CN1047327C - Process for preparing Cu-Cr catalyst - Google Patents
Process for preparing Cu-Cr catalyst Download PDFInfo
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- CN1047327C CN1047327C CN95111385A CN95111385A CN1047327C CN 1047327 C CN1047327 C CN 1047327C CN 95111385 A CN95111385 A CN 95111385A CN 95111385 A CN95111385 A CN 95111385A CN 1047327 C CN1047327 C CN 1047327C
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- ammonium dichromate
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Abstract
The present invention relates to a method for preparing a Cu-Cr catalyst. The molar ratio of Cu to Cr is 0.6 to 1.4, an ammonium dichromate aqueous solution is dropped in a cupric nitrate aqueous solution or a cupric ammine complex aqueous solution during stirring, and the pH value of reaction liquid is kept to be 5.4 to 6.4. The solution is aged for 2 to 4 hours at a constant temperature of 25 to 65 DEG C after dropping, and obtained precipitation is filtered, washed, dried and processed for 2 to 5 hours via thermal decomposition at 300 to 350 DEG C in N2. The obtained Cu-Cr catalyst has the advantages of high activity and no induction period, and the catalyst can be directly used in the production process of synthesizing methanol and methyl formate at low temperature in a liquid phase by a one-step method without reduction.
Description
This method belongs to the preparation method of chemical reaction catalyst, particularly is raw material synthesizing methanol and methyl formate Preparation of catalysts method with the synthesis gas.
Methyl alcohol and methyl formate (MF) all are in great demand, very promising important chemical products.Its production method has multiple route, wherein to use synthesis gas (CO and H
2) be raw material, be catalyst with the copper chromium compound, the low temperature liquid phase synthesis technique of one-step method synthesizing methanol and methyl formate (MF) is the most advanced.And the used Cu-Cr catalyst its preparation method of this technology is: copper nitrate aqueous solution is splashed in the ammonium dichromate aqueous solution, pH value with ammoniacal liquor conditioned reaction system is 5.8～6.0 simultaneously, obtain chromic acid cuprammonium precipitation, after filtration, washing, dry, abrasive dust, (WO86/03190, WO84/00360) pyrolytic in air or in the nitrogen and getting.The Cu-Cr catalyst activity of this method preparation is still not high, and also handy high pressure hydrogen reduces earlier during use, has induction period in addition.
The object of the present invention is to provide a kind of method for preparing Cu-Cr catalyst, prepared Cu-Cr catalyst is active high, no induction period, must not reduce and can be directly used in one-step method low-temperature liquid phase synthesis of methanol and the methyl formate production technology.
The object of the present invention is achieved like this: with (NH
4)
2Cr
2O
7(ammonium dichromate) aqueous solution under agitation splashes in the copper nitrate aqueous solution or the cupric ammine complex aqueous solution, the pH value of keeping reactant liquor is between 5.4～6.4, after ammonium dichromate aqueous solution dropwises, wore out 2～4 hours in 25 ℃～65 ℃ following constant temperature, the precipitation that obtains, after filtration, after the washing, drying,, obtain Cu-Cr catalyst of the present invention in 300～350 ℃ of following thermal decompositions 2～5 hours.Wherein the pH value of cupric ammine complex is 10～12, with the reaction of copper nitrate aqueous solution and ammoniacal liquor and make.
During thermal decomposition, if feed nitrogen or other inert gas shielding, the Cu-Cr catalyst better effects if that makes.
Adjust the consumption of ammonium dichromate and copper nitrate, can prepare the Cu/Cr mol ratio and be 0.6～1.4 high activity Cu-Cr catalyst.
The present invention is owing to the employing ammonium dichromate aqueous solution splashes in the copper nitrate aqueous solution or the cupric ammine complex aqueous solution, and heat ageing, and the precipitation that obtains helps Cu
+Generation, therefore, prepared Cu-Cr catalyst, active high, must not reduce no induction period, average response speed can reach more than the 50g/l.h (methyl alcohol), and initial reaction rate can reach more than the 90g/l.h (methyl alcohol), can improve respectively more than 0.5 times and 1 times than prior art.
Below be embodiments of the invention, the average response speed (r in methyl alcohol and the MF synthetic reaction wherein
Flat) be that the methyl alcohol and the MF total amount of gained calculated after finishing according to reaction, and initial reaction rate (r
o) be to calculate according to methyl alcohol that reaction generated and MF in initial 1 hour, unit is g/l.h (methyl alcohol), the MF of generation is scaled methyl alcohol.
Reference example:
Press the preparation of WO86/03190 patent, copper nitrate aqueous solution is splashed in the ammonium dichromate aqueous solution, the pH value of using ammoniacal liquor conditioned reaction liquid simultaneously is 5.8～6.0.After dripping off copper nitrate aqueous solution, filter, wash the gained precipitation with water, then 105 ℃ dry 16 hours down, wear into fine powder, again in 105 ℃ dry 20 hours down, thermal decomposition is 2 hours in 305 ℃ of following nitrogen, Cu-Cr catalyst, be designated as CatA.Get 4 gram CatA, 6.1 gram sodium methoxides, 30ml methyl alcohol, 170ml mixed xylenes (ε
20 ℃=2.32), add in the 500ml autoclave, speed of agitator is 500 rev/mins, feeds H
2React r under the synthesis gas of/CO=2,110 ℃, 4MPa
oBe 43.7g/l.h, r
FlatBe 33.8g/l.h.CatA is reduced in hydrogen, and its temperature is 200～230 ℃, and the time is 4 hours, drops in the above-mentioned synthetic reaction its r again
oBe 12.6g/l.h, r
FlatBe 6.4g/l.h.
Embodiment 1:
Press Cu/Cr mol ratio=1 metering, the 1M ammonium dichromate aqueous solution is under agitation slowly splashed in the 1M copper nitrate aqueous solution, the pH with concentrated ammonia liquor conditioned reaction liquid is 5.8～6.4 simultaneously.After ammonium dichromate aqueous solution dropwises, continue down to stir 3 hours, filter then, with distilled water washing gained precipitation, until no NO at 50 ℃
3 -Till.To be deposited in 120 ℃ of following dryings 16 hours, wear into fine powder then, following dry 20 hours in 120 ℃ again.This fine powder is placed high pure nitrogen, and in 300～350 ℃ of following thermal decompositions 2 hours, the Cu-Cr catalyst that makes was designated as CatB, was the black fine powder, and good fluidity is standby in the dry vial of packing into while hot.With carry out the methyl alcohol synthetic reaction under reference example the same terms, catalyst is without reduction, no induction period is at the H of synthesis gas
2/ CO is 1 o'clock, r
oBe 74.6g/l.h, r
FlatBe 37.2g/l.h.
Embodiment 2:
By the Cu/Cr mol ratio is 1 metering, earlier the 1M copper nitrate aqueous solution is mixed with concentrated ammonia liquor, makes pH and be 11 cupric ammine complex solution.Under agitation the ammonium dichromate aqueous solution (pH=4) of 1M is splashed in the cupric ammine complex solution then.Wait to splash into a half, the pH to 6 with red fuming nitric acid (RFNA) accent reactant liquor continues to splash into second half ammonium dichromate aqueous solution again.The temperature of entire reaction is 50 ℃.After dropwising, stir down in 50 ℃ again and wore out 3 hours, filter then, with distilled water washing gained precipitation, until no NO
3 -Till.Filter cake was 120 ℃ of dryings 16 hours.Later preparation technology is identical with embodiment 1.The gained Cu-Cr catalyst is designated as CatC
oWith carry out the methyl alcohol synthetic reaction under reference example the same terms, catalyst is without reduction, no induction period, r
oBe 63.3g/L.h, r
FlatBe 45.4g/L.h, respectively than the CatA high 44.9% and 34.3% of reference example.At synthesis gas is H
2/ CO is 1 o'clock, r
oBe 92.3g/l.h, r
FlatBe 41.8g/l.h, respectively than the CatB high 23.7% and 12.4% of embodiment 1.
Embodiment 3:
Change into copper ammon solution is splashed into the ammonium dichromate aqueous solution except that dripping order, all the other preparation technologies are with embodiment 2.The gained Cu-Cr catalyst is designated as CatD.Carry out the methyl alcohol synthetic reaction by embodiment 2 the same terms, catalyst is without reduction, no induction period, r
oBe 54.9g/l.h, r
FlatBe 38.5g/l.h, the CatC than embodiment 2 hangs down 68.1% and 7.9% respectively.
Embodiment 4:
Make post precipitation by embodiment 2 identical technologies, be washed with distilled water to no NO
3 -, in 120 ℃ times dry 16 hours, wear into fine powder then again, place nitrogen stream, in 300～350 ℃ of following thermal decompositions 3 hours, the Cu-Cr catalyst that obtains was designated as Cat E.At synthesis gas H
2During/CO=1, and carry out the methyl alcohol synthetic reaction under reference example the same terms, catalyst is without reduction, no induction period, r
oBe 97.8g/l.h, r
FlatBe 51.5g/l.h, respectively than the CatA high 123.8% and 52.4% of reference example.
Embodiment 5:
Except carrying out in air the thermal decomposition, all the other technologies are identical with embodiment 2.The gained Cu-Cr catalyst is designated as CalF.With carry out the methyl alcohol synthetic reaction under reference example the same terms, catalyst is without reduction, no induction period, r
oBe 42.3g/l.h, r
FlatBe 37.9g/l.h.
Embodiment 6:
Except that changing the Cu/Cr mol ratio into Cu: Cr=0.8: 1, all the other preparation technologies are with embodiment 2, and the gained Cu-Cr catalyst is designated as CatG, at synthesis gas H
2During/CO=1, by carrying out the methyl alcohol synthetic reaction under reference example the same terms, catalyst is without reduction, no induction period.r
oBe 94.7g/l.h, r
FlatBe 47.8g/l.h.
Embodiment 7:
Except that changing the Cu/Cr mol ratio into Cu: Cr=1.2: 1, all the other preparation technologies are with embodiment 6, and the gained Cu-Cr catalyst is designated as CatH, at synthesis gas H
2During/CO=1, by carrying out the methyl alcohol synthetic reaction under reference example the same terms, catalyst is without reduction, no induction period.r
oBe 78.4g/l.h, r
FlatBe 37.3g/l.h.
Embodiment 8:
The influence of pH value when present embodiment is mainly investigated the preparation precipitation, except that the pH difference, all the other preparation technologies and evaluation method are with embodiment 2.The results are shown in table 1.
Table 1
| Precipitation pH value | H 2/CO=2∶1 | H 2/CO=1∶1 | Remarks | ||
| r o(g/l.h) | r Flat(g/l.h) | r o(g/l.h) | r Flat(g/l.h) | ||
| 5.4 | 67.4 | 46.3 | 97.4 | 51.6 | |
| 5.8 | 64.1 | 46.7 | 92.7 | 42.1 | |
| 6.0 | 63.3 | 45.5 | 92.3 | 41.8 | Embodiment 2 |
| 6.4 | 59.6 | 41.4 | 82.7 | 37.7 | |
Embodiment 9:
Present embodiment is mainly investigated the influence of ageing time, and except that the ageing time difference, all the other preparation technologies and evaluation method are with embodiment 4.The results are shown in table 2.
Table 2
| Ageing time (hr) | r o(g/l.h) | r Flat(g/l.h) | Remarks |
| 2.0 | 96.8 | 51.0 | |
| 2.5 | 96.7 | 50.2 | |
| 3.0 | 97.8 | 51.5 | Embodiment 4 |
| 4.0 | 97.2 | 50.9 |
Embodiment 10:
Present embodiment is mainly investigated precipitation and is reached Temperature Influence when wearing out, and except that the temperature difference, all the other preparation technologies and evaluation method are with embodiment 4.The results are shown in table 3.
Table 3
| The temperature that precipitates and wear out (℃) | r o(g/l.h) | r Flat(g/l.h) | Remarks |
| 25 | 96.9 | 49.7 | |
| 35 | 97.3 | 50.1 | |
| 50 | 97.8 | 51.5 | Embodiment 4 |
| 65 | 96.1 | 49.4 |
Embodiment 11:
Present embodiment is mainly investigated the influence of thermal decomposition time, and except that the resolving time difference, all the other preparation technologies and evaluation method are with embodiment 4.The results are shown in table 4.
Table 4
| Thermal decomposition time (hr) | r o(g/l.h) | r Flat(g/l.h) | Remarks |
| 2 | 92.3 | 41.8 | Embodiment 2 |
| 3 | 97.8 | 51.5 | Embodiment 4 |
| 4 | 97.3 | 51.1 | |
| 5 | 95.7 | 50.9 |
Claims (3)
1. the preparation method of a Cu-Cr catalyst, it is characterized in that by the Cu/Cr mol ratio be 0.6～1.4 metering, ammonium dichromate aqueous solution is under agitation splashed in the copper nitrate aqueous solution or the cupric ammine complex aqueous solution, the pH value of keeping reactant liquor is 5.4～6.4, after dropwising, ammonium dichromate aqueous solution wore out 2～4 hours in 25 ℃～65 ℃ following constant temperature again, the precipitation that obtains after filtration, after the washing, drying, in 300 ℃～350 ℃ following thermal decompositions 2～5 hours, obtain Cu-Cr catalyst.
2. the preparation method of Cu-Cr catalyst according to claim 1 is characterized in that the pH value of cupric ammine complex is 10～12, is with the reaction of copper nitrate aqueous solution and ammoniacal liquor and get.
3. the preparation method of Cu-Cr catalyst according to claim 1 and 2 can feed nitrogen or other inert gas when it is characterized in that thermal decomposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111385A CN1047327C (en) | 1995-05-30 | 1995-05-30 | Process for preparing Cu-Cr catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111385A CN1047327C (en) | 1995-05-30 | 1995-05-30 | Process for preparing Cu-Cr catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1136979A CN1136979A (en) | 1996-12-04 |
| CN1047327C true CN1047327C (en) | 1999-12-15 |
Family
ID=5078682
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111385A Expired - Fee Related CN1047327C (en) | 1995-05-30 | 1995-05-30 | Process for preparing Cu-Cr catalyst |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0327514D0 (en) * | 2003-11-26 | 2003-12-31 | Davy Process Techn Ltd | Catalyst |
| CN100402149C (en) * | 2006-07-07 | 2008-07-16 | 宁夏大学 | Catalyst of low temperature synthesis for methanol in slurry state phase and its preparation method |
| DE102007038711A1 (en) * | 2007-08-14 | 2009-02-19 | Uhde Gmbh | Catalyst, process for its preparation and its use |
| CN103769115B (en) * | 2012-10-24 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of copper-chromium catalyst |
| CN103480376B (en) * | 2013-10-14 | 2015-01-14 | 中国科学院山西煤炭化学研究所 | Preparation method and application of synthetic carboxylate copper-mesoporous zirconium bifunctional catalyst |
| CN104148115A (en) * | 2014-08-18 | 2014-11-19 | 淄博恒增化工有限公司 | Preparation method of catalyst foaming body for production of 2-methylfuran through furfural hydrogenation |
| CN107473935B (en) * | 2017-08-08 | 2021-01-08 | 中国科学院成都有机化学有限公司 | Method for preparing ethanol from low-temperature liquid-phase synthesis gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221652A (en) * | 1991-03-26 | 1993-06-22 | The University Of Pittsburgh | Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis |
-
1995
- 1995-05-30 CN CN95111385A patent/CN1047327C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221652A (en) * | 1991-03-26 | 1993-06-22 | The University Of Pittsburgh | Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis |
| US5384335A (en) * | 1991-03-26 | 1995-01-24 | University Of Pittsburgh | Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite |
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|---|---|
| CN1136979A (en) | 1996-12-04 |
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