Demulsification compound for oil separation from waste streams

Abstract

A method for producing an additive for reclaiming oil from a fluid product stream and a treated silica with controlled hydrophobicity are disclosed. The method includes the steps of providing silica or silicate with a particle size of between 3.0 m to 20 m, the silica or silicates having an agglomerate size of between 10 m to 100 m and being chosen to achieve the desired particle-size range and with a controlled level of hydrophobicity; treating the silica or silicate with a silicone or silane to make it hydrophobic; and controlling the hydrophobicity of the silica or silicate by varying the temperature and treatment time of the silica or silicate, amount of a treating material used to treat the silica or silicate, and the molecular weight of the treating material. The additive improves oil extraction and concentration from a fluid product stream.

Claims

1. A treated silica with a hydrophobicity comprising a silica or silicate with a particle size of between 3.0 m to 20 m and a level of hydrophobicity measured by a methanol wet out testing procedure, the silica or silicate having an agglomerate size of between 10 m to 100 m and with a level of hydrophobicity measured by the methanol wet out testing, the silica or silicate having a Specific Surface Area of 100 m.sup.2/g to 200 m.sup.2/g, the treated silica being an additive for reclaiming oil from a fluid product stream.

2. The treated silica of claim 1 wherein the oil is either an internal phase or an external phase of an emulsion process.

3. The treated silica of claim 1 further including a surfactant for oil recovery from a fluid product stream.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The drawings illustrate a preferred embodiment including the above-noted characteristics and features of the invention. The invention will be readily understood from the descriptions and drawings. In the drawings:

(2) FIG. 1 is a simplified flow diagram of an oil/water separation process in which a demulsifying chemical additive is introduced without a retention vessel; and

(3) FIG. 2 is a simplified flow diagram of an oil/water separation process in which a demulsifying chemical additive is introduced with a retention vessel.

(4) FIG. 3 illustrates two comparative photographs of silica blends;

(5) FIG. 4 is Table 1 illustrating the test results from Ethanol Plant 1;

(6) FIG. 5 is Table 2 illustrating the test results from Ethanol Plant 2;

(7) FIG. 6 is Table 3 illustrating the test results from Ethanol Plant 3;

(8) FIGS. 7-9 are charts illustrating Mill Test Data; and

(9) FIGS. 10-13 are charts illustrating the performance of different silica blends.

DETAILED DESCRIPTION OF THE INVENTION

(10) Exemplary additive for reclaiming oil from fluid product stream compositions, methods of making the chemical additive, and applications of such chemical additive will now be described in detail with respect to the detailed description, FIGS. 1-13, and examples that follow. The preferred embodiments described herein are not intended to be exhaustive or to limit the invention to the precise forms disclosed. The section headings provided herein are for convenience only and are not intended to limit the scope of the invention in any way.

(11) As noted above, and also in FIGS. 1 and 2, the formulated additive for reclaiming oil from fluid product stream compositions increases the oil separation rate and efficiency when added in specific amounts and under specific conditions.

(12) It has been known to those skilled in the art that surfactants help with the separation of organic oils/materials and dewatering since before the late 1990's. The use of silicates such as precipitated or fumed silicon dioxide, diatomaceous earth, talc, or volcanic ash, for example, has been shown in some instances to improve the recovery of oils above the use of surfactants alone. There are some cases where hydrophilic silicates perform better than hydrophobic silicates and vice versa. One silicate with certain particle size or agglomerate size may perform better in an application than another. This is true even in the same industries which use similar production methods.

(13) There is typically a large variation from plant to plant, and therefore a broader conceptual approach is necessary to have a product which will work well across a wide range of applications. This invention encompasses silicate compounds with a wide range of particle and agglomerate sizes. The invention also controls the level of hydrophobicity. With both approaches this allows the silicate to work over a wider range of facilities within the same business and in the same application, minimizing the need for a special formula for each facility.

(14) The level of hydrophobization is controlled by the amount or percentage of treating material applied to the silicate and the molecular weight of the material treating the silicate along with the particle size and surface area of the silicate. This differs from mixing hydrophilic and hydrophobic silica in that all of the silica has some degree of hydrophobicity when treated in the manner of the invention versus mixing the hydrophilic and hydrophobic silica. In the photograph labeled as Photo 1 (left side) in FIG. 3, the mixture of hydrophobic and hydrophilic silicas are blended and then put into deionized water (also referred to as DI Water). The deionized water wets out the hydrophilic silica, giving a cloudy appearance to the water. The silica treated in the manner of the invention does not wet out in deionized water; thus showing its hydrophobic properties.

(15) When the silica treated in the manner of the invention (Photo 2 in FIG. 3) is put into a 35% methanol and 65% deionized water solution the silica wets out, showing the hydrophilic nature of the silica when compared to a commercially available hydrophobic precipitated silica, such as AMSil 35-FGK from Applied Material Solutions, Inc. which does not wet out in the methanol solution.

(16) The controlled hydrophobicity of the silicate and wide span of particle size allows the silicates treated to be used over a wide range of facilities within an application. The hydrophobicity of the silicate, the particle size, and agglomerate size can be adapted to fit new applications.

(17) Tables 1-3, in FIGS. 4-6, show the precipitated silica blends, the percent silicone, and the silicone viscosity used to treat the silica.

(18) Procedure for Preparing the Silica:

(19) The dry roaster used is a proprietary design by Applied Material Solutions, Inc. The dry roaster allows powders to be mixed at a fixed temperature. The temperature range is from ambient to 260 C. The dry roaster can be run with an inert atmosphere, it can allow moisture or other by products, or it can be sealed.

(20) The steps for preparing the silica are as follows: 1. The silica is weighed out in parts per experimental conditions; for sample 1, for example, 1 part Silica 1 is used and then 1 part Silica 2, and next 1 part Silica 3, etc. This is 94% of the formula and the balance is 6% 1,000 cs silicone. The other 30 samples are calculated in a similar manner. 2. The silica is put into a dry roaster, the temperature is set to typically 230 to 260 C., a N.sub.2 blanket is applied, the heater is turned on, and the agitator is turned on. 3. The silicone is added while the silica is heating and mixing per experimental conditions. 4. The dry roaster mixes the silica and silicone mixture at 230 to 260 C. for 5 hours. 5. After 5 hours at 230 to 260 C. the heat is turned off and the silica is cooled overnight.
Sample Preparations for Silica Evaluation

(21) During testing of the inventive method, samples were prepared in the following manner.

(22) Treated silica was dispersed into the test mixture using a cowles bade. Three types of additions were used to test the efficacy of the silica. A typical standard level of silica was added to the test mixture. These mixtures were evaluated in thin stillage from three different ethanol factories which derive their ethanol from fermented corn. The samples made were used to extract corn oil from the thin stillage.

(23) Evaluation for the Extraction Testing Procedure

(24) It is important to note that the testing is relative to the other samples and not indicative of actual corn oil recovery in the ethanol process. The goal was to determine which silica performs best when compared to the other silica samples and how they interact with the chosen surfactants.

(25) Dosage level and centrifuge speed were based on the behavior of the stillage used. The same samples were screened at different rpms ranging from 500 rpms to 2,000 rpms. The goal was to have the minimum dosage of the silica mix and minimum rpms necessary to achieve corn oil separation with maximum differentiation between samples.

(26) The standard procedure was to add 50 ml of thin stillage into a centrifuge tube. The filled centrifuge tube was then placed into a hot water bath and the temperature of the thin stillage in the centrifuge tube was raised to 85 C. Once the temperature reached 85 C. the thin stillage in the centrifuge tube was dosed with the demulsifying compound, placed in the centrifuge, and spun in the centrifuge at the determined rpms for 1 minute.

(27) Next, the centrifuge tube was removed and the corn oil separated from the thin stillage was measured in millimeters (mm). The more oil which was extracted, the better the demulsifier performed. During testing, thirty-one samples were evaluated along with a blank (no additives) and a control (no silica in the blend) in thin stillage samples from three different ethanol plants.

(28) All particle size was measured in Volume %. As can be seen in Tables 1-3 in FIGS. 4-6, Silica 1 had an average particle size of 9.0 m and an agglomerate size of 13.25 m. The Specific Surface Area or SSA of Silica 1 is 170 m.sup.2/g. Silica 2 had an average particle size of 12 m and an agglomerate size of 17.31 m. The Specific Surface Area or SSA of Silica 2 is 140 m.sup.2/g. Silica 3 had an average particle size of 4.5 m and an agglomerate size of 13.25 m. The Specific Surface Area or SSA of Silica 3 is 180 m.sup.2/g. The testing results are shown in charts 1 through 7 in FIGS. 7-13.

(29) Histograms and Particle Size Data of Silicas Used in Testing

(30) The particle size was measured using a Cilas 990 and the dispersant liquid used was deionized water with no sonification. The particle size measured was the agglomerate size. The particle size was information obtained from the supplier.

(31) Based on the above results, it became evident that no particular silica treatment or treatment level was effective across all surfactants and/or thin stillage. It was found that the treated silica blends with the wider particle and agglomerate size range and with controlled hydrophobicity were more effective across a wider range of surfactants and thin stillage.

(32) The more hydrophobic blends and those blends with a narrower range proved to be the most effective in one or two tests, but not across a wide range of surfactants or stillages. When the testing was viewed as a whole, the silicas which proved to be effective in a broader spectrum of surfactants and thin stillages were those silica blends with controlled hydrophobicity and a wide particle and agglomerate size range.

(33) The hydrophobicity was controlled through the use of the silicone viscosity. Specifically, the thinner the silicone viscosity or lower molecular weight, the more effective it was in making the silica hydrophobic, and the converse of this statement was also true. For example, this indicated that 100 cs silicone will make a more hydrophobic silica than 1,000 cs silicone, etc.

(34) The research and product testing showed that using a silicate which has been either insufficiently treated or treated with the wrong substrate can result in a hydrophobic silicate yielding less oil separation than a hydrophilic silicate. When the proper amount of the correct substrate is used to treat the silicate to make it hydrophobic and subsequently used in the oil separation compound, superior results are achieved as shown in the inventive method and inventive silica/silicate.

(35) Wide varieties of materials are available for the various parts discussed and illustrated herein. While the principles of this invention and related method have been described in connection with specific embodiments, it should be understood clearly that these descriptions are made only by way of example and are not intended to limit the scope of the application. It is believed that the invention has been described in such detail as to enable those skilled in the art to understand the same and it will be appreciated that variations may be made without departing from the spirit and scope of the invention.