CN1153166A - Method for preparing gluconate in presence of Bi-Pd/C metal catalyst - Google Patents
Method for preparing gluconate in presence of Bi-Pd/C metal catalyst Download PDFInfo
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- CN1153166A CN1153166A CN 96106774 CN96106774A CN1153166A CN 1153166 A CN1153166 A CN 1153166A CN 96106774 CN96106774 CN 96106774 CN 96106774 A CN96106774 A CN 96106774A CN 1153166 A CN1153166 A CN 1153166A
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Abstract
An industrial process for preparing gluconate features that in the presence of metal catalyst (Bi-Pd/C) and under the condition of catalytic oxidation, glucose, oxygen-containing gas and alkali are used to prepare gluconate. A spray oxidation equipment, A Bi-Pd/C catalyst and its preparing method are also disclosed.
Description
The present invention relates to a kind of method of suitability for industrialized production gluconate.More particularly, the present invention relates to a kind ofly in the presence of bismuth-palladium/charcoal metal catalyst, under the catalyzed oxidation condition, prepare the method for gluconate by glucose, oxygen-containing gas and alkali.The invention still further relates to and be used for catalyzed oxidation and prepare the jet paraffin oxidation equipment of gluconate method and be used for bismuth-palladium/charcoal metal catalyst that catalyzed oxidation prepares gluconate and preparation method thereof.
Glucose is oxidized to the industrialized preparing process of glyconic acid and salt thereof, all also adopts biological fermentation process, its flow process complexity at present at home and abroad, raw material, energy consumption are higher, and the three wastes are difficult to handle, and microorganism is difficult to be separated, the difficult control of by product, thereby cost is high and influential to quality product.Since the fifties, domestic and international many scientific workers have proposed to prepare with catalytic oxidation the method for gluconate in order to overcome the shortcoming of biological fermentation process, and have delivered many patents, for example, and EP47984; The clear 59-225140 of Japanese Patent (C07C51/23); The clear 59-205343 of Japanese Patent; The clear 59-205340 of Japanese Patent; The clear 60-92240 of Japanese Patent; The clear 58-72538 of the day disclosure; Day disclosure clear 228093 (1987); EP48794 and Deutsches Reichs-Patent 3823301 (C07C59/105); In above-mentioned patent documentation, many investigators adopt the monometallic palladium to be stated from the gac when the selecting catalyst metallic element, its oxidation activity is very low, and speed of reaction is very slow, long reaction time, if implement suitability for industrialized production, cost is also higher than fermentation method, and no industrial applications is worth.Many investigators Pt-Pd that in catalyst formulation, knows clearly, Pd-Pb, the all metallic elements of Pd-Se, its common shortcoming is active not high with selectivity, weather resistance is relatively poor, owing to pore-creating, the physicals of carrier, the absorption sequential scheduling reason of metallic element on carrier to carrier, cause catalyzer when using, to come off, and separation difficulty.
At the problems referred to above, the inventor has carried out the improvement research work of metal catalyst, emphasis made years of researches to the separation method of the pre-treatment of the proportioning of the selection of reactive metal element, prescription, absorption order, carrier active carbon, catalyzer, resurrection regeneration techniques behind the catalyst deactivation and industrialized preparing process, specific equipment etc., opened up the industrialized preparing process that a brand-new chemical catalytic oxidation legal system is equipped with gluconate.
An object of the present invention is to provide a kind ofly in the presence of bismuth-palladium/charcoal metal catalyst, under the catalyzed oxidation condition, prepare the method for gluconate by glucose, oxygen-containing gas and alkali.
Another object of the present invention provides a kind of air spray oxidation furnaces that catalyzed oxidation prepares the gluconate method that is used for.
Another object of the present invention provides a kind of bismuth-palladium/charcoal metal catalyst that catalyzed oxidation prepares gluconate and preparation method thereof that is used for.
In this manual, comprised following accompanying drawing, wherein:
Accompanying drawing 1 is the present invention is prepared gluconate through catalyzed oxidation by glucose a process flow sheet.
Accompanying drawing 2 is to be used for the synoptic diagram of air spray oxidation furnaces that catalyzed oxidation of the present invention prepares the method for gluconate.
Accompanying drawing 3 is Electronic Speculum figure of explanation catalyst B i of the present invention and Pd distribution situation on gac.
Accompanying drawing 4 is the qualitative energy of X diffraction spectrograms of explanation catalyzer of the present invention.
Accompanying drawing 5 is X diffractometer diffracting spectrums of preferred catalyst of the present invention.
Accompanying drawing 6 is histogram and the isothermal maps that obtain with specific surface instrument analysis preferred catalyst of the present invention.
The invention discloses the method that a kind of catalytic oxidation by glucose prepares gluconate, it is lower that it comprises that bismuth-palladium/charcoal metallic catalyst exists, under the catalytic oxidation condition, make glucose and oxygen-containing gas under alkali condition, react the preparation gluconate, wherein in carrier active carbon, described bismuth palladium charcoal metallic catalyst contains the bismuth (in metal) of 3-6% (weight), the palladium (in metal) of 4-10% (weight), and, the atomic ratio of bismuth and palladium is 0.3-1.5: 1, and with dried glucose meter, the consumption of catalyst is 1.2-1.5% (weight).
Take the preparation calcium gluconate as example, method of the present invention represents with following reaction equation:
Referring to accompanying drawing 1, the method that the present invention is prepared gluconate is described in detail. Raw materials of glucose (1) and water (2) are dissolved in unit (3), be prepared into sugar aqueous solution, add therein bismuth-palladium of the present invention/charcoal metallic catalyst (4) (about composition and the preparation method of catalyst of the present invention will specify hereinafter), to be mixed with the sugar aqueous solution of catalyst with carrying out jet paraffin oxidation in high-pressure pump (5) the input jet paraffin oxidation device (6) (relevant jet paraffin oxidation device of the present invention will specify hereinafter) subsequently, oxygen-containing gas (7) (preferred air) sucks by spraying, carry out the continuous circulation jet paraffin oxidation, add simultaneously alkali (8), the pH value of strict control oxidation reaction is 8.5-11, reaction temperature is 30-80 ℃, alkali and glucose etc. are when reaction, after the alkali of metering adds, the stopping of reaction, pH value drops to below 7.8, oxidation reaction is namely accused and is finished, and the reaction time is 4-8 hour. Conversion ratio selectively is 97-99% usually at 95-98%. The oxidation liquid that obtains is isolated catalyst (10) in separator (9), catalyst after pure water washing, capable of circulation reusing. The oxidation liquid that has separated catalyst is decoloured with active carbon in unit (11), and evaporation and concentration in unit (12) subsequently is again in the static crystallization of crystallizer (13) more than 18 hours. Through sedimentator (14) centrifugation washing, obtain crystalline solid. Crystalline solid obtains gluconate (16) product through fluidized drying (15).
According to a preferred embodiment of the invention, it is for the preparation of calcium gluconate or gluconic acid sodium salt, and then employed alkali is preferably calcium hydroxide and NaOH.
According to another embodiment of the invention, it also comprises the step that is obtained glyconic acid by the gluconate product by H+ ion-exchange.
About catalyzer, the inventor has studied single-metal reforming catalyst such as palladium, platinum and nickel, and its result can not be satisfactory.The inventor has studied multi-metallic catalyst again, acid has played main effect to catalytic oxidation of glucose to draw palladium, but the oxygenizement of single palladium element can not be satisfactory, the inventor is surprised to find, and when add bismuth element in catalyzer after, palladium disperses more evenly on gac, active and selectivity improves greatly, through electronic microscope photos, Bi and Pd exist with alloy morphology, distribute to reach um level (referring to accompanying drawing 3).
The inventor proposes after the absorption on carrier active carbon is studied in proper order to metallic element, and the preferred metallic element of the present invention is palladium after the absorption on the carrier active carbon is first bismuth in proper order.Adsorb bismuth after having adsorbed the metallic element palladium on the carrier active carbon again, because both can not form alloy morphology on gac, though active also not poor, weather resistance is relatively poor, and catalyzer can only be multiplexing three to five times when catalyzed oxidation.Have only when absorption in proper order for behind the first bismuth during palladium, bismuth and palladium are to exist with alloy morphology, weather resistance improves greatly, multiplexing number can reach more than ten times.About the difference absorption of metallic element in catalyst preparation process order to the influence of catalyzer referring to table 1.The difference of the different absorption orders of metallic element in table 1 catalyst preparation process
Test conditions: 10% (W/V) D/W, 4000 grams, catalyzer 7 grams, calcium hydroxide 72 grams, PH8.5-11, temperature 30-60 ℃, reaction terminating PH＜7.8, both test conditionss are identical.
| ????Pd＋Bi | ?????????????Bi＋Pd | ||
| Reaction times | Active (reaction times/minute) | Reaction times | Active (reaction times/minute) |
| ????1 | ????62′ | ????1 | ????46′ |
| ????2 | ????109′ | ????2 | ????63′ |
| ????3 | ????134′ | ????3 | ????64′ |
| ????4 | ????142′ | ????4 | ????68′ |
| ????5 | ????158′ | ????5 | ????79′ |
| ????6 | ????227′ | ????6 | ????92′ |
| ????7 | Inactivation | ????7 | ????98′ |
| ????8 | ????100′ | ||
| ????9 | ????112′ | ||
| ????10 | ????113′ | ||
| ????11 | ????108′ | ||
| ????12 | ????109′ | ||
| ????13 | ????112′ | ||
| ????14 | ????112′ | ||
| ????15 | ????115′ | ||
| ????16 | ????120′ | ||
| ????17 | ????128′ | ||
The inventor has also done a large amount of research to carrier active carbon.The carrier active carbon that can be used as catalyzer of the present invention is nutshell class gac and timber gac, and inventor's suggestion is preferably used the timber gac, especially under the situation of industrial applications.In addition, carrier active carbon of the present invention preferably carries out acidification in advance.The preprocessing process of carrier active carbon comprises, makes carrier active carbon pulp in excessive greatly water, adds an amount of acid then, handle appropriate time after, after filtration, and wash with water remove acid group after, drying obtains the carrier active carbon that the present invention preferably uses.The present invention has obtained gratifying carrier active carbon by repeatedly experiment, and its specific surface area reaches 1200 meters squared per gram.Table 2 has been listed the integrated data preferred catalyst of the present invention is used the processing of picture processing instrument after the specific surface instrument is measured after.Simultaneously, accompanying drawing 4-6 has provided the graphic representation of explanation preferred catalyst performance of the present invention.Table 2
| Relative pressure | Adsorption volume | Pore radius | Pore volume | The accumulation pore volume | The relative opening volume |
| ??0.0009 ??0.0426 ??0.0841 ??0.1258 ??0.1674 ??0.209 ??0.2806 ??0.2922 ??0.3338 ??0.3754 ??0.4159 ??0.4585 ??0.5003 ??0.5418 ??0.5834 ??0.6249 ??0.6664 ??0.7081 ??0.7501 ??0.7913 ??0.8329 ??0.8744 ??0.9159 ??0.9576 ??0.9994 | ??175.117 ??240.289 ??263.443 ??280.832 ??264.769 ??267.662 ??269.792 ??271.554 ??273.043 ??274.378 ??275.58 ??276.653 ??277.661 ??278.578 ??279.5 ??280.422 ??281.313 ??282.18 ??283.106 ??284.09 ??285.273 ??286.31 ??288.322 ??291.648 ??392.943 | ????5.20 ????0.03 ????9.28 ????10.36 ????11.39 ????12.42 ????13.48 ????14.50 ????15.81 ????17.13 ????18.58 ????20.20 ????22.07 ????24.20 ????26.71 ????29.72 ????33.40 ????38.08 ????44.27 ????52.63 ????68.03 ????85.35 ????125.00 ????240.87 ???15965.48 | ????270.8710 ????371.6790 ????392.0766 ????403.1466 ????408.6282 ????414.0041 ????417.3143 ????420.0397 ????422.3429 ????424.4079 ????426.2671 ????427.9269 ????429.4860 ????430.3046 ????432.3306 ????433.7667 ????435.1349 ????436.4750 ????437.9084 ????439.4304 ????441.2603 ????443.1737 ????446.9766 ????461.1211 ????607.8042 | ????0.4457 ????0.6115 ????0.6450 ????0.8633 ????0.6138 ????0.6611 ????0.6066 ????0.8911 ????0.6949 ????0.6983 ????0.7013 ????0.7041 ????0.7066 ????0.7090 ????0.7113 ????0.7136 ????0.7159 ????0.7181 ????0.7205 ????0.7230 ????0.7260 ????0.7291 ????0.7338 ????0.7422 ????1.0000 | ????0.4457 ????0.1659 ????0.0310 ????0.0183 ????0.0106 ????0.0074 ????0.0054 ????0.0045 ????0.0038 ????0.0034 ????0.0031 ????0.0027 ????0.0026 ????0.0023 ????0.0023 ????0.0023 ????0.0023 ????0.0022 ????0.0024 ????0.0025 ????0.0030 ????0.0031 ????0.0046 ????0.0085 ????0.2578 |
Though catalyzer of the present invention has good endurance, the advantage that multiplexing number is many for a commercial process, still needs to exist the regeneration recovery technology of catalyzer.In the present invention, the regeneration recovery method of catalyzer comprises the catalyzer ashing of serious inactivation, with chloroazotic acid ash is dissolved, reclaim the precious metal palladium in the catalyzer then, the rate of recovery is more than 95%, and the concentration of palladium is still more than 99.5%, thereby the catalyzer cost is reduced to greatest extent.
Therefore, on the other hand, the invention provides a kind of catalyst for catalytic oxidation, it contains (a) bismuth; (b) palladium and (c) carrier active carbon, wherein in carrier active carbon, described bismuth palladium charcoal metal catalyst contains the bismuth (in metal) of 3-6% (weight), the palladium (in metal) of 4-10% (weight), and the atomic ratio of bismuth and palladium is 0.3-1.5: 1.Wherein, the atomic ratio of bismuth and palladium is preferably 0.35-1.2: 1, and more preferably, the atomic ratio of bismuth and palladium is 0.4-0.8: 1.
Catalyzer of the present invention can prepare with ordinary method.But preferably adopt following method preparation, it comprises bismuth metal salt and palladium metal salt is dissolved in the hydrochloric acid, carrier active carbon is suspended in the resulting solution, flood and co-precipitation, then with formaldehyde or sodium formiate reduction, the Bi/Pd alloy is stated from the gac altogether, and after washing, drying obtains product catalyst.Wherein, more preferably, carrier active carbon carries out pore-creating with nitric acid treatment in advance.
In Preparation of catalysts method of the present invention, the order of carrier active carbon absorption metal is preferably palladium behind the first bismuth.In Preparation of catalysts method of the present invention, bismuth metal salt is preferably bismuth oxide, Bismuth trinitrate, Bismuth carbonate or Bismuth Subcarbonate, and palladium metal salt is preferably palladous chloride, palladous sulfate or palladium hydroxide.
Above-mentioned catalyzer of the present invention is preferred for preparing gluconate by glucose catalyticing oxidation.
In the conventional industrialization application technology of catalyzed oxidation, usually adopt stirring means, because oxygen-containing gas can not be smashed necessary degree, oxidation rate can not reach requirement, the inventor has developed a kind of jet paraffin oxidation device that is used for catalytic oxidation process, has solved this difficult problem.Is example with air as oxygen-containing gas, in jet paraffin oxidation device of the present invention, air molecule is crushed to about 0.2um by high-pressure spray, makes that oxygen molecule is fully utilized in the air, improved the utilization ratio of oxygen greatly, made the volume coefficient of oxidation reactor reduce to bottom line.Simultaneously, jet paraffin oxidation device of the present invention directly under high pressure mixes catalyzer, air and D/W, thereby has obtained great reaction table area, and catalyzer passes to the aldehyde radical of glucose with airborne oxygen molecule, makes it be oxidized to carboxyl.And hydroxy group of glucose can be not oxidized, therefore obtained high transformation efficiency and selectivity (95-99%).
Below, be further described referring to 2 pairs of air spray oxidizers of the present invention of accompanying drawing.In accompanying drawing 2, reaction raw materials (D/W) and catalyzer are added in the air spray oxidizer (23) by inlet (20), when the reaction beginning, material by the bottom after high-pressure pump (24) is sent in the injector (21) by material circulation tube (22), spurt in the jet paraffin oxidation device, suck the air of being sent into by air introduction pipe line (26) by jet paraffin oxidation device upper inlet (25) simultaneously, alkali is added in the reactive system by inlet (28).Behind the reactor EO, discharge oxidation liquid by outlet (27) and carry out later purification step.In jet paraffin oxidation device of the present invention, the jet paraffin oxidation device typically have a diameter from the 1200-1800 millimeter, highly be 7-12 rice.The injector diameter is the 159-218 millimeter, and injector preferably is immersed in the reaction solution, and spraying pressure can be 0.5-1.0mpa.
Below will the present invention is further illustrated by embodiment, embodiment is not a limitation of the present invention.14.4 kilograms of commercially available gacs (carbo lignius) are got in the preparation (A) of embodiment 1 catalyst for catalytic oxidation, stir dipping with 20-50 times of water, regulate PH to 1.0-3.5 with nitric acid, dipping spends the night, be washed with water to no nitrate radical after the filtration, subsequently 105 ℃ of dry for standby; (B) take by weighing Bismuth trinitrate 1080 gram, with 1: 1HCl is moistening, and the water mixed dissolution is mixed well again, and the gac that above-mentioned (A) prepares is poured in the aqueous solution of bismuth, violent stirring 3-10 hour, dissolves fully to bismuth salt; (C) take by weighing Palladous chloride (PdCl
2) 950 grams, with 1: the moistening back of 1HCl water is mixed well into palladium glue, and concentration is about 10-30%, dripped in 10-40 minute in bismuth charcoal solution under the agitation condition, fully stirred 3-6 hour, hydro-oxidation sodium is transferred PH to 8-11, heat to 80 ℃ or boil, be washed with water to no chlorine root after the filtration; (D) in the catalyzer that above-mentioned (C) obtains, add an amount of reductive agent formaldehyde, fully stirred 1-2 hour, be washed with water to no chlorine root, 105 ℃ of dry for standby.Embodiment 2 is prepared the method for calcium gluconate through catalyzed oxidation by glucose
500 kilograms of material crystal glucose (doing meter) are used water dissolution, be prepared into 5M
310% (W/V) sugar aqueous solution, add 6.25 kilograms of the bismuth-palladiums of embodiment 1 preparation/charcoal metal catalyst therein, the sugar aqueous solution that will be mixed with catalyzer is subsequently imported in the jet paraffin oxidation device with high-pressure pump by the bottom of oxidizer, carry out jet paraffin oxidation, air is sucked by the oxidizer upper inlet by spraying, circulate continuously, jet paraffin oxidation, solution flow is 180-250M
3, the suction air capacity is 240-280M
3Carried out continuously 4-8 hour, add calcium hydroxide simultaneously, the pH value of strict controlled oxidation reaction is 8.5-11, and temperature of reaction is 30-80 ℃, calcium hydroxide and glucose etc. are when reaction, after the alkali of metering adds, the stopping of reaction, pH value drops to below 7.8, oxidizing reaction is promptly accused and is finished, and obtains the water white reaction solution.Transformation efficiency is 95-98%, and selectivity is 97-99%.The oxidation liquid that obtains is isolated catalyzer in separator, obtained separating the oxidation liquid 7.3M of catalyzer
3, concentration 8%, wherein containing solid thing is about 600 kilograms, and residual sugar is less than 1%, and the calcium gluconate growing amount is about 582 kilograms.With gac it is decoloured, evaporation concentration is to proportion 1.08-1.20 subsequently, static crystallization more than 18 hours in crystallizer again.Through sedimentator centrifugation washing, obtain 873 kilograms of white crystals bodies, moisture 40-50%.Xln is through fluidized drying, is dried to moisturely 0.5%, obtains 436.5 kilograms of finished product calcium gluconates.Reuse in the calcium gluconate mother liquor Returning process that whizzer is separated.The quality situation of above-mentioned finished product, analytical results is as follows:
Proterties: meet the requirements
Differentiate: meet the requirements
Moisture: 0.27%
Muriate: 70ppm
Vitriol: 60ppm
Arsenic salt: do not have
Heavy metal: 3ppm
Reduzate: meet the requirements
Magnesium salts and an alkali metal salt: 0.34%
Calcium gluconate content: 99.51%
Above-mentioned analytical results shows that quality product of the present invention meets the standard of Chinese Pharmacopoeia, American Pharmacopeia, British Pharmacopoeia simultaneously.Wherein several unapproachable standards such as vitriol, heavy metal, magnesium salts and an alkali metal salt muriate all are significantly less than the highest British Pharmacopoeia standard of requirement.
According to embodiment 2 measuring and calculating, it is as follows to produce the main supplementary material of commodity calcium gluconate per ton consumption and the energy:
1.43 tons of W-Gums
1.43 kilograms of catalyzer
200 kilograms in calcium hydroxide
2.7 tons of coals
Electricity 1036 degree
113 tons in water
According to the market survey that the inventor carries out,, produce the main supplementary material of commodity calcium gluconate per ton consumption and the energy following (1994) for the method that adopts the fermentative Production calcium gluconate:
2.0 tons of W-Gums
4.5 kilograms in ammonium sulfate
2.5 kilograms in sal epsom
3.1 kilograms of potassium primary phosphates
40 kilograms of limes
1000 kilograms in solo flight powder
4.0 tons of coals
Electricity 3000 degree
120 tons in water
According to above-mentioned measuring and calculating, compare with traditional fermentation method, prepare calcium gluconate with catalysed oxidation processes of the present invention, (cornstarch) 28.5% that can economize in raw materials, energy savings (water, electricity) 42 % reduce cost 20%, and essentially no three waste discharge has positive effect.
Claims (16)
1. the catalyzed oxidation by glucose prepares the method for gluconate, it comprises that bismuth-palladium/charcoal metal catalyst exists down, under the catalyzed oxidation condition, make glucose and oxygen-containing gas prepared in reaction gluconate under alkaline condition, wherein in carrier active carbon, described bismuth-palladium/charcoal metal catalyst contains the bismuth (in metal) of 3-6% (weight), the palladium (in metal) of 4-10% (weight), and, the atomic ratio of bismuth and palladium is 0.3-1.5: 1, and with dried glucose meter, catalyst consumption is 1.2-1.5% (weight).
2. method according to claim 1, wherein, the atomic ratio of bismuth and palladium is 0.35-1.2: 1.
3. method according to claim 2, wherein, the atomic ratio of bismuth and palladium is 0.4-0.8: 1.
4. according to the described method of one of claim 1-3, wherein, catalytic oxidation 30-80 ℃ down and pH value be to carry out under the 8.5-11.
5. according to the described method of one of claim 1-3, wherein, oxygen-containing gas is an air.
6. according to the described method of one of claim 1-5, wherein, described gluconate is calcium gluconate or gluconic acid sodium salt.
7. according to the described method of claim 1-6, it also comprises the step that is obtained glyconic acid by gluconate by H+ ion-exchange.
8. according to the described method of claim 1-7, wherein catalytic oxidation process carries out in the air spray oxidizer.
9. catalyst for catalytic oxidation, it contains (a) bismuth; (b) palladium and (c) carrier active carbon, wherein in carrier active carbon, described bismuth palladium charcoal metal catalyst contains the bismuth (in metal) of 3-6% (weight), the palladium (in metal) of 4-10% (weight), and the atomic ratio of bismuth and palladium is 0.3-1.5: 1.
10. catalyzer according to claim 9, wherein, the atomic ratio of bismuth and palladium is 0.35-1.2: 1.
11. catalyzer according to claim 9, wherein, the atomic ratio of bismuth and palladium is 0.4-0.8: 1.
12. the described Preparation of catalysts method of claim 9-11, it comprises bismuth metal salt and palladium metal salt is dissolved in the hydrochloric acid, carrier active carbon is suspended in the resulting solution, flood and co-precipitation, then with formaldehyde or sodium formiate reduction, the Bi/Pd alloy is stated from the gac altogether, and after washing, drying obtains product catalyst.
13. according to the method for claim 12, wherein, carrier active carbon carries out pore-creating with nitric acid treatment in advance.
14. according to the method for claim 12, wherein, the order of carrier active carbon absorption metal is a palladium behind the first bismuth.
15. according to the method for claim 12-14, wherein, bismuth metal salt is bismuth oxide, Bismuth trinitrate, Bismuth carbonate or Bismuth Subcarbonate, palladium metal salt is palladous chloride, palladous sulfate or palladium hydroxide.
16. the described catalyzer of claim 9-11 is in the application that is prepared by glucose catalyticing oxidation in the gluconate.
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| CN 96106774 CN1153166A (en) | 1996-07-09 | 1996-07-09 | Method for preparing gluconate in presence of Bi-Pd/C metal catalyst |
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| CN 96106774 CN1153166A (en) | 1996-07-09 | 1996-07-09 | Method for preparing gluconate in presence of Bi-Pd/C metal catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816935A (en) * | 2010-03-18 | 2010-09-01 | 游汉生 | Carbon-carried palladium catalyst and preparation method thereof |
| CN102247844A (en) * | 2011-05-12 | 2011-11-23 | 游汉生 | Carbon-supported palladium bismuth bimetallic catalyst, preparation method and application thereof |
| CN102701952A (en) * | 2012-06-13 | 2012-10-03 | 河南科之杰新材料有限公司 | Method for preparing retarded sodium gluconate |
| CN103467275A (en) * | 2013-09-14 | 2013-12-25 | 河南兴发精细化工有限公司 | Catalytic oxidation production method of sodium gluconate liquid by means of activated carbon treatment |
| CN112892527A (en) * | 2021-01-21 | 2021-06-04 | 福州宏通建材有限公司 | Palladium-carbon catalyst for catalyzing liquid sodium gluconate and production process thereof |
-
1996
- 1996-07-09 CN CN 96106774 patent/CN1153166A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816935A (en) * | 2010-03-18 | 2010-09-01 | 游汉生 | Carbon-carried palladium catalyst and preparation method thereof |
| CN101816935B (en) * | 2010-03-18 | 2012-08-08 | 游汉生 | Carbon-carried palladium catalyst and preparation method thereof |
| CN102247844A (en) * | 2011-05-12 | 2011-11-23 | 游汉生 | Carbon-supported palladium bismuth bimetallic catalyst, preparation method and application thereof |
| CN102701952A (en) * | 2012-06-13 | 2012-10-03 | 河南科之杰新材料有限公司 | Method for preparing retarded sodium gluconate |
| CN103467275A (en) * | 2013-09-14 | 2013-12-25 | 河南兴发精细化工有限公司 | Catalytic oxidation production method of sodium gluconate liquid by means of activated carbon treatment |
| CN112892527A (en) * | 2021-01-21 | 2021-06-04 | 福州宏通建材有限公司 | Palladium-carbon catalyst for catalyzing liquid sodium gluconate and production process thereof |
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