ES2350076B1 - GLYCERINE CONVERSION IN METHANOL - Google Patents

Abstract

Conversion of glycerin into methanol. # Which consists of converting glycerin (1) stored as a waste of biodiesel production into methanol (10), for which, in a first process, it is subjected to a temperature of 225 ° using a catalyst of Platinum (2), converting it into Synthesis Gas (3), which will be purified by reacting it with sodium hydroxide at a temperature of 180º Celsius and 8 atmospheres of pressure (4), obtaining sodium formate (5), solid and hydrogen (6 ) # Sodium formate (5) decomposes thermally, at a temperature of 360º in hydrogen (7) and sodium oxalate (8). # Hydrogen (6 and 7) from the process of purification of synthesis gas and from After the thermal decomposition of the sodium formate, the glycerin is reacted again, at a temperature of 100º C and at a pressure of 20 bar, using zinc oxide as catalyst (9), and the chemical reaction occurs: CH {sub , 2} OH-CHOH-CH {sub, 2} OH + H {sub, 2}? 3CH {sub, 3} OH, which convert glycerin into methanol (10). # The residue obtained is sodium oxalate (8), which is used in industry.

Description

Conversion of glycerin into methanol.

Background of the invention

One of the serious problems facing global development is the dependence on fossil fuels as a source of energy. The increase in the demand for hydrocarbons, by emerging countries, such as China, India, etc., with annual economic growth of over ten percent and continuous population increases, predicts a greater demand for energy in the very near future.

The reserves of hydrocarbons, formed over millions of years, are evaluated and consequently we start from an energy whose availability is limited in time, so it is necessary to postpone the depletion of the same as long as possible, while waiting for the introduction of efficient and alternative energies that can replace it depending on the energy based in hydrocarbons.

An alternative to fossil fuels is biodiesel, which is considered renewable energy, because it is produced from vegetable oils. Biodiesel is produced by a mixture of vegetable oils with methanol and sodium hydroxide, producing glycerin as a byproduct. The problem of biodiesel production is the mass production of glycerin as a byproduct, which has collapsed the market and converted glycerin into a waste, with the cost that this entails for the production of biodiesel.

The present invention aims to convert glycerin into methanol, whereby we convert the theoretical residue, which is glycerin into raw material, with significant cost savings and a significant reduction in environmental impact, which involves the elimination of glycerin.

Object of the invention

The object of the present invention is to convert glycerin into methanol, by means of a process that takes place in two successive stages, but which are carried out continuously, so that we can talk about a continuous process. In a first stage, we convert glycerin into synthesis synthesis, at a temperature of 225 degrees Celsius, using platinum-based catalysts, according to the formula

CH2OH-CHOH-CH2OH -------------- 3CO + 4H2

The synthesis will be purified by reaction with sodium hydroxide, at a temperature of 180 degrees Celsius and eight atmospheres of pressure, to obtain sodium formate, in solid form, and hydrogen.

In order to obtain a better yield in the process of converting glycerin into methanol, we can obtain hydrogen again, by means of the thermal decomposition of the formate, (H-COO-Na) that at a temperature of three hundred and sixty degrees Celsius is decomposed into sodium Hydrogenyoxalate, releasing the hydrogen in the process.

The hydrogen obtained, both in the first process from synthesis gas, and that obtained by the thermal decomposition of sodium formate, is reacted again with glycerin, at a temperature of 100 degrees Celsius and a pressure of 20 bar, using zinc oxide as a catalyst, according with the following chemical reaction:

CH2OH-CHOH-CH2OH + H2 --------------------- 3CH3OH

The reaction of glycerin with hydrogen under the reaction conditions described converts glycerin into methanol. The residue obtained in the process is sodium oxalate, (Na2C2O4) widely used in industry.

Description of the invention

The invention of the system for "Conversion of glycerin into methanol", consists in the process that we will describe below, whereby we convert the waste from the production of biodiesel, which is glycerin, as raw material, is decirelmethanol, with significant cost savings and environmental impact reduction.

The process has two stages, successive, that we carry out continuously, so it is a continuous process.

In a first stage, the glycerin is subjected to a temperature of 225 degrees Celsius, using platinum-based catalysts, converting it into "synthesis gas", according to the following formula:

CH2OH-CHOH-CH2OH -------------- 3CO + 4H2

The synthesis gas is purified by reacting it with sodium hydroxide at a temperature of 180 degrees Celsius and eight atmospheres of pressure, in this way we obtain sodium formate, solid state, and hydrogen.

In order to obtain a better yield in the process from the sodium formate obtained in the previous process, we again obtain hydrogen again, by means of the thermal decomposition of the sodium formate, (H-COO-Na) subjected to a temperature of three hundred and sixty degrees Celsius.

In this way, the formate is broken down into sodium hydrogen peroxide, releasing the hydrogen in the process.

The hydrogen obtained, both in the first process from synthesis gas, and that obtained from sodium formate, is reacted again with glycerin, at a temperature of 100 degrees Celsius and a pressure of 20 bars, using zinc oxide as a catalyst, and the following chemical reaction occurs:

CH2OH-CHOH-CH2OH + H2 ------------------ 3CH3OH

The reaction of glycerin with hydrogen under the reaction conditions described converts glycerin into methanol. The residue obtained in the process is sodium oxalate, (Na2C2O4) widely used in industry.

Brief statement of the figure

In Figure 1, the set of elements that make up this new system of “Glycerin conversion into methanol” is represented graphically, and where (1) represents glycerin, which we have stored as waste from biodiesel production.

Then, through a platinum catalyst, and at a temperature of 225º (2), glycerin is converted into “synthesis gas” (3).

The synthesis, as well as obtained, is purified by reaction with sodium hydroxide at a temperature of 180 degrees Celsius and eight atmospheres of pressure (4), obtaining sodium formate (5), solid, and hydrogen (6).

Successively but continuously, the sodium formate (5) obtained in the previous process, we subject it to a temperature of 360 degrees Celsius, achieving its decomposition into hydrogen (7) sodium ioxalate (8).

The hydrogen obtained, both in the first process from synthesis gas (6), and that obtained from sodium formate (7), is reacted again with the glycerin (1) stored as a waste of biodiesel production, at a temperature of 100 degrees Celsius and a pressure of 20 bars, using oxide as a catalyst, (9) and consequently the following chemical reaction occurs:

CH2OH-CHOH-CH2OH + H2 ----------------------- 3CH3OH

The reaction of glycerin with hydrogen under the reaction conditions described converts glycerin into methanol (10), which is the object of the invention. The residue obtained in the process is sodium oxalate (8), (Na2C2O4) widely used in the industry.

Description of the way to perform the invention

The following is a brief description of the way to carry out the procedure for the "Conversion of glycerin into methanol", where (1) represents glycerin, which comes from and as a waste of biodiesel production, is stored.

Then, through a platinum catalyst, and at a temperature of 225º (2), glycerin is converted into “synthesis gas” (3).

After synthesis, we make it react with sodium hydroxides at a temperature of 180 degrees Celsius and eight atmospheres of pressure (4), with which we manage to purify it and obtain sodium formate (5), in solid state, and hydrogen (6).

The sodium formate (5) obtained in the previous process, we subject it to a temperature of 360º Celsius, achieving its decomposition in Hydrogen (7) and sodium oxalate (Na2C2O4) (8), which is the residue obtained from the whole process, which can be widely used in the industry.

The hydrogen obtained from the synthesis (6), such as that obtained from sodium formate (7), is reacted again with glycerin (1), and by means of a zinc oxide catalyst (9) at a temperature of 100 degrees Celsius and a pressure of 20 bars, resulting in the following chemical reaction :

CH2OH-CHOH-CH2OH + H2 --------------------- 3CH3OH

That chemical reaction produced between hydrogen and glycerin has converted glycerin into methanol (10), which is the object of the invention.

Claims (6)

1. Conversion of glycerin into methanol, consisting of a chemical process that transforms glycerin into synthesis gases, at a temperature of 225 degrees Celsius, with a catalyst based on platinum. Hydrogen synthesis slides to obtain hydrogen, by setting carbon monoxide into sodium formate, by reacting it with sodium hydroxide, at 180 degrees centigrade temperature and 8atmospheres of pressure.Sodium formate, by thermal decomposition at 360º Celsius temperature, decomposes into sodium hydrogen oxylate. The hydrogen obtained, both for the purification of the synthesis gas, and for the thermal decomposition of the sodium formate, is reacted with the glycerin. The hydrogen reacts with glycerin at 100 degrees Celsius of temperature and 20 bars of pressure, with a zinc oxide catalyst, to produce methanol.

2.

Conversion of glycerin into methanol, according to the first claim, consisting of the decomposition of glycerin synthesis synthesis by a platinum-based catalyst at 225 centigrade.

3.

Conversion of glycerin into methanol, according to the first and second claim, consisting of the purification of synthesis gas, to obtain hydrogen, by the reaction of carbon monoxide with sodium hydroxide, at a temperature of 180 ° and 8 pressure atmospheres, producing sodium formate in the solid state.

Four.

Conversion of glycerin into methanol, according to the first, second and third claim, consisting of the thermal decomposition of sodium formate, at 360 ° to obtain sodium Hydrogenyoxalate.

5.

Conversion of glycerin into methanol, according to the first, second, third and fourth claims, consisting of the reaction of glycerin with Hydrogen at 100 ° temperature and 20 bar pressure, using zinc oxide as catalyst, which converts glycerin into methanol .

5 6 SPANISH PATENTS AND BRANDS OFFICE Application no .: 200901333 SPAIN Date of submission of the application: 05.26.2009

REPORT ON THE STATE OF THE TECHNIQUE

Priority Date: 00-00-0000 00-00-0000 00-00-0000

51 Int. Cl.:

C07C 29/00 (2006.01)

 RELEVANT DOCUMENTS  

Category

56 Documents cited Claims Affected

TO

WO 2008140617 A2 (VIRENT ENERGY SYSTEMS INC et al.) 20.11.2008, example 2, paragraph [0080]. 1-5

TO

US 2007225383 A1 (CORTRIGHT RANDY D; DUMESIC JAMES A) 27.09.2007, paragraphs [0027] - [0029]. 1-5

TO

VIAN, A. &quot; Introduction to industrial chemistry &quot; Ed. Reverte, 1999, page 411, [online], [retrieved on 09/21/2010]. Recovered from internet <URL: http://books.google.com/books?id= Rkk04SmHTKEC &amp; pg = PA411 &amp; lpg = PA411 &amp; dq = decomposition + of + formate + sodium + into + oxalate + sodium &amp; source = bl &amp; ots = pyLOIQZ4xY &amp; sig = m9ishvCkCIjA831xBv_9_PvfQ-k &amp; hl = es &amp; ei = cfFkTMynKMWq4Aab63_Cg &amp; sa = X &amp; oi = book_result &amp; ct = result &amp; v = v &amp; qn = ve # q = fa 1-5

TO

WO 2008041038 A1 (GRIMLEY SMITH ASSOCIATES LTD; ANDREW GRIMLEY) 10.04.2008, page 2, lines 3-10. 1-5

TO

CHRISTIANSEN, R. U.K. researchers convert glycerin to methanol [online]. November 11, 2008 [retrieved 09.20.2010]. Recovered from internet: <URL: http://www.biodieselmagazine.com/ article.jsp? Article_id = 2929> 1-5

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims □ for claims no:

Date of realization of the report 21.09.2010

Examiner I. Gonzalez Balseyro Page 1/4

Application number: 200901333 REPORT ON THE STATE OF THE TECHNIQUE Minimum documentation sought (classification system followed by classification symbols) C07C Electronic databases consulted during the search (name of the database and, if possible, search terms used) INVENES, EPODOC, XPESP, TXTUS  WRITTEN OPINION Application number: 200901333 Date of Completion of Written Opinion: 09.21.2010

Statement

Novelty (Art. 6.1 LP 11/1986)

Claims 1-5 YES

Claims _____________________________________

NO

Inventive activity

Claims 1-5 YES

(Art. 8.1 LP11 / 1986)

Claims _____________________________________ NO

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published.  WRITTEN OPINION Application number: 200901333 1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

WO 2008140617 A2 11/20/2008

D02

US 2007225383 A1 09.27.2007

D03

VIAN, A. &quot; Introduction to industrial chemistry &quot; 1999

D04

WO 2008041038 A1 04.10.2008

D05

CHRISTIANSEN, R. U.K. researchers convert methanol glycerin to 11.11.2008

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of the invention is a process for obtaining methanol from glycerin. Document D01 discloses a process for obtaining synthesis gas from glycerin in a reactor with a platinum catalyst at a temperature of 250 ° C. (See example 2, paragraph [0080]). Document D02 discloses a process for obtaining synthesis gas using glycerin as the raw material, the process taking place at 277 ° C-347 ° C with a platinum catalyst. (See paragraphs [0027] - [0029]). Document D03 discloses a process for obtaining sodium oxalate by decomposing at 375 ° C the sodium formate previously obtained from the reaction of sodium hydroxide with carbon monoxide at 200 ° C and 10 atm. (See page 411 point 14.6.6.4). Document D04 discloses a process for obtaining methanol from glycerin and hydrogen, on a zinc oxide catalyst at a temperature of 300-800 ° C. (See page 2, lines 3-10). Document D05 discloses a process of transforming glycerin into methanol at 100 ° C and 20 bar pressure using a platinum compound as a catalyst. None of the documents D01-D05 cited or any relevant combination thereof reveals a process of obtaining methanol from glycerin where the steps of obtaining synthesis gas from glycerin follow, purification of the above synthesis gas for obtaining hydrogen by reacting with sodium hydroxide and obtaining methanol by reacting glycerin and hydrogen obtained in the previous stages, using a zinc oxide catalyst, at a temperature of 100 ° C and 20 bar pressure. Therefore, it is considered that the invention set forth in claims 1-5 meets the requirements of novelty and inventive activity, as set forth in Articles 6.1 and 8.1 of the Patent Law. Report on the State of the Art (Written Opinion) Page 4/4