[go: up one dir, main page]

US3030429A - Process for the direct hydrogenation splitting of - Google Patents

Process for the direct hydrogenation splitting of Download PDF

Info

Publication number
US3030429A
US3030429A US3030429DA US3030429A US 3030429 A US3030429 A US 3030429A US 3030429D A US3030429D A US 3030429DA US 3030429 A US3030429 A US 3030429A
Authority
US
United States
Prior art keywords
hydrogenation
splitting
saccharose
glycerol
nickel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Publication date
Application granted granted Critical
Publication of US3030429A publication Critical patent/US3030429A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C07C31/205—1,3-Propanediol; 1,2-Propanediol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/26—Hexahydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/22—Trihydroxylic alcohols, e.g. glycerol
    • C07C31/225—Glycerol

Definitions

  • the invention hereinafter described relates to a process for the hydrogenation splitting of saccharose (cane sugar) directly to glycerol and glycols.
  • saccharose cane sugar
  • Numerous processes have been described for converting cane sugar and other carbohydrates into hexitols and polyalcohols with a lower number of carbon atoms by hydrogenation, or hydrogenation splitting.
  • the process employed usually comprises inverting the cane sugar with acid and then removing the acid after converting it into a diicultly soluble salt.
  • the invert sugar obtained is then hydrogeuated under certain given conditions to a mixture of sorbitol and mannitol. If it is desired to obtain glycerol and glycols, the said mixture of sorbitol and mannitol must be subjected to hydrogenation splitting under vigorous conditions. In order to obtain glycerol and glycols, therefore, three steps are usually necessary:
  • Patent 2,004,1305 for example, a process is described by which the hydrogenation is carried out in the presence of a hydrogenation catalyst which contains a weakly basic compound.
  • a hydrogenation catalyst which contains a weakly basic compound.
  • the instructions also are to work at a pH of about 8, i.e., under slightly alkaline conditions, but this is for the classical method of (a) inversion, (b) hydrogenation to sorbitol and mannitol, (c) hydrogenation splitting to glycerol and glycol.
  • the hydrogenation splitting of the saccharose may also be carried out in the presence of Raney nickel or nickel-magnesium oxalate (according to Langenbeck) if the initial pH is adjusted to l2 by addition of alkali.
  • Raney nickel or nickel-magnesium oxalate according to Langenbeck
  • sugars in general, including saccharose are very sensitive to alkalis.
  • the temperature at which this process is carried out is preferably ISO-250 C.
  • the pressure may be varied within the widest limits. Excellent results are obtained at 60 atmospheres above atmospheric pressure.
  • the proportion of the most valuable of the splitting products, namely glycerol may be further increased by raising the pressure to 1,000 atmospheres above atmospheric pressure, whereby the yield in glycerol, calculated on the conversion, may rise to more than 40%.
  • the reaction mixture always remains exposed for a uniform length of time to the reaction conditions so that reductions in yield'cannot be caused either by too long or by too short durations of dwell.
  • the hydrogen is saturated with steam, to an extent depending on the reaction conditions.
  • the steam condenses and separates.
  • the reaction product can be concentrated to a greater or lesser extent during hydrogenation, according to the amount of hydrogen circulated.
  • the concentration yattained during this process cannot bring about any decomposition of the saccharose because the saccharose enters the reaction chamber in the form of a dilute solution and, under the reaction conditions selected in accordance with the invention, the saccharose is converted before the concentration can rise to a level at which decomposition of the saccharose might occur.
  • reaction times which were about 2-3 hours in the older processes, are reduced to less than minutes, preferably between 2 and 5 minutesV in the new process.
  • the process according to the invention has one further advantage. More volatile constituents which always are formed in small amounts in hydrogenation splitting, namely lower alcohols, acids, etc., are removed with the condensate. The product leaving the reaction tube, therefore, has a greater degree of purity than the products obtained by the previous processes.
  • Example 1 A 10% aqueous saccharose solution is subjected to hydrogenation splitting at 180 C. and at 60 atmospheres excess pressure for 3 hours in the presence of nickel on kieselguhr, with thorough mixing.
  • the pH is adjusted to 12 with Ca(OI-I)2, for which 10% Ca(OH)2 calculated on the sugar is required.
  • the hydrogenation product obtained is clear, colorless and odorless.
  • the conversion is 42.5%. The following are obtained, the percentage being calculated on the conversion: 12.2% pentitol, 18.2% erythritol, 34.2% ⁇ glycerol, 10.6% ethylene glycol and 6.1% propylene glycol.
  • sorbitol- Y cane sugar manmtol The efciency and conversion rate thus are just as good in the direct hydrogenation splitting of cane sugar as in the hydrogenation splitting of a mixture of sorbitol and mannitol, but in the former there is the added advantage that inversion and hydrogenation to sorbitol are bypassed, which makes the process very much simpler.
  • Example 5 The advantage of the process become particularly marked when the operation is carried out continuously. 5 liters per hour of a 10% aqueous saccharose ysolution mixed lwith 12% hydrogenation catalyst (nickel on kieselguhr) are conveyed from a mixing vessel 1 with stirrer by means of pump 2 through pipe 3 to an autoclave 6 which has a capacity of 16 liters and which is provided with a heating jacket 5. At the same time, fresh ⁇ hydrogen is supplied to the autoclave from compressor 7 through pipe 8. rIhe hydrogen not consumed in the reaction vessel is decompressed and, after passing through condensor 9 and separator 10, is conveyedthrough pipe 11 and compressor 12 to be mixed with the fresh hydrogen coming from compressor 7.
  • a 10% aqueous saccharose ysolution mixed lwith 12% hydrogenation catalyst nickel on kieselguhr
  • reaction product 5 liters per hour of the reaction product are removed from the reaction vessel 6 through pipe 13 to pass through valve 14 into an expansion vessel where it is decompressed. From there, the decompressed reaction product is pumped by a pump 16 to iilter 17, where it is freed from catalyst. Most of the catalyst is returned to the mixing vessel 1 to be usedv again.
  • the reaction product which is freed from catalystA through the cycle is 350 liters per hour, measured'underV the pressure of the reaction, and the amount of fresh hydrogen supplied is 200 liters per hour, measured at atmospheric pressure.
  • the pressure is 60 atmospheres excess pressure, the temperature 210 C. A conversion of 82.9% is obtained. This comprises 11.4% erythritol, 42.8% glycerol, 17.8% ethylene glycol, and 24.6% propylene glycol. From this, it may be seen that the continuous method gives good results even when there is only a slight excess pressure.
  • Example 6 In the same apparatus and under otherwise similar conditions as in Example a pressure of 300 atmospheres is employed instead of 60 atmospheres. The following results are obtained.
  • Example 7 In an apparatus similar to the one described in Example 5, but in which the autoclave 6 is filled with Raschig rings, a starting solution of saccharose in water is treated with hydrogen, the temperature of the reaction being 200 C. and the pressure 300 atmospheres. Nickel on kieselguhr is used as catalyst. The duration of dwell is 3 minutes, the amount of hydrogen circulated is 200 1./h., the throughput of saccharose solution is 6 1./h. The rate of production is approximately 2 1./h., the rate of condensation is 4 l./h. The concentration of the reaction solution after leaving the autoclave is 30%.
  • Example 8 The conditions are the same as in Example 7. Raney nickel is used as catalyst. The circulated quantity of hydrogen is 300 l./h. The concentration of the reaction solution is approximately 40%. The conversion is 97%.
  • Example 9 Same conditions as in Example 1. By the old method, the reaction product contains approximately 3% lower alcohols (methyl alcohol, ethyl alcohol, propyl alcohol) calculated on the cane sugar initially charged. By the new method, the reaction product is free from lower alcohols.
  • a process for the direct production of glycerol and glycols from aqueous saccharose solutions in a single stage by catalytic hydrogenation splitting which comprises starting said hydrogenation at a pH of substantially 12, and carrying out said hydrogenation within 2-10 minutes at temperatures of 180-250o C., at pressures of -250 atmospheres and with hydrogenation catalysts selected from the group consisting of nickel on kieselguhr, nickel on aluminum oxide and Raney nickel.
  • a process for the direct continuous production of glycerol and glycols from aqueous saccharose solutions in a single stage by hydrogenation splitting in a reactor which comprises continuously passing said solutions downward in said reactor in thin layers, and contacting the same countercurrently with hydrogen, while carrying out said hydrogenation at a constant pH of substantially 12, at temperatures of -250" C., at pressures of 50-250 atmospheres for 2-10 minutes, using catalysts selected from the group consisting of nickel on kieselguhr, nickel on aluminum oxide and Raney nickel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

April 17, 1962 F. coNRADlN ETAL. 3,030,429 PRocEss FOR THE DIRECT HYDROGENATION SPLITTING oF sAccHARosE To GLYCEROL AND GLYcoLs Filed July '7, 1959 Jaya/wv G/EsE/y Unite rates hice PROCESS FOR THE DIRECT HYDRGGENATIN SPLITTING F SACCHAROSE T0 GLYCEROL AND GLYCLS Fritz Conradin, Tamins, Giuseppe Bertossa, Ems, and lloharln Giesen, Haldenstein, near Chur, Switzerland, assignors to inventa, A G. fr Forschung und Patentverwertung, Zurich, Switzerland Filed July 7, 1959, Ser. No. 825,427 Claims priority, application Switzerland July 9, 1958 2 Claims. (Cl. 26d- 635) The invention hereinafter described relates to a process for the hydrogenation splitting of saccharose (cane sugar) directly to glycerol and glycols. Numerous processes have been described for converting cane sugar and other carbohydrates into hexitols and polyalcohols with a lower number of carbon atoms by hydrogenation, or hydrogenation splitting. The process employed usually comprises inverting the cane sugar with acid and then removing the acid after converting it into a diicultly soluble salt. The invert sugar obtained is then hydrogeuated under certain given conditions to a mixture of sorbitol and mannitol. If it is desired to obtain glycerol and glycols, the said mixture of sorbitol and mannitol must be subjected to hydrogenation splitting under vigorous conditions. In order to obtain glycerol and glycols, therefore, three steps are usually necessary:
(1) Inversion of cane sugar.
(2) Hydrogenation of the invert sugar to a mixture of sorbitol and mannitol.
(3) Hydrogenation splitting of the sorbitol-mannitol mixture to glycerol and glycols.
Processes have been described by which polysaccharides are hydrogenated directly to glycerols and glycols. Thus the oldest German patent specification related to this subject, namely patent specification No. 541,362, gives examples showing how saccharose, starch or cellulose, for instance, can be hydrogenated directly to glycerol and glycols. But here again the method basically consists in first carrying out inversion or hydrolysis by means of the acid formed in the treatment of the dior polysaccharide, this hydrolysis being followed by hydrogenation of the resulting monosaccharides to hexitol and hydrogenation splitting of the hexitol to glycerol and glycols.
Furthermore, it is known that these direct hydrogenations of dior polysaccharides only take place with strong decomposition and poor yields since the catalysts used are very sensitive to acid.
It has already been proposed to work with special catalysts which split off acid substances or substances which are acid in reaction, as for example in Dutch specication No. 60,860. Here also the dior polysaccharide is first inverted or hydrolyzed and then hydr-ogenated. But, as mentioned above, hydrogenation in acid medium gives poor yields and is accompanied by the formation of decomposition products. It has also been known for a long time that hydrogenation of monosaccharides to hexitols and hydrogenation splitting of the hexitols to glycerol and glycols proceed better in a slightly alkaline medium than in a neutral or, worse still, an acid medium. Thus, in U.S. Patent 2,004,135, for example, a process is described by which the hydrogenation is carried out in the presence of a hydrogenation catalyst which contains a weakly basic compound. For the known glycerogen process (FIAT 872) which has been carried out on a technical scale for many years, the instructions also are to work at a pH of about 8, i.e., under slightly alkaline conditions, but this is for the classical method of (a) inversion, (b) hydrogenation to sorbitol and mannitol, (c) hydrogenation splitting to glycerol and glycol.
It also has previously been recommended, when using special catalysts, to use sodium carbonate as promoter for the direct hydrogenation of carbohydrates as, for example, in the U.S. patent speciiication No. 2,201,235. In this process, an alkaline carbonate in a quantity of 0.1- 10% calculated on the catalysts or 0.0l-1% calculated on the saccharose is preferably used as promoter. Furthermore, hydrogenation is carried out in the presence of methanol. In U.S. Patent 2,325,206, the process is also carried out in the presence of alkali, at an initial pH of 10.8. The particulars given only apply, however, when special copper catalysts are used. According to U.S. Patent 2,325,207, it also is necessary to work with very special copper catalysts, and for that reason, in a solution of aqueous methanol, which does not render the process more economical.
All the previously known processes for obtaining glycerol and glycols from saccharose have either the disadvantage that the process must be carried out in three steps, namely (a) inversion, (b) hydrogenation to sorbitol, (c) hydrogenation splitting to glycerol and glycol, or the disadvantage that it is necessary to work in the presence of special catalysts (in some cases in methanolic solution).
It has now been found that the hydrogenation splitting of saccharose to glycerol and glycols can be carried out in the presence of practically any technically feasible catalyst, provided that alkali is added to ensure a pH of 11- 12.5, preferably 12, at least at the start of the hydrogenation. For technical purposes, it is preferable to use catalysts which are simple and inexpensive to prepare, relatively insensitive to poisons, and which can be used repeatedly and are easily regenerated, particularly nickel catalysts which are precipitated on carriers, such as kieSelguhr or aluminum oxide. The process according to the invention, however, is, by no means, limited to the use of these catalysts. The hydrogenation splitting of the saccharose may also be carried out in the presence of Raney nickel or nickel-magnesium oxalate (according to Langenbeck) if the initial pH is adjusted to l2 by addition of alkali. Quite recently, it has been proposed to convert the monosaccharides directly to glycerol and glycols in the presence of very special nickel copper catalysts, the hexitol stage being by-passed. In this process, however, it still is necessary to carry out the complicated step of inversion, when using saccharose, and to neutralize the acid used and then separate it. As is known, sugars in general, including saccharose, are very sensitive to alkalis. Particularly at high temperatures, eg., above C., complete decomposition of the sugar may occur. t, therefore, was very surprising to iind that the hydrogenation splitting of saccharose, which takes place only with strong decomposition or with poor yields when carried out under weakly acid, neutral or weakly alkaline conditions up to pH 10, proceeds smoothly and without any decomposition if the saccharose solution which is being hydrogenated is adjusted to a pH of 12. The other reaction conditions may be varied within wide limits.
The temperature at which this process is carried out is preferably ISO-250 C. The pressure may be varied within the widest limits. Excellent results are obtained at 60 atmospheres above atmospheric pressure. The proportion of the most valuable of the splitting products, namely glycerol, may be further increased by raising the pressure to 1,000 atmospheres above atmospheric pressure, whereby the yield in glycerol, calculated on the conversion, may rise to more than 40%.
As the process of the invention was further developed, it was discovered that the yield in glycerol and glycols could be still further improved to a considerable extent if the hydrogenation splitting of the saccharose solution was carried out in thin layers, the hydrogen being passed in countercurrent to the saccharose solution.
By this thin layer treatment of the saccharose solution,
acechan in which the saccharose solution preferably trickles downwards in a tube packed with lling bodies such as Raschig rings or saddle bodies while the hydrogen is passed upward inside the tube, the reaction mixture always remains exposed for a uniform length of time to the reaction conditions so that reductions in yield'cannot be caused either by too long or by too short durations of dwell.
In this method, the hydrogen is saturated with steam, to an extent depending on the reaction conditions. YWhen the hydrogen has left the column, the steam condenses and separates. The reaction product can be concentrated to a greater or lesser extent during hydrogenation, according to the amount of hydrogen circulated.
This manner of raising Vthe concentration was not possible in the previous processes, because it would have led to a simultaneous increase in the concentration of the saccharose, with consequent decomposition of the saccharose. In the process according to the invention, the reaction product trickles in the form of a thin film, e.g., over the yfilling bodies, while no intermixing takes place between the saccharose solution entering the tube and the converted reaction product. Consequently, the yields rise to about 95-100%. The concentration yattained during this process cannot bring about any decomposition of the saccharose because the saccharose enters the reaction chamber in the form of a dilute solution and, under the reaction conditions selected in accordance with the invention, the saccharose is converted before the concentration can rise to a level at which decomposition of the saccharose might occur.
The reaction times, which were about 2-3 hours in the older processes, are reduced to less than minutes, preferably between 2 and 5 minutesV in the new process.
The process according to the invention has one further advantage. More volatile constituents which always are formed in small amounts in hydrogenation splitting, namely lower alcohols, acids, etc., are removed with the condensate. The product leaving the reaction tube, therefore, has a greater degree of purity than the products obtained by the previous processes.
The invention now will be further illustrated by the following examples. However, it should be understood that these are given merely by way of explanation, not of limitation, and that numerous changes in the details may be made without departing from the spirit and the scope of the present invention as hereinafter claimed.
In all the results given in the examples, the following should be noted: In no case is there any unconverted saccharose left; the conversions stated relate to sorbitol and -rnannitol which have been formed and not converted. The figures given for lthe yields refer to the conversion of sorbitol and mannitol to glycols. The catalyst, which generally contains the metal components in a quantity of -25 percent by weight calculated on the saccharose initially charged, is generally used in a quantity of 10-l5% by weight.
Example 1 A 10% aqueous saccharose solution is subjected to hydrogenation splitting at 180 C. and at 60 atmospheres excess pressure for 3 hours in the presence of nickel on kieselguhr, with thorough mixing. The pH is adjusted to 12 with Ca(OI-I)2, for which 10% Ca(OH)2 calculated on the sugar is required. The hydrogenation product obtained is clear, colorless and odorless. The conversion is 42.5%. The following are obtained, the percentage being calculated on the conversion: 12.2% pentitol, 18.2% erythritol, 34.2%`glycerol, 10.6% ethylene glycol and 6.1% propylene glycol.
Strong decomposition occurs if the calcium hydroxide is omitted. The hydrogenation product then is yellow to brown in color, has a strong, pungent odor and reduces Fehlings solution in the cold, owing to the presence of acetal.
E f Example 2 Example? Comparison of hydrogenation splitting of v saccharose with that of sorbitol/mannitol. If saccharose and sorbitol/mannitol, respectively, are subjected to hydrogenation splitting under the same conditions, namely 230 C., atmospheres excess pressure, 11/2 hours, pH 12, 10% solution, nickel on kieselguhr, the following results are obtained:
sorbitol- Y cane sugar manmtol The efciency and conversion rate thus are just as good in the direct hydrogenation splitting of cane sugar as in the hydrogenation splitting of a mixture of sorbitol and mannitol, but in the former there is the added advantage that inversion and hydrogenation to sorbitol are bypassed, which makes the process very much simpler.
Example' 4 200 C., 130 atmospheres excess pressure,l 3 hours, pH 12, 10% solution, nickel onaluminum oxide. Conversion 50.0%, pentitol 4.7%, erythritol 12.7%, glycerol 36.6%, ethylene glycol 21.2%, propylene glycol 25.8%.
The following examples, 5-8, are continuous operations and are given with reference to the accompanying drawing which is a owsheet for such processes.
Example 5 The advantage of the process become particularly marked when the operation is carried out continuously. 5 liters per hour of a 10% aqueous saccharose ysolution mixed lwith 12% hydrogenation catalyst (nickel on kieselguhr) are conveyed from a mixing vessel 1 with stirrer by means of pump 2 through pipe 3 to an autoclave 6 which has a capacity of 16 liters and which is provided with a heating jacket 5. At the same time, fresh` hydrogen is supplied to the autoclave from compressor 7 through pipe 8. rIhe hydrogen not consumed in the reaction vessel is decompressed and, after passing through condensor 9 and separator 10, is conveyedthrough pipe 11 and compressor 12 to be mixed with the fresh hydrogen coming from compressor 7. 5 liters per hour of the reaction product are removed from the reaction vessel 6 through pipe 13 to pass through valve 14 into an expansion vessel where it is decompressed. From there, the decompressed reaction product is pumped by a pump 16 to iilter 17, where it is freed from catalyst. Most of the catalyst is returned to the mixing vessel 1 to be usedv again. The reaction product which is freed from catalystA through the cycle is 350 liters per hour, measured'underV the pressure of the reaction, and the amount of fresh hydrogen supplied is 200 liters per hour, measured at atmospheric pressure.
The pressure is 60 atmospheres excess pressure, the temperature 210 C. A conversion of 82.9% is obtained. This comprises 11.4% erythritol, 42.8% glycerol, 17.8% ethylene glycol, and 24.6% propylene glycol. From this, it may be seen that the continuous method gives good results even when there is only a slight excess pressure.
Example 6 In the same apparatus and under otherwise similar conditions as in Example a pressure of 300 atmospheres is employed instead of 60 atmospheres. The following results are obtained.
Conversion 56.5%, erythritol 11.8%, glycerol 48.5%, ethylene glycol 4.2%, propylene glycol 16.9%. Corresponding to the higher pressure, the conversion at 300 atmospheres is less than at 60 atmospheres, but the formation of undesirable byproducts also is reduced.
Example 7 In an apparatus similar to the one described in Example 5, but in which the autoclave 6 is filled with Raschig rings, a starting solution of saccharose in water is treated with hydrogen, the temperature of the reaction being 200 C. and the pressure 300 atmospheres. Nickel on kieselguhr is used as catalyst. The duration of dwell is 3 minutes, the amount of hydrogen circulated is 200 1./h., the throughput of saccharose solution is 6 1./h. The rate of production is approximately 2 1./h., the rate of condensation is 4 l./h. The concentration of the reaction solution after leaving the autoclave is 30%.
Example 8 The conditions are the same as in Example 7. Raney nickel is used as catalyst. The circulated quantity of hydrogen is 300 l./h. The concentration of the reaction solution is approximately 40%. The conversion is 97%.
6 Example 9 Same conditions as in Example 1. By the old method, the reaction product contains approximately 3% lower alcohols (methyl alcohol, ethyl alcohol, propyl alcohol) calculated on the cane sugar initially charged. By the new method, the reaction product is free from lower alcohols.
We claim as our invention:
1. A process for the direct production of glycerol and glycols from aqueous saccharose solutions in a single stage by catalytic hydrogenation splitting, which comprises starting said hydrogenation at a pH of substantially 12, and carrying out said hydrogenation within 2-10 minutes at temperatures of 180-250o C., at pressures of -250 atmospheres and with hydrogenation catalysts selected from the group consisting of nickel on kieselguhr, nickel on aluminum oxide and Raney nickel.
2. A process for the direct continuous production of glycerol and glycols from aqueous saccharose solutions in a single stage by hydrogenation splitting in a reactor, which comprises continuously passing said solutions downward in said reactor in thin layers, and contacting the same countercurrently with hydrogen, while carrying out said hydrogenation at a constant pH of substantially 12, at temperatures of -250" C., at pressures of 50-250 atmospheres for 2-10 minutes, using catalysts selected from the group consisting of nickel on kieselguhr, nickel on aluminum oxide and Raney nickel.
References Cited in the le of this patent UNITED STATES PATENTS l 1,990,245 Muener et al. Feb. 5, 1935 2,325,206 Stengel July 27, 1943 FOREIGN PATENTS 1,004,157 Germany Mar. 14, 1957 688,515 Great Britain Mar. 11, 1953

Claims (1)

1. A PROCESS FOR THE DIRECT PRODUCTION OF GLYCEROL AND GLYCOLS FROM AQUEOUS SACCHOROSE SOLUTIONS IN A SINGLE STAGE BY CATALYTIC HYDROGENATION SPLITTING, WHICH COMPRISES STARTING SAID HYDROGENATION AT A PH OF SUBSTANTIALLY 12, AND CARRYING OUT SAID HYDROGENATION WITHIN 2-10 MINUTES AT TEMPERATURES OF 180-250*C., AT PRESSURES OF 50-250 ATMOSPHERES AND WITH HYDROGENATION CATALYSTS SELECTED FROM THE GROUP CONSISTING OF NICKEL ON KIESELGUHR, NICKEL ON ALUMINUM OXIDE AND RANEY NICKEL.
US3030429D Process for the direct hydrogenation splitting of Expired - Lifetime US3030429A (en)

Publications (1)

Publication Number Publication Date
US3030429A true US3030429A (en) 1962-04-17

Family

ID=3450638

Family Applications (1)

Application Number Title Priority Date Filing Date
US3030429D Expired - Lifetime US3030429A (en) Process for the direct hydrogenation splitting of

Country Status (1)

Country Link
US (1) US3030429A (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3341609A (en) * 1967-09-12 Process reactor
US3396199A (en) * 1967-01-03 1968-08-06 Atlas Chem Ind Hydrogenolysis of reducible sugars to obtain a high percentage of glycerol
US3471580A (en) * 1968-04-19 1969-10-07 Hydrocarbon Research Inc Production of glycerol from saccharides
US3691100A (en) * 1970-02-05 1972-09-12 Atlas Chem Ind Tungsten oxide promoted and supported nickel catalyst
JPS5490394A (en) * 1977-12-16 1979-07-18 Bayer Ag Preparation of low molecular weight polyhydroxyl compound
US4404411A (en) * 1982-02-01 1983-09-13 E. I. Du Pont De Nemours And Company Hydrogenolysis of polyols to ethylene glycol in nonaqueous solvents
US4496780A (en) * 1983-06-22 1985-01-29 Uop Inc. Hydrocracking of polyols
US5026927A (en) * 1989-11-16 1991-06-25 The United States Of America As Represented By The United States Department Of Energy Hydrocracking of carbohydrates making glycerol, glycols and other polyols
US5107018A (en) * 1989-08-26 1992-04-21 Basf Aktiengesellschaft Process for the preparation of lower polyhydric alcohols
US5118883A (en) * 1990-07-21 1992-06-02 Basf Aktiengesellschaft Preparation of glycols from formaldehyde
US6291725B1 (en) 2000-03-03 2001-09-18 Board Of Trustees Operating Michigan State University Catalysts and process for hydrogenolysis of sugar alcohols to polyols
US6479713B1 (en) 2001-10-23 2002-11-12 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen
US20030119952A1 (en) * 2001-10-23 2003-06-26 Werpy Todd A. Hydrogenolysis of 6-carbon sugars and other organic compounds
US20090264686A1 (en) * 2008-04-16 2009-10-22 Holladay Johnathan E Hydrogenolysis processes and hydrogenolysis catalyst preparation methods
US20100019191A1 (en) * 2006-12-15 2010-01-28 Basf Se Method for producing 1,2-ethylene glycol and 1,2-propylene glycol by means of the heterogeneously catalysed hydrogenolysis of a polyol
US20100094066A1 (en) * 2007-01-17 2010-04-15 The Curators Of The University Of Missouri Gas phase reaction process for polyhydric compounds
WO2015119767A1 (en) 2014-02-10 2015-08-13 Archer Daniels Midland Company Improved multiphase low mixing processes
WO2017097839A1 (en) * 2015-12-09 2017-06-15 Shell Internationale Research Maatschappij B.V. Process for the preparation of glycols

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1990245A (en) * 1926-11-18 1935-02-05 Ig Farbenindustrie Ag Production of polyhydric alcohols
US2325206A (en) * 1940-05-11 1943-07-27 Commercial Solvents Corp Catalyst and process for the hydrogenation of polyhydroxy compounds
GB688515A (en) * 1950-04-06 1953-03-11 Bataafsche Petroleum Process for preparing polyhydric alcohols by catalytic reduction of carbohydrates
DE1004157B (en) * 1955-07-06 1957-03-14 Hoechst Ag Process for the hydrogenation of carbohydrates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1990245A (en) * 1926-11-18 1935-02-05 Ig Farbenindustrie Ag Production of polyhydric alcohols
US2325206A (en) * 1940-05-11 1943-07-27 Commercial Solvents Corp Catalyst and process for the hydrogenation of polyhydroxy compounds
GB688515A (en) * 1950-04-06 1953-03-11 Bataafsche Petroleum Process for preparing polyhydric alcohols by catalytic reduction of carbohydrates
DE1004157B (en) * 1955-07-06 1957-03-14 Hoechst Ag Process for the hydrogenation of carbohydrates

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3341609A (en) * 1967-09-12 Process reactor
US3396199A (en) * 1967-01-03 1968-08-06 Atlas Chem Ind Hydrogenolysis of reducible sugars to obtain a high percentage of glycerol
US3471580A (en) * 1968-04-19 1969-10-07 Hydrocarbon Research Inc Production of glycerol from saccharides
US3691100A (en) * 1970-02-05 1972-09-12 Atlas Chem Ind Tungsten oxide promoted and supported nickel catalyst
JPS5490394A (en) * 1977-12-16 1979-07-18 Bayer Ag Preparation of low molecular weight polyhydroxyl compound
US4404411A (en) * 1982-02-01 1983-09-13 E. I. Du Pont De Nemours And Company Hydrogenolysis of polyols to ethylene glycol in nonaqueous solvents
US4496780A (en) * 1983-06-22 1985-01-29 Uop Inc. Hydrocracking of polyols
US5107018A (en) * 1989-08-26 1992-04-21 Basf Aktiengesellschaft Process for the preparation of lower polyhydric alcohols
US5026927A (en) * 1989-11-16 1991-06-25 The United States Of America As Represented By The United States Department Of Energy Hydrocracking of carbohydrates making glycerol, glycols and other polyols
US5118883A (en) * 1990-07-21 1992-06-02 Basf Aktiengesellschaft Preparation of glycols from formaldehyde
US6291725B1 (en) 2000-03-03 2001-09-18 Board Of Trustees Operating Michigan State University Catalysts and process for hydrogenolysis of sugar alcohols to polyols
US20030119952A1 (en) * 2001-10-23 2003-06-26 Werpy Todd A. Hydrogenolysis of 6-carbon sugars and other organic compounds
EP1939161A1 (en) 2001-10-23 2008-07-02 Battelle Memorial Institute Hydrogenolysis of sugars and sugar alcohols
US6677385B2 (en) 2001-10-23 2004-01-13 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols and compositions for reactions involving hydrogen
US20040064003A1 (en) * 2001-10-23 2004-04-01 Werpy Todd A. Hydrogenolysis of 5-carbon sugars, sugar alcohols, and methods of making propylene glycol
US6841085B2 (en) 2001-10-23 2005-01-11 Battelle Memorial Institute Hydrogenolysis of 6-carbon sugars and other organic compounds
US7038094B2 (en) 2001-10-23 2006-05-02 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols, and methods of making propylene glycol
EP1935487A1 (en) 2001-10-23 2008-06-25 Battelle Memorial Institute Composition comprising sugars or sugar alcohols
US6479713B1 (en) 2001-10-23 2002-11-12 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen
EP1942092A1 (en) 2001-10-23 2008-07-09 Battelle Memorial Institute Preparation of propylene glycol by hydrogenating lactate or lactic acid
US20100019191A1 (en) * 2006-12-15 2010-01-28 Basf Se Method for producing 1,2-ethylene glycol and 1,2-propylene glycol by means of the heterogeneously catalysed hydrogenolysis of a polyol
US20100094066A1 (en) * 2007-01-17 2010-04-15 The Curators Of The University Of Missouri Gas phase reaction process for polyhydric compounds
US20090264686A1 (en) * 2008-04-16 2009-10-22 Holladay Johnathan E Hydrogenolysis processes and hydrogenolysis catalyst preparation methods
WO2015119767A1 (en) 2014-02-10 2015-08-13 Archer Daniels Midland Company Improved multiphase low mixing processes
WO2017097839A1 (en) * 2015-12-09 2017-06-15 Shell Internationale Research Maatschappij B.V. Process for the preparation of glycols

Similar Documents

Publication Publication Date Title
US3030429A (en) Process for the direct hydrogenation splitting of
US2004135A (en) Production of polyhydric alcohols
US3953517A (en) Process for preparing methyl isobutyl ketone and catalyst
EP0340970B1 (en) Preparation of mixtures of butanediols
US2965679A (en) Process for the production of glycerol
GB1463266A (en) Preparation of hydroxypivaldehyde
US2485989A (en) Process for converting lower-boiling aldehydes into higher-boiling aldehydes
US3090815A (en) Isomerization of alkylene oxide
US4590312A (en) Process for preparing 2-alkyl-1,4-butanediols
US4859801A (en) Synthesis of mixtures of butanediols
US2372602A (en) Process for preparation of pentaerythritol
US2325206A (en) Catalyst and process for the hydrogenation of polyhydroxy compounds
US5756865A (en) Method for production of tetritols, specifically meso-erythritol
US2516826A (en) Process for catalytic semihydrogenation of tertiary acetylenic monohydric alcohols
US2866826A (en) Method of making menthol from pinene
US2975218A (en) Production of dialcohols
US3773842A (en) Process for the preparation of 1,2,6-hexanetriol
US3763246A (en) Process for producing mannitol
US3078316A (en) Production of menthol
US3232996A (en) Purification of butynediol
US1915431A (en) Process of hydrogenating polyhydroxy compounds and substances obtainable thereby
US2862978A (en) Synthetic glycerine production with intermediate removal of acrolein
US4133965A (en) Process for producing tricyclo(5,2,1,02,6)-3-decene-8 (or 9)-ol
US2325207A (en) Catalyst and process for the hydrogenation of polyhydroxy compounds
US3359324A (en) Method of preparing 2, 3-dimethyl-4-pentenal