KR20210089005A - Manufacturing method of microorganism energy source from wasted glycerin's recycling process - Google Patents

Abstract

The present invention relates to a method for manufacturing a microorganism energy source which is relatively cheap, by purifying glycerine pitch which is a byproduct generated during a glycerine purification process, so that the glycerine pitch is usable as a microorganism activator which is a microorganism activation anergy source. The present invention comprises: a first step of adding hydrochloric acid into glycerine pitch containing glycerine, organic impurities and ash (salt), adding water, and then stirring the same while heating; a second step of leaving the same for a predetermined time and removing organic impurities separated to the upper layer part through a centrifugation process; a third step of removing, through an electrolysis process, ash (salt) from crude glycerine from which organic impurities are removed; a fourth step of collecting, in water, chlorine gas generated from a cathode and hydrogen gas generated from an anode, so as to obtain a hydrochloric acid aqueous solution; and a fifth step of adding acetic acid to basic crude glycerine containing sodium hydroxide generated by removing the chlorine gas, thereby generating sodium acetate so as to generate a microorganism activator in which glycerine, sodium acetate and water are mixed. According to the present invention, glycerine is produced by enhancing the concentration of glycerine contained in a glycerine pitch and lowering the amount of impurities so that the glycerine is not completely purified but is only purified so as to be usable in a waste water treatment facility. Therefore, relatively cheap microorganism activator can be effectively prepared.

Description

Manufacturing method of an energy source for microorganisms using recycled waste glycerin {Manufacturing method of microorganism energy source from wasted glycerin's recycling process}

The present invention relates to a method for producing an energy source for microorganisms, and in particular, by purifying glycerin pitch, a by-product generated in the glycerin purification process, to the extent that it can be used as a microbial activator, a microbial activation energy source, to a relatively inexpensive method for producing an energy source for microorganisms. will be.

Glycerin pitch is a by-product generated during the glycerin purification process. Glycerin generated in the refining process of biodiesel, soap and oil is crude glycerin containing impurities.

Such crude glycerin contains ash (sodium chloride) along with some fatty acids (FREE FATTY ACID), oil (TRIGLYCERIDE), and organic impurities (monk) along with a large amount of glycerin.

Accordingly, through several purification processes, 99.5% or more of purified glycerin is produced. Glycerin is used for various purposes such as cosmetics, pharmaceuticals, toothpaste, and sweeteners.

In the production process of purified glycerin, purified glycerin is produced through distillation. The pitch from this distillation process contains a large amount of glycerin along with fatty acids (FREE FATTY ACID), fats and oils (TRIGLYCERIDE), organic impurities (mon ) and ash (sodium chloride) is concentrated. However, this pitch has many difficulties in producing purified glycerin through a refining process. Therefore, it is being disposed of by methods such as landfilling and incineration of waste.

Meanwhile, in the recent wastewater treatment, a biological treatment process, not a conventional chemical treatment process, is being activated. At this time, it is most important to activate the microorganisms in the biological treatment process, and glycerin is a very effective nutrient for the activation of microorganisms. It has the advantage that microorganisms can be easily used as a nutrient source, and various minerals are contained as components derived from plants and animals. However, there is a disadvantage in that the price is relatively expensive to use purified glycerin.

Methanol, acetic acid, or sodium acetate, which are widely used as existing microbial activators, have a small molecular weight and are quickly used by microorganisms and are very good for energy and activator use. However, in the case of glycerin, the molecular weight is larger than methanol, and microorganisms use it as an activator. Below, it has the disadvantage of reacting slower than methanol and acetic acid.

However, methanol is a dangerous and toxic substance, so it has the disadvantage of having to use a separate device for hazardous substances and toxic substances when used in a wastewater treatment plant.

In addition, when acetic acid is used, the smell is very strong, and it has a problem of being easily solidified.

In particular, in the case of methanol and acetic acid, when used near the city center, there is a disadvantage of causing damage to the residents living in the vicinity.

Therefore, if sodium acetic acid in powder form is used, it can quickly become effective as a microbial activator, but it has the disadvantage of being very expensive.

As a prior art patented technology in the related field, (a) adding and mixing biodiesel wastewater containing 5% by weight of glycerin to food waste at 5% (v/v) to 20% (v/v), and (b) ) A method for producing biogas from food waste by recycling glycerin-containing biodiesel wastewater including the step of anaerobically digesting the mixture has been proposed (see Patent Document 1).

In addition, (A) separating the alcohol from the esterification reaction product of oils and fats and alcohol, and then separating crude glycerin and crude biodiesel; (B1) After mixing the crude glycerin separated in step (A) with the following intermediate water, tri- (tri-), di- (di-), mono- (mono-) glycerides remaining in the crude glycerin are hydrolyzed decomposition to convert glycerin and fatty acids; (B2) obtaining condensed water by evaporating and condensing moisture from the residue after separating the fatty acids produced in step (B1); (C) washing the crude biodiesel separated in step (A) with the condensed water obtained in step (B2), and then separating purified biodiesel and intermediate water containing impurities; A method for simultaneously purifying crude glycerin and crude biodiesel produced by a biodiesel manufacturing process comprising a (see Patent Document 2) has been proposed.

Domestic Patent Publication 10-2016-0048464 Domestic registered patent 10-1099367

The present invention does not produce fully purified glycerin by increasing the concentration of glycerin contained in the glycerin pitch and lowering the content of impurities, but only refining it to the extent that it can be used in a wastewater treatment plant, and a method for producing an energy source for microorganisms using relatively inexpensive recycled waste glycerin Its purpose is to provide

In order to achieve the above object, the method for producing an energy source for microorganisms using recycled waste glycerin according to the present invention is a method for producing a microbial activator for wastewater treatment using glycerin pitch, a by-product generated in the glycerin purification process. , a first step of adding hydrochloric acid to the glycerin pitch containing organic impurities and ash, adding water, and then heating and stirring; A second step of removing the organic impurities separated into the upper layer after standing for a predetermined time through a centrifugal separation process; a third step of removing ash (salt) from the crude glycerin from which organic impurities have been removed through an electrolysis process; a fourth step of collecting chlorine gas generated from the anode and hydrogen gas generated from the cathode in water to obtain an aqueous hydrochloric acid solution; By removing chlorine gas, sodium hydroxide is generated and acetic acid is added to basic crude glycerin contained therein to produce sodium acetate, comprising a fifth step of producing a microbial activator in which glycerin, sodium acetate, and water are mixed. do.

Here, in the first step, 1 to 10 parts by weight of hydrochloric acid is added with respect to 100 parts by weight of glycerin pitch, 5 to 30 parts by weight of water is added, and then stirred for 30 minutes to 3 hours after heating to 30 to 60° C., In the second stage, it can be left still for 1 to 12 hours.

In addition, the aqueous hydrochloric acid solution obtained in the fourth step may be used when adding hydrochloric acid in the first step.

According to the present invention, it is possible to effectively prepare a relatively inexpensive microbial activator by increasing the concentration of glycerin contained in the glycerin pitch and by purifying only enough to be used in a wastewater treatment plant, rather than producing completely purified glycerin by lowering the content of impurities.

In addition, in the case of using a microbial activator for wastewater treatment in which glycerin, sodium acetate, and water are properly mixed according to the present invention, sodium in crude glycerin is used to compensate for the disadvantage that the activation time is delayed when glycerin is used alone as a microbial activator. Sodium acetic acid is synthesized by reacting with acetic acid using acetic acid, and microorganisms are activated using sodium acetic acid until glycerin is activated, thereby shortening the microbial activation time compared to conventional glycerin.

1 is a flowchart of a method for manufacturing an energy source for microorganisms using recycled waste glycerin according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

The method for producing an energy source for microorganisms using recycled waste glycerin according to the present invention increases the concentration of glycerin contained in the glycerin pitch and lowers the content of impurities to produce completely purified glycerin, but only to the extent that it can be used in a wastewater treatment plant. is an important technical feature.

As shown in the drawing. The method for producing an energy source for microorganisms using recycled waste glycerin according to the present invention is a method for producing a microbial activator for wastewater treatment using glycerin pitch, which is a by-product generated in the glycerin purification process. First, in the case of glycerin pitch, organic impurities other than glycerin Since it contains excess ash (sodium chloride: salt) and has high viscosity due to organic impurities and ash, it is difficult to self-treat, so hydrochloric acid is added to glycerin pitch, water is added, and then heated and stirred (S110).

At this time, 1 to 10 parts by weight of hydrochloric acid is added with respect to 100 parts by weight of glycerin pitch, and 5 to 30 parts by weight of water is added, and then heated to 30 to 60° C. and stirred for 30 minutes to 3 hours to expect the optimal effect.

If the amount of hydrochloric acid is less than 1 part by weight, it is difficult to expect a separation action to remove organic impurities. As the amount increases in excess, there is a fear that the subsequent electrolysis process becomes long and difficult.

And, if the amount of water is less than 5 parts by weight, it is impossible to lower the viscosity of the glycerin pitch, so even if hydrochloric acid is added, the viscosity is high, so it is difficult to remove organic impurities. Conversely, if it exceeds 30 parts by weight, the viscosity can be significantly lowered, but the glycerin content This becomes low, and there is a possibility that the effect as a microorganism activator may be lowered.

For reference, glycerin pitch contains 40 to 60% of glycerin, 5 to 20% of organic impurities (monks), and 10 to 30% of ash.

In the next step, the organic impurities separated into the upper layer after standing for 1 to 12 hours are removed through a centrifugal separation step (S120).

In the next process, ash (salt) is removed from crude glycerin from which organic impurities have been removed through an electrolysis process, which is a process of decomposing substances through an electrochemical redox reaction by applying electric energy from the outside (S130) . At this time, since crude glycerin from which organic impurities are primarily removed contains a large amount of water, chlorine gas (Cl _{2 ) is ejected from the anode, which is the oxidation electrode, and hydrogen gas (H 2)} is generated from the cathode, which is the reduction electrode.

In the next step, chlorine gas generated from the anode and hydrogen gas generated from the cathode are collected in water to obtain an aqueous hydrochloric acid solution (S140). The aqueous hydrochloric acid solution thus obtained can be used when hydrochloric acid is added in step S110.

Finally, as Cl- decomposed through electrolysis is removed with chlorine gas, the remaining Na+ groups are generated as sodium hydroxide (NaOH). The crude glycerin solution is converted to basic crude glycerin and added to crude glycerin containing sodium hydroxide. By adding acetic acid to produce sodium acetate, glycerin, sodium acetate, and water are mixed to produce a microbial activator (S150). That is, by reacting sodium hydroxide with acetic acid to produce sodium acetate, glycerin, sodium acetate, and water are appropriately mixed to produce a microbial activator.

As such, the microbial activator produced using glycerin pitch, a by-product generated in the glycerin purification process, contains glycerin and sodium acetate, which are nutrients that are very effective in activating microorganisms, so it can be very usefully used for wastewater treatment.

On the other hand, if wastewater treatment is performed by adding the microbial activator in a ratio of 4 to 10 based on the C/N ratio according to the amount of N remaining in the wastewater, the wastewater standard of the effluent after wastewater treatment is nitrogen, which is the range of the wastewater treatment standard The content can be managed at 10 or less and COD 20 or less.

[Production Example]

80 g of hydrochloric acid was added to 1,000 g of glycerin pitch containing glycerin, organic impurities, and ash, 200 g of water was added, heated to 40° C., and stirred at 200 rpm for 1 hour. After standing for 2 hours, the organic impurities separated into the upper layer are removed through a centrifugal separation process.

Thereafter, the ash is removed through the electrolysis process of the electrolysis device.

First, crude glycerin from which organic impurities are removed contains a large amount of water, chlorine gas is ejected from the anode of the electrolysis device, and hydrogen gas is generated from the cathode.

At this time, an aqueous hydrochloric acid solution can be obtained by collecting chlorine gas and hydrogen gas in water.

The aqueous hydrochloric acid solution generated in this process can be used to remove organic impurities from the glycerin pitch in the future.

After the chlorine gas is removed, sodium hydroxide is produced in the crude glycerin remaining. Therefore, the remaining crude glycerin is converted into a basic substance.

Then, acetic acid is added to the basic crude glycerin, and sodium hydroxide and acetic acid are reacted to prepare sodium acetate.

Therefore, in the glycerin prepared through the above process, glycerin, sodium acetate and water are mixed.

Glycerin and sodium acetate contained in the mixture are very useful components as an activator of microorganisms.

The specifications of glycerin obtained through the above process are shown in Table 1 below.

As shown in Examples 1 to 3, the thus-prepared microbial activator for wastewater treatment can be added during wastewater treatment to increase microbial activity and function as a carbon source.

Example 1

After lowering the viscosity by adding 20 g of water to 100 g of glycerin pitch, 8 g of hydrochloric acid is added. Turn the stirrer at 200rpm and increase the temperature to 60℃. Stirring is continued for about 2 hours while maintaining the temperature at 60°C. After standing for about 1 hour, organic impurities in the upper layer are removed through centrifugation, and impurities such as proteins in the lower layer are removed.

After removing organic impurities in this way, only glycerin, water, and NaCl are contained.

Thereafter, electricity is injected between the cathode and the anode to electrolyze Nacl contained in the aqueous glycerin solution.

cl- separated from the anode and h+ generated from the cathode are put in water to obtain an aqueous hcl solution and used as hydrochloric acid in the organic impurity removal process.

After NaCl electrolysis, the remaining Na is converted to NaOH, and the aqueous glycerin solution becomes basic.

Sodium acetate is synthesized by adding acetic acid to this basic glycerin.

After synthesizing sodium acetate, a mixture of glycerin and water sodium acetate is obtained.

A microbial activator of COD 1,088,000 can be obtained from the mixture.

Example 2

Add 10 g of water to 100 g of glycerin pitch to lower the viscosity, and then add 10 g of hydrochloric acid. Turn the stirrer at 200rpm and increase the temperature to 60℃. Stirring is continued for about 2 hours while maintaining the temperature at 60°C. After standing for about 1 hour, organic impurities in the upper layer are removed through centrifugation, and impurities such as proteins in the lower layer are removed.

After removing organic impurities in this way, only glycerin, water, and NaCl are contained.

Then, electricity is injected between the anode and the cathode to electrolyze Nacl contained in the aqueous glycerin solution.

cl- separated from the anode and h+ generated from the cathode are put in water to obtain an aqueous hcl solution and used as hydrochloric acid in the organic impurity removal process.

After NaCl electrolysis, the remaining Na is converted to NaOH, and the aqueous glycerin solution becomes basic.

Sodium acetate is synthesized by adding acetic acid to this basic glycerin.

After synthesizing sodium acetate, a mixture of glycerin and water sodium acetate is obtained.

A microbial activator of COD 1,182,000 can be obtained from the mixed solution.

Example 3

After lowering the viscosity by adding 20 g of water to 100 g of glycerin pitch, 3 g of hydrochloric acid is added. Turn the stirrer at 200rpm and increase the temperature to 60℃. Stirring is continued for about 2 hours while maintaining the temperature at 60°C. After standing for about 1 hour, organic impurities in the upper layer are removed through centrifugation, and impurities such as proteins in the lower layer are removed.

After removing organic impurities in this way, only glycerin, water, and NaCl are contained.

Then, electricity is injected between the anode and the cathode to electrolyze Nacl contained in the aqueous glycerin solution.

cl- separated from the anode and h+ generated from the cathode are put in water to obtain an aqueous hcl solution and used as hydrochloric acid in the organic impurity removal process.

After NaCl electrolysis, the remaining Na is converted to NaOH, and the aqueous glycerin solution becomes basic.

Sodium acetate is synthesized by adding acetic acid to this basic glycerin.

After synthesizing sodium acetate, a mixture of glycerin and water sodium acetate is obtained.

A microbial activator of COD 1,182,000 can be obtained from the mixed solution.

On the other hand, although the method for producing an energy source for microorganisms using recycled waste glycerin according to the present invention has been described in accordance with limited examples, the scope of the present invention is not limited to specific examples, and those of ordinary skill in the art Various alternatives, modifications, and changes can be implemented within the range that is obvious to the person concerned.

Accordingly, the embodiments disclosed in the present invention and the accompanying drawings are intended to explain, not to limit the technical spirit of the present invention, and the scope of the technical spirit of the present invention is not limited by these embodiments and the accompanying drawings. . The protection scope of the present invention should be construed by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (3)

As a method of manufacturing an energy source for microorganisms using recycled waste glycerin,
A first step of adding hydrochloric acid to glycerin pitch containing glycerin, organic impurities, and ash (salt), adding water, and then heating and stirring;
a second step of removing the organic impurities separated into the upper layer after standing for a certain period of time through a centrifugal separation process;
a third step of removing ash (salt) from the crude glycerin from which organic impurities have been removed through an electrolysis process;
a fourth step of collecting chlorine gas generated from the anode and hydrogen gas generated from the cathode in water to obtain an aqueous hydrochloric acid solution;
Recycling waste glycerin comprising a fifth step of producing a microbial activator in which glycerin, sodium acetate, and water are mixed by adding acetic acid to basic crude glycerin containing sodium hydroxide by removing chlorine gas to produce sodium acetate A method for producing an energy source for microorganisms using The method according to claim 1,
In the first step, 1 to 10 parts by weight of hydrochloric acid is added with respect to 100 parts by weight of glycerin pitch, 5 to 30 parts by weight of water is added, and then stirred for 30 minutes to 3 hours after heating to 30 to 60° C.,
In the second step, a method for producing an energy source for microorganisms using recycled waste glycerin, which is left standing for 1 to 12 hours. The method according to claim 1,
A method for producing an energy source for microorganisms using recycled waste glycerin using the aqueous hydrochloric acid solution obtained in the fourth step when adding hydrochloric acid in the first step.

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