AU2002224485A1 - Gaseous acid catalysis - Google Patents
Gaseous acid catalysisInfo
- Publication number
- AU2002224485A1 AU2002224485A1 AU2002224485A AU2002224485A AU2002224485A1 AU 2002224485 A1 AU2002224485 A1 AU 2002224485A1 AU 2002224485 A AU2002224485 A AU 2002224485A AU 2002224485 A AU2002224485 A AU 2002224485A AU 2002224485 A1 AU2002224485 A1 AU 2002224485A1
- Authority
- AU
- Australia
- Prior art keywords
- furfural
- acid
- reactant
- manufacture
- reactor
- 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.)
- Granted
Links
Description
GASEOUS ACID CATALYSIS
TECHNICAL FIELD OF THE INVENTION
This invention relates to gaseous acid catalysis and in particular gaseous acid catalysis of the conversion of pentose or pentosan to furfural.
BACKGROUND ART
Acid catalysis, a common reaction mechanism in organic chemistry, implies the involvement of oxonium, or hydronium, ions, H3O+. "Acid catalysis" is inherently understood to be a process that occurs in aqueous solution. As far as the applicant is aware nobody seems to have used a gas as an acid catalyst, and with good reason. As shown in Figure 1, gases are not ionized until very high temperatures are reached. As can be seen, there is no significant thermal ionization below 2500°C for water and below 5000°C for HCl. Ionization by cosmic rays and ambient radioactivity has also been shown to be negligible, together amounting to no more than 10 ion pairs/(s cm3) with a life span of 70 s. Thus, gases at all but extremely high temperatures may be considered completely nonionized, as demonstrated by their being perfect electrical insulators.
Obviously, a nonionized gas cannot be an "acid catalyst", therefore, it has been the universal belief that acid-catalyzed processes must be carried out in the liquid phase. However, recent studies of stratospheric chemistry and the depletion of the ozone layer have shown that HCl vapour, usually stable, becomes ionized in the presence of ice crystals that are abundant in the stratosphere. HCl and water vapour molecules are strongly adsorbed on the surface of the ice crystals. In the state of adsorption, each HCl molecules reacts preferentially with four water molecules to form an ionized cluster, H3O+(H2O)3Cr, in which the three water molecules form the equatorial plane of a trigonal bipyramid, with Cf and H3O+ ions at the apexes. The chlorine atom carries a charge of -0.80 e and the oxonium ion a charge of +0.85 e, so that the electrical activity of the cluster is almost equal to that of free Cf and H3O+ ions. The role of the solid surface is to permit HCl molecules
to come into contact with four water molecules, which is not possible via collisions in a gas phase devoid of adsorbing surfaces.
It is therefore one object of this invention to provide a method for gaseous acid catalysis.
The applicant has further noted the similarity between ice crystals and other solids having multiple polar hydroxyl groups, for example sugars, and in particular pentose or pentosan.
It is therefore a further object of this invention to provide a method for gaseous acid catalysis catalysed hydrolysis of sugars to form aldehydes and in particular, pentosan and pentose to furfural.
DISCLOSURE OF THE INVENTION
According to the invention, a method of gaseous acid catalysis includes the steps of introducing a reactant in solid form into a reactor, the reactant including one or more hydroxyl groups; introducing superheated steam into the reactor until the reactant is dry and the temperature within the reactor is above that of the dewpoints of both water and the catalyst to be used; introducing the acid into the reactor together with the superheated steam by means of a vaporiser; and condensing the gas formed.
In the preferred form of the invention, the reactant is capable of forming an ionised cluster complex with water and at least a portion of the acid.
Also in the preferred form, the reaction is carried out at atmospheric pressure. The reactant should be completely dry. In the preferred form, the acid is hydrochloric acid.
In this form of the invention, the reaction must be carried out at a temperature above the boiling point of the maximum HCl - H20 azeotrope. This typically occurs at
20.2 wt% of HCl with a boiling point of 108,6°C and accordingly the reaction should be carried out above this temperature.
In one form of the invention, the reactant is a sugar.
In one form of the invention, the reactant is pentosan and/or pentose and the solid substance is a comminuted raw material high in pentosan content, for example sunflower stems, corn cobs or bagasse.
DESCRIPTION OF AN EXAMPLE OF THE INVENTION
A typical gaseous acid catalysis process using hydrochloric acid is illustrated in Figure 2. Reactor 1 is charged with comminuted raw material of high pentosan content, such as sunflower stems, corncobs, or bagasse. Steam at atmospheric pressure is passed through a superheater 2 typically fuelled by combustion gas, and this stream is then passed through the charge to first completely dry the charge and then heat it to a temperature far above the maximum atmospheric dew point of hydrochloric acid. The charge will heat rapidly once the moisture has been stripped from it. When the desired temperature is reached, a small quantity of hydrochloric acid is continuously dispersed into the superheated stem by means of a vaporizer 3 to give the gas stream an HCl content of approximately 1.5 wt%. The gas stream leaving the reactor is liquefied in a condenser 4, and the condensate is collected in a buffer tank 5 before it enters a separation plant 6 that isolates furfural, low boiling compounds, and carboxylic acids and recovers HCl as its azerotrope with water. This hydrochloric acid is used to feed the vaporiser 3, so that the catalyst is contained in a closed circuit. The "pervaporisation" of the charge is continued until no more furfural is produced. Then, the residue is discharged under nitrogen, to prevent self-ignition, and a new batch is started.
When this reaction is carried out at 155°C, the applicant found that the existing gas stream was heavily loaded with furfural, low boiling compounds and carboxylic acids.
What is most surprising about this result is the presence of the furfural as a gas even though the process is carried out at a temperature below its boiling point (161.7°C).
An important advantage of this new process is that the absence of a liquid phase greatly increases the furfural yield. In convention furfural process, the furfural generated dissolves in the liquid phase, where, under the catalyzing influence of oxonium ions, it undergoes loss reactions with itself and with intermediates of the pentose-to-furfural conversion. In addition, with sulphuric acid as the customary catalyst, there are losses by sulfontation. Consequently, the yield in conventional furfural plants is only on the order of 50%. By contrast, in gaseous acid catalysis, with no liquid phase in which to dissolve, the generated furfural is instantly vaporised and loss reactions are avoided.
In a laboratory test, yields of the order of 95% have been achieved.
In conventional furfural processing, high pressures are needed to keep the aqueous catalyst in the liquid state, and the customary catalyst, sulphuric acid, is nonvolatile, so that it is lost in the residue where it presents a disposal problem.
As compared to this conventional processing, the new gaseous catalysis process has the following advantages :
1 At any chosen temperature, the process can be carried out at atmospheric pressure.
2. As the H20/HC1 catalyst is used far above its dew point, there is no corrosion, so that the reactor can be made of mild steel.
3. The acid portion of the catalyst can be completely recovered, to be run in a closed circuit, so that there is no acid consumption and no acid disposal problem. Known technology is available for the acid recovery.
4. The residue is dry and free of acid, thus being eminently suited for a simple combustion without any problems. By partial combustion in air, it is also possible
to use the residue for the manufacture of "producer gas" consisting mostly of carbon monoxide, hydrogen and nitrogen.
5. The yield is close to 100 percent as there is no liquid phase where loss reactions could take place. Yields of up to 95.8 percent have been measured.
It should be noted that although an example of a batch process is described hereinabove, the applicant submits that a continuous process may be used.
Claims (12)
1. A method of gaseous acid catalysis characterised in that it includes the steps of introducing a reactant in solid form into a reactor, the reactant including one or more hydroxyl groups; introducing superheated steam into the reactor until the reactant is dry and the temperature within the reactor is above that of the dewpoints of both water and the catalyst to be used; introducing the acid together with the superheated steam into the reactor by means of a vaporiser; and condensing the gas formed.
2. A method according to claim 1 characterised in that the reactant is capable of forming an ionised cluster complete with water and at least a portion of the acid.
3. A method according to claim 1 or claim 2 characterised in that the reaction is carried out at atmospheric pressure.
4. A method according to any of the above claims characterised in the acid is hydrochloric acid.
5. A method according to claim 4 characterised in that the reaction is carried out at a temperature above the boiling point of the maximum HCl - H20 azeotrope.
A method according to claim 1 characterised in that the reactant is a sugar.
7. A process for the manufacture of aldehydes from sugars characterised in that the hydrolysis of the sugar is catalysed by a method of gaseous acid catalysis according to claim 1.
8. A process for the manufacture of furfural from pentosan according to claim 7 5 characterised in that the hydrolysis of pentosan and/or pentose and subsequent dehydration to furfUral is catalysed by gaseous hydrochloric acid according to the method of catalysis of claim 1.
9. A process for the manufacture of furfural characterised in that the hydrochloric acid is recycled as its azeotrope with water.
10 10. A process for the manufacture of furfural according to claim 7 characterised in that the reaction is carried out at 155°C.
11. A process for the manufacture of furfural according to claim 7 characterised in that the yield of furfural is greater than 90%.
12. A process according to claim 7 characterised in that it is continuous.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10045465A DE10045465A1 (en) | 2000-09-14 | 2000-09-14 | Process for the atmospheric production of furfural using a gaseous catalyst |
DE10045465.8 | 2000-09-14 | ||
PCT/ZA2001/000146 WO2002022593A1 (en) | 2000-09-14 | 2001-09-14 | Gaseous acid catalysis |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2002224485A1 true AU2002224485A1 (en) | 2002-06-13 |
AU2002224485B2 AU2002224485B2 (en) | 2007-01-18 |
Family
ID=7656178
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2448502A Pending AU2448502A (en) | 2000-09-14 | 2001-09-14 | Gaseous acid catalysis |
AU2002224485A Ceased AU2002224485B2 (en) | 2000-09-14 | 2001-09-14 | Gaseous acid catalysis |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2448502A Pending AU2448502A (en) | 2000-09-14 | 2001-09-14 | Gaseous acid catalysis |
Country Status (12)
Country | Link |
---|---|
US (1) | US7173142B2 (en) |
EP (1) | EP1317436B1 (en) |
AP (1) | AP2099A (en) |
AT (1) | ATE281445T1 (en) |
AU (2) | AU2448502A (en) |
BR (1) | BR0113877B1 (en) |
CA (1) | CA2425127C (en) |
DE (2) | DE10045465A1 (en) |
ES (1) | ES2232673T3 (en) |
MX (1) | MXPA03002238A (en) |
WO (1) | WO2002022593A1 (en) |
ZA (1) | ZA200302020B (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10304055A1 (en) * | 2003-02-01 | 2004-08-12 | Degussa Ag | Process for the production of ketals |
WO2012041990A1 (en) | 2010-09-30 | 2012-04-05 | Shell Internationale Research Maatschappij B.V. | Process for producing furfural |
US9126964B2 (en) | 2011-06-09 | 2015-09-08 | Micromidas, Inc. | Utilizing a multiphase reactor for the conversion of biomass to produce substituted furans |
KR20150072453A (en) | 2012-10-26 | 2015-06-29 | 마이크로마이다스, 인코포레이티드 | Methods for producing 5-(halomethyl) furfural |
KR102247145B1 (en) | 2013-03-14 | 2021-05-04 | 마이크로마이다스, 인코포레이티드 | Methods for purifying 5-(halomethyl)furfural |
BR112015023218A2 (en) | 2013-03-14 | 2017-07-18 | Micromidas Inc | 5- (halomethyl) furfural solid forms and methods for preparing same |
WO2014193889A1 (en) | 2013-05-31 | 2014-12-04 | Shell Oil Company | Glycol recovery with solvent extraction |
BR112015021060A2 (en) | 2013-05-31 | 2017-07-18 | Shell Int Research | process for the recovery of 1,4-butanediol and at least one selected co-product |
WO2014191509A1 (en) | 2013-05-31 | 2014-12-04 | Shell Internationale Research Maatschappij B.V. | Process for the separation of an alkylene glycol |
CN105764890A (en) | 2013-09-20 | 2016-07-13 | 微麦德斯公司 | Methods for producing 5-(halomethyl) furfural |
JP5791838B1 (en) * | 2014-03-07 | 2015-10-07 | 花王株式会社 | Method for producing furfural |
CN106132942A (en) | 2014-03-31 | 2016-11-16 | 国际壳牌研究有限公司 | Method from furfural production furan |
RU2689115C2 (en) | 2014-03-31 | 2019-05-24 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method of producing furan and derivatives thereof |
CN107001203A (en) | 2014-12-18 | 2017-08-01 | 国际壳牌研究有限公司 | The method that n-butanol and 1,4 butanediols are produced by furans |
WO2016162397A1 (en) | 2015-04-09 | 2016-10-13 | Shell Internationale Research Maatschappij B.V. | Process for the production of 1,4-butanediol and tetrahydrofuran from furan |
US20180186760A1 (en) | 2015-06-30 | 2018-07-05 | Shell Oil Company | Process for the production of 1,4-butanediol and tetrahydrofuran from furan |
US10752602B2 (en) | 2015-09-10 | 2020-08-25 | Shell Oil Company | Process for the production of 1,4-butanediol and tetrahydrofuran from furan |
US10351496B2 (en) | 2015-10-15 | 2019-07-16 | Shell Oil Company | Process for the production of 1,4-butanediol and tetrahydrofuran from furan |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2559607A (en) * | 1948-07-02 | 1951-07-10 | John W Dunning | Production of furfural from pentose liquors |
US4001283A (en) | 1974-09-23 | 1977-01-04 | Wells Jr Preston A | Method for the manufacture of furfural using hydrogen chloride |
US4076733A (en) * | 1976-03-31 | 1978-02-28 | Carbos Ag | Process for the preparation of furfural |
US4154744A (en) * | 1976-10-12 | 1979-05-15 | Sumitomo Chemical Company, Limited | Process for producing a furan derivative |
US4533743A (en) * | 1983-12-16 | 1985-08-06 | Atlantic Richfield Company | Furfural process |
DE3842825A1 (en) * | 1988-01-08 | 1989-07-20 | Krupp Gmbh | METHOD AND DEVICE FOR PRODUCING FURFURAL |
-
2000
- 2000-09-14 DE DE10045465A patent/DE10045465A1/en not_active Withdrawn
-
2001
- 2001-09-14 AP APAP/P/2003/002760A patent/AP2099A/en active
- 2001-09-14 CA CA2425127A patent/CA2425127C/en not_active Expired - Fee Related
- 2001-09-14 EP EP01984638A patent/EP1317436B1/en not_active Expired - Lifetime
- 2001-09-14 AT AT01984638T patent/ATE281445T1/en active
- 2001-09-14 WO PCT/ZA2001/000146 patent/WO2002022593A1/en active Application Filing
- 2001-09-14 BR BRPI0113877-4A patent/BR0113877B1/en not_active IP Right Cessation
- 2001-09-14 ES ES01984638T patent/ES2232673T3/en not_active Expired - Lifetime
- 2001-09-14 AU AU2448502A patent/AU2448502A/en active Pending
- 2001-09-14 MX MXPA03002238A patent/MXPA03002238A/en active IP Right Grant
- 2001-09-14 US US10/380,417 patent/US7173142B2/en not_active Expired - Fee Related
- 2001-09-14 DE DE60106955T patent/DE60106955T2/en not_active Expired - Lifetime
- 2001-09-14 AU AU2002224485A patent/AU2002224485B2/en not_active Ceased
-
2003
- 2003-03-13 ZA ZA200302020A patent/ZA200302020B/en unknown
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1317436B1 (en) | Gaseous acid catalysis | |
AU2002224485A1 (en) | Gaseous acid catalysis | |
Bergius | Conversion of wood to carbohydrates | |
US3212933A (en) | Hydrolysis of lignocellulose materials with solvent extraction of the hydrolysate | |
US7632479B2 (en) | Process for producing ammonia and sulfuric acid from a stream comprising ammonium sulfate | |
Tang et al. | Complete recovery of cellulose from rice straw pretreated with ethylene glycol and aluminum chloride for enzymatic hydrolysis | |
KR20150036368A (en) | Supercritical hydrolysis of biomass | |
EP2435363B1 (en) | Method for concentrating dilute sulfuric acid and an apparatus for concentrating dilute sulfuric acid | |
EP1171665B1 (en) | Process for the production of furfural from lignosulphonate waste liquor | |
US4155878A (en) | Process for making activated carbon with control of metal ion concentration in phosphoric acid | |
CA2995560C (en) | Process for the recovery of hydrochloric acid | |
USRE31093E (en) | Process for making activated carbon with control of metal ion concentration in phosphoric acid | |
Zeitsch | Gaseous acid catalysis: An intriguing new process | |
WO2023193425A1 (en) | Method for preparing 2-methyltetrahydrofuran by using waste biomass | |
JPH02108682A (en) | Production and concentration of furfural | |
US4642400A (en) | Process for finishing vinyl chloride monomer | |
US2779770A (en) | Recovery of furfural by preferential absorption of the vapor on solids | |
US864217A (en) | Process of concentrating nitric acid. | |
CN114436769B (en) | Method for synthesizing 1,2-butanediol by using monosaccharide | |
Kim et al. | Evaluation and utilization of dicarboxylic acids (DCA) as an alternative to strong mineral acids for selective extraction of C5-sugars in an integrated biorefinery | |
US20170121745A1 (en) | Method of Manufacturing Cellulosic Sugar from Biomass Through Effective Separation of Impurities and Sugar | |
HU187696B (en) | Step by step method for producing furfurol from pentosane-containing vaste materials of plants or from pentose solutions | |
GB774789A (en) | Process for the production of hexamethylenetetramine |