology of combined methanol.
Description
The present invention relates to a kind of being used for CO and H
2The catalyst of synthesizing methanol.
Methyl alcohol is important chemical products, is the important intermediate raw material of carbon one chemical industry.At first, methyl alcohol is all taken from the dry distillation of wood.CO and H
2Synthesizing methanol starts from nineteen twenty-three, and at that time, high-pressure process is all adopted in synthesizing methanol industry, and (300 ℃～400 ℃, 25MPa～30MPa), catalyst was ZnO/Cr
2O
3At the beginning of the fifties, Poland at first uses ternary CuO/ZnO/Al
2O
3The research of catalysis jizi for making dumplings synthesizing methanol.With ZnO/Cr
2O
3Catalyst is compared, and copper-based catalysts has low temperature, low pressure and advantage of high activity, but to poisonous substances and hot extremely sensitive such as sulphur.Along with the development of gas purification technique and the further raising of catalyst heat endurance, the sixties, the application of copper-based catalysts entered a new developing stage.Britain I.C.I company had developed copper radical synthesizing methanol low pressure process (5MPa～10MPa, 240 ℃～260 ℃) in 1966, and catalyst is CuO/ZnO/Al
2O
3West Germany Luigi company had developed another kind of low pressure methanol synthesis technology (4MPa～5MPa, 230 ℃～250 ℃) in 1971, and catalyst is CuO/ZnO/Al
2O
3/ V
2O
5Since 20th century the mid-1970s, methanol device newly-built in the world and enlarging all adopts the copper-based catalysts low-pressure process.The catalyst that uses sees Table 1.
Table 1: the composition of external low pressure methanol synthesis catalyst
| Company | Form (W%) | Patent and document | |||
| CuO | ZnO | Al 2O 3 | V 2O 5 | ||
| I.C.I BASE Du pont Luigi | 24 53 60 12 66 59 | 38 27 22 62 17 32 | 38 6 8 25 17 4 | 5 | GB 2302658 (1973) FB 1489682 (1967) FB 2037567 (1970) GB 1965007 (1970) GB 2056612 (1972) Feng Yuanqi; Connection alcohol is produced Chemical Industry Press (1990) |
Methanol production of China (single alcohol) and synthetic ammonia coproducing methanol (claiming that connection is pure) technology nearly all use copper radical synthesizing methanol catalysis chaste tree in, the low pressure synthesis technique.Domestic catalyst sees Table 2.
Table 2: the composition (W%) of internal copper base catalyst for methanol
| Model | CuO | ZnO | Al 2O 3 | V 2O 5 |
| C207 C301 C301-1 | 38～42 45～60 ～50 | 35～43 30～25 ～25 | 5～6 3～6 ～10 | |
| C302 | ≥50 | ≥25 | ～4 | 3 |
Recently, patent has been reported the new system of copper-based catalysts again both at home and abroad, for example:
U.S. Pat 5254520 discloses a kind of coprecipitation and has prepared Cu, Zn, Al, IV B family and/or VII B family metal oxide catalst for synthesis of methanol, its typical proportion (atomic ratio): Cu 30%～70%, Zn 20%～50%, Al 2%～10%, Zr 1%～15%, Mn O.5%～5%, Mo is O.1%～1%.
The metal Cu that U.S. Pat 4863894 discloses a kind of mixing method add ZnO and (or) CO conversion or the methanol synthesis catalyst of MgO.Its typical proportioning is 10%～80% (wt) Cu, and each Cu atom is joined 0.3～2.5 molecule ZnO and MgO, also can adopt Al.V.Cr and rare-earth oxide etc. to replace ZnO or MgO.
Shen state patent CN87105506 has introduced the preparation method of a kind of copper-zinc-zirconium fluidisation catalst for synthesis of methanol.
Three component C uO/ZnO/Al
2O
3Initial activity height, the selectivity of catalst for synthesis of methanol are good, but activity decay is fast, lack (generally using 2～4 months) service life, has a strong impact on productivity.
Purpose of the present invention is intended to develop the synthesizing methanol copper-based catalysts of the five components coexistence of a kind of low temperature, high activity, Heat stability is good.
Detailed description of the present invention:
Catalyst of the present invention is Cu, Zn, Al, M ', the M " metal oxide of five components coexistences.M ' is selected from metal scandium (Se), yttrium (Y) or lanthanide rare, especially La, Ce or the mixed heavy rare earth of III B family; M " is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Ne), tantalum (Ta), molybdenum (Mo), tungsten (W) of IV B family or V B family or VI B family etc.Its proportioning (atomic ratio): Cu is 20～80, is preferably 20～60; Zn is 20～70, is preferably 25～45; Al is 6～15, is preferably 8～10; M " is 0.1～10, is preferably 0.1～5; M " be 0.1～10, preferably 0.1～6.The raw material that catalyst uses: Cu, Zn, M ' and M " are selected from first C1
-Do not have
Soluble-salt, nitrate especially; Al is selected from the Al (OH) of powder (100 orders～120 orders)
3Soda ash is selected from content 〉=98.5%, C1
-≤ 0.1% Na
2CO
3
Preparation of catalysts of the present invention adopts the co-precipitation mixing method.The metering Cu, Zn, M ' and M " soluble-salt be made into mixed liquor, under agitation be added to 65 ℃～75 ℃ Na
2CO
3In the solution, control PH=7.0～7.5 are terminal point, at 70 ℃～80 ℃, stop to add thermal agitation behind especially 74 ℃～76 ℃ aging 0.5h～1h, arrive no C1 with deionized water washing sediment
-, add the Al (OH) that measures
3Powder also stirred 10～20 minutes, and filtration is drained, 110 ℃～120 ℃ oven dry, pulverize after the cooling is 40 orders～60 orders, and in 350 ℃ of calcination 2h～3h, fine ground then is 80 orders～100 orders, add 1%～3% graphite and 8%～15% deionized water, mixing, compression molding.
Catalyst activation (reduction) is carried out at fixed bed reactors, adopts low H
2Concentration (H
2/ N
2=3/97, V/V) reduction 16h～20h, reduction temperature is 230 ℃～240 ℃.
Catalysis Ji activity rating adopts two kinds of methods:
1. the laboratory adopts the shunting of one road gas to enter two fixed bed reactors, carries out heating reduction and activity rating abreast.Reaction temperature is controlled automatically by precision temperature controller, and reaction pressure is regulated by pressure-regulating valve, loaded catalyst 1ml, and unstripped gas is formed CO/H
2/ CO
2/ N
2=12/70/3/15, reaction pressure 5.OMPa, air speed 2 * 10
4h
-1The activity rating temperature is 220 ℃～280 ℃, and heat-resisting back activity refers to the activity of catalyst behind 400 ℃ of heat-resisting 3h.Product is analyzed with the 102GD gas chromatograph.Catalyst activity is with space-time yield (g.ml
-1 Cat.h
-1) expression.
2. join pure synthesis gas detection system: reactor is four groove towers, and CO detects with infrared CO analyzer, and connection raw polyol gas contains CO 2.5%～4.5%, CO
20.1%～0.3%, H
2) 75%, reaction pressure 10mpa, air speed 2 * 10
4h
-1, 240 ℃～250 ℃ of determination of activity temperature, heat-resisting 450 ℃ of 5h, sample granularity 16 orders～40 orders, the sample loading amount 2ml of being treated to.Catalyst activity is represented with CO conversion ratio (%).
Table 3 illustrates three kinds of active comparing results in the heat-resisting front and back of catalyst.NC208 (L) represents the laboratory sample of one of the present invention's prescription, and NC208 refers to the sample through scale-up, and C207 is an industry connection alcohol catalyst.See that from table 3 NC208 is after heat-resisting processing, the CO conversion ratio is 74.2%, than high about 5 percentage points of C207; Under the laboratory reaction condition, the methyl alcohol yield is 1.35g.h after the heat treatment of NC208 catalyst tolerates
-1.ml
-1 Cat, than C207 high about 46%.
Table 3: three kinds of active comparing results in the heat-resisting front and back of first ferment synthetic catalyst
| Catalyst (source) | Side pressure strength (N/cm) | Methyl alcohol yield (g.h -1.ml -1 cat) | CO conversion ratio (%) | ||
| Initial activity | After heat-resisting | Initial activity | After heat-resisting | ||
| NC208 (L) ((laboratory) NC208 (scale-up product) C207 (industrial products) | - 220.8 183 | 1.80 1.65 1.39 | 1.50 1.35 0.81 | 86.5 86.5 86.1 | 76.7 74.2 69.4 |
Catalyst of the present invention relatively has following characteristics with similar Cu/Zn/Al catalyst:
(the D low temperature active is better.The active temperature scope is 210 ℃～280 ℃, low 5 ℃～10 ℃ of optimal reaction temperature.
(2) better heat stability.In connection raw polyol gas 450 ℃ heat-resisting 5 hours, its CO conversion ratio exceeds 2～5 percentage points.
(3) methyl alcohol selectivity height.Methanol content improves 2%～5% in the thick methyl alcohol; Methanol yield amplification can reach 10%～30%.
(4) service life is longer.Can prolong 1～3 month (prolonging 15%～45% eventually).
The invention will be further described below by embodiment.
The embodiment I
(1) joins mixed liquor.Get 1.1M Cu (NO
3)
2160ml, 1.1M Zn (NO
3)
280ml, 0.2M La (NO
3)
314.7ml and 0.2M (NH
4)
2MoO
414.7ml be mixed in the 400ml beaker.
(2) neutralization.Get 590ml 0.25M Na
2CO
3Solution is put in the sub-1000ml beaker and is heated to 74 ℃, under stirring condition, (1) mixed liquor is added to Na with the speed of 20ml/min
2CO
3In the solution, be terminal point when PH=7.2, stop to add thermal agitation behind the aging 0.5h.
(3) washing.After treating (2) sedimentation, clean (with 70 ℃ of deionized waters) sediment to there not being C1 with gradient method
-, 2.4g Al (OH)
3Powder is added in the sediment and stirs 10min.
(4) suction filtration, 110 ℃ dry, pulverize, 350 ℃ of calcination 2h.
(5) compression molding.(4) gained mixed oxide is added 1% graphite and 8%H
2O mixes thoroughly, compressing tablet, that fragmentation is screened into 16 orders～40 orders is standby.
Above-mentioned prescription is Cu: Zn: Al: La: Mo=60: 30: 8: 1: 1 (atomic ratio).This catalyst is CO/H at gas ingredients
2/ CO
2/ N
2=12/70/3/15, pressure is that 5.0MPa, air speed are 2 * 10
4h
-1, reaction temperature is that initial activity is (methyl alcohol space-time yield) 1.75g.ml under 240 ℃ the laboratory evaluation condition
-1 Cat.h
-1Heat-resisting back activity is 1.42g.ml
-1 Cat.h
-1.
Embodiment 2 to 5 is except that composition of raw materials, and all the other conditions and shop method are with implementing side 1.Result such as table 4
Table 4: the evaluation result of different formulations
| Embodiment | Composition of raw materials | Methyl alcohol yield (g.ml -1cat.h -1) | |
| (atomic ratio) | Initial activity | Heat-resisting back is active | |
| Example 2 examples 3 examples 4 examples 5 | Cu: Zn: Al: Ce: Mo=60: 30: 8: 1: 1 Cu: Zn: Al: Ce: Zr=60: 30: 8: 1: 5 Cu: Zn: Al: heavy rare earth: Mo=60: 30: 8: 3: 5 Cu: Zn: Al: Se: V=60: 30: 8: 3: 2 | 1．77 1．7 1．89 1．72 | 1．45 1．35 1．49 1．28 |
Embodiment 6
Get 1.1M Cu (NO
3)
2115ml, 1.1M Zn (NO
3)
2115ml, 0.2M La (NO
3)
328ml, 0.2M (NH
4)
5H
5[H
2(WO
4)
6] 28ml, Al (OH)
32.3g.Its Cu: Z: Al: La: W=45 that fills a prescription: 45: 8: 2: 2 (atomic ratios).
(1) change preparation temperature, all the other conditions and method for making are with embodiment 1.Result such as table 5.
Table 5: the neutralization reaction temperature is to the influence of catalyst activity
| Preparation temperature (℃) | Methyl alcohol yield (g.ml -1cath -1) | Sinking speed | |
| Neutralization is aging | Initial activity | Heat-resisting back is active | |
| 69～70 70～75 72～75 76～80 | 1.78 1.85 | 1.42 1.55 | Slow fast |
(2) PH of change neutralization reaction terminal point, all the other conditions and method for making are with embodiment 1.Result such as table 6.
Table 6:PH value is to the influence of catalyst activity
| PH value | Methyl alcohol yield (g.ml -1 cath -1) | |
| Initial activity | Heat-resisting back is active | |
| 6 9 7～7.5 | 1.06 1.53 1.83 | 0.52 1.33 1.54 |
Claims (6)
1. one kind is used for CO and H
2The catalyst of synthesizing methanol, " the metal oxide of five components coexistences; M ' is selected from metal scandium (Se), yttrium (Y) or the lanthanide rare of III B family; M that is Cu, Zn, Al, M ', M " be selected from titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Ne), tantalum (Ta), molybdenum (Mo), the tungsten (W) of IV B family or V B family or VI B family, its set of dispense is Cu 20～80, Zn 20～70, Al 6～15, M ' 0.1～10, M " 0.1～10 than (atomic ratio).
2. a kind of CO and H of being used for as claimed in claim 1
2The catalyst of synthesizing methanol is characterized in that M ' is La, Ce or mixed heavy rare earth.
3. a kind of CO and H of being used for as claimed in claim 1
2The catalyst of synthesizing methanol is characterized in that each set of dispense is Cu 30～60, Zn 25～45, Al 8～10, M ' 0.1～5, M " 0.1～6 than (atomic ratio).
4. one kind is used for CO and H
2The manufacture method of the catalyst of synthesizing methanol is characterized in that adopting the co-precipitation mixing method, the metering Cu, Zn, M ' and M " soluble-salt be made into mixed liquor, under agitation be added to 65 ℃～75 ℃ Na
2CO
3In the solution, control PH=7.0～7.5 be terminal point, are stopping to add thermal agitation at 70 ℃～80 ℃ after wearing out down 0.5～1h, with deionized water washing sediment to there not being Cl
-, add the Al (OH) that measures
3Powder also stirred 10～20 minutes, and filtration is drained, and in 110 ℃～120 ℃ oven dry, pulverizing after the cooling is 40～60 orders, and in 350 ℃ of calcination 2～3h, fine ground then is 80～100 orders, added 1%～3% graphite and 8%～15% deionized water, mixing, compression molding.
5. a kind of CO and H of being used for as claimed in claim 4
2The manufacture method of the catalyst of synthesizing methanol is characterized in that aging temperature is 74 ℃～76 ℃.
6. a kind of CO and H of being used for as claimed in claim 4
2The manufacture method of the catalyst of synthesizing methanol is characterized in that Cu, Zn, M ' and M " soluble-salt be nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101425A CN1060409C (en) | 1997-01-23 | 1997-01-23 | Catalyst for synthetizing carbinol from and CO and hydrogen and its prodn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101425A CN1060409C (en) | 1997-01-23 | 1997-01-23 | Catalyst for synthetizing carbinol from and CO and hydrogen and its prodn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1173393A CN1173393A (en) | 1998-02-18 |
| CN1060409C true CN1060409C (en) | 2001-01-10 |
Family
ID=5165729
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97101425A Expired - Fee Related CN1060409C (en) | 1997-01-23 | 1997-01-23 | Catalyst for synthetizing carbinol from and CO and hydrogen and its prodn. method |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556538C (en) | 2006-12-14 | 2009-11-04 | 太原理工大学 | A kind of slurried catalyst and preparation method thereof |
| CN102531819A (en) * | 2010-12-30 | 2012-07-04 | 中国科学院大连化学物理研究所 | Method for preparing methane and methanol by using synthesis gas |
| CN102580753A (en) * | 2012-03-05 | 2012-07-18 | 昆明理工大学 | Catalyst for synthesizing methanol by taking multi-carbon sources in metallurgical fume as raw materials and preparation method of catalyst |
| CN108043471B (en) * | 2017-11-21 | 2021-01-01 | 南京邮电大学 | Protective agent for copper-based methanol synthesis catalyst and preparation method thereof |
| CN109078638A (en) * | 2018-08-30 | 2018-12-25 | 海门海康生物医药科技有限公司 | A kind of catalyst and preparation method thereof synthesizing deuterated methanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4863894A (en) * | 1987-06-22 | 1989-09-05 | Imperial Chemical Industries Plc | Process for the manufacture of a catalyst |
| US5254520A (en) * | 1990-09-18 | 1993-10-19 | Csir | Catalyst for the synthesis of methanol |
-
1997
- 1997-01-23 CN CN97101425A patent/CN1060409C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4863894A (en) * | 1987-06-22 | 1989-09-05 | Imperial Chemical Industries Plc | Process for the manufacture of a catalyst |
| US5254520A (en) * | 1990-09-18 | 1993-10-19 | Csir | Catalyst for the synthesis of methanol |
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| Publication number | Publication date |
|---|---|
| CN1173393A (en) | 1998-02-18 |
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