WO2020150040A1 - Procédé de production de propylène glycol - Google Patents

Procédé de production de propylène glycol Download PDF

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Publication number
WO2020150040A1
WO2020150040A1 PCT/US2020/012486 US2020012486W WO2020150040A1 WO 2020150040 A1 WO2020150040 A1 WO 2020150040A1 US 2020012486 W US2020012486 W US 2020012486W WO 2020150040 A1 WO2020150040 A1 WO 2020150040A1
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Prior art keywords
product
acetol
propylene glycol
ethylene glycol
dioxolane
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PCT/US2020/012486
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English (en)
Inventor
Amit Goyal
Jadid Samad
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Southern Research Institute
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Publication of WO2020150040A1 publication Critical patent/WO2020150040A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • 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
    • C07C29/143—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 ketones
    • C07C29/145—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 ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes

Definitions

  • compositions, articles, and methods disclosed herein relates to the production of propylene glycol and other useful chemicals.
  • a method comprising the steps of: a) contacting a mixture of glycerol, ethylene glycol and propylene glycol with a dehydration/dehydrogenation catalyst, thereby producing a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane; b) separating the acetol from the i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane in the first product to produce a second product comprising at least 95 wt % acetol on dry basis; and c) hydrogenating the second product to produce a third product comprising at least 95 wt % propylene glycol on dry basis.
  • FIG. 1A and FIG. IB show two non-limiting examples of the method disclosed herein.
  • FIG. 2 shows the conversion and selectivity of glycerol to acetol, and propylene glycol to acetol as feeds and using Cu/C ⁇ Cb as catalyst at 280 °C.
  • FIG. 3 shows conversion of ethylene glycol to 4-methyl 1,3-Dioxolane, 2-methyl-l,3- dioxolane and 2, 3-dihydro-l, 3-Dioxin at various temperatures.
  • FIG. 4 shows the conversion and selectivity for the production of acetol obtained from co-feeding glycerol and propylene glycol at 240 °C using (Ai/(3 ⁇ 4q 3 as catalyst.
  • “Optional” or“optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.
  • the phrase“optionally comprising an adhesive material” means that the adhesive material can or cannot be present and that the description includes both situations.
  • Ranges can be expressed herein as from“about” one particular value, and/or to“about” another particular value. When such a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent“about,” it will be understood that the particular value forms a further aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. For example, if the value“10” is disclosed, then“about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • a weight percent (wt. %) of a component is based on the total weight of the therapeutic composition or composition or material, in which the component is included.
  • X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the composition.
  • compositions of the invention Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
  • compositions disclosed herein have certain functions.
  • the disclosed method can be a cost-effective method for the production of high purity USP/EP food grade (99.8%) propylene glycol.
  • the disclosed method produces a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane (low boiling point intermediates) from a mixture of glycerol, ethylene glycol and propylene glycol by contacting the mixture of glycerol, ethylene glycol and propylene glycol with a
  • the glycerol can be converted to acetol, acrolein, and methanol; propylene glycol (PG) can be converted to acetol, acetone, propanal, and hydrogen; and ethylene glycol (EG) can be converted to dioxolane and dioxin. As described above, some of the ethylene glycol might not converted to dioxolane and dioxin in the disclosed method.
  • the boiling points of the feed (glycerol, ethylene glycol and propylene glycol) and products are listed in Table 1.
  • the method disclosed herein utilizes favorable conditions for high propylene glycol purity and yield.
  • glycerol to propylene glycol conversion takes place in two steps: first dehydration to acetol and then hydrogenation to propylene glycol.
  • the dehydration which is performed at 200-320 °C, is favored at much higher temperatures than the hydrogenation, which can be performed at 110-150 °C.
  • Producing propylene glycol in these two steps at their respective favorable temperatures improves the overall propylene glycol selectivity at milder operating conditions (Akiyama, Masaki, et al. Applied Catalysis A: General 371.1 (2009): 60-66).
  • ethylene glycol formation is produced directly from glycerol or propylene glycol, and not from acetol, at higher temperatures and in presence of Fh (Dieuzeide, M. L, et al. Catalysis Today (2017)), which is preferably circumvented by the method disclosed herein by conducting the dehydration step in absence of 3 ⁇ 4 and the hydrogenation step uses acetol at low temperature, which eliminates further significant ethylene glycol formation.
  • Rivera-Ramos et al. conducted a series of carefully conducted experiments at various temperatures and pressures to study the equilibrium of glycerol to propylene glycol reaction (Lizanette Rivera-Ramos, MSC thesis, University of Missouri-Columbia, 2006).
  • dehydration/dehydrogenation step disclosed herein could maximize the formation of acetol from both glycerol and propylene glycol as higher temperatures (200-320 °C) and lower pressures (atmospheric) are applied.
  • acetol as reactant and showed that its conversion to propylene glycol is maximized at lower temperatures and moderate pressures which also justifies the use of similar condition (110-150 °C and 1-4 atmosphere) for the hydrogenation step.
  • the method disclosed herein is less capital and energy intensive, as compared to traditional methods.
  • the acetol is separated from the i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane in the first product to produce a second product comprising at least 95 wt % acetol on dry basis.
  • the second product can be hydrogenated to produce a third product comprising at least 95 wt % propylene glycol on dry basis.
  • a method comprising the steps of: a) contacting a mixture of glycerol, ethylene glycol and propylene glycol with a dehydration/dehydrogenation catalyst, thereby producing a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane; b) separating the acetol from the i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane in the first product to produce a second product comprising at least 95 wt % acetol on dry basis; and c) hydrogenating the second product to produce a third product comprising at least 95 wt % propylene glycol on dry basis.
  • the first product can further comprise acetaldehyde and glyoxal. In another aspect, the first product can further comprise acetaldehyde, glyoxal, and methanol.
  • the second product can comprise at least 96 wt % acetol on dry basis.
  • the second product can comprise at least 97 wt % acetol on dry basis.
  • the second product can comprise at least 99 wt % acetol on dry basis.
  • the second product can comprise at least 99.8 wt % acetol on dry basis.
  • the second product can comprise at least 99.9 wt % acetol on dry basis.
  • the third product can comprise at least 96 wt % propylene glycol on dry basis.
  • the third product can comprise at least 97 wt % propylene glycol on dry basis.
  • the third product can comprise at least 98 wt % propylene glycol on dry basis.
  • the third product can comprise at least 99 wt % propylene glycol on dry basis.
  • the third product can comprise at least 99.5 wt % propylene glycol on dry basis.
  • the third product can comprise at least 99.8 wt % propylene glycol on dry basis.
  • the third product can comprise at least 99.9 wt % propylene glycol on dry basis.
  • the third product can high purity USP/EP food grade propylene glycol, which has a purity of at least 99.8 wt% on dry basis.
  • the step a) of contacting a mixture of glycerol, ethylene glycol and propylene glycol with a dehydration/dehydrogenation catalyst, thereby producing a first product comprising acetol is performed with no or limited addition of hydrogen.
  • the term “limited addition of hydrogen” refers to atmospheric hydrogen.
  • the step can take place at or near atmospheric pressure, for example from about 1 bar to about 4 bar.
  • FIGs. 1A and IB Two non-limiting schemes of the method disclosed herein is shown in FIGs. 1A and IB.
  • the glycols and glycerol are co-processed in a fixed bed reactor where glycerol and propylene glycol are dehydrated and dehydrogenated, respectively to acetol (also known as hydroxyacetone) in absence of Fh over a Cu/Cr203 catalyst or Cu/AhCb catalyst at full conversion and >95% selectivity, see Example section.
  • acetol also known as hydroxyacetone
  • acetol hydrogenation is performed at full conversion and high selectivity on over a Cu/C ⁇ Cb catalyst or C11/AI2O3 catalyst at mild conditions resulting in high purity food grade propylene glycol (purity of about 99.8%) as the final product (Akiyama, Masaki, et al. Applied Catalysis A: General 371.1 (2009): 60-66).
  • the multifunctional catalyst comprises one or more metals selected from the group consisting of Cu, Zn, Sn, Ni, Pt, Pd, Ru, and Re, and a support.
  • the support is selected from the group consisting of C ⁇ Cb, AI2O3, SiCb, TiCh, ZrCb, MgO, and alumino-silicate, or a mixture thereof.
  • the support can be selected from the group consisting of Cr 2 Cb, AI 2 O 3 , and SiCb, TiCb, ZrCb, and MgO or a mixture thereof.
  • the support is Cr 2 0 3.
  • the support is AI 2 O 3 .
  • the support is S1O2. In yet another example, the support is T1O2. In yet another example, the support is Zr02. In yet another example, the support is MgO. In yet another example, the support is alumino-silicate.
  • the multifunctional catalyst comprises Cu and a support.
  • the multifunctional catalyst comprises Cu and a support selected from the group consisting of Cr203, AI2O3, S1O2, T1O2, Zr02, MgO, and alumino-silicate, or a mixture thereof.
  • the multifunctional catalyst comprises Cu and a support selected from the group consisting of Cr203, AI2O3, and S1O2, T1O2, Zr02, and MgO or a mixture thereof.
  • the multifunctional catalyst comprises Cu and 3 ⁇ 40 3.
  • the multifunctional catalyst comprises Cu and AI2O3.
  • the multifunctional catalyst comprises Cu and S1O2.
  • the multifunctional catalyst comprises Cu and T1O2. In yet another example, the multifunctional catalyst comprises Cu and Zr0 2 . In yet another example, the multifunctional catalyst comprises Cu and MgO. In yet another example, the multifunctional catalyst comprises Cu and alumino-silicate.
  • the multifunctional catalyst is Cu/C ⁇ Cb. In another aspect, the multifunctional catalyst is Cu/AhCb
  • the mixture comprises from about less than 10 wt % of ethylene glycol, and from about 70 wt % to about 98 wt % of propylene glycol and glycerol.
  • the first product comprises from about less than 5 wt % of ethylene glycol, and from about 80 wt % to about 97 wt % of propylene glycol and glycerol.
  • the mixture comprised a ratio of propylene glycol to ethylene glycol from about 7: 1 to 18: 1, such as from about 9: 1 to 14: 1.
  • the method can further comprise the step of contacting the mixture of ethylene glycol, propylene glycol, and glycerol with a dehydration/dehydrogenation catalyst disclosed herein, thereby producing a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane.
  • the dehydration/dehydrogenation catalyst comprises Cu and a support.
  • the support is selected from the group consisting of C ⁇ Cb, AhCb, SiCb, TiCb, ZrCh, MgO, and alumino-silicate, or a mixture thereof.
  • the support can be selected from the group consisting of Cr203, AI2O3, and S1O2, T1O2, Zr02, and MgO or a mixture thereof.
  • the support is Cr 2 0 3.
  • the support is AI 2 O 3 .
  • the support is S1O 2 .
  • the support is T1O 2 .
  • the support is Zr0 2 .
  • the support is MgO.
  • the support is alumino-silicate.
  • the dehydration/dehydrogenation catalyst comprises Cu and a support.
  • the dehydration/dehydrogenation catalyst comprises Cu and a support selected from the group consisting of 3 ⁇ 403, AI2O3, S1O2, T1O2, Zr02, MgO, and alumino-silicate, or a mixture thereof.
  • the dehydration/dehydrogenation catalyst comprises Cu and a support selected from the group consisting of Cr203, AI2O3, and S1O2, T1O2, Zr02, and MgO or a mixture thereof.
  • the dehydration/dehydrogenation catalyst can comprise Cu and 3 ⁇ 40 3.
  • the dehydration/dehydrogenation catalyst can comprise Cu and AI2O3. In yet another example, the dehydration/dehydrogenation catalyst can comprise Cu and S1O2. In yet another example, the dehydration/dehydrogenation catalyst can comprise Cu and TiC . In yet another example, the dehydration/dehydrogenation catalyst can comprise Cu and ZrC . In yet another example, the dehydration/dehydrogenation catalyst can comprise Cu and MgO. In yet another example, the dehydration/dehydrogenation catalyst can comprise Cu and alumino-silicate.
  • the dehydration/dehydrogenation catalyst is Cu/C ⁇ Cb. In another aspect, the dehydration/dehydrogenation catalyst is C11/AI2O3.
  • hydrogenating the second product to produce a third product comprising at least 95 wt % propylene glycol on dry basis comprises contacting the second product with a hydrogenation catalyst.
  • the hydrogenation catalyst comprises Cu and a support.
  • the support is selected from the group consisting of C ⁇ Cb, AI2O3, SiCh, TiCh, ZrCh, MgO, and alumino-silicate, or a mixture thereof.
  • the support can be selected from the group consisting of 3 ⁇ 40 3 , AI 2 O 3 , and S1O 2 , T1O 2 , Zr0 2 , and MgO or a mixture thereof.
  • the support is Cr 2 0 3.
  • the support is AI 2 O 3 . In yet another example, the support is S1O 2 . In yet another example, the support is T1O 2 . In yet another example, the support is Zr0 2 . In yet another example, the support is MgO. In yet another example, the support is alumino-silicate.
  • the hydrogenation catalyst comprises Cu and a support.
  • the hydrogenation catalyst comprises Cu and a support selected from the group consisting of 3 ⁇ 40 3 , AI2O3, S1O2, T1O2, Zr0 2 , MgO, and alumino-silicate, or a mixture thereof.
  • the hydrogenation catalyst can comprise Cu and a support selected from the group consisting of Cr203, AI2O3, and S1O2, T1O2, Zr02, and MgO or a mixture thereof.
  • the hydrogenation catalyst can comprise Cu and Cr203 .
  • the hydrogenation catalyst can comprise Cu and AI2O3.
  • the hydrogenation catalyst can comprise Cu and S1O2.
  • the hydrogenation catalyst can comprise Cu and T1O2. In yet another example, the hydrogenation catalyst can comprise Cu and Zr02. In yet another example, the hydrogenation catalyst can comprise Cu and MgO. In yet another example, the hydrogenation catalyst can comprise Cu and alumino-silicate.
  • the hydrogenation catalyst is Cu/Cr203. In another aspect, the hydrogenation catalyst is C11/AI2O3.
  • the step of contacting a mixture of glycerol, ethylene glycol and propylene glycol with a dehydration/dehydrogenation catalyst, thereby producing a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane, is performed at a temperature from about 190 °C to about 320 °C, for example from about 200 °C to about 260 °C, for example from about 230 °C to about 250 °C, such as for example about 240 °C.
  • the glycerol and propylene glycol are converted to acetol, while the ethylene glycol has much lower reaction rates toward the conversion to glyoxal and acetaldehyde.
  • the step of hydrogenating the second product to produce a third product comprising at least 95 wt % propylene glycol on dry basis is performed at a temperature from about 100 °C to about 170 °C, for example from about 110 °C to about 150 °C.
  • step a) is performed in the absence of 3 ⁇ 4. In one aspect, step a) is performed without the addition of Fb.
  • the first product comprises acetol, and ii) acrolein, acetone, propanal, dioxin, and dioxolane.
  • the first product comprises acetol, and i) ethylene glycol and ii) acrolein, acetone, propanal, dioxin, and dioxolane.
  • the separation in step b) of the acetol from the i) ethylene glycol and ii) acrolein, acetone, propanal, dioxin, and dioxolane in the first product comprises the steps of: 1) separating ethylene glycol from the acetol, acrolein, acetone, propanal, dioxin, and dioxolane; and 2) separating acetol from the acrolein, acetone, propanal, dioxin, and dioxolane, thereby producing the second product comprising at least 95 wt % acetol on dry basis.
  • separating ethylene glycol from the acetol, acrolein, acetone, propanal, dioxin, and dioxolane can be done via distillation (FIG. 1 A).
  • separating acetol from the acetone, propanal, dioxin, and dioxolane, thereby producing the second product comprising at least 95 wt % acetol on dry basis can also be done using distillation (FIG. IB).
  • multiple distillation stages can be used to increase the purity of the acetol in the second product.
  • 3-15 distillation stages can be used to increase the purity of the acetol in the second product, such as for example 5-10 distillation stages can be used to increase the purity of the acetol in the second product.
  • the method disclosed herein can be performed in a continuous process. In another aspect, the method disclosed herein can be performed in a batch process. [0056] In one aspect, the method disclosed herein can be performed on an industrial scale.
  • a method comprising the steps of: a) contacting a mixture of glycerol, ethylene glycol and propylene glycol with a dehydration/dehydrogenation catalyst, thereby producing a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane; b) separating the acetol from the i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane in the first product to produce a second product comprising at least 95 wt % acetol on dry basis; and c) hydrogenating the second product to produce a third product comprising at least 95 wt % propylene glycol on dry basis.
  • Aspect 2 The method of aspect 1, wherein the dehydration/dehydrogenation catalyst comprises Cu.
  • Aspect 3 The method of aspect 1, wherein the dehydration/dehydrogenation catalyst comprises Cu and a support comprising C ⁇ Cb, AI2O3, SiCh, TiCh, ZrCh, MgO, or alumino silicate, or a mixture thereof.
  • Aspect 4 The method of aspect 1, wherein the dehydration/dehydrogenation catalyst comprises Cu and a support comprising (3 ⁇ 40 3 , AfCb, or SiCh, or a mixture thereof.
  • Aspect 5 The method of aspect 1, wherein the dehydration/dehydrogenation catalyst comprises Cu/C ⁇ Cb or C11/AI2O3.
  • Aspect 6 The method of any one of aspects 1-5, wherein step a) is performed in the absence of Tf.
  • Aspect 7 The method of any one of aspects 1-6, wherein the first product comprises acetol, and ii) acrolein, acetone, propanal, dioxin, and dioxolane.
  • Aspect 8 The method of any one of aspects 1-6, wherein the first product comprises acetol, and i) ethylene glycol and ii) acrolein, acetone, propanal, dioxin, and dioxolane.
  • Aspect 9 The method of aspect 8, wherein the separation in step b) of the acetol from the i) ethylene glycol and ii) acrolein, acetone, propanal, dioxin, and dioxolane in the first product comprises the steps of: 1. separating ethylene glycol from the acetol, acrolein, acetone, propanal, dioxin, and dioxolane; and 2. separating acetol from the acrolein, acetone, propanal, dioxin, and dioxolane, thereby producing the second product comprising at least 95 wt % acetol on dry basis.
  • Aspect 10 The method of any one of aspects 1-9, wherein the second product comprises at least 99 wt % acetol on dry basis.
  • Aspect 11 The method of any one of aspects 1-10, wherein the hydrogenation in step c) comprises contacting the second product with a hydrogenation catalyst.
  • Aspect 12 The method of aspect 11, wherein the hydrogenation catalyst comprises Cu.
  • Aspect 13 The method of aspect 11, wherein the hydrogenation catalyst comprises Cu and a support comprising (3 ⁇ 403, AI2O3, S1O2, T1O2, ZrCh, MgO, or alumino-silicate, or a mixture thereof.
  • Aspect 14 The method of aspect 11, wherein the hydrogenation catalyst comprises Cu and a support comprising (3 ⁇ 403, AI2O3, or S1O2, or a mixture thereof.
  • Aspect 15 The method of aspect 11, wherein the dehydration/dehydrogenation catalyst comprises Cu/toCb or C11/AI2O3.
  • Aspect 16 The method of any one of aspects 1-15, wherein the third product comprises at least 99 wt % propylene glycol on dry basis.
  • Aspect 17 The method of any one of aspects 1-16, wherein the step of contacting a mixture of glycerol, ethylene glycol and propylene glycol with a dehydration/dehydrogenation catalyst, thereby producing a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane, is performed at a temperature from about 190 °C to about 320 °C.
  • Aspect 18 The method of any one of aspects 1-17, wherein the step of hydrogenating the second product to produce a third product comprising at least 95 wt % propylene glycol on dry basis, is performed at a temperature from about 100 °C to about 170 °C.
  • Aspect 19 The method of any one of aspects 1-18, wherein the step of contacting a mixture of glycerol, ethylene glycol and propylene glycol with a dehydration/dehydrogenation catalyst, thereby producing a first product comprising acetol, and i) ethylene glycol and/or ii) acrolein, acetone, propanal, dioxin, and dioxolane, is performed at a temperature from about 200 °C to about 260 °C.
  • Aspect 20 The method of any one of aspects 1-19, wherein the method is performed continuously for at least 5 hours.
  • FIGs. 2-4 show the advantages of co-processing the mixed feed of glycerol, propylene glycol, and ethylene glycol at low temperatures.
  • FIG. 2 shows the conversion and selectivity of glycerol to acetol, and propylene glycol to acetol as individual feeds and using Cu/C ⁇ Ch as catalyst at 280 °C. The reaction was performed at atmospheric pressure in the absence of Eh.
  • FIG. 3 also shows the conversion of ethylene glycol to acrolein, acetone, propanal, dioxin, and dioxolane (low boiling point intermediates) using Cu/C ⁇ CE as catalyst at 240 °C, 280 °C, and 320 °C at atmospheric pressure.
  • FIG. 3 shows that at 240 °C the conversion of ethylene glycol is small ( ⁇ 5%). The conversion increases as the reaction temperature increases.
  • FIG. 4 shows the conversion and selectivity for the production of acetol obtained from co-feeding glycerol and propylene glycol at 240 °C using Cu/C ⁇ CE as catalyst. The reaction was performed at atmospheric pressure in the absence of Eh. [0084] FIG. 4 also shows that glycerol and propylene glycol can be co-fed and converted selectively to acetol at high conversion at moderate temperatures (at or below 240 °C) for which EG conversion is very small (see FIG. 3).
  • glycerol, propylene glycol, and ethylene glycol can be co-processed to produce acetol along with acrolein, acetone, propanal, dioxin, and dioxolane unreacted ethylene glycol.
  • glycerol and propylene glycol selectively convert to a lower boiling point product, acetol, and majority of the ethylene glycol remains unconverted.
  • This product substantially alleviate the difficulty of separation of ethylene glycol from glycerol and propylene. It also obviates the use of expensive many stage and/or high vacuum/temperature distillation or solvent extraction processes currently used for the same purpose.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention concerne un procédé utile dans un procédé de production de propylène glycol de grande pureté.
PCT/US2020/012486 2019-01-14 2020-01-07 Procédé de production de propylène glycol WO2020150040A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008057263A2 (fr) * 2006-10-27 2008-05-15 Cargill, Incorporated Procédé de purification de compositions brutes contenant des polyols utilisant un gaz de lavage
EP1727875B1 (fr) * 2004-03-25 2015-11-04 Galen J. Suppes Procédé de production d'acétol à partir de glycérol
WO2018038968A1 (fr) * 2016-08-24 2018-03-01 Southern Research Institute Compositions et procédés associés à la fabrication d'acrylonitrile

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1727875B1 (fr) * 2004-03-25 2015-11-04 Galen J. Suppes Procédé de production d'acétol à partir de glycérol
WO2008057263A2 (fr) * 2006-10-27 2008-05-15 Cargill, Incorporated Procédé de purification de compositions brutes contenant des polyols utilisant un gaz de lavage
WO2018038968A1 (fr) * 2016-08-24 2018-03-01 Southern Research Institute Compositions et procédés associés à la fabrication d'acrylonitrile

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