BRPI0901399A2 - process for obtaining dichloropropanols - Google Patents

Abstract

PROCEDURE FOR OBTAINING DICLOROPROPANS The present invention relates to a process for obtaining dichloro-propanols, notably 1,3-dichloro-2-propanol or 2,3-dichloro-1-propanol, which may be employed as a raw material in the manufacture of the product. epichlorohydrin, which is itself used to obtain epoxy resin. The process is to promote the reaction of glycerine or its derivatives or precursors with hydrochloric acid and water in at least one continuous reaction zone having a fixed catalytic bed composed of a mixture of glycerine or its derivatives or precursors in high concentrations of one or more. organic acids at reaction temperatures between about 110 ° C and 180 ° C, with continuous removal of unconverted products and reagents.

Description

PROCESS FOR OBTAINING DICHLOROPROPANOLS

APPLICATION FIELD

The present invention relates to a process for obtaining dichloropropanols, notably 1,3-dichloro-2-propanol or 2,3-dichloro-1-propanol or mixtures thereof, from glycerol, glycerine or propanotriol, which may be employed as raw material in the manufacture of epichlorohydrin, which in turn is used to obtain epoxy resin.

TECHNICAL STATE

According to the state of the art in known processes, epichlorohydrin is obtained using petrochemical resources from the multi-step chloroprene reaction producing dichloropropanols (mixture of 1,3 dichloro-2-propanol and 2,3 dichloro-1-propanol) , whose reaction with soda generates aepichlorohydrin. Dichloropropanols are obtained in a highly dilute solution having a titer of 5 to 15% by weight, requiring a significant energy expenditure to purify it.

A recent route of industrialization employs renewable raw materials and is based on the hydroconversion of glycerol producing dichloropropanois which is converted to epichlorohydrin from reaction with soda, depotassium hydroxide or hydrated lime.

Glycerol obtained from renewable raw materials has several origins, one of them and perhaps the largest current source being crude glycerin obtained as a biodiesel by-product, and may also have other origins related to the conversion of fats or oils of vegetable or animal origin. such as saponification, transesterification or hydrolysis reactions. Glycerolsynthetic is obtained from epichlorohydrin obtained through petrochemical resources.

Glycerol can be a crude product or a purified product. Crude glycerol obtained from renewable raw materials may comprise impurities such as water and a metal salt, in particular a chloretometallic, which is preferably selected from the group comprising salts: NaCl, KCl1 MgCl2 and CaCl2. The metal salt may also be selected from metal sulfates such as sodium sulfate and potassium sulfate. The crude product may also contain organic impurities such as carbonyl compounds, in particular aldehydes, fatty acids or fatty acid esters, such as monoglycerides or diglycerides, optionally in combination with water and / or metal chloride, in addition to proteins and sugars, and others in smaller quantities.

When purified glycerol is employed in the process of obtaining organic compounds such as dichloropropanes or epichlorohydrin, it may be obtained from a crude product which undergoes one or more purification operations such as distillation, evaporation, extraction or operation. concentration followed by a separation operation such as sedimentation, filtration or centrifugation. It is also possible to employ resin, ion exchange or even electrodialysis in this process.

US 4113746 of 1975 reports a continuous process of producing epichlorohydrin comprising the reaction of chlorine and an aqueous allyl chloride, followed by neutralization and saponification, resulting in an acidified solution of hydrochloric acid containing dichlorohydrin glycerol with alkali to form a solution containing epichlorohydrin.

US 4634784 of 1984 deals with a process for producing deepchlorhydrin which involves a two step process: reaction of allyl alcohol with aqueous chlorine solution to result in dichloropropanol and saponification with calcium hydroxide suspension.

US 4704463 of 1986 deals with a continuous process of producing epichlorohydrin which comprises several steps including: reaction of allyl chloride, chlorine and water to produce a dichlorohydrin solution; reaction with excess basic substance; separation of the obtained epichlorohydrin, cooling followed by electrodialysis and reverse osmosis.

Document P 0416756 of 2003 deals with the process for producing chloropropanol, organic compounds, epichlorohydrin and epoxy resin using glycerol from renewable raw materials. The continuous process involves reaction of glycerol with a chlorinating agent in the absence of acetic acid, preferably anhydrous hydrogen chloride, in the presence of at least one organic solvent, with continuous removal of water from the meioreaction phase continuously. According to this document the catalyst is not fixed and the reactor feed line occurs together with the glycerol and hydrochloric acid feed lines. "Glycerol obtained from renewable raw materials" such as biodiesel production, or glycerol obtained from the conversion of fats or oils of general vegetable or animal origin, which is in crude form must be purified before use and subjected to one or more purification operations such as distillation, evaporation, extraction or even a concentration operation followed by a total separation operation such as sedimentation, filtration or centrifugation. Preferably the glycerol is distilled.

The document WO 2005021476 of 2003 deals with a catalytic method of glycerine and / or monochloropropanediols hydrochlorination to obtain dichloropropanols, occurring in at least one continuous reaction zone at a reaction temperature of 70 ° to 140 ° C and also with continuous removal of aqueous reaction. ; The feed liquid contains at least 50% by weight of glycerine and / or monochloropropanediols.

WO 2007054505 deals with a process for producing dichloropropanol by glycerol chlorination whereby the medium liquid is in equilibrium with the vapor phase, such that condensation of a fraction containing the vapor phase composition is avoided.

OBJECTIVES OF THE INVENTION

The invention has as its object or features the following innovative features:

the catalyst remaining in the reaction bed forming a fixed bed, eliminating the need for continuous or intermittent catalyst feeding or removal;

The high mass concentration of catalyst in its catalytic bed, above 10% by weight of catalyst, preferably above 20% by stoichiometric value, permitting a low molar excess ratio between agglicerin and hydrochloric acid relative to the state of the art. This is:

• low molar excess of HCI over glycerine is used (the state of the art uses molar excesses above 100% HCI relative to the stoichiometric value);

The proposed invention utilizes excess HCl of less than 100%, preferably below 70% (relative to the stoichiometric value);

the use of reaction temperatures above 1100C1 preferably above 140 ° C. Since the prior art employs molar excess UP to 100% hydrochloric acid or acid at temperatures above 140 ° C there would be dehydration and carbonization of the bed according to this invention as catalysts for pure or mixed organic acids of high boiling temperature at ambient pressure. , with a minimum temperature of 1100 ° C, preferably above 180 ° C and soluble in the reaction medium, the removal of reagents and products made in gas phase and / or steam or mixtures, with the lowest possible drag of catalyst, and the outflow may serve as entry of another bed of similar characteristics, and the process can be employed in a single stage of continuous operation or a cascade of reactors;

Allows the use of blonde glycerin which is purified by lower cost process than prior art processes using distillation to purify glycerol as it involves hydrochloric acid saturation and precipitation of precipitated salts with removal of fatty acids through the use of active charcoal ;

Reduction of process time, as it operates by employing a catalyst in a leitofix, with temperatures much higher than the processes of obtaining dichloropropanols known to the man of the art, reduction in the cost of the final product compared to conventional methods, obtaining a high grade final product. of purity.

BRIEF DESCRIPTION OF THE INVENTION

The present invention is a process for obtaining organic compounds such as diclopropanes, comprising reacting glycerin with one or more chlorinating agents in at least one continuous reaction zone having a fixed catalytic bed containing a high decatalyst mass concentration, above 10% relative to the stoichiometric value. preferably above 20%, the catalyst mass being one or more organic acids at reaction temperatures between about 1100 ° C and about 180 ° C, with continuous removal of unconverted products and reagents.

DETAILED DESCRIPTION OF THE INVENTION

The process according to the invention consists of placing in contact glycerine, glycerol or propanethriol or derivatives or precursors thereof with at least one chlorinating agent to obtain finally chlorinated organo compounds. The chlorinating agent can be an agent for oxidative chlorination or substitutive chlorination. As oxidative chlorinating agent we can cite chlorine and as substitutive chlorinating agent we can cite hydrogen chloride.

A replacement chlorinating agent such as the mixture of hydrochloric acid and water or simply an aqueous hydrogen chloride solution is preferred. Optionally, in situ generated hydrogen chloride within the reaction medium may be employed as the chlorinating agent, for example, starting from a common inorganic acid such as sulfuric acid or phosphoric acid, and a suitable chloretometallic such as NaCl, KCI or CaCl2. Still optionally HCl may be employed in gaseous and / or anhydrous form.

The chlorination reaction takes place in at least one continuous reaction zone, preferably one, having a fixed catalytic bed composed of a mixture of glycerine or its derivatives or precursors at high concentrations of one or more organic acids at reaction temperatures of about 1100 ° C and 180 °. C, with continuous removal of unconverted products and reagents.

The present invention is a high glycine conversion catalytic hydrochloride method or process, whether bi-distilled or blonde glycerine of animal or plant origin, or mixtures thereof, for conversion to dichloropropanols such as 1,3-dichloro-2-propanol and or 2,3-dichloro-1-propanol or by-products, carried out in at least one continuous reaction zone at reaction temperatures in the range 1100C to 180 ° C, with continuous removal of unconverted products and reagents in the form of vapor and gas. Reagent feeds may be liquid, or vapor, or gaseous, or a mixture. The method can be performed in a continuous-bed, continuous-mix, single-stage reactor or a cascade of reactors.

Development:

According to a preferred embodiment of the invention, the new method proposes the preparation and use of a fixed catalytic bed, where glycerine, hydrochloric acid and water are fed in liquid or steam or gas form or mixtures, the products being removed in vapor and / or gas form. , together with the unconverted rulers.

Fixed bed preparation:

The catalytic fixed bed is innovatively prepared from a mixture of glycerine (or glycerol or propanotriol) and one or more carboxylic acids, which may optionally be in the form of anhydride or organic salt. Monocarboxylic, dicarboxylic, tricarboxylic and polycarboxylic acids may be employed as carboxylic acids. The accompanying TABLE 1 presents a list of monocarboxylic and dicarboxylic acids studied for the present invention, their respective synonyms, CAS, melting points and boiling at 0 ° C.

Preferably the organic or carboxylic acid is selected from the group comprising the group of poly (carboxylic acids) comprising: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid.

The carboxylic acids or mixtures thereof should be employed at concentrations preferably greater than 20% by weight of organic acid, relative to the total mass of the glycerine and organic acid mixture in the fixed bed of the reactor.

The total amount of hydrochloric acid added in the preparation of the leopod may be at least 80% of the amount required for the conversion of todaglycerin to monochloropropanediols.

The organic acids used should have a boiling temperature at ambient pressure above 180 ° C, preferably above 200 ° C, to minimize drag on the bed outlet vapors.

Bed preparation involves heating the mixture of glycerine and organic acid to temperatures above 100 ° C, preferably greater than 130 ° C, followed by the addition of a mixture of hydrochloric acid and water, called hydrochloric acid.

In the preparation of the bed this method has the advantage of allowing the use of hydrochloric acid and water mixture in any concentration of hydrochloric acid, even the most dilute, ie below 1% hydrochloric acid.

This method also has the advantage of allowing the use of highly concentrated hydrochloric acid including anhydrous hydrochloric acid, ie 100% hydrochloric acid.

The fixed bed of the reactor may also be prepared by replacing all or part of the glycerine mass with 1-monochlor-2-3-propanediole or 2-monochlor-1-3-propanediol, or a mixture thereof, whether or not containing 1,3- dichloro-2-propanol and / or 2,3-dichloro-1-propanol.

The bed may also be prepared from the mixture of organic acid catalyst and 1,3-dichloro-2-propanol and / or 2,3-dichloro-1-propanol or mixtures thereof and may or may not contain 1-monochlor-2-3. -propanediol and / or 2-monocloro-1-3-propanediol.The mixture of hydrochloric acid and water (concentration 0.1% to 100% hydrochloric acid) may be added in liquid or vapor form provided the bed is maintained. the temperature above 100 ° C is preferably higher than 130 ° C, so the temperature of the hydrochloric acid mixture (from 0.1% to 100% hydrochloric acid concentration) may range from the temperature of its melting point to values well above its peak. boiling range, the recommended operating range ranges from 5 ° C to 180 ° C, preferably from 70 ° C to 170 ° C.

With the bed prepared, the reaction temperature is adjusted to the range 130 ° C to 180 ° C.

Reagents for the production of dichloropropanols are glycerine, hydrochloric acid and water, and monochloropropanols.

Reagents may be mixed together, separately or partially mixed and separated.

The inlet temperature of the reactants will depend on the reactor energy balance, therefore, some of the reactants may come in vapor form and either in liquid form or both liquid or both vapor.

Therefore, the individual inlet or mixing temperature may range from 5 ° C to 180 ° C, preferably from 70 ° C to 170 ° C.

The ratio of hydrochloric acid and water reagents may range from 1:10 mass to 1: 100 mass, preferably should be operated in the range of 1: 1.5 to 1: 2.5 mass. These reagents may come together or apart or part together and part apart.

The ratio of glycerine and monochloropropane reagents is the one with the highest operating range, assuming any relationship between these reagents, including the use of all of them. That is, considering the totality of glycerine and monochloropropane masses, we can use from 0 to 100% glycerine. These reagents may come together or separately or part together and parts apart.

The reaction may take place in a continuous-bed, single-stage continuous-mix reactor, or in a cascade of reactors, optionally in a negative, positive, inert, or vacuum atmosphere.

The use of vacuum improves the removal of reaction products.

The method innovates by allowing the use of bidistilled glycerin or blonde glycerin or crude glycerol or purified glycerol of animal or vegetable origin. In the case of blonde glycerine or crude glycerol, which needs to be purified, the blonde glycerine or glycerol is mixed with hydrochloric acid causing salt appreciation, which may be removed by filtration step, may be: simple decantation, filter press or other filtration medium, or by any other purification method. Both clarified as well as pure glycerin can be refined by receiving activated carbon addition at a reagent mass concentration ranging from 0.01% to 10% being removed by another filtration or decantation step. The treated mixture is added at room temperature or heated in the reactor, the method innovates by allowing salts which eventually enter the reactor to be trapped in the catalytic bed so as to precipitate upon reaching their critical solubility concentration. In this case, bones may be removed by the bed filtration process or by decanting the bed. In the end, "dichloropropanols" are obtained which mean a mixture of isomers consisting essentially of 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol or mixtures thereof. Products may be removed in a vapor and / or gas form together with unconverted conductors.

In a variant of the process according to the invention for producing chlorinated organic compounds the reaction takes place in the presence of at least one organic solvent or carrier solvent, which may be a solvent chosen from the group consisting of: chlorinated, alcohols, ketones, esters or ethers, or both. mixtures.

The amount of heavy compounds such as chlorohydroxypropane or dichloropropanol may be reduced by the use of a non-aqueous solvent that is susceptible to glycerol or the other reaction products. Examples of such a solvent are: dichloropropanol, dioxane, phenol and cresol. Chlorodihydroxypropan may also be employed as a glycerol diluent when aiming to produce chloropropanol.

The following are examples which serve to further elucidate the scope of the invention, but should not be used for limiting purposes thereof.

EXAMPLE 1: Reaction with Succinic Acid

1.a) Bed preparation:

The 2 liter reactor was charged with 750 g glycerol, and then agitation was adjusted to 200 RPM, then the reactor heating system was turned on by setting the temperature to 120 ° C in the glycerol. After the temperature of 120 ° C was reached, 606.63 g of succinic acid was slowly added under stirring and the temperature was maintained until complete solubility thereof.

After solvation of the acid, the mass was heated to 140 ° C in the mass to initiate the HCl feed at room temperature. The accompanying TABLE 2 shows the results of this addition and TABLE 3 below indicates parameters such as total addition time, total weight collected at reactor output and HCI content in the collected phase after reactor:

<table> table see original document page 10 </column> </row> <table>

TABLE 3

1.b) Hydrochlorination reaction:

After bed preparation it was heated to 150 ° C. Hydrochlorination was carried out using a solution prepared with 782.8 g of 33% HCl and glycerol 217.2 g, which we will call the 1st kilogram of solution. The attached TABLE 4 presents the results of this addition and the TABLE 5 below gives further complementary parameters:

<table> table see original document page 10 </column> </row> <table>

TABLE 5

On the addition of the 12th kilo, the results were presented as TABLE 6 attached and TABLE 7 below indicates other complementary parameters:

<table> table see original document page 10 </column> </row> <table>

TABLE 7

EXAMPLE 2: Reaction with azelaic acid

2.a) Bed Preparation: The 2 liter reactor was charged with 750 g glycerol and then agitated and adjusted to 200 RPM, then the reactor heating system was turned on by setting the temperature to 120 ° C. in glycerol. After the temperature of 120 ° C was reached, 788 g of azelaic acid was slowly added under stirring and the temperature was maintained until complete solubility. After acid dissolution, the mass was heated to 140 ° C in the mass to initiate HCl feed at room temperature. TABLE 8 below indicates other complementary parameters:

<table> table see original document page 11 </column> </row> <table>

TABLE 8

2.b) Hydrochlorination reaction:

After bed preparation it was heated to 150 ° C. Hydrochlorination was carried out using a solution prepared with 782.8 g of 33% HCl and glycerol 217.2g, which we will call the 1st kilogram of solution. TABLE 9 below indicates other complementary parameters:

<table> table see original document page 11 </column> </row> <table>

TABLE 9

On the addition of the 11th kilo the results were presented as TABLE 10 below.

<table> table see original document page 11 </column> </row> <table>

TABLE 10

EXAMPLE 3: Reaction with oxalic acid 3.a) Bed preparation:

The 2 liter reactor was charged with 750 g glycerol, and then agitation was adjusted to 200 RPM, then the reactor heating system was turned on by setting the temperature to 120 ° C in the glycerol. After the temperature of 120 ° C was reached, 642 g of oxalic acid dihydrate was slowly added under stirring and the temperature was maintained until complete solubility. After solvation of the acid, the mass was heated to 140 ° C in the mass to initiate the HCl feed at room temperature. TABLE 11 below indicates other complementary parameters:

<table> table see original document page 12 </column> </row> <table>

TABLE 11

3.b) Hydrochlorination reaction:

After bed preparation it was heated to 150 ° C. Hydrochlorination was performed using a solution prepared with 782.8 g of 33% HCI glycerol 217.2 g. TABLE 12 below presents the results of this addition.

<table> table see original document page 12 </column> </row> <table>

TABLE 12

EXAMPLE 4: Reaction with Sebacic Acid

4.a) Bed preparation:

The 2 liter reactor was charged with 750 g glycerol and then agitated and adjusted to 200 RPM, then the reactor heating system was turned on by adjusting the temperature to 120 ° C in the glycerol. After the temperature of 120 ° C was reached, 1039 g of sebacic acid was slowly added with stirring and the temperature was maintained until complete solubility.

After solvation of the acid, the mass was heated to 140 ° C in the mass to initiate HCl feeding at room temperature. TABLE 13 below indicates other complementary parameters: <table> table see original document page 13 </column> </row> <table>

TABLE 13

4.b) Hydrochlorination reaction:

After bed preparation it was heated to 150 ° C. Hydrochlorination was carried out using a solution prepared with 782.8 g of 33% HCl and glycerol 217.2 g, which we will call the 1st kilogram of solution. TABLE 14 below presents the results of this addition.

<table> table see original document page 13 </column> </row> <table>

TABLE 14

On the addition of the 11th kilo the results were presented according to TABLE 15 below.

<table> table see original document page 13 </column> </row> <table>

TABLE 15

EXAMPLE 5: Reaction with adipic acid

5.a) Bed preparation:

The 2 liter reactor was charged with 750 g glycerol, and then agitation was adjusted to 200 RPM, then the reactor heating system was turned on by setting the temperature to 120 ° C in the glycerol. After the temperature of 120 ° C was reached, 750 g of adipic acid was slowly added with stirring and the temperature was maintained until complete solubility. After acid dissolution, the mass was heated to 140 ° C in the mass to initiate HCl feed at room temperature. TABLE 16 below indicates other complementary parameters: <table> table see original document page 14 </column> </row> <table>

TABLE 16

5.b) Hydrochlorination reaction:

After bed preparation it was heated to 150 ° C. Hydrochlorination was carried out using a solution prepared with 782.8 g of 33% HCl and glycerol 217.2 g, which we will call the 1st kilogram of solution. TABLE 17 below presents the results of this addition.

<table> table see original document page 14 </column> </row> <table>

TABLE 17

On the addition of the 11th kilo the results were presented as TABLE 18 below.

<table> table see original document page 14 </column> </row> <table>

TABLE 18

The attached TABLE 19 reproduces the results of the tests with different catalysts.

As shown in the previous tables, reaction yield and selectivity are very similar regardless of the catalysts used. Thus, any catalyst with boiling point above 180 ° C soluble in the reaction medium can be used in this new process. <table> table see original document page 15 </column> </row> <table>

TABLE 1 <table> table see original document page 16 </column> </row> <table> <table> table see original document page 17 </column> </row> <table> <table> table see original document page 18 </column> </row> <table> <table> table see original document page 19 </column> </row> <table>

Claims (29)

1. PROCEDURE FOR OBTAINING DICHLOROPROPANOLES characterized by understanding the reaction of glycerin with one or more dechlorinating agents in at least one continuous reaction zone presenting fixed catalyst containing high catalyst mass concentration, above 10% in relation to the stoichiometric value. catalyst mass composed of one or more organic acids at reaction temperatures of about 1100 ° C and about 180 ° C, with continuous removal of unconverted products and agents. 2. PROCESS FOR OBTAINING DICLOROPROPANOLES according to claim 1, characterized in that the catalyst mass concentration is preferably above 20% relative to the stoichiometric value. Process for obtaining dichloropropanols according to claims 1 or 2, characterized in that the fixed bed is composed of a mixture of glycerine (or glycerol or propanotriol) and one or more carboxylic acids. 4. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 3 characterized in that monocarboxylic, dicarboxylic, tricarboxylic and polycarboxylic acids may be employed. Process for obtaining dichloropropananes according to claims 1, 3 or 4, characterized in that the organic acid may be chosen from the group of poly (carboxylic acids) comprising: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid. . 6. PROCEDURE FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the carboxylic acids or mixtures thereof may be employed in concentrations preferably greater than 20% by weight of organic acid relative to the total mass of glycerine and organic acids in the fixed bed of the reactor. . 7. PROCESS FOR OBTAINING DICLOROPROPANOLES According to claims 1 or 4, characterized in that the organic acids have a boiling temperature at ambient pressure above 180 ° C, preferably above 200 ° C, to minimize drag on the bed outlet vapors. Process for obtaining dihydrochloropanols according to claim 1, characterized in that the preparation of the bed involves the heating of the mixture of glycerine and organic acid to a temperature above 100 ° C followed by the addition of a mixture of hydrochloric acid and water or hydrochloric acid. 9. Process for obtaining dichloropropanes according to claim 8, characterized in that such mixture may be added to a steam or liquid reactor at room temperature or heated to a maximum of 100 ° C. 10. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the total amount of hydrochloric acid added in the bed preparation is at least 80% of the amount required for the conversion of all glycerine to monochloropropanediols. 11. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the fixed bed of the reactor may be prepared by totally or partially replacing the glycerine mass with 1-monochlor-2-3-propanediol and / or 2-monochlor-1-3-propanediol; or mixtures thereof, whether or not containing 1,3-dichloro-2-propanol and / or 2,3-dichloro-1-propanol. 12. Process for obtaining dichloropropanes according to claim 1, characterized in that the bed may be prepared from the mixture of organic acid catalyst and 1,3-dichloro-2-propanol and / or 2,3-dichloro-1-propanol or a mixture thereof. whether or not it contains 1-monochlor-2-3-propanediol and / or 2-monocloro-1-3-propanediol. 13. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the mixture of hydrochloric acid and water (concentration between 0,1% and 100% hydrochloric acid) may be added in liquid or vapor form, provided that the bed is maintained at temperatures above 100 ° C, preferably above 130 ° C. 14. PROCESS FOR OBTAINING DICLOROPROPANOLES According to Claims 1 or 13, characterized in that the temperature of the hydrochloric acid mixture (from a concentration of 0.1% to 100% hydrochloric acid) could vary from the temperature of its melting point to values well above its peak. boiling point being the recommended operating range between 5 ° C and 180 ° C, preferably 70 ° C to 170 ° C. 15. PROCESS FOR OBTAINING DICLOROPROPANOLS SECOND Claim 1 characterized in that, with the prepared bed, the reaction temperature is adjusted to the range of 130 ° C to 180 ° C. 16. PROCEDURE FOR OBTAINING DICLOROPROPANOLS according to claim 1, characterized in that the reagents for the production of dichloropropanols are glycerine, hydrochloric acid and water, in chlorochloropropanols. 17. PROCESS FOR OBTAINING DICLOROPROPANOLES according to claims 1 or 16, characterized in that the reagents may be mixed together, separately or mixed and separated. 18. PROCEDURE FOR OBTAINING DICLOROPROPANOLES SECOND Claim 17 characterized in that the individual inlet or mixing temperature may vary from 5 ° C to 180 ° C, preferably from 70 ° C to 170 ° C. 19. PROCEDURE FOR OBTAINING DICLOROPROPANOLES SECOND CLAIMS 1 or 16 characterized in that the ratio of the hydrochloric acid and water reagents may range from 1:10 mass to 1: 100 mass, preferably it shall be operated in the range of 1: 1.5. at 1: 2.5 by mass. 20. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the reaction may occur in a continuous mixing and fixed bed reactor, single continuous operation stage, or in a reactor housing. 21. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the reaction may occur in a negative atmosphere, a positive, inert or vacuum atmosphere. 22. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the use of glycerinabid distilled or blonde glycerin or crude glycerol or purified glycerol, whether original or vegetable, may be employed. 23. PROCESS FOR OBTAINING DICLOROPROPANOLES According to Claims 1 or 22, characterized in that the blonde glycerin or glycerolbrute is purified by mixing it with the hydrochloric acid, followed by a filtration step, which may be used for decanting, filtering or other filtration. or be purified by any other purification method. Process for obtaining dichloropropanols according to claims 1 or 23, characterized in that either the clarified or the proper glycerin may be refined by the addition of activated charcoal at a concentration to reagent mass which may range from 0.01% to 10% and is removed. by further filtration or decantation. 25. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that an organic solvent may be employed. 26. Process for obtaining dichloropropanols according to claim 25, characterized in that the organic solvent may be chosen from the group consisting of: chlorides, alcohols, ketones, esters or ethers, or mixtures thereof. Process for obtaining dichloropropanes according to claims 1 or 25, characterized in that the solvent may be chosen from the group consisting of: dichloropropanol, dioxane, phenol, cresol, chlorodihydroxypropane, or mixtures thereof. 28. PROCESS FOR OBTAINING DICLOROPROPANOLES SECOND Claim 1 characterized in that the products are removed in the form of steam and / or gas together with the unconverted rulers. 29. PROCESS FOR OBTAINING DICHLOROPROPANOLES SECOND Claim 1 characterized in that 1,3-dichloro-2-propanol or 2,3-dichloro-1-propanol or mixtures thereof are obtained in the end.