KR101272171B1 - Heavy oil emulsifier and method for preparing emulsified heavy oil - Google Patents

Abstract

In the present invention, at least one compound (A) selected from polyoxyethylene alcohol and at least one compound (B) selected from alkylpolyethylene polypropylene block copolymer materials as an emulsifier component are mixed at a weight ratio of 1: 100 to 100: 1 to form an emulsifier. It is characterized by using. Alcohol components in polyoxyethylene alcohol include nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, cetyl alcohol ethoxylate, oleyl alcohol ethoxylate, stearyl alcohol ethoxylate, tridecyl Alcohol ethoxylate, sorbitan ester, and the like. Alkyl polyethylene polypropylene block copolymer The alkyl component in the nonyl phenol, lauryl alcohol, glycerol stearate, branched decyl alcohol and the like. The emulsifier thus prepared is added to 0.01% to 15% by weight in a fuel in which A heavy oil or B heavy oil or C heavy oil or crude oil and water are mixed at a weight ratio of 1 to 60% by weight, and emulsified by mechanical emulsification or ultrasonic wave. It is emulsified to have a particle diameter of 0.1 to 20 μm to emulsify A heavy oil, B heavy oil, or C heavy oil around the water, or to make the particle diameter of the crude oil 1 to 1,000 μm to surround the crude oil with water. It is done. Ultrasonic or mechanical emulsification of these emulsifiers to produce emulsified heavy oil fuel, and when the combustion inside the engine finely exploded in the fine oil inside the heavy oil to make it close to the complete combustion by reducing the nitrogen oxides and soot emissions As a result, it greatly contributes to the improvement of the atmospheric environment, and has the characteristics of contributing to the reduction of carbon dioxide emission which is a greenhouse gas as an alternative fuel using water.

Description

Heavy oil emulsifier and manufacturing method of emulsified heavy oil {HEAVY OIL EMULSIFIER AND METHOD FOR PREPARING EMULSIFIED HEAVY OIL}

In the present invention, heavy oils such as A heavy oil, B heavy oil, C heavy oil, crude oil, etc. are mixed with water and mechanical or ultrasonic to make an emulsion fuel to smoothly transport, soot and nitrogen, which are air pollutants during combustion. In order to improve the atmospheric environment by reducing oxides, and to emulsify crude oil and water to reduce the viscosity during transportation, it is possible to save energy by facilitating the transfer, and to save energy by reducing the consumption of heavy oil by mixing water. It is about.

Compressive ignition diesel engines emit more nitrous oxide (NOx) and particulate matter due to their lean burning characteristics than gasoline engines. Nitrogen oxides cause photochemical reactions by sunlight to cause ozone, causing respiratory diseases, etc. Fine dust is small particles with a particle size of 10 ㎛ or less that easily penetrates into the respiratory tract and is adsorbed into the lungs. It is known to cause. In particular, due to the characteristics of Korea's metropolitan areas, populations are concentrated, traffic jams are long, distances between roads and residential areas are short, and the operation of diesel vehicles such as large buses and trucks is frequent. It is urgent.

The low NOx technology includes pretreatment methods to improve fuel pretreatment and combustion equipment. Fuel injection timing delay, combustion chamber shape modification, fuel injection system improvement, exhaust recirculation (EGR), water injection method, diesel oil-water emulsion Examples of post-treatment methods for removing NOx contained in fuel use and exhaust gas include catalytic decomposition, catalytic reduction, absorption, and adsorption.

The use of water together with liquid fuel in an emulsified state has recently attracted new attention as a technology that can simultaneously reduce NOx, particulates, CO, and HC without substantially reducing thermal efficiency. The main factors that contribute to this effect include lowering the flame temperature by adding water, lowering the flame temperature by the rapid evaporation of water, microexplosion of oil droplets due to the rapid evaporation of water, and increasing the amount of ambient air due to the increase in spray penetration. Can be.

In addition, the high viscosity when transferring the crude oil brings a lot of energy loss, it is possible to reduce the energy by simplifying the transfer by emulsifying with water.

On the other hand, ships are expected to reduce NOx by more than 80% when Tier 3 takes effect in 2016. As a solution to this, emulsion fuel of heavy oil is emerging.

According to the present invention, the emulsion state does not last long with the conventional emulsion technology and the water particles are recombined with each other and the oil and water separation phenomenon occurs due to the crystal growth of the water particles. B. Emulsify by mechanical method and make heavy oil and emulsion fuel such as water, A heavy oil, B heavy oil, C heavy oil and crude oil to provide stable fuel without oil and water separation. The purpose of the present invention is to provide a method for improving air pollution by reducing soot or nitrogen oxide, an air pollutant.

In the present invention, at least one compound (A) selected from polyoxyethylene alcohol and at least one compound (B) selected from alkylpolyethylene polypropylene block copolymer materials as an emulsifier component is used in a weight ratio of A: B = 1: 1-100-100: 1. It is characterized by being used as an emulsifier by mixing. When compound A or compound B is 2 or more types, it mixes so that the ratio of the sum of compound A and the sum of compound B may be a weight ratio of 1: 100-100: 1. The polyoxyethylene alcohol is characterized in that the repeating unit (polymerization degree) of polyoxyethylene is 1 to 30, and the repeating unit (polymerization degree) of the alkylpolyethylene polypropylene block copolymer is characterized in that 1 to 30. In the polyoxyethylene alcohol, alcohol components include nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, cetyl alcohol ethoxylate, oleyl alcohol ethoxylate, stearyl alcohol ethoxylate, Tridecyl alcohol ethoxylate, sorbitan ester, and the like. The alkyl component in the alkyl polyethylene polypropylene block copolymer is nonylphenol, lauryl alcohol, glycerol stearate, branched decyl alcohol, and the like.

The emulsifier thus prepared is added to 0.01% to 15% by weight in a fuel in which A heavy oil or B heavy oil or C heavy oil or crude oil and water are mixed at a weight ratio of 1 to 60% by weight, and emulsified by mechanical emulsification or ultrasonic wave. It is emulsified to have a particle diameter of 0.1 to 20 μm to emulsify A heavy oil, B heavy oil, or C heavy oil around the water, or to make the particle diameter of the crude oil 1 to 1,000 μm to surround the crude oil with water. It is done. If the amount of added emulsifier is less than 0.01%, emulsification does not occur well, and if it is larger than 15%, the economic efficiency is lost, and the properties of A heavy oil, B heavy oil, C heavy oil, and crude oil are affected. When using ultrasonic waves, the amplitude is 5 to 200 μm, and when the amplitude is smaller than 5 μm, emulsification does not occur. When it is larger than 200 μm, too strong energy is injected to vaporize the oil, which is rather hindering the emulsification.

The present invention can be used because the phase separation of water and A heavy oil or B heavy oil or C heavy oil or crude oil even at high storage temperature in summer, and also the phase separation problem of water and A heavy oil, B heavy oil, C heavy oil, crude oil even in long-term storage Can be overcome completely. Also, in case of A heavy oil, B heavy oil or C heavy oil, the heavy oil such as A heavy oil, B heavy oil or C heavy oil is wrapped around the water, so there is no corrosion problem of fuel tank, fuel supply system, and combustion in diesel engine, marine engine or boiler. The fine-grained water inside A heavy oil, B heavy oil, or C heavy oil makes explosives close to complete combustion, reducing carbon monoxide and hydrocarbons and contributing to the improvement of the atmospheric environment. Contribute to emission reduction In the case of crude oil, water is surrounded by crude oil, which reduces the viscosity and saves energy during transportation.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, which are emission reductions. However, the scope of the present invention is not limited by these embodiments, and those skilled in the art can variously modify the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. And can be changed.

200 ml of A heavy oil or B heavy oil or C heavy oil and crude oil prepared from Examples and Comparative Examples were put in a measuring cylinder, and placed in a constant temperature water bath at 80 ° C. for 12 hours to observe the degree of phase separation. It is shown in Table 1. Emulsion Stability Index (ESI) was calculated using the simple and sensitive "Volumetric method" as follows.

ESI = 100-(So + Sw), So = (Vo / V _a ) × 100, Sw = (Vw / V _a ) × 100

Where So is the separation of the oil layer, Sw is the separation of the aqueous layer, Va is the total volume of the emulsification system, Vo is the volume of the oil layer separated from the emulsification system over time, and Vw is the time This means the volume of the water layer separated from the emulsification system. If the ESI is 100%, it means a stable state without any phase separation.

In addition, the exhaust gas reduction performance was tested using A heavy oil, B heavy oil, or C heavy oil emulsified by adding water prepared in Examples and Comparative Examples, and is shown in Table 2. And the viscosity of the crude oil and the emulsified crude oil is shown in Table 3 by measuring the kinematic viscosity. The compression ignition engine used in the performance test was a series upright four-stroke engine, and the combustion method was direct injection type. The engine was used with kg · m / 1,400rpm, maximum output / engine speed = 780Nm / 2,200rpm, and exhaust gas irradiation was operated in ND-13 mode using AVL's engine dynamometer and the EXL-1628 exhaust analyzer from Firm Ware Technology Was used.

Example 1

5 g of polyoxyethylene lauryl alcohol ethoxylate having a repeating unit (polymerization degree) of polyoxyethylene alcohol as compound A and nonylphenol polyoxy having a repeating unit (polymerization degree) of alkylpolyethylene polypropylene block copolymer as 10 compound An emulsifier mixed with 5 g of ethylene propylene block copolymer was placed in 10 kg of A heavy oil mixed with 30 wt% of water, and irradiated with ultrasonic waves having a 20 μm amplitude for 15 minutes. The average particle diameter of water became 2 μm. It became.

Example 2

5 g of polyoxyethylene cetyl alcohol ethoxylate with a repeating unit of polyoxyethylene alcohol as compound A and 5 g of glycerol stearate polyoxyethylene propylene block copolymer with a repeating unit of alkylpolyethylene polypropylene block copolymer as a compound B of 20 The emulsifier was mixed with 10 kg of B heavy oil mixed with 30% by weight of water, and irradiated with ultrasonic waves having an amplitude of 20 μm for 15 minutes. The average particle diameter of the water was 2 μm, and the B oil was wrapped around the outside of the water.

Example 3

As compound A, 2.5g of polyoxyethylene stearyl alcohol ethoxylate having a repeating unit of 20 polyoxyethylene alcohol, 2.5g of polyoxyethylene tridecyl alcohol ethoxylate having a repeating unit of 20 and a compound B of alkylpolyethylene polypropylene 30 weight% of an emulsifier mixed with 2.5 g of glycerol stearate polyoxyethylene propylene block copolymer having a repeating unit of 20 and 2.5 g of lauryl alcohol polyoxyethylene propylene block copolymer having a repeating unit of 20 After the ultrasonic wave of 20㎛ amplitude was put into 10kg of C heavy oil for 15 minutes, the average particle diameter of water became 2㎛ and the C oil was wrapped around the water.

Example 4

Block A copolymer of polyoxyethylene oleyl alcohol ethoxylate 2.5g with 10 repeating units of polyoxyethylene alcohol as compound A and 2.5g of polyoxyethylene octyl alcohol ethoxylate with 10 repeating units and B copolymer A heavy oil containing 30% by weight of water in an emulsifier mixed with 2.5 g of glycerol stearate polyoxyethylene propylene block copolymer having a repeating unit of 10 and 2.5 g of octylphenol polyoxyethylene propylene block copolymer having a repeating unit of 10 After the ultrasonic wave of 20㎛ amplitude was put into 10kg for 15 minutes, the average particle diameter of water became 2㎛, and the oil of A was wrapped around the outside of the water.

Example 5

5 g of polyoxyethylene cetyl alcohol ethoxylate with a repeating unit of polyoxyethylene alcohol as compound A and 5 g of glycerol stearate polyoxyethylene propylene block copolymer with a repeating unit of alkylpolyethylene polypropylene block copolymer as a compound B of 20 The emulsifier was mixed into 20kg of Saudi Arabian crude oil mixed with 20% by weight of water and stirred at 200rpm at 40 ° C. for 15 minutes to emulsify the outside of the crude oil.

Comparative Example 1

Only 10 g of polyoxyethylene lauryl alcohol ethoxylate having 10 repeating units (polymerization degree) of polyoxyethylene alcohol as compound A was placed in 10 kg of A heavy oil mixed with 30 wt% of water and irradiated with ultrasonic waves having a 20 μm amplitude for 15 minutes.

Comparative Example 2

As a compound B, only 10 g of nonylphenolpolyoxyethylene propylene block copolymer having 10 repeating units (polymerization degree) of an alkyl polyethylene polypropylene block copolymer was placed in 10 kg of A heavy oil mixed with 30% by weight of water and subjected to ultrasonic waves having a 20 μm amplitude for 15 minutes. Investigate.

Comparative Example 3

Ultrasound having a 20 μm amplitude was irradiated for 10 minutes to 10 kg of A heavy oil mixed with 30 wt% water.

Comparative Example 4

Ultrasound of 20 μm amplitude was irradiated to 10 kg of B heavy oil mixed with 30 wt% of water for 15 minutes.

Comparative Example 5

Ultrasound of 20 μm amplitude was irradiated to 10 kg of C heavy oil mixed with 30 wt% water for 15 minutes.

Comparative Example 6

20 kg of Saudi Arabian crude oil mixed with 20% by weight of water was stirred at 40 ° C. at 200 rpm for 15 minutes.

Phase separation degree of emulsified heavy oil Degree of phase separation (ESI%) over time in a thermostatic chamber at 80 ℃ Example 1 hours 2 hours 6 hours 12 hours Example 1 100 100 100 100 Example 2 100 100 100 100 Example 3 100 100 100 100 Example 4 100 100 100 100 Example 5 100 100 100 100 Comparative Example 1 76 32 0 0 Comparative Example 2 79 36 0 0 Comparative Example 3 15 0 0 0 Comparative Example 4 24 8 0 0 Comparative Example 5 33 12 0 0 Comparative Example 6 0 0 0 0

  As shown in Table 1, in the case of Examples 1 to 5, in which A compound and B compound were mixed and used as an emulsifier, emulsification was good and phase separation between water and heavy oil did not occur, and thus it could be used safely.

Emissions analysis Example Smoke reduction (%) Nitrogen oxide reduction (%) Example 1 57 65 Example 2 64 67 Example 3 72 68 Example 4 58 66 Comparative Example 1 17 43 Comparative Example 2 19 45 Comparative Example 3 13 26 Comparative Example 4 14 28 Comparative Example 5 16 29

  As shown in Table 2, when the oil is used to emulsify the heavy oil as in the embodiment of the present invention, water that has been finely granulated inside the heavy oil causes microexplosion in the engine to finely split the heavy oil particles to smoothly contact with oxygen. It reduces the smoke by more than 50% by inducing close to complete oxidation, and takes the latent heat when the microparticles of water inside the heavy oil causes microexplosion inside the engine to lower the temperature inside the engine to suppress the generation of nitrogen oxides. It has been shown to reduce nitrogen oxide emissions by more than 60%. Therefore, it is judged that the air pollutants can be greatly contributed to the improvement of the atmospheric environment by reducing the air pollutants by the effect of the present invention, and the energy can be reduced by the use of water, and the effect of reducing the carbon dioxide emission of greenhouse gases can be simultaneously obtained.

Effects of Crude Viscosity on Oil Temperature Example Dynamic Kinematic Viscosity (cSt) 20 ℃ 30 ℃ 40 ℃ Example 5 67 44 23 Comparative Example 6 214 155 84

Claims (8)

At least one compound (A) selected from polyoxyethylene alcohol and at least one compound (B) selected from alkylpolyethylene polypropylene block copolymer materials are mixed at a weight ratio of 1: 100 to 100: 1,
When the compound A or the compound B is two or more kinds, the sum of the sum of the compound A and the compound B on the basis of weight is from 1: 100 to 100: 1,
In the polyoxyethylene alcohol, the repeating unit (polymerization degree) of polyoxyethylene is 1 to 30, and the repeating unit (polymerization degree) of the alkylpolyethylene polypropylene block copolymer is 1 to 30,
The alcohol component in the polyoxyethylene alcohol is nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, cetyl alcohol ethoxylate, oleyl alcohol ethoxylate, stearyl alcohol ethoxylate, tri It is selected alone or in combination from the group consisting of decyl alcohol ethoxylate and sorbitan ester, and the alkyl component in the alkyl polyethylene polypropylene block copolymer is nonylphenol, lauryl alcohol, glycerol stearate and branched decyl alcohol. Heavy oil emulsifier, characterized in that selected from the group consisting of alone or in combination. delete delete delete The heavy oil emulsifier according to claim 1 is prepared by adding 0.01% to 15% by weight to a fuel in which A heavy oil or B heavy oil or C heavy oil or crude oil and water are mixed at a weight ratio of 1 to 60%. . Emulsified heavy oil, characterized in that the emulsifier according to claim 1 is emulsified using mechanical emulsification or ultrasonic wave so that the particle size of the water is 0.1 ~ 20㎛ emulsified so that A heavy oil, B heavy oil or C heavy oil wrapped around the water . The emulsified heavy oil according to claim 6, wherein the amplitude is 5 to 200 mu m when using ultrasonic waves. Emulsified heavy oil, characterized in that the emulsifier prepared in claim 1 is emulsified using a mechanical emulsification or ultrasonic wave so that water is wrapped around the crude oil.