GB2095231A - Conversion of aldoses to polyols - Google Patents
Conversion of aldoses to polyols Download PDFInfo
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- GB2095231A GB2095231A GB8138638A GB8138638A GB2095231A GB 2095231 A GB2095231 A GB 2095231A GB 8138638 A GB8138638 A GB 8138638A GB 8138638 A GB8138638 A GB 8138638A GB 2095231 A GB2095231 A GB 2095231A
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- sorbitol
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
-
- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A two-stage process for the catalytic conversion of an aldose to a polyol comprises passing a feedstock containing at least 20% by weight monosaccharide solution having a pH >/= 7 at a temperature of from 130-180 DEG C over a fixed bed of high- activity metal catalyst in the presence of hydrogen, withdrawing the alditol product and passing it together with a promoter and hydrogen over a second fixed-bed containing stabilized high- activity metal catalyst at a temperature of 204-271 DEG C, withdrawing the product stream and recovering the polyol therefrom. A portion of the sugars produced from the second hydrogenolysis stage is recycled back to the first hydrogenation stage for further conversion.
Description
SPECIFICATION
Two-stage aldoses to polyols process
This invention relates to the catalytic hydrogenation of aldoses such as glucose to produce polyols.
It relates more particularly to a two-stage process wherein a portion of the sugars produced from the second or alditol (sorbitol) hydrogenolysis stage is recycled back to the first or aldose (glucose) hydrogenation stage for further conversion.
It has been noted that the catalytic hydrogenolysis of alditols such as sorbitol in a fixed-bed reactor using nickel catalyst on an inert support to produce polyols such as glycerol and glycols also forms some polyglycerols, aldoses and glucose from the feed of alditols and sorbitol, respectively.
Dehydrogenation of alcohols to sugars and dehydration of glycerol to polyglycerols present the problem of build-up of such substances in the recovery step because of the usual recycle stream to the sorbitol cracking reaction zone. Such a recycle stream not only contains unconverted sorbitol and alditols but also the sugars and polyglycerols which are neither removed in the distillation step, nor extracted out by solvent in an extraction step, if used. To prevent such build-up of sugars and related materials, which is detrimental to process operations, withdrawal of a purge stream from the distillation separation step has been used. However, such a purge stream presents a loss of valuable products and reactants along with sugars from the process, thereby decreasing yields and increasing product costs. Thus, it is desirable to recover these sugars by some appropriate reprocessing steps.
A disclosure regarding hydrogenolysis of sorbitol is provided by Clark in Industrial 8 Engineering
Chemistry, Vol. 50, No. 8 (Aug. 1958), page 1125. An aqueous solution containing 40% of 99%
D-sorbital was used with 1% calcium hydroxide promotor and 50% nickel-on-kieselguhr catalyst suspended in a slurry with the feed in a stirred reactor. The conditions used were 2000-5600 psi (141-394kg/cm2) hydrogen partial pressure, 21 5-2450C (41 9-4730F) temperature and reaction times up to 400 minutes (6.7 hours) to produce glycerol, ethylene glycol, propylene glycol, and other more minor products.
U.S. Patent No. 2,965,679 to Conradin discloses a similar process for producing glycerol and glycols from sugar alcohols using a suspended nickel-on-kieselguhr catalyst in an autoclave type reactor. The reaction conditions are 200-3000C temperature, 500-1 000 atmospheres pressure and a pH of 8-10, followed by filtration to remove catalyst and separation of the products.
Van Ling et al. disclosed in Journal of Chemistry, Vol. 1 9, pages 43-45, hydrogenation experiments using a slurried catalyst in an autoclave reactor on feeds of sucrose, glucose and fructose in methanol-water solution to produce glycerol. The catalyst used was CuO-CeO2-SiO2 with 0--5%
Ca(OH)2 addition to the feed. The reaction conditions used were 200-2500C temperature, 100-300 atmospheres pressure and 10--120 minutes reaction time.
U.S. Patent No. 3,471,580 to Hellwig et al. discloses that by using a single or multi-stage upflow ebullated bed catalytic reaction at 200-5500F (93-2880C) temperature and 700-3500 psia (49-246 kg/cm2) hydrogen partial pressure, glycerol and glycols can be produced from saccharides.
Examples of the conditions used for converting a sorbitol type feed to glycerol in a single-stage reaction were about 3750F (191 0C) temperature, 1700 psia (120 kg/cm2) hydrogen partial pressure, 1.2 liquid hourly space velocity (LHSV), and using nickel-on-alumina catalyst to produce roughly 50 W % glycerol and 20 W % ethylene glycol and propylene glycol, with the remainder being methanoi, ethanol, isopropanol, and other products (col. 5, lines 40-53).
It is believed that none of these known processes are presently being used commercially to produce glycerol and related products on a continuous basis. Thus, further process improvements in conversion of aldoses and alditols are desired, not only for achieving continuous operations, reduced reaction conditions and increased glycerol product yields, particularly using improved catalysts in fixed bed reactors, but also to prevent loss of unconverted sugars which are usually removed by a purge stream.
The present invention provides a process for the catalytic conversion of monosaccharides to produce polyols, comprising the steps of: (a) providing a feedstream containing at least 20 W % monosaccharide solution and having a pH of 7to 14;
(b) preheating the feed and hydrogen gas to at least 1 000 C, and passing the heated feedstream mixture through a first stage fixed bed catalytic reaction zone containing a high-activity metal catalyst;
(c) maintaining said first reaction zone at conditions of 130-1 800C temperature, 500-2000 psig (35-141 kg/cm2) partial pressure of hydrogen, and 0.5-3.5 V/Hr/V space velocity, to achieve at least 90W % conversion of the feed to alditols;;
(d) withdrawing product containing alditol solution and passing it with a promotor material and hydrogen gas to a second-stage fixed-bed reaction zone containing a particulate high-activity stabilized metal catalyst;
(e) maintaining said second reaction zone conditions within the range of 400-5200F (204-271 OC) temperature, 1200-2000 psig (84-141 kg/cm2) hydrogen partial pressure. and 1.5-3.0 liquid hourly space velocity (LHSV) to achieve at least 30 W % conversion of the alditol to products;;
(f) withdrawing from the second reaction zone a product stream in which the alditol is converted from 30 to 80 W % to yield glycerol and glycol products, and passing the polyol-containing stream to a recovery step from which mainly glycerol product is withdrawn; and
(g) recycling a heavy purge stream containing aldoses and alditols to the first- and second-stage reaction zones for further conversion to alditols and glycerols, respectively.
The present invention discloses an improved two-stage catalytic process for hydrogenation of monosaccharides and aldoses such as glucose to produce glycerol and polyol products. The aldoses such as glucose solution are catalytically hydrogenated in a first-stage, fixed-bed reaction zone to produce alditols such as sorbitol, which are further hydrocracked in a second-stage reaction zone to produce glycerol and other polyol products. The feedstream pH to each reactor is controlled to between about 7 and 14 by adding an alkaline promotor material such as calcium hydroxide to prevent acidic leaching of metal from the catalyst.The first-stage reaction zone conditions are maintained at 130--1800C temperature, 500-2000 psig (35-141 kg/cm2) hydrogen partial pressure, and a ratio of hydrogen gas/liquid feed within the range of from 1000-5000. The feedstream liquid space velocity
is maintained within the range of 0.5-3.5 V > /hr/Vc. The first-stage reaction uses a high-activity catalyst preferably containing nickel to produce at least about 90 W % conversion of aldoses to alditols such as sorbitol solution.
The resulting alditol, such as a 1 5-40 W % sorbitol solution in water, is catalytically
hydrocracked in a second-stage fixed-bed reaction step usually using a high-activity nickel catalyst to
produce at least about 30 W % conversion to glycerol and glycol products. The second-stage reaction zone conditions are maintained at400-5200F (204--271 OC) temperature, 1200-2000 psig (84-141 kg/cm2) hydrogen partial pressure, and a liquid hourly space velocity of 1.5 to 3.0. To
maintain desired catalyst activity and glycerol yield, the catalyst is regenerated to provide a catalyst age
within the range of 8-200 hours.The reaction products are separated in a recovery step, and any
unconverted alditol feed can be recycled to the second-stage reaction zone for further hydrogenolysis to
produce 40-90 W % glycerol product. Sorbitol conversion is maintained preferably at between about 40-95 W % and a purge stream containing unconverted sugars is withdrawn and recycled to the
second-stage reaction zone for further conversion to alditols and polyols.
To prevent undesired loss of unconverted sugars from the second or alditol hydrogenolysis step
caused by their usual withdrawal in a purge stream following product distillation, it has been found
beneficial to recycle a portion of the purge stream containing such sugars back to the first or aldose-to
alditol hydrogenation reaction step. Here the sugars are catalytically hydrogenated to produce alditols
and alcohols in the presence of a catalyst such as supported nickel. It is expected that the other aldose
materials present will also be converted to alditols in the presence of the same catalyst. By such recycle, whatever sugars are produced in the second or sorbitol cracking stage are converted back to alcohols,
and thus any significant loss of reactant and product from the process is avoided.
It should be noted that, in addition to sugar formation in the second stage sorbitol hydrogenolysis
reactor, a certain amount of polyglycerol (produced by dehydration and polymerisation reactions) and
other compounds similar to polyglycerol may be produced in the sorbitol cracking reactor. Formation of
these compounds is expected to increase as the temperature of reaction increases above about 4000F (2040 C). Thus, the purge stream also prevents build-up of polyglycerols, if this compound does not
crack at a rate faster than it is being produced in the second stage reactor.Although it is desirable to
control concentration of undesired sugars in the polyol products by adjusting the sorbitol catalytic
cracking reaction conditions such that polyglycerol does not build up in the system, it is usually
necessary to withdraw a purge stream from the distillation step to prevent build-up of polyglycerols and
to increase the yield of glycerol product. In accordance with this invention, a portion of such purge
stream is recycled to the first-stage reaction zone for further catalytic conversion to alditols.
The accompanying drawing shows a two-stage catalytic process for hydrogenation of glucose to
produce polyols, with recycle of by-product sugars to the first or glucose hydrogenation step for further
conversion, according to a preferred embodiment of the invention.
As shown in the drawing, a glucose-water feed solution at 10 is mixed with an alkaline promotor
material at 11 such as calcium hydroxide. The mixture is pumped at 12 with hydrogen from 13 through
a preheater 14 to a fixed-bed catalytic reactor 1 6 for hydrogenation reaction to produce mainly sorbitol.
The promotor material added at 11 should be sufficient to control the pH of the feedstream 1 5 to a
range of 7-1 3 to prevent damage to the catalyst in the reactor 1 6. The catalyst is preferably a reduced
and stabilized nickel on silica-alumina support, and usually contains 50-66 W % nickel. A catalyst
particle size within the range of 0.060 to 0.250 inch (1.52-6.35 mm) can be used.The reactor
conditions which can be used are 1 30--1 800C (266-3560F) temperature, 500-2000 psig (35-141 kg/cm2) hydrogen partial pressure, and 0.5-3.5 Vf/hr/Vc space velocity to achieve at least
about 95 W % conversion of the glucose feed to sorbitol solution.
The resulting sorbitol solution is withdrawn from the reactor 1 6 as a stream 1 7 and passed to a
phase separation step 18, from which an overhead vapour stream 1 9 containing mainly hydrogen is
withdrawn and passed to a hydrogen purification step 44. If desired, some sorbitol product can be
withdrawn from the process at 20. The remaining liquid portion 21 is passed with recycled hydrogen at
45 and fresh hydrogen from 23 through a heater 24 to a fixed-bed reactor 26 containing a bed 27 of high nickel catalyst, such as about 50-66 W % nickel supported on a silica-alumina support, for hydrogenolysis of the sorbitol. Again, sufficient alkaline promotor material should be added at 11 a to control the pH of the feed 25 to a range of 7-14.
Reaction conditions useful in the reactor 26 are 420-5000F (21 6--2600C) temperature, 1200--2000 psig (84-141 kg/cm2) hydrogen partial pressure, 1.5-3.0 Vf/hr/Vc liquid hourly space velocity for achieving about 40-95 W % conversion of the sorbitol (or other alditol) feed to polyols, principally glycerol and a lesser concentration of glycols and related compounds. The catalyst age is maintained between about 10 and 200 hours by periodic regeneration of the catalyst as necessary to maintain its activity, such as by providing dual reactors 26 and 26a connected in parallel, with one reactor being in use while the catalyst in the other reactor is regenerated alternately.The used catalyst is regenerated by first washing with a solvent such as water, and then contacting the catalyst with a reducing gas such as hydrogen at a temperature above the reaction temperature; e.g., 500--6500F (260--3430C) temperature, and at a reduced pressure such as atmospheric pressure for 2 to 10 hours duration.
The reaction products from the reactor 26 (or parallel reactor 26a) are withdrawn at 28 and passed to a recovery or separation step 30, from which hydrogen-containing gas is removed at 29 and is passed to the hydrogen purification step 44. The remaining liquid stream 32 is pressure-reduced at 31 and passed to a recovery step 34, which usually comprises two or more distillation columns, with the final column operating at sub-atmospheric pressure. A vapour stream containing alcohols is removed at 33, water vapour is removed at 35, glycols are withdrawn at 36, and 50-90 W % glycerol product is withdrawn at 37. Unreacted sorbitol is removed at 39 and passed to a distillation column 40, operating at 5-100 mm mercury pressure. A vapour stream 41, containing additional glycerol, is combined with the product stream 38.The heavy liquid stream 42, containing unreacted sorbitol and sugars, is partially recycled to the stream 21 and passed to the hydrogenolysis reactor 26 (or 26a) for further processing. A heavy liquid stream 43 containing undesired sugars is recycled to the first-stage hydrogenation reactor 1 6 for reconversion of such sugars to sorbitol and related products. The remaining heavy liquid is withdrawn as a purge stream 50.
This invention is further illustrated by the following Examples, which should not be construed as limiting the scope of the invention.
EXAMPLE 1
In the catalytic hydrogenolysis of sorbitol solution to produce mainly glycerol, a liquid purge stream is usually withdrawn from the bottom of the distillation recovery step to prevent an undesired increase in the concentration of sugars in the glycerol products. A typical composition of this liquid purge stream is shown in Table 1 for distillation conditions of 50 mm Hg pressure and 4755000 F (246--2600C) temperature.
TABLE 1
Typical Composition of Bottom Purge Stream from Distillation Step
Aldoses and Alditols(1) 0.677
1,2,4-Butanetriol 0.161
Glycerol 0.155
1,2,3,4-Butanediol 0.0039
Propanol-2 < 0.001
Butanol-2 < 0.001
(1) The weight percents are: erythritol -- 0.033, arabinose -- 0.078, arabitol -- 0.043, xylose - 0.169, xylitol -- 0.103, mannose -- 0.022, mannitol -0.088, glucose -- 0.086, and sorbitol -- 0.378.
The benefits of recycling a portion of this liquid purge stream containing mainly unconverted sugars (aldoses and alditols) to the first-stage catalytic reaction step for further hydrogenation, compared to (a) once-through operation and (b) recycle of purge liquid to the second or sorbitol reactor stage only, is shown in Table 2 for typical reaction conditions.The results are based on 1000 pounds (454 kg) of sorbitol feed to the second or sorbitol reaction stage (at stream 21) and for reaction conditions of about 5000F (260or) temperature, 1400--1800 psig (98-127 kg/cm2) hydrogen partial pressure, 2.0 cc/hr cc space velocity, 0.173 inch (4.39 mm) equivalent diameter catalyst particle size, 6-inch (15 cm) bed height, and 25 W % sorbitol concentration in the feedstream to the catalytic reactor 26.
TABLE 2
Glycerol
Total Re- Yield (36)
cycle Flow, Purge
Catalyst Ib/hr (kg/hr) Stream (39) Ib/lb
Operations Age, (Stream Ib/hr Ib/hr Feed
Mode Hrs. 37 + 38) (kg/hr) (kg/hr) (kg/kg)
No recycle of liquid 16 - - 57.1 0.251
purge (25.9)
Recycle to sorbitol 16 20.6 23.8 57.3 0.241
reactor 26 (9.3) (10.8) (26.0)
Recycle to both 16 24.5 20.7 58.3 0.243
reactors (11.1) (9.4) (26.4)
No recycle of liquid 20 - - 55.0 0.246
purge (24.9)
Recycle to sorbitol 20 23.3 26.1 55.3 0.234
reactor 26 (10.6) (11.8) (25.1)
Recycle to both 20 27.3 22.8 56.3 0.236
reactors (12.4) (10.3) (25.5)
No recycle of liquid 70 - - 29.3 0.177
purge (13.3)
Recycle to sorbitol 70 67.2 62.8 29.0 0.142
reactor 26 (30.5) (28.5) (13.2)
Recycle to both 70 87.6 47.5 32.6 0.151
reactors (39.7) (21.5) (14.8)
Results for reaction conditions same as for Table 2 except for 36 W % sorbitol concentration in the feedstream are given in Table 3.
TABLE 3
Glycerol
Total Yield (36)
Recycle Purge
Catalyst Flow, Ib/hr Stream (39) Ib/lb
Operations Age, (Stream Ib/hr Ib/hr Feed
Mode Hrs. 37 + 38) (kg/hr) (kg/hr) (kg/kg)
No recycle of liquid 16 - - 90.5 0.261
purge (41.1)
Recycle to sorbitol 16 14.5 21.4 89.9 0.255
reactor 26 (9.7) (40.8)
Recycle to both 16 1 7.6 19.0 90.5 0.256
reactors (8.6) (41.1)
From the results shown in Table 2 and 3, it is apparent that recycling a portion of the liquid purge stream back to the first, or glucose hydrogenation reaction step, not only reduces the amount of variable sugars usually discarded in the purge stream, but also results in increasing the yield of glycerol product by an amount which is significant for a process plant.
Claims (13)
1. A process for the catalytic conversion of monosaccharides to produce polyols, comprising the steps of:
(a) providing a feedstream containig at least 20 W % monosaccharide solution and having a pH of 7 to 14;
(b) preheating the feed and hydrogen gas to at least 1 000C, and passing the heated feedstream mixture through a first stage fixed bed catalytic reaction zone containing a high-activity metal catalyst;
(c) maintaining said first reaction zone at conditions of 130--1800C temperature, 500-2000 psig (35-141 kg/cm2) partial pressure of hydrogen, and 0.5-3.5 V/hr/V space velocity.
to achieve at least 90 W % conversion of the feed to alditols;
(d) withdrawing product containing alditol solution and passing it with a promotor material and hydrogen gas to a second-stage fixed-bed reaction zone containing a particulate high-activity stabilized metal catalyst;
(e) maintaining said second reaction zone conditions within the range of 400-5200F (204-271 C) temperature, 1200--2000 psig (84-141 kg/cm2) hydrogen partial pressure, and 1.5-3.0 liquid hourly space velocity (LHSV) to achieve at least 30 W % conversion of the alditol to products;;
(f) withdrawing from the second reaction zone a product stream in which the alditol is converted from 30 to 80 W % to yield glycerol and glycol products, and passing the polyol containing stream to a recovery step from which mainly glycerol product is withdrawn; and
(g) recycling a heavy purge stream containing aldoses and alditols to the first- and second-stage reaction zones for further conversion to alditols and glycerols, respectively.
2. A process as claimed in claim 1, wherein the catalyst in the first reaction zone is stabilized highactivity nickel on silica-alumina support containing 50-66 W % of porous nickel and having a 0.060-0.250-inch (1.52-6.35 mm) diameter particle size and a surface area of 140-180 m2/g.
3. A process as claimed in claim 1 or 2, wherein the catalyst in the second reaction zone comprises 50-65 W % of porous nickel on an inert support, has a 4-12 mesh (0.187-0.066 inch or 4.75-1.68 mm) particle size (U.S. Sieve Series), and the catalyst age is 8-200 hours before regeneration to maintain its activity.
4. A process as claimed in any of claims 1 to 3, wherein the pH of the feedstream to each reaction zone is controlled within the range of from 7.5 to 1 2 by adding sodium hydroxide comprising 0.1 to 2.0 W % of the feedstream to avoid leaching of metal from the catalyst.
5. A process as claimed in any of claims 1 to 4, wherein the first reaction zone conditions are maintained at 140-1 700C temperature, 750-1600 psig (53-112 kg/cm2) partial pressure of hydrogen, and 0.6-3.3 V/hr/V space velocity and hydrogen gas/liquid feed ratio of 1000-5000 at standard conditions.
6. A process as claimed in any of claims 1 to 5, wherein the feed to the first stage zone is 30-60 W % glucose in water solution and the glucose conversion therein is 98.5-99.9 W % to sorbitol.
7. A process as claimed in any of claims 1 to 5, wherein the feedstream to said first zone is 20-50 W % mannose solution and the product is mannitol solution.
8. A process as claimed in any of claims 1 to 6, wherein the feedstream to the second reaction zone contains 20-50 W % sorbitol, the reaction zone conditions are maintained within the range of 440-4800F (227-2490C) temperature, 1400-1900 psig (98-134kg/cm2) hydrogen partial pressure, and 2.0-2.7 liquid hourly space velocity, and the catalyst age is 1 0-200 hours before regeneration and wherein the sorbitol feed solution is converted about 40-99 W % to yield mainly glycerol product with the remainder being glycols.
9. A process as claimed in any of claims 1 to 6 and 8, wherein the feedstream to the first stage is 30-60 W % glucose in alcohol solution and the feed to the second stage reaction zone is 1 5-50 W % sorbitol in alcohol solution.
1 0. A process as claimed in any of claims 1 to 9, wherein the catalyst in the second stage reaction zone is regenerated following at least about 20 hours use by washing said catalyst with a solvent and contacting it with hydrogen at 500-6500F (260--3430C) temperature for at least 2 hours, then returning the catalyst to use.
11. A process for producing glycerol by the catalytic conversion of monosaccharides, comprising the steps of:
(a) providing a feedstream containing about 20-60 W % monosaccharide solution in water and having a pH of 7.5 to 12 to avoid leaching metal from the catalyst;
(b) preheating the feed and hydrogen gas to 1000--1200C, and passing the heated feedstream mixture through a first stage fixed bed catalytic reaction zone containing a high-activity nickel catalyst which contains 50-66 W % of nickel on a silica-alumina support and having a particle size within the range of from 0.062-0.250 inch (1.57-6.35 mm);;
(c) maintaining said first reaction zone at conditions of 140-1 700C temperature, 750-1 600 psig (53-112 kg/cm2) partial pressure of hydrogen, and 0.6-3.3 V/hr/V space velocity, and a hydrogen gas/liquid feed ratio of 1200-4000 at standard conditions for achieving at least about 90 W % conversion of the feed to alditols;;
(d) withdrawing product containing substantially sorbitol in water solution and passing it with hydrogen and a promotor material to a second stage reacton zone maintained within the range of 440-4800F (227-2490C) temperature, 1400--1900 psig (98-134kg/cm2) hydrogen partial pressure, 2.0--2.7 liquid hourly space velocity (LHSV), and a catalyst age of 12-100 hours before regeneration, for achieving 30-70 W % conversion of the sorbitol to yield glycerol with the remainder being glycols; ;
(e) withdrawing from the second reaction zone a stream containing glycerol and glycol products and passing it to a distillation section including a vacuum distillation recovery step maintained at 5-100 mm Hg pressure to remove alcohols and water vapour and produce a high-purity glycerol product; and
(f) recycling unconverted sorbitol to the second stage reaction, and recycling a heavy purge stream containing alditose and alditol to said first and second stage reaction zones for further conversion to alditols and glycerols, respectively.
12. A process as claimed in Claim 1, substantially as hereinbefore described with reference to the
Example and/or the accompanying drawing.
13. A polyol produced by a process as claimed in any of claims 1 to 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22699981A | 1981-01-21 | 1981-01-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2095231A true GB2095231A (en) | 1982-09-29 |
| GB2095231B GB2095231B (en) | 1985-06-12 |
Family
ID=22851337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8138638A Expired GB2095231B (en) | 1981-01-21 | 1981-12-22 | Conversion of aldoses to polyols |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS57159732A (en) |
| CA (1) | CA1202643A (en) |
| DE (1) | DE3141907A1 (en) |
| GB (1) | GB2095231B (en) |
| NL (1) | NL8105092A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007067426A1 (en) * | 2005-12-08 | 2007-06-14 | Sud-Chemie Inc. | Catalyst for the production of polyols by hydrogenolysis of carbohydrates |
| WO2017143118A1 (en) * | 2016-02-19 | 2017-08-24 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
| RU2807479C1 (en) * | 2016-02-19 | 2023-11-15 | Интерконтинентал Грейт Брендс Ллк | Methods for producing multiple valuable flows from biomass-based sources |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3341609A (en) * | 1967-09-12 | Process reactor | ||
| GB801732A (en) * | 1955-07-29 | 1958-09-17 | Melle Usines Sa | Improvements in or relating to a process for producing polyalcohols by hydrogenationof corresponding sugars |
| DE1129939B (en) * | 1958-07-09 | 1962-05-24 | Inventa A G Fuer Forschung | Process for the production of glycerine and glycols by hydrogenation cleavage of sucrose |
| DE1277832B (en) * | 1962-07-20 | 1968-09-19 | Atlas Chem Ind | Process for the production of glycerine by continuous one-step hydrogenolysis of reducible sugars |
| US3471580A (en) * | 1968-04-19 | 1969-10-07 | Hydrocarbon Research Inc | Production of glycerol from saccharides |
| US3965199A (en) * | 1972-04-26 | 1976-06-22 | Ici United States Inc. | Hydrogenation and hydrogenolysis of carbohydrates with tungsten oxide promoted supported nickel catalyst |
-
1981
- 1981-10-22 DE DE19813141907 patent/DE3141907A1/en not_active Withdrawn
- 1981-11-10 NL NL8105092A patent/NL8105092A/en not_active Application Discontinuation
- 1981-12-22 GB GB8138638A patent/GB2095231B/en not_active Expired
-
1982
- 1982-01-18 CA CA000394342A patent/CA1202643A/en not_active Expired
- 1982-01-21 JP JP57006900A patent/JPS57159732A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007067426A1 (en) * | 2005-12-08 | 2007-06-14 | Sud-Chemie Inc. | Catalyst for the production of polyols by hydrogenolysis of carbohydrates |
| WO2017143118A1 (en) * | 2016-02-19 | 2017-08-24 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
| US20190039981A1 (en) * | 2016-02-19 | 2019-02-07 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
| RU2710554C1 (en) * | 2016-02-19 | 2019-12-27 | Интерконтинентал Грейт Брендс Ллк | Methods for formation of multiple valuable streams from biomass sources |
| US10759727B2 (en) | 2016-02-19 | 2020-09-01 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
| RU2807479C1 (en) * | 2016-02-19 | 2023-11-15 | Интерконтинентал Грейт Брендс Ллк | Methods for producing multiple valuable flows from biomass-based sources |
| US11840500B2 (en) | 2016-02-19 | 2023-12-12 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2095231B (en) | 1985-06-12 |
| DE3141907A1 (en) | 1982-10-14 |
| CA1202643A (en) | 1986-04-01 |
| JPS57159732A (en) | 1982-10-01 |
| NL8105092A (en) | 1982-08-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19921222 |