CN102247840B - Catalyst used for sodium formate process and preparation method thereof - Google Patents
Catalyst used for sodium formate process and preparation method thereof Download PDFInfo
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- CN102247840B CN102247840B CN 201110130681 CN201110130681A CN102247840B CN 102247840 B CN102247840 B CN 102247840B CN 201110130681 CN201110130681 CN 201110130681 CN 201110130681 A CN201110130681 A CN 201110130681A CN 102247840 B CN102247840 B CN 102247840B
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- catalyst
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- sodium formate
- honey comb
- load capacity
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Abstract
The invention discloses a catalyst used for the sodium formate process and a preparation method thereof. The catalyst contains a honeycomb ceramic carrier, Al2O3 attached to the carrier and active metal attached to the Al2O3, wherein the mass of the active metal accounts for 0.1% to 0.6% of the mass of the catalyst. The preparation method comprises the following steps of: soaking pretreated honeycomb ceramics in a slurry containing the active metal, taking out and blowing the residual slurry off from the honeycomb ceramics, thoroughly drying, and calcining for 1 to 5 hours at 450 DEG C to 800 DEG C to obtain a catalyst precursor; and completely reducing the catalyst precursor to obtain the catalyst finished product. The catalyst disclosed by the invention plays a significant catalytic role in the sodium formate process, and can reduce the reaction temperature and greatly increase the yield of products. Besides, the preparation method is simple and feasible, does not need special equipment, and is suitable for industrial production.
Description
Technical field
The invention belongs to catalyst technical field, particularly a kind of Catalysts and its preparation method for sodium formate method.
Background technology
Sodium formate is one of primary raw material of producing formic acid and oxalic acid, also is the raw material of producing sodium hydrosulfite.In leather processing, dope dyeing and electroplating industry, it is used separately as rawhide inorganic agent, dye leveller and promoter, and this is that it can also be used for the delustring of artificial silk.Because it can resolve into hydrogen and sodium acid carbonate at low temperatures, so it or a kind of good storage hydrogen material.
The mode of existing production sodium formate mainly is synthetic method, and namely CO and NaOH solution react under HTHP and directly generates sodium formate.China Patent Publication No. is CN 101367718A, open day was that on February 18th, 2009, denomination of invention are the patent of " utilizing tail gas of yellow phosphorus boiler through to produce the method for high-purity sodium formate ", this patent is with tail gas of yellow phosphorus boiler through and alkaline reaction synthesising acid sodium, and its synthesis condition is 230 ℃, 2.3～2.5MPa.Also have, China Patent Publication No. is CN 1456546A, open day was that on November 19th, 2003, denomination of invention are the patent of " method for preparing potassium formate, sodium take calcium carbide stove exhaust as raw material ", this patent discloses with the synthetic potassium formate of calcium carbide stove exhaust and alkaline reaction, sodium, and its synthesis condition is 1.2～2.4MPa, 120～220 ℃.Above-mentioned patent shows that sodium formate method must carry out under the HTHP strong alkali environment, the HTHP strong alkali environment not only needs to consume a large amount of energy, and quite serious to equipment corrosion.
Summary of the invention
Deficiency for prior art exists the present invention proposes a kind of catalyst for sodium formate method, preparation method and application thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is as follows:
One, a kind of catalyst for sodium formate method is by honeycomb ceramic carrier, be attached to the Al on the carrier material
2O
3, and be attached to Al
2O
3On active metal composition, wherein, the reactive metal quality accounts for 0.1～0.6% of catalyst quality.
As preferably:
1, honeycomb ceramic carrier is cordierite honeycomb ceramic;
2, reactive metal is one or more the composition in palladium, nickel, copper, lanthanum, silver, the cerium, and wherein, palladium is at Al
2O
3On load capacity be 0～10%, nickel is at Al
2O
3On load capacity be 0～20%, copper is at Al
2O
3On load capacity be 0～20%, lanthanum is at Al
2O
3On load capacity be 0～0.2%, silver at Al
2O
3On load capacity be 0～10%, cerium is at Al
2O
3On load capacity be 0～5%;
3, Al
2O
3Be γ-Al
2O
3, and γ-Al
2O
3Be nanometer fibrous aluminium oxide.
Two, the preparation method of above-mentioned catalyst may further comprise the steps:
1) ceramic honey comb is placed hydrochloric acid, sulfuric acid or the salpeter solution of 1～3mol/L boil, and keep boiling 1～3h, with distilled water it is cleaned behind the taking-up ceramic honey comb, and fully dry;
2) take by weighing soluble-salt, the Al of reactive metal
2O
3And polyethylene glycol, with the soluble-salt of reactive metal rear adding Al soluble in water
2O
3And polyethylene glycol, through stirring, obtain slurry; Wherein, reactive metal is one or more the composition in palladium, nickel, copper, lanthanum, silver, the cerium, and palladium is at Al
2O
3On load capacity be 0～10%, nickel is at Al
2O
3On load capacity be 0～20%, copper is at Al
2O
3On load capacity be 0～20%, lanthanum is at Al
2O
3On load capacity be 0～0.2%, silver at Al
2O
3On load capacity be 0～10%, cerium is at Al
2O
3On load capacity be 0～5%; Every gram Al
2O
3With 5～8mL water; Al
2O
3With the mass ratio of polyethylene glycol be 1: (0～2);
3) will be by step 1) ceramic honey comb after processing is in step 2) flood 1～3min in the slurry that obtains, make slurry evenly be coated on the ceramic honey comb with unnecessary slurry on the gases at high pressure blowing ceramic honey comb after taking out, through fully dry, in 450～800 ℃ of lower calcinings 1～5 hour, obtain catalyst precursor again;
4) catalyst precursor is reduced fully, obtain the catalyst finished product.
As preferably:
1, polyethylene glycol is PEG400;
2, used reducing agent is coal gas step 4);
3, the soluble metallic salt of reactive metal is one or more combination in nitrate, villaumite, sulfate, the acetate.
Three, the application of above-mentioned catalyst in adopting the synthetic formic acid of sodium formate method, sodium formate, calcium formate can significantly improve the output of formic acid, sodium formate, calcium formate.
The reaction principle of sodium formate method is: CO+OH
-=HCOO
-, it is in fact two-step reaction:
CO+H
2O＝HCOOH (1)
HCOOH+OH
-＝HCOO
-+H
2O (2)
Reaction equation (1) is the reaction rate-determining step, because CO and H
2The reaction activity that the direct reaction needed of O is higher is so need to carry out under the condition of high temperature, high pressure.Above-mentioned catalyst is used for reaction (1), CO and H
2O can form the lower transition state molecule of activation energy in the reactive metal surface in catalyst, just can generate the HCOOH molecule under lower temperature and pressure, thereby reduce reaction temperature and the pressure of sodium formate method.
Compared with prior art, the present invention has following advantage and beneficial effect:
1, reactive metal is evenly distributed in the catalyst of the present invention, and the reactive metal consumption is low, thereby cost is lower;
2, catalyst of the present invention is used for sodium formate method, can reduces reaction temperature, significantly improve the output of product, catalytic effect is remarkable;
3, the preparation method of catalyst of the present invention is simple, need not special installation, is fit to suitability for industrialized production.
The specific embodiment
Further set forth the present invention below by embodiment.
Embodiment 1
1) cordierite honeycomb ceramic is placed the hydrochloric acid of 3mol/L boil, and keep taking out ceramic honey comb behind the boiling 1h, clean with distilled water, and fully dry;
2) take by weighing 0.501g two water palladium nitrates, 2g γ-Al
2O
3, the 4g PEG400, add γ-Al after two water palladium nitrates are dissolved in the 10ml water
2O
3And PEG400, after stirring, obtain slurry;
3) with step 1) ceramic honey comb that obtains is immersed in step 2) 1min in the slurry that obtains, take out ceramic honey comb, blowing unnecessary slurry off with air blast makes slurry evenly be coated on the ceramic honey comb, place drying box through fully dry ceramic honey comb, then in 450 ℃ of lower calcining 5h, obtain catalyst precursor;
4) with the complete reduction step 3 of coal gas) catalyst precursor of gained, namely obtain catalyst.
Adding the catalyst of the present embodiment and 250ml industrial production pass into coal gas simulation sodium formate with NaOH solution, under 150 ℃, 3.4MPa condition industry in the synthetic analogue means of simple and easy sodium formate synthesizes, behind the reaction 2h, the mass percent that adopts permanganimetric method to measure sodium formate in the solution is 34.37%, sees Table 1.
Embodiment 2
1) cordierite honeycomb ceramic is placed the sulfuric acid of 2mol/L boil, and keep taking out ceramic honey comb behind the boiling 1h, clean with distilled water, and fully dry;
2) take by weighing 2g nickel nitrate, 0.34g copper nitrate, lanthanum nitrate (0.2%), 2g γ-Al
2O
3, the 1g PEG400, add γ-Al after nickel nitrate, copper nitrate and lanthanum nitrate be dissolved in the 16ml water
2O
3And polyethylene glycol, through stirring, obtain Al
2O
3The slurry that solid content is;
3) with step 1) ceramic honey comb that obtains is immersed in step 2) 3min in the slurry that obtains, take out ceramic honey comb, blowing unnecessary slurry off with air blast makes slurry evenly be coated on the ceramic honey comb, place drying box through fully dry ceramic honey comb, then in 800 ℃ of lower calcining 1h, obtain catalyst precursor;
4) with the complete reduction step 3 of coal gas) catalyst precursor of gained, namely obtain catalyst.
Adding the catalyst of the present embodiment and 250ml industrial production pass into coal gas simulation sodium formate with NaOH solution, under 150 ℃, 3.4MPa condition industry in the synthetic analogue means of simple and easy sodium formate synthesizes, behind the reaction 1h, the mass percent that adopts permanganimetric method to measure sodium formate in the solution is 26.42%, sees Table 1.
Embodiment 3
1) cordierite honeycomb ceramic is placed the hydrochloric acid of 1mol/L boil, and keep taking out ceramic honey comb behind the boiling 3h, clean with distilled water, and fully dry;
2) take by weighing 0.32g silver nitrate, 0.34g copper nitrate, 2g γ-Al
2O
3, the 2g PEG400, add γ-Al after being dissolved in silver nitrate and copper nitrate in the 14ml water
2O
3And PEG400, obtain slurry through stirring;
3) with step 1) ceramic honey comb that obtains is immersed in step 2) 2min in the slurry that obtains, take out ceramic honey comb, blowing unnecessary slurry off with air blast makes slurry evenly be coated on the ceramic honey comb, place drying box through fully dry ceramic honey comb, then in 500 ℃ of lower calcining 3h, obtain catalyst precursor;
4) with the complete reduction step 3 of coal gas) catalyst precursor of gained, namely obtain catalyst.
Adding the catalyst of the present embodiment and 250ml industrial production pass into coal gas simulation sodium formate with NaOH solution, under 150 ℃, 3.4MPa condition industry in the synthetic analogue means of simple and easy sodium formate synthesizes, behind the reaction 1h, the mass percent that adopts permanganimetric method to measure sodium formate in the solution is 20.38%, sees Table 1.
Embodiment 4
1) cordierite honeycomb ceramic is placed the nitric acid of 3mol/L boil, and keep taking out ceramic honey comb behind the boiling 1h, clean with distilled water, and fully dry;
2) take by weighing 1g nickel nitrate, 0.31g cerous nitrate, 0.012g lanthanum nitrate (0.34%), 2g γ-Al
2O
3, silver nitrate and copper nitrate are dissolved in the rear γ-Al of adding in the 15ml water
2O
3, obtain slurry through stirring;
3) with step 1) ceramic honey comb that obtains is immersed in step 2) 3min in the slurry that obtains, take out ceramic honey comb, blowing unnecessary slurry off with air blast makes slurry evenly be coated on the ceramic honey comb, place drying box through fully dry ceramic honey comb, then in 600 ℃ of lower calcining 2h, obtain catalyst precursor;
4) with the complete reduction step 3 of coal gas) catalyst precursor of gained, namely obtain catalyst.
Adding the catalyst of the present embodiment and 250ml industrial production pass into coal gas simulation sodium formate with NaOH solution, under 150 ℃, 3.4MPa condition industry in the synthetic analogue means of simple and easy sodium formate synthesizes, behind the reaction 1h, the mass percent that adopts permanganimetric method to measure sodium formate in the solution is 21.1%, sees Table 1.
Embodiment 5
1) cordierite honeycomb ceramic is placed the nitric acid of 2mol/L boil, and keep taking out ceramic honey comb behind the boiling 2h, clean with distilled water, and fully dry;
2) take by weighing 1.52g copper nitrate, 0.31g cerous nitrate, 2g γ-Al
2O
3, silver nitrate and copper nitrate are dissolved in the rear γ-Al of adding in the 10ml water
2O
3, through stirring, obtain slurry;
3) with step 1) ceramic honey comb that obtains is immersed in step 2) 3min in the slurry that obtains, take out ceramic honey comb, blowing unnecessary slurry off with air blast makes slurry evenly be coated on the ceramic honey comb, place drying box through fully dry ceramic honey comb, then in 650 ℃ of lower calcining 2h, obtain catalyst precursor;
4) with the complete reduction step 3 of coal gas) catalyst precursor of gained, namely obtain catalyst.
Adding the catalyst of the present embodiment and 250ml industrial production pass into coal gas simulation sodium formate with NaOH solution, under 150 ℃, 3.4MPa condition industry in the synthetic analogue means of simple and easy sodium formate synthesizes, behind the reaction 1h, the mass percent that adopts permanganimetric method to measure sodium formate in the solution is 20.82%, sees Table 1.
Among above-described embodiment 1-5, used PEG400 can be replaced by Macrogol 600, cetomacrogol 1000, Macrogol 2000, also can be replaced by the composition of PEG400, Macrogol 600, cetomacrogol 1000 and Macrogol 2000, and the products therefrom performance is had no significant effect; Used γ-Al
2O
3Can be by α-Al
2O
3Replace; The nitrate of used reactive metal can be replaced by the villaumite of this reactive metal, sulfate, acetate, also can be replaced by the composition of the nitrate of this reactive metal, villaumite, sulfate, acetate; Step 2) soluble metallic salt of described reactive metal is one or more combination in nitrate, villaumite, sulfate, the acetate; And the products therefrom performance had no significant effect.
Embodiment 6
Blank test: in the synthetic analogue means of simple and easy sodium formate, do not add catalyst, only adding the 250ml industrial production, pass into the industry of coal gas simulation sodium formate with NaOH solution, under 150 ℃, 3.4MPa condition synthetic, when reaction 1h and 2h, adopt permanganimetric method to measure the mass percent of sodium formate in the solution, during reaction 1h, the mass percent 14.96% of sodium formate in the solution is during reaction 2h, the mass percent of sodium formate is 16.39% in the solution, sees Table 1.
It can be seen from the table, embodiment 1 gained catalyst is used for the sodium formate synthetic reaction, during reaction 2h, the mass percent of sodium formate has improved 17.98% in the solution, and increase of production is up to 110.3%; Embodiment 2 gained catalyst are used for the sodium formate synthetic reaction, and during reaction 1h, the mass percent of sodium formate has improved 11.46% in the solution, increase of production 76.6%; Embodiment 3 gained catalyst are used for the sodium formate synthetic reaction, and during reaction 1h, the mass percent of sodium formate has improved 5.42% in the solution, increase of production 36.2%; Embodiment 4 gained catalyst are used for the sodium formate synthetic reaction, and during reaction 1h, the mass percent of sodium formate has improved 6.14% in the solution, increase of production 41%; Embodiment 5 gained catalyst are used for the sodium formate synthetic reaction, and during reaction 1h, the mass percent of sodium formate has improved 5.86% in the solution, increase of production 39.17%.
Table 1 adopts catalyst of the present invention and does not adopt the contrast of catalyst synthesising acid sodium output
Claims (7)
1. a preparation method who is used for the catalyst of sodium formate method is characterized in that, described catalyst by honeycomb ceramic carrier, be attached to the Al on the carrier material
2O
3, and be attached to Al
2O
3On active metal composition, wherein, the reactive metal quality accounts for 0.1～0.6% of catalyst quality,
The preparation of catalyst may further comprise the steps:
1) ceramic honey comb is placed hydrochloric acid, sulfuric acid or the salpeter solution of 1～3mol/L boil, and keep boiling 1～3h, with distilled water it is cleaned behind the taking-up ceramic honey comb, and fully dry;
2) take by weighing soluble-salt, the Al of reactive metal
2O
3And polyethylene glycol, with the soluble-salt of reactive metal rear adding Al soluble in water
2O
3And polyethylene glycol, through stirring, obtain slurry; Wherein, reactive metal is one or more the composition in palladium, nickel, copper, lanthanum, silver, the cerium, and palladium is at Al
2O
3On load capacity be 0～10%, nickel is at Al
2O
3On load capacity be 0～20%, copper is at Al
2O
3On load capacity be 0～20%, lanthanum is at Al
2O
3On load capacity be 0～0.2%, silver at Al
2O
3On load capacity be 0～10%, cerium is at Al
2O
3On load capacity be 0～5%; Every gram Al
2O
3With 5～8mL water; Al
2O
3With the mass ratio of polyethylene glycol be 1:(0～2), wherein the quality of polyethylene glycol does not get 0;
3) ceramic honey comb after will processing by step 1) is in step 2) flood 1～3min in the slurry that obtains, make slurry evenly be coated on the ceramic honey comb with unnecessary slurry on the gases at high pressure blowing ceramic honey comb after taking out, through fully dry, in 450～800 ℃ of lower calcinings 1～5 hour, obtain catalyst precursor again;
4) catalyst precursor is reduced fully, obtain the catalyst finished product.
2. preparation method according to claim 1 is characterized in that:
Described honeycomb ceramic carrier is cordierite honeycomb ceramic.
3. preparation method according to claim 1 is characterized in that:
Described Al
2O
3Be γ-Al
2O
3
4. preparation method according to claim 3 is characterized in that:
Described γ-Al
2O
3Be nanometer fibrous aluminium oxide.
5. preparation method according to claim 1 is characterized in that:
Described polyethylene glycol is PEG400.
6. preparation method according to claim 1 is characterized in that:
Used reducing agent is coal gas in the described step 4).
7. preparation method according to claim 1 is characterized in that:
The soluble metallic salt of described reactive metal is one or more combination in nitrate, sulfate, the acetate.
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|---|---|---|---|
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|---|---|---|---|
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| CN102247840B true CN102247840B (en) | 2013-03-06 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304792A (en) * | 2000-09-14 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst for catalytic cleaning of car tail gas and its preparing process |
| CN101138728A (en) * | 2007-10-19 | 2008-03-12 | 华南理工大学 | Metallic oxide mixture catalyzer for purifying organic waste gas and method of preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100124523A1 (en) * | 2008-11-19 | 2010-05-20 | Basf Catalysts Llc | Emissions Treatment Catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304792A (en) * | 2000-09-14 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst for catalytic cleaning of car tail gas and its preparing process |
| CN101138728A (en) * | 2007-10-19 | 2008-03-12 | 华南理工大学 | Metallic oxide mixture catalyzer for purifying organic waste gas and method of preparing the same |
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